Investigating the role of interphases in composite electrolytes by solid- state NMR

Uni e sidad del País Vasco / Euskal He iko Unibe si a ea
In es iga ing he ole o in e phases in
composi e elec oly es by solid-s a e NMR
Ped am Gho banzade
Thesis Di ec o s:
P o . Senen xu Lance os-Mendez
D . Juan Miguel López del Amo
2024
(cc) 2025 Ped am Gho banzade (cc by-nc-sa 4.0)
In memo y o Nima Tahe khani,
my kindes iend, wi h he mos joy ul laugh e .
Acknowledgmen s
Th oughou his esea ch, I ha e been o una e o ecei e p o essional and pe sonal suppo
and encou agemen om many people. I wish o ex end my hea el hanks o hose whose
con ibu ions made his possible.
To my supe iso s, D . Juan Miguel Lopez del Amo and P o . Senen xu Lance os-Mendez.
Senen xu, hank you o making hings easy and o e ing you help whene e I needed i . Juan
Miguel, he e a e no wo ds o exp ess how pleased and p oud I am abou wo king wi h you. I
am e y g a e ul o all he hings you augh me, and he eedom you ga e me o p opose
and ollow my ideas. You a e an amazing supe iso and pe son, and I am g a e ul o you
con inuous suppo in hese yea s. I wouldn’ ha e been his simple wi hou you.
To my co-au ho s, especially Michel, Ped o, Roshan, G azia, A ianna, and Ke man, o
collabo a ing on my p ojec h ough help ul ad ice o hei assis ance wi h he expe imen s.
I was a pleasu e wo king wi h you in a eam. Also, Pie e Ranque, who helped me a lo in my
i s ew mon hs a CIC, ook me o he igh ack and mindse and ga e me he sel -
con idence I eally needed. I was amazing ha ing you a ound and I app ecia e you help.
To my supe iso s a he Uni e si y o Camb idge, P o . Dame Cla e G ey, D . Ch is O’Kee e,
and D . Sundeep Vema, o hos ing me and o e ing hei suppo wi h my p ojec du ing my
s ay. I lea ned a lo om you, bo h abou science and wo k e hics. Thanks o making my 3-
mon h s ay an un o ge able expe ience. Also, o gi ing me he chance o p esen my wo k
a he g oup mee ing, which I uly enjoyed. To Angela, Ramon, Mohammed, Richa d, Jana,
As id, S e an, Fa heen, Kie an, Megan, and o he g oup membe s o he socializa ion in he
can een, climbing gym, o he pub.
To my amazing iends, he membe s o he Malaka g oup, who gua an eed my men al heal h.
Especially, o Liam, Remy, Ross, Ade, A ianna, And ei, Rosa, Dimi is, Lu, Simon, Da ide, Pie e,
Paul, S e en, Nico, and Elisabe a. Thanks o you company and o le ing me be mysel . I
made wonde ul memo ies wi h you, om ou s ay a he u al house o he mo ie nigh s and
pin xo-po es. You we e he bes pa o my li e in he las 3 yea s and I’m supe happy o ha e
you a ound.
To my NMR ma e, Nahom, o all hose long scien i ic and non-scien i ic cha s we had, and he
ping-pong games we played oge he . Besides you big hea and humo , you passion o
science and dedica ion a e inspi ing. I am happy o ha e you as a iend in he las 5 yea s.
To my g ea colleagues a CIC, o all he un ime we spen oge he inside and ou side wo k.
The oo ball games, Saga do egias, Ku xi nigh s, ping-pong games, Ba bacoas, To illas, eam
building ac i i ies, e c. Also, o helping me lea n Spanish and in eg a e. E en he lab cleaning
is un wi h you!
To Asie , Es i, Me cedes, and Sa a, o hei g ea suppo wi h all he pape wo k ega ding my
eloca ion and immig a ion. I uly app ecia e you assis ance which s a ed long be o e I
joined CIC and will las un il my inal day he e. To Elena, who manages o ind g ea solu ions
o any complica ed case and makes e e yone’s wo k a CIC easy. You a e amazing.

To my old iends, Mahsa and Ghazal, whom I miss a lo . I eel so ene gized wi h you and I
can’ wai o see you again. E e y ime spen wi h you is quali y ime! Also, o my Couchsu ing
iend, Aya o hos ing me in Vienna, bu especially o ou week-long hike in he Py enees.
E en i s memo ies make me app ecia e li e and eel happy.
I also hank my dea amily, who ha e always suppo ed me and gi en me he con idence and
eedom o make decisions. Being a om you hasn’ been easy, bu I’m happy abou he
g ea memo ies we made when we me in Tu key, Aus ia, and Nepal. Each o hese ips was
a boos o ene gy and mo i a ion o me, and I hope all o us can ga he some ime soon.
Finally, I would like o hank he whole DESTINY eam, pa icula ly P o . Masquelie , Bea ice,
and Louise o hei g ea wo k in o ganizing his amazing p ojec . I eel e y p oud o ha e
been pa o his amazing p og am. This p ojec has ecei ed unding om he Eu opean
Union’s Ho izon 2020 esea ch and inno a ion p og amme unde G an Ag eemen N°945357.
Table o Con en s
Summa y ............................................................................................................................... 1
Resumen ............................................................................................................................... 5
1. In oduc ion ................................................................................................................... 10
1.1 Ene gy s o age scena io .......................................................................................... 10
1.2 De elopmen o Ba e ies........................................................................................ 11
1.3 Li-ion ba e ies ....................................................................................................... 13
1.4 Solid S a e Ba e ies................................................................................................ 14
1.4.1 Solid Polyme Elec oly es ................................................................................... 16
1.4.2 Solid ino ganic elec oly es .................................................................................. 17
1.4.3 Composi e elec oly es ....................................................................................... 19
1.5 Solid-S a e NMR ..................................................................................................... 22
1.5.1 One-Pulse and Hahn Echo ................................................................................... 25
1.5.2 Sa u a ion Reco e y ............................................................................................ 26
1.5.3 Exchange Spec oscopy ....................................................................................... 27
1.5.4 C oss Pola iza ion and He e onuclea Co ela ion ................................................... 28
1.5.5 CP-spin di usion ................................................................................................ 30
1.5.6 Iso ope-exchange expe imen s ............................................................................ 30
1.5.7 Va iable Tempe a u e solid-s a e NMR .................................................................. 31
1.5.8 Pulse Field G adien NMR and Di usion Expe imen s ............................................. 31
1.6 Scope and ield o esea ch ..................................................................................... 33
2. Me hodologies .............................................................................................................. 34
2.1 Composi e Elec oly e P epa a ion ........................................................................... 34
2.2 Cha ac e iza ion Techniques .................................................................................... 35
2.2.1 Solid-s a e NMR................................................................................................ 35
2.2.2 Elec ochemical Cha ac e iza ions .................................................................... 36
2.2.3 Scanning Elec on Mic oscopy .......................................................................... 37
2.2.4 Powde X- ay Di ac ion .................................................................................... 37
2.2.5 Raman Spec oscopy ........................................................................................ 37
2.2.6 Mechanical Tes ing ........................................................................................... 37
2.2.7 The mog a ime ic Analysis .............................................................................. 38
2.2.8 Di e en ial Scanning Calo ime y ...................................................................... 38
3. Gene al Objec i e ......................................................................................................... 39
4. Resul Summa y and Discussion ................................................................................... 41
5. Re e ences: .................................................................................................................. 44
6. Concluding Rema ks and Fu u e Impac s ...................................................................... 49
7. Annex ........................................................................................................................... 50
7.1 Publica ion #1: ..................................................................................................... 50
7.2 Publica ion #2: ..................................................................................................... 62
7.3 Publica ion #3: ..................................................................................................... 72
7.4 Publica ion #4: ..................................................................................................... 80
7.5 Publica ion #5: ..................................................................................................... 97
7.6 Publica ion #6: ................................................................................................... 106
1
Summa y
The mi iga ion o global wa ming and clima e change, as one o he bigges challenges ahead
o humans, equi es a apid ansi ion in ene gy sou ces om ossil uels o enewable
ene gies. Elec i ica ion o he anspo sec o is conside ed a p io i y o achie e he
wo ldwide goal o limi ing he global empe a u e ise below 2°C. This elec i ica ion equi es
he de elopmen o ad anced ba e y echnologies o a ious applica ions.
Comme cialized in 1990, Li hium-ion ba e ies (LIBs) a e cu en ly he mos ma u e and
ad anced ba e y echnology, o e ing a combina ion o high ene gy and powe densi y. These
ba e ies consis o a nega i e elec ode (usually g aphi e), a posi i e elec ode (usually
li hium nickel manganese cobal oxide (NMC) o li hium i on phospha e (LFP)), and a liquid
elec oly e (LiPF6 dissol ed in o ganic sol en s). Wi h mo e han 30 yea s o esea ch and
de elopmen , comme cial LIBs deli e high g a ime ic and olume ic ene gy densi ies abo e
200 Wh/kg and 400 Wh/L. Howe e , he ola ile and lammable o ganic sol en s used in he
elec oly e o LIBs aise non-negligible sa e y conce ns ega ding hei applica ion in Elec ic
Vehicles (EVs). In addi ion, despi e hei me i s, LIBs a e no able o mee he pe o mance
equi emen s o a wide ange o applica ions. Fo ins ance, he cha ac e is ics o ba e ies
used in an EV a e signi ican ly di e en om he ones used o g id applica ions. Thus, mee ing
he huge ene gy demand equi es he ad ancemen o al e na i e ba e y echnologies wi h
di e en cha ac e is ics.
Solid-s a e ba e ies a e an eme ging ba e y echnology, aiming o imp o e bo h he sa e y
and ene gy densi y o LIBs. Solid-s a e ba e ies (SSBs) di e om LIBs in ha he liquid
elec oly e and sepa a o a e eplaced by a solid memb ane, which has supe io he mal and
mechanical s abili y and can e ec i ely block he g ow h o Li dend i es. These p ope ies
enable he use o Li me al as he nega i e elec ode, which has a ema kably highe heo e ical
ene gy densi y compa ed o he commonly used g aphi e elec odes. These ad an ages make
solid-s a e ba e ies an a ac i e choice o nex -gene a ion ba e ies.
The e a e h ee main ypes o solid elec oly es used in SSBs. The i s is polyme elec oly es,
which o e excellen p ocessabili y and lexibili y, allowing o good in e acial con ac wi h
he elec odes. Howe e , hei oom- empe a u e ionic conduc i i y is ela i ely low, limi ing
hei pe o mance in ce ain applica ions. The second ype includes ino ganic li hium-
conduc ing elec oly es such as oxides, sul ides, and halides. These ma e ials exhibi high ionic
8
pa icula men e cuando se manipulan pol os de LLZO pa a CPEs. Además, se de allan las
o alezas y limi aciones de las écnicas de ca ac e ización más u ilizadas, como el análisis
e mog a imé ico (TGA), la di acción de ayos X (XRD), la espec oscopía Raman, la
esonancia magné ica nuclea (RMN), la espec oscopía de o oelec ones de ayos X (XPS), y
la espec oscopía de impedancia elec oquímica (EIS) en el análisis de LLZO.
El siguien e abajo enía como obje i o diseña CPEs de al as p es aciones basados en una
ma iz polimé ica plas i icada a base de PEO y pa ículas de Li1.3Al0.3Ti1.7(PO4)3 (LATP). Es e
es udio in es igó las in e acciones en e el LATP y la ma iz polimé ica, y empleó a ias
écnicas de RMN de es ado sólido pa a dilucida el mecanismo de anspo e de iones an o
en co as dis ancias (dinámica local) como a la gas dis ancias. Los esul ados mos a on que
la pa icipación del LATP en el anspo e de iones a la ga dis ancia se obse a p incipalmen e
a al as empe a u as, lo que se a ibuye p incipalmen e al aumen o del in e cambio de Li+ en
la in e ase en e las ases o gánicas e ino gánicas. El análisis de CPEs con di e en es
con enidos de LATP concluyó que, a pesa de su mínima con ibución al anspo e iónico, la
p esencia de LATP en acciones mode adas (10 ol%) mejo a signi ica i amen e las
p opiedades mecánicas de la memb ana y su esis encia al c ecimien o de dend i as de li io.
El siguien e es udio de es a esis se cen a en las in e ases o madas en un CPE compues o
po a gi odi as Li6PS5Cl y una ma iz de PEO-LiTFSI. En es e abajo, se u ilizó ampliamen e la
RMN de es ado sólido pa a iden i ica las especies p esen es en la in e ase y demos a su
papel en el anspo e iónico. Los esul ados mos a on que, al en a en con ac o con el PEO,
el Li6PS5Cl se descompone en sus p ecu so es, o mando complejos con PEO como P(EO)3-LiCl
y PEO-Li3PS4. Es os complejos exhiben una mo ilidad muy limi ada, lo que alen iza el
in e cambio de Li a a és de la in e ase en e las dos ases. Se demos ó que la composición
química y el g ado de deso den de las a gi odi as a ec an sus ancialmen e su asa de
descomposición y la ex ensión de las especies p esen es en la in e ase. Se concluyó que, pa a
ealiza el po encial de los CPEs, es necesa io op imiza la composición de ambas ases pa a
mejo a la compa ibilidad.
La in es igación inal p o undizó en la compa ibilidad y las eacciones in e aciales en e los
elec oli os de halu o Li2.1Ga0.1Z 0.9Cl6 y los a gi odi os Li6PS5Cl. Una combinación de EIS, DRT
y RMN en es ado sólido e eló que es os elec oli os son químicamen e incompa ibles y
su en una descomposición pa cial al en a en con ac o, o mando ases secunda ias en la
in e ase. Debido a su mo ilidad local más len a, es as ases secunda ias aumen an la

9
esis encia al anspo e de iones a a és de la in e ase. A pesa de la incompa ibilidad, las
eacciones in e aciales se es abilizan con ela i a apidez, pe mi iendo el uncionamien o de
la celda a la go plazo. No obs an e, se obse ó que es as eacciones pueden p og esa aún
más con el calen amien o, lo que con ie e a la empe a u a en un pa áme o impo an e en
la manipulación y el uncionamien o de es os elec oli os. Es impo an e des aca que se
obse ó un in e cambio espon áneo de iones de Li en e los elec oli os de halu o y a gi odi a,
pa icipando di ec amen e en es e p oceso las ases secunda ias de la in e ase.
La p esen e esis des aca pa áme os c í icos que gobie nan el anspo e iónico en CPEs,
pa icula men e el papel de las in e ases en el in e cambio de iones en e las ases o gánicas
e ino gánicas. Al descub i los mecanismos subyacen es, es e abajo p opo ciona in o mación
aliosa pa a el diseño es a égico de CPEs con mayo conduc i idad iónica a empe a u a
ambien e y un endimien o mejo ado, ace cando el po encial de la ecnología de CPE a
aplicaciones p ác icas.
10
1. In oduc ion
1.1 Ene gy s o age scena io
Mo e han a cen u y o bu ning ossil uels as well as unsus ainable ene gy and land use ha e
con ibu ed o an inc ease in he global su ace empe a u e, eaching 1.1°C abo e p e-
indus ial le els.1 The u u e nega i e impac s o clima e change a e expec ed o be as ,
cos ing signi ican ly mo e han p e en ing i .2 Thus, keeping he global empe a u e ise below
2°C by 2050 has been se as a wo ldwide goal o mi iga e he se e e consequences o clima e
change.3 As epo ed by he In e na ional Renewable Ene gy Agency (IRENA)3, abou wo-
hi ds o g eenhouse gas emissions o igina e om ene gy p oduc ion and consump ion.
The e o e, mee ing he below 2°C goal equi es a p o ound ans o ma ion in he ene gy
sys em.
Renewable ene gy and inc easing ene gy e iciency no only can educe 90% o CO2 emissions,
bu hey also p o ide o he bene i s such as making ene gy access a o dable and imp o ing
ene gy secu i y3, an issue ha was highligh ed du ing he a med con lic in Uk aine.4 In
addi ion, al hough his ene gy ansi ion equi es a huge in es men om he go e nmen s,
i would gene a e millions o addi ional jobs and make economic sense when aking he cos -
sa ings in he long e m in o accoun .3 Ne e heless, i mus be no ed ha he ene gy sec o
alone canno p o ide all he solu ions o he majo issue o clima e change.
Acco ding o IRENA, elec i ica ion is a op sho and mid- e m p io i y o se he ene gy
sys em on he pa h needed o achie e he below 2°C objec i e.5 Elec i ica ion is a key solu ion
o educing gas emissions, pa icula ly i pai ed wi h enewable ene gy sou ces.2 The impac
o elec i ica ion, enewables, and ene gy e iciency is shown in Figu e 1. A combina ion o
enewable ene gy and deep elec i ica ion can educe CO2 emissions by 60%. Adding ene gy
e iciency and di ec use o enewables, his sha e eaches a ema kable 90%.2
Figu e 1 The sha e o di e en sec o s in annual ene gy- ela ed CO2 emissions and he impac o elec i ica ion and
enewables in educing he emissions. Rep oduced wi h pe mission om IRENA.2
11
Th ee main sec o s ha equi e elec i ica ion a e buildings, indus y, and anspo . Wi hin
he anspo sec o , elec ici y p o ides less han 1% o he o al ene gy consumed o global
anspo a ion, including passenge s and ca go.5 The elec i ica ion o his sec o is mainly
associa ed wi h he use o Ba e y Elec ic Vehicles (BEVs), Hyd ogen and Fuel Cell Elec ic
Vehicles (FECVs). BEVs ha e de eloped signi ican ly and expe ienced huge ma ke g ow h in
he las decade. Fo ins ance, be ween 2017 and 2023, EV sales ha e inc eased om 1 o
a ound 14 million, eaching an 18% sha e in o al new ca s sold in 2023.6 In Eu ope, he second
la ges EV ma ke , mo e han one in e e y 5 ca s sold was elec ic.6
The exponen ial g ow h o elec ic ca s ock in he las decade is demons a ed in Figu e 2.
Besides na ional policies and incen i es, one o he main easons behind his apid g ow h is
ha EVs a e becoming mo e compe i i e ela i e o in e nal combus ion engine ehicles, bo h
in pe o mance and p ice.7 This imp o ed compe i i i y also s ems om he ad ancemen s in
Li-ion ba e y (LIB) echnology o e he las decades, since hei comme cializa ion in 1991 by
SONY. Fo ins ance, he g a ime ic and olume ic ene gy densi y o LIBs ha e inc eased om
80 Wh/kg and 200 Wh/L in 1991 o a ound 260 Wh/Kg and 700 Wh/L in 20158, while he p ice
o LIBs on he pack le el has d opped by a ac o o 7.9
Figu e 2 Global elec ic ca s ock ends be ween 2010 – 2023. Rep in ed wi h pe mission om Re .6
Despi e all hese imp o emen s and he huge g ow h o he EV ma ke , he anspo sec o ,
wi h a 25% sha e o global ene gy- ela ed CO2 emissions,10 s ill lags in he ene gy ansi ion
and equi es accele a ion.2,3 In addi ion, elec i ica ion equi es a wide a ie y o ba e ies o
a b oad ange o applica ions. Fo ins ance, a ba e y designed o a ia ion equi es a much
highe powe han po able de ices, wi h cos being o lowe impo ance.9 Thus, he
de elopmen o ba e ies in di e en echnologies o chemis ies is i al.
1.2 De elopmen o Ba e ies
A ba e y is a de ice ha s o es ene gy and ypically consis s o mul iple cells pu oge he .
Each cell con ains wo elec odes wi h di e en elec ical po en ials, sepa a ed by an
elec oly e. Ba e ies ope a e based on educ ion-oxida ion ( edox) eac ions ha occu a he
elec odes. In hese eac ions, elec ons and ions a e ans e ed: elec ons low h ough an
12
ex e nal ci cui connec ing he elec odes, while ions mig a e h ough he elec oly e. The
elec oly e acili a es ion di usion bu blocks elec on low, p e en ing sho ci cui s. The
speci ic edox eac ions a each elec ode, along wi h he di ec ions o ion and elec on low
du ing cha ging and discha ging, a e illus a ed schema ically in Figu e 3.
Figu e 3 Schema ic ep esen a ion o a ba e y du ing cha ge and discha ge.
Two c i ical me ics ha de e mine a ba e y's pe o mance a e ene gy densi y and powe
densi y. Ene gy densi y e e s o he amoun o ene gy a ba e y can s o e pe uni olume o
weigh . A highe ene gy densi y allows o longe ope a ion imes be ween cha ges. This is
especially impo an in applica ions like elec ic ehicles and po able elec onics, whe e
maximizing he ene gy s o ed in a limi ed space is c ucial. Powe densi y, on he o he hand,
measu es how quickly ene gy can be deli e ed by he ba e y o a gi en olume o weigh . A
ba e y wi h high powe densi y can p o ide a la ge amoun o ene gy in a sho pe iod, c i ical
o de ices ha equi e quick accele a ion o immedia e esponse, such as powe ools o
elec ic ehicles.
The ba e ies a e usually classi ied in o p ima y and seconda y. The p ima y ba e ies each
hei end-o -li e a ull discha ge s a e, while seconda y ba e ies can be echa ged and eused.
Al hough p ima y ba e ies a e impo an in many applica ions pa icula ly in medical and
mili a y ields, add essing he p e iously discussed global wa ming issues equi es ad anced
seconda y ba e ies.
The a he simple concep o ba e ies has led o he de elopmen o a wide a ie y o
ba e ies, om nickel-cadmium (Ni-Cd) and lead-acid o li hium-ion ba e ies, and mo e
ecen ly, sodium-ion ba e ies. Thanks o he high elec ochemical po en ial o li hium and i s
low weigh , li hium-ion ba e ies a e he mos popula , because hey o e a combina ion o
high ene gy densi y, high powe , and long cyclabili y, making hem ideal o a b oad ange o
applica ions.11 The supe io i y o Li-based ba e ies compa ed o o he ma u e echnologies
is demons a ed in Figu e 4.
Nega i e Elec ode
Posi i e Elec ode
Oxida ion Reduc ion
Nega i e Elec ode
Posi i e Elec ode
Reduc ion Oxida ion
13
Figu e 4 The g a ime ic and olume ic ene gy densi y o di e en seconda y ba e y echnologies. Rep in ed wi h
pe mission om Kubo a e al.12
1.3 Li-ion ba e ies
Wi h mo e han 3 decades o esea ch and de elopmen , LIBs a e cu en ly he mos ad anced
ype o ba e ies, o e ing g a ime ic and olume ic ene gy densi ies abo e 200 Wh/Kg and
400 Wh/L.13,14 In comme cial LIBs, schema ically illus a ed in Figu e 5, g aphi e is he ma e ial
o choice o he nega i e elec ode. The cha ge s o age mechanism o g aphi e anodes is
based on he in e cala ion o Li a oms be ween he g aphi e planes, which can con inue up o
one Li pe 6 ca bon a oms.15 Upon discha ge, dein e cala ion akes place and he Li ions lea e
he g aphi e planes and mo e owa d he posi i e elec ode.
Figu e 5 illus a ion o a ypical Li-ion ba e y and i s di e en componen s.
G aphi e’s g a ime ic capaci y o 372 mAh/g is lowe han o he anode ma e ials such as LTO,
Si, Ge, and Li me al. Ne e heless, g aphi e, is s ill he p e e ed op ion in comme cial
ba e ies, as i o e s a good balance be ween cos , li hia ion po en ial, Li di usi i y, elec ical
conduc i i y, and low olume change.15,16 On he posi i e elec ode, LiNi1-x-yCoxAlyO2 (NCA)
LiNixCoyMnzO2 (NMC), and LiFePO4 (LFP) a e he mos common ac i e ma e ials. While NCA
and NMC o e a highe ene gy densi y, LFP is cheape and shows a be e a e-pe o mance
and cycle li e.17,18 Thus, he choice o he ca hode ma e ial depends on he applica ion
equi emen s.

14
A key componen in LIBs is he sepa a o , a po ous memb ane ypically made o glass ibe o
polyp opylene. I physically sepa a es he elec odes while enabling ion anspo by being
soaked in elec oly e. Some o he mos impo an cha ac e is ics o a sepa a o include i s
chemical s abili y, hickness, po osi y, mechanical and he mal p ope ies, o uosi y,
elec oly e up ake, and cos .19 While some o hese pa ame e s can di ec ly a ec he a e
pe o mance, cyclabili y, and sa e y o he cell,19 he e icacy o he sepa a o is closely ied o
he choice and p ope ies o he elec oly e.
Al hough he elec oly es should in heo y be selec ed based on he p ope ies and
equi emen s o he anode and ca hode ma e ials, he elec oly e used in mos comme cial
LIBs is Li hium hexa luo ophospha e sal (LiPF6), dissol ed in o ganic sol en s. This is mainly
due o i s balanced p ope ies such as i s high elec ochemical s abili y limi o 4.5 V and a
a he low cos . 20 Ins ead o changing he majo elec oly e componen s, mos esea ch
ac i i ies a ge ed elec oly e addi i es o con ol he in e ace and elec oly e p ope ies.20
The addi i es a e gene ally designed o decompose a a ce ain ol age po en ial and o m
speci ic decomposi ion p oduc s in he o m o a p o ec i e laye on he su ace o he
elec odes.20–22 Depending on he s uc u e and concen a ion o he addi i e, he p o ec i e
laye can a ec he chemical composi ion and he mo phology o he solid elec oly e
in e phase (SEI) and impac he pe o mance and cycle li e o he cell.21,22
LIBs cu en ly o e he highes pe o mance and a e expec ed o con inue domina ing he
ma ke in he coming yea s. None heless, he e a e s ill some conce ns and issues wi h LIBs.
Fi s ly, LIBs a e app oaching hei physicochemical limi .13 Al hough hei g a ime ic and
olume ic ene gy densi ies ha e been inc easing a a decen pace, wi hou any un o eseen
echnological de elopmen , hey a e unlikely o su pass hei physicochemical limi es ima ed
a a ound 400 Wh/kg and 800 Wh/L.13 Secondly, LIBs a e insu icien o all ypes o
applica ions as each has di e en speci ic equi emen s. While LIB is he op con ende o
EVs, o he echnologies migh be ad an ageous o ma i ime, a ia ion, o g id ene gy
s o age.9,23 Finally, LIBs con ain combus ible liquid o ganic elec oly es and hus a e s ill
associa ed wi h sa e y conce ns, pa icula ly in ele a ed- empe a u e and high- a e
applica ions.13,24 Mul iple elec ochemical eac ions occu ing inside he ba e y gene a e
hea ha may no be e icien ly dissipa ed in he case o mechanical, elec ical, o he mal
abuse. In his case, he sepa a o is damaged causing a sho ci cui , o oxygen is eleased
om he ca hode side, enabling u he (elec o)chemical eac ions. This leads o he mal
unaway which can gene a e smoke, i e, o explosion.25 Conside ing hese limi a ions,
esea ch and de elopmen in al e na i e ba e y echnologies a e essen ial. These al e na i e
echnologies do no necessa ily compe e wi h LIBs bu a he collabo a e o mee he huge
ene gy equi emen s p e iously men ioned. These ba e ies could po en ially o e di e en
cha ac e is ics such as lowe cos (Na-ion o aqueous), long li e (Li-O), as cha ge (o ganic,
no el a chi ec u e), o highe ene gy densi y and sa e y (solid-s a e).
1.4 Solid S a e Ba e ies
Solid s a e ba e ies (SSBs) ha e a ac ed huge a en ion in ecen yea s, and oge he wi h
Na-ion ba e ies a e among he mos p omising echnologies as al e na i es o Li-ion ba e ies.
15
SSBs di e om LIBs in ha he elec oly e is an ion-conduc ing solid ha also plays he
sepa a o ole (see Figu e 6).
Figu e 6 illus a ion o Li-ion ba e ies and solid-s a e ba e ies. Rep oduced wi h pe mission om G ady e al. 26
Mo ing om a lammable liquid elec oly e o a solid memb ane wi h highe mechanical and
he mal s abili y in heo y imp o es he sa e y o he ba e y cells13, al hough his is ye o be
p o ed in la ge -scale ba e y packs. In addi ion, highe mechanical p ope ies o solids in
p inciple hinde he g ow h o Li dend i es, acili a ing he use o Li me al as he nega i e
elec ode which o e s signi ican ly highe speci ic capaci y and ene gy densi y.13 Finally, in
ino ganic solid elec oly es, huge concen a ion g adien s a e a oided because he Li ions a e
he only mobile species. As a esul , highe cu en densi ies and as e cell cha ge/discha ge
a e possible.13
Solid elec oly es a e assessed based on a comp ehensi e se o c i e ia ha de e mine hei
sui abili y o applica ion in a ba e y cell. Ionic conduc i i y is one o he mos c i ical ac o s,
as i ep esen s how quickly and e icien ly ions can a el h ough he elec oly e. High ionic
conduc i i y is c ucial o achie ing high cha ge and discha ge a es, as well as main aining
ol age s abili y. While ionic conduc i i y akes he mobili y o bo h ca ions and anions in o
accoun , anspo numbe ( + o -) indica es he ac ion o cha ge ha is ca ied by he
ca ions o anions.27 A low ca ion anspo numbe can lead o he o ma ion o a sal
concen a ion g adien in he elec oly e, which ul ima ely limi s he a e capabili y o he cell
and causes dend i e g ow h.27,28 The nex key pa ame e is in e acial esis ance, which e e s
o he esis ance encoun e ed a he in e ace be ween he elec oly e and he elec odes.
This esis ance, which is pe haps one o he mos challenging aspec s o solid-s a e ba e ies,
has a signi ican impac on he a e-capabili y o he elec oly e and he o e all cell
pe o mance.
In addi ion o hese elec ochemical p ope ies, mechanical p ope ies a e also i al, as he
elec oly e mus wi hs and s esses and s ains du ing ope a ion wi hou c acking o
de o ming. Addi ionally, he mal, chemical, and elec ochemical s abili y a e c ucial, as
deg ada ion a high po en ials (agains high- ol age ca hodes) o e y low po en ials (agains
li hium) is undesi able and leads o ba e y ailu e. Las ly, elec oly es mus be cos -e ec i e
and easy o p ocess. While hese ac o s may be less c i ical in lab-scale esea ch, hey a e
essen ial o comme cializa ion and la ge-scale p oduc ion.
16
Solid elec oly es a e commonly di ided in o h ee main g oups29: i) solid polyme elec oly es
ii) solid ino ganic elec oly es and iii) composi e elec oly es. Each o hem is discussed below.
1.4.1 Solid Polyme Elec oly es
Solid Polyme Elec oly es (SPEs) consis o a Li sal inco po a ed in a polyme ma ix. The main
ad an age o SPEs is hei excellen p ocessabili y and lexibili y, enabling hin memb anes
wi h low elec ode/solid elec oly e in e ace esis ance. On he o he hand, SPEs ha e
ela i ely low oom empe a u e ionic conduc i i ies (<10-4 S.cm-1) and low anspo numbe s
(<0.3)30. While he ionic conduc i i y inc eases wi h he empe a u e, ope a ion abo e 80°C
sac i ices he mechanical p ope ies and elec ochemical s abili y o he SPE31–33, inc easing
he chance o Li dend i e g ow h and sho ci cui . Thus, i is essen ial o enhance he oom-
empe a u e ionic conduc i i y o SPEs, wi hou comp omising hei he mal, elec ochemical,
and mechanical p ope ies. The mos common app oaches a e adding plas icize s,
inco po a ing ionic liquids, de eloping new sal s, o modi ying he polyme (g a ed
copolyme s).
The mos ex ensi ely esea ched polyme elec oly e is Poly(e hylene oxide) (PEO), which is a
semic ys alline polye he . Wi h a high dono numbe , PEO o ms complexes wi h Li+, and i s
chain lexibili y acili a es in a- and in e -chain anspo o Li+34, as shown in Figu e 7.
Figu e 7 Mechanism o ion anspo in PEO. Rep oduced wi h pe mission om Xue e al.34
Among many Li sal s explo ed o PEO sys ems, Li hium bis( i luo ome hanesul onyl)imide
(LiTFSI) is he mos popula , hanks o i s bulky na u e ha ensu es acile sal dissocia ion,
equi ed o high ionic conduc i i y. The s uc u e o his Li sal is shown in Figu e 8. Inc easing
he sal con en in SPE dec eases he c ys allini y o PEO bu comp omises he mechanical
p ope ies o PEO and he mobili y o EO g oups. Conside ing his ade-o , he EO: Li a ios
o 20:1 o 16:1 a e he mos common.
17
Figu e 8 Molecula s uc u e o LiTFSI
1.4.2 Solid ino ganic elec oly es
Solid ino ganic elec oly es ha e e y di e en p ope ies om polyme s. They p esen
excellen he mal and mechanical p ope ies and signi ican ly highe ionic conduc i i y up o
10-3 S.cm-1. A signi ican cha ac e is ic o ino ganic elec oly es is hei Li+ anspo numbe
o ~1 because Li ions a e he only mobile species. This p e en s concen a ion g adien s,
enables high- a e applica ions, and imp o es ba e y li e ime and sa e y.35
In a c ys alline solid elec oly e, he mobile ions pass be ween wo c ys allog aphic si es o
li hium, along he minimum ene gy pa hway. This ene gy ba ie , called mig a ion ene gy,
g ea ly impac s he ionic conduc i i y o he elec oly e. Ion anspo and conduc i i y a e
also in luenced by de ec s, which could be in he o m o in e s i ials, acancies, pa ial
occupancy, e c.35,36 Signi ican e o s in designing c ys al s uc u es wi h op imal mig a ion
pa hs and op imal de ec s ha e esul ed in se e al g oups o highly conduc i e elec oly es,
wi h oxides, sul ides, and halides being he mos p omising ones.37,38
1.4.2.1 Ga ne s
The high ionic conduc i i y (0.1 – 1 mS/cm) and excellen s abili y agains Li me al, make
Li7La3Z 2O12 (LLZO) a g ea candida e o solid-s a e Li-me al ba e ies.39 In he LLZO c ys al
s uc u e, he e a e 3 in e s i ial si es o Li-ions namely i) e ahed al (24d), ii) oc ahed al
(48g), and iii) dis o ed oc ahed al (96h). The 24d e ahed a and 48g/96h oc ahed a sha e a
ace, which signi ican ly acili a es Li-ion mig a ion, achie ing high ionic conduc i i ies.40 LLZO
has wo main polymo phs namely cubic and e agonal. In he e agonal phase, he
e ahed al Li si es a e ully illed. As a esul , i is wo o de s o magni ude less conduc i e
han he cubic phase.40 Thus, LLZO is commonly doped wi h elemen s such as Ta, Ga, Nb, and
Al o s abilize he highly conduc i e cubic phase a oom empe a u e and enhance i s ionic
conduc i i y by gene a ing acancies and diso de .41,42
The wide elec ochemical s abili y window o LLZO, which is he ol age ange i can wi hs and
wi hou unde going edox eac ions,36 makes i compa ible wi h Li me al and high- ol age
ca hodes such as NMC (LiNi0.8Co0.1Mn0.1O2) when he kine ic limi a ions a e conside ed.40,43
This makes LLZO an ideal ma e ial o a undamen al unde s anding o he chemical and
elec ochemical p ocesses in solid-s a e ba e ies.
F om a p ac ical s andpoin , i is necessa y o sin e LLZO a high empe a u es o educe he
p esence o g ain bounda ies. This is c ucial because g ain bounda ies can obs uc he
24
• Chemical shi aniso opy (CSA): The magne ic ield expe ienced by each nucleus
depending on hei o ien a ion e sus he B0. These in e ac ions called CSA con ibu e
o he elaxa ion p ocess and b oaden he obse ed NMR signal.70
• Dipola coupling: The magne ic momen associa ed wi h each nucleus can gene a e a
weak magne ic ield ha can be sensed by he nea by nuclei. These in e ac ions a e
e e sible, meaning ha he i s spin can also expe ience he magne ic ield c ea ed
by he second spin. These in e ac ions which a e e y sensi i e o in e nuclea
dis ances, a e known as dipola coupling and induce elaxa ion.70
• Quad upola coupling: In nuclei wi h a spin numbe o I > ½, he elec on cha ge
dis ibu ion a ound he nucleus is asymme ic and non-sphe ical. This c ea es an
elec ic ield g adien (EFG) which in e ac s wi h he nucleus, causing elaxa ion and
line b oadening.
• Pa amagne ic elaxa ion: This mechanism occu s only in species ha ing unpai ed
elec ons. Unpai ed elec ons wi h la ge magne ic momen s gene a e a s ong local
magne ic ield which can in e ac wi h he nea by nuclei, causing apid elaxa ion.70
Solid ma e ials con ain nume ous c ys alli es, each o ien ed a di e en angles ela i e o he
magne ic ield. Since he aniso opic NMR in e ac ions, such as chemical shi aniso opy
(CSA), dipola coupling, and quad upola coupling, depend on hese o ien a ions, each
c ys alli e expe iences a sligh ly di e en magne ic ield. As a esul , he NMR spec um o a
powde ed sample ends o be b oad and asymme ic, o ming a dis inc i e pa e n known as
powde pa e n, which ep esen s he dis ibu ion o c ys alli e o ien a ions ela i e o he
magne ic ield. Unlike in liquids, whe e apid molecula umbling a e ages ou hese
aniso opies and esul s in sha p signals, he absence o such mo ion in solids leads o b oad
and complex spec a. This issue can be add essed by in oducing a i icial mo ions h ough a
echnique called Magic Angle Spinning (MAS). By spinning he sample a a e y as a e a an
angle o 54.7 deg ees ela i e o he B0, MAS e ec i ely a e ages ou many o hese
aniso opic in e ac ions, leading o na owe signals and highe esolu ion. Fo MAS o be
e ec i e, he spinning a e mus exceed he linewid hs o he aniso opic in e ac ions, which
can be in he ange o se e al kHz. Al hough aniso opic in e ac ions we e once iewed as a
signi ican challenge in NMR, hey con ain aluable s uc u al and dynamic in o ma ion. Thus,
in some cases, i may be necessa y o es o e hese in e ac ions using echniques like
Ro a ional Echo Double Resonance (REDOR) which ein oduces he dipola in e ac ions o
s udy pa ame e s like in e nuclea dis ances.
While mos elemen s ha e an NMR-ac i e iso ope and can heo e ically be measu ed,
eco ding an NMR spec um wi h easonable quali y using a s anda d magne gene ally
equi es he nuclei o ha e a combina ion o high na u al abundance, high gy omagne ic a io,
and low quad upole momen . This es ic s he ange o nuclei ha can be easily s udied,
excluding nuclei like 17O, and 35Cl, due o he complexi y o sample p epa a ion, measu emen ,
o da a in e p e a ion. Howe e , se e al elemen s in ol ed in ba e y sys ems a e well-sui ed
o NMR analysis and could be measu ed wi h ela i e ease. These include:
• P o on (1H): Bene i ing om he highes gy omagne ic a io among all nuclei and an
iso ope na u al abundance close o 100%, p o on (1H) is a highly sensi i e nucleus wi h

25
s ong NMR signals, ideal o s udying hyd ogen-con aining samples. Fo ins ance, he
su ace eac i i y and p o ona ion du ing s o age o p ocessing s eps can easily be
analyzed using 1H NMR. Howe e , due o he dipola couplings, he 1H spec a su e
om signal b oadening in solid-s a e NMR, making MAS o en c ucial.
• Fluo ine (19F): Thanks o i s high gy omagne ic a io and 100% abundance, 19F NMR
measu emen s a e ai ly simple. The wide chemical shi ange o 19F allows o he
esolu ion o dis inc luo ine en i onmen s, making i especially use ul in he analysis
o complex elec oly es and he iden i ica ion o di e en luo ide species. Gi en i s
p esence in nea ly all o ganic Li-sal s, 19F is an impo an nucleus o s udying
elec oly e ma e ials. In he ba e y ield, 19F NMR is used o in es iga e sal
agglome a ion o decomposi ion p ocesses. In addi ion, 19F di usion expe imen s a e
equen ly employed in liquid, gel, and solid polyme elec oly es o p obe he long-
ange dynamics o he anions.
• Phospho us (31P): Wi h 100% abundance and a decen gy omagne ic a io, 31P is an
impo an nucleus in NMR, especially since i is p esen in a wide ange o o ganic and
ino ganic ma e ials. The chemical shi and shielding e ec s in 31P NMR p o ide
de ailed in o ma ion abou he local en i onmen , making i a powe ul ool o
s udying he coo dina ion chemis y o phospho us in elec oly e o mula ions. In
solid-s a e ba e y esea ch, 31P NMR is commonly employed o in es iga e sul ide-
based elec oly es (LPSCl), NASICON- ype elec oly es (LATP), and Oxyni ides (LiPON).
• Li hium (6Li and 7Li): As he main elemen in ba e ies, Li hium has wo NMR-ac i e
nuclei, bo h widely used in NMR s udies. 7Li, he mo e abundan iso ope (92.5%), has
a highe gy omagne ic a io, esul ing in g ea e sensi i i y and in ense signals. On he
o he hand, 6Li, while less abundan , has a lowe quad upola momen , leading o
sha pe signals and highe - esolu ion spec a. The e o e, 6Li is o en p e e ed o in-
dep h in es iga ion o local chemical en i onmen s, al hough a he cos o equi ing
highe sample concen a ions o longe expe imen imes. In e es ingly, he lowe
abundance o 6Li could be ad an ageous in pa icula cases such as EXSY expe imen s,
whe e he undesi ed spin di usion is minimized. O e all, bo h 6Li and 7Li NMR a e
in aluable o no only s uc u al de e mina ion bu also o s udying he ion- anspo
mechanisms and Li dynamics in elec oly es. As an impo an ea u e, me allic Li
exhibi s a knigh shi , a phenomenon ha signi ican ly shi s i s NMR signal om ha
o diamagne ic li hium. This shi , which occu s due o in e ac ions be ween he
nucleus and he unpai ed elec ons in me als,75 enables he s udy o Li pla ing and Li
dend i e g ow h in he ba e ies.
He ein, some o he mos use ul and common echniques used in s udying solid composi e
elec oly es a e explained.
1.5.1 One-Pulse and Hahn Echo
One-pulse is a simple bu widely used pulse sequence in NMR spec oscopy. In his pulse
sequence (shown in Figu e 12.a) a 90° pulse lips he magne iza ion om he z-axis o he xy
plane, and hen he FID is eco ded. In some cases, apid magne iza ion dephasing due o T2
elaxa ion causes in o ma ion loss and signal decay. Addi ionally, one-pulse su e s om dead
26
ime issue, which e e s o a sho pe iod ( ypically a ew mic oseconds) immedia ely a e he
applied pulse du ing which he ecei e canno de ec he signal due o elec onic limi a ions.
Thus, he ini ial po ions o he FID and i s co esponding in o ma ion a e los , and he
spec um is sligh ly dis o ed.76
To add ess hese challenges, he Hahn Echo pulse sequence is p oposed, which is mainly
applied o nuclei wi h spin numbe I = ½.77 In his pulse sequence (shown in Figu e 12.b) a e
he 90° pulse and a delay ime (τ), a 180° pulse is applied o e e se he magne iza ion
dephasing in he xy plane. A e ano he delay ime (τ), he spins a e ephased, and he FID is
eco ded.78 The wo d “echo” in his pulse sequence e e s o he ini ial dephasing and
subsequen ephasing o he signal. This pulse sequence allows o eco e ing he in o ma ion
los bo h du ing he dephasing and he dead ime. Hahn Echo is ypically limi ed o nuclei wi h
spin numbe I = ½, as in quad upola nuclei wi h I > ½ he e ocusing o he spins in o an echo
signal is challenging. Conduc ing echo expe imen s o hese nuclei equi es o he pulse
sequences such as quad upole echo and Mul iple Quan um Magic Angle Spinning (MQMAS)
which a e ou o he scope o his wo k.76,77
Figu e 12 Pulse sequence o a) One-Pulse and b) Hahn-Echo NMR expe imen s.
1.5.2 Sa u a ion Reco e y
In his expe imen which aims a measu ing he T1 elaxa ion ime, magne iza ion is ini ially
o ced o ze o by a ain o pulses. The nulli ied magne iza ion is allowed o eco e du ing a
ime gap 1, and hen a 90° pulse is applied o eco d he signal. As shown in Figu es 13.a and
13.b, Repea ing his expe imen a di e en ime in e als esul s in a build-up cu e om
which he ime cons an can be calcula ed.79 Since T1 elaxa ion imes can a y be ween
di e en species due o di e ences in s uc u e and local dynamics, analyzing hese elaxa ion
imes p o ides aluable insigh s in o he composi ion, molecula s uc u e, and dynamic
beha io o he sample.
b
90
180
n o
90
a n - l
27
Figu e 13 a) Pulse sequence and b) build-up cu e o Sa u a ion Reco e y expe imen . Rep oduced om Fo se.80
1.5.3 Exchange Spec oscopy
In many sys ems, ions o molecules unde go spon aneous and con inuous exchange be ween
wo dis inc en i onmen s o si es. Unde s anding he dynamics and cha ac e is ics o such
exchanges could be c ucial, o ins ance o de e mining he ion anspo mechanisms in solid
composi e elec oly es. This ype o exchange p ocess can be e ec i ely in es iga ed using
exchange spec oscopy (EXSY) expe imen s. Like o he wo-dimensional NMR echniques, his
expe imen comp ises se e al sequen ial s eps: p epa a ion, e olu ion, mixing, and
de ec ion,70 as Figu e 14 illus a es.
Figu e 14 a) Schema ic p esen a ion, b) pulse sequence, and c) da a ep esen a ion o an EXSY NMR expe imen .
Rep oduced om Keele .70
The pulse sequence in an EXSY expe imen in ol es h ee 90° pulses. While hese pulses a ec
all spins uni o mly, i is concep ually simple o ocus on an indi idual spin. The i s pulse lips
he magne iza ion o he XY plane, whe e i e ol es du ing he 1. The second pulse hen
e u ns his magne iza ion o he z-axis, e ec i ely equency labeling he spin by encoding i s
en i onmen . Du ing he subsequen mixing ime, a chemical exchange be ween he spin a
wo di e en si es may occu . In his case, he magne iza ion ini ially gene a ed on spin-1 is
ans e ed o spin-2. The inal pulse hen o a es his magne iza ion back o he XY plane,
allowing o he acquisi ion o he FID, which achie es he spec um in he F2 (o di ec )
dimension a e he Fou ie ans o ma ion. By a ying he 1 ac oss mul iple expe imen s and
applying a second Fou ie ans o ma ion, spec a a e ob ained in a new dimension, called F1
o indi ec dimension. As shown in Figu e 14.c, he esul ing EXSY NMR da a a e ypically
90
1
90
n
a b
T1 ms
In ensi y
P epa a ion Mixing
E olu ion
1
De ec ion
2
90
90 90
a b
1 mix
F2
F1
Exchanged
No Exchanged
c
28
displayed as con ou plo s, whe e he X and Y axes co espond o he chemical shi s in he F2
and F1 dimensions, espec i ely. Signals ha appea along he diagonal line ep esen nuclei
ha did no unde go exchange du ing he mixing ime and hus emained in hei o iginal
en i onmen . Con e sely, nuclei ha pa icipa ed in exchange p ocesses p oduce o -diagonal
peaks, also known as c oss-peaks.
Conduc ing EXSY expe imen s a a ying mixing imes allows o he s udy o he a e a which
exchange p ocesses occu . Howe e , his analysis equi es high-quali y da a and ca e ul
analysis, as oo long mixing imes can lead o he decay o signal in ensi y due o he elaxa ion
o magne iza ion. In ac , one o he limi a ions o EXSY expe imen s is he equi emen ha
he mixing ime mus be sho e han he elaxa ion ime o he spins.81 The e o e, selec ing
an app op ia e mixing ime is c i ical and ypically es ic ed o a ew hund ed milliseconds in
mos solid composi e elec oly es.
I is impo an o no e ha he magne iza ion ans e du ing he mixing ime which gi es ise
o he c oss-peaks may no only esul om chemical exchange bu also om spin di usion, a
phenomenon caused by homonuclea dipola in e ac ions be ween wo abundan spins. In
his p ocess, as opposed o exchange, magne iza ion is ans e ed be ween wo spa ially ixed
spins.82 This p ocess, which depends bo h on he gy omagne ic a io o he nucleus and he
in e nuclea dis ances, can be s udied using a nuclea O e hause e ec spec oscopy
(NOESY) expe imen , which is iden ical o he EXSY bu ollows a di e en pu pose.70
Dis inguishing be ween hese wo mechanisms as he sou ces o c oss-peaks in EXSY
expe imen s o Li-based ba e ies can be ealized by conduc ing EXSY expe imen s on 6Li
ins ead o 7Li. Thanks o i s lowe gy omagne ic a io and lowe na u al abundance ( hus
highe in e nuclea dis ance), 6Li educes he likelihood o spin di usion, allowing c oss-peaks
o be a ibu ed mo e con iden ly o chemical exchange.
1.5.4 C oss Pola iza ion and He e onuclea Co ela ion
C oss Pola iza ion (CP) is a widely used NMR echnique ha can signi ican ly imp o e he
sensi i i y o he NMR spec a o nuclei wi h low gy omagne ic a io o low na u al abundance.
In he CP expe imen , magne iza ion is ans e ed om an abundan nucleus, such as 1H o
19F, o a less abundan nucleus, like 6Li o 13C. This ans e is based on h ough-space dipola
in e ac ions, which a e in e sely p opo ional o he cube o he in e nuclea dis ance,
acco ding o equa ion 2.80
equa ion (2): 𝜔12 ∝ 𝛾1𝛾2
𝑟3
As shown in Figu e 15.a, he CP pulse sequence ypically begins wi h he exci a ion o he
abundan nucleus, ollowed by a con ac pe iod du ing which he magne iza ion is ans e ed
o he less abundan nucleus. The Fou ie T ans o m o he eco ded FID esul s in a single
spec um along he chemical shi axis o he less-abundan nucleus. In his spec um, each
signal co esponds o a si e o he non-abundan nucleus ha is close o and hus e ec i ely
coupled wi h he abundan nucleus. I a pa icula si e in he low-abundance nucleus does no
29
pa icipa e in he magne iza ion ans e , due o dis ance o example, i will no appea in he
spec um.
CP is highly bene icial o imp o ing he sensi i i y o he NMR spec a o nuclei wi h low
gy omagne ic a io o low abundance. The maximum sensi i i y imp o emen o a single scan
is 𝛾𝐼𝛾𝑠
⁄. Howe e , since he abundan nucleus ypically has a sho e elaxa ion ime, CP
allows o a highe numbe o scans o be eco ded wi hin he same ime ame compa ed o
di ec exci a ion, esul ing in u he enhancemen o he signal- o-noise a io.80 This is c ucial
o analyzing nuclei wi h low abundance like 13C in sys ems whe e di ec obse a ion is
challenging due o low signal in ensi y.
Building on he p inciples o CP, 2D He e onuclea Co ela ion (HETCOR) is a sligh ly mo e
ad anced e sion o CP designed o in es iga e he in e ac ions be ween di e en ypes o
nuclei wi hin a sample. As shown in Figu e 15.b, he HETCOR pulse sequence di e s om he
one o CP in ha i includes an addi ional e olu ion s ep be o e he c oss-pola iza ion. Once
he magne iza ion o he abundan nucleus is exci ed, i unde goes a pe iod o e olu ion o
encode in o ma ion abou i s local en i onmen . This e olu ion ime e e ed o as 1, is
sys ema ically a ied h oughou he expe imen o in oduce an ex a dimension o he da a
and cons uc a wo-dimensional spec um in which co ela ion signals indica e h ough-space
magne iza ion ans e , hence spa ial p oximi y.83 The e o e, HETCOR is in aluable o
cha ac e izing complex ma e ials like solid elec oly es, whe e unde s anding he local
s uc u e and in e ac ions be ween componen s is c ucial.
Figu e 15 G aphical p esen a ion o he pulse p og am o a) CP-MAS and b) HETCOR wi h hei co esponding da a
ep esen a ion.
I mus be no ed ha al hough CP and HTECOR a e bene icial o enhancing signal sensi i i y
and p o iding s uc u al in o ma ion, hese me hods a e no inhe en ly quan i a i e. This is
because he e iciency o magne iza ion ans e depends on he size o he dipola
a
b
F2
CP
CP
Decoupling
op ional
2
90
I
S
F2
F1
Co ela ion signal
No co ela ion
CP
CP
Decoupling
op ional
1
2
90
I
S

30
in e ac ions and, he e o e on se e al ac o s such as he p oximi y o nuclei, and he
elaxa ion dynamics o he sys em. These ac o s can a y signi ican ly ac oss di e en si es
wi hin a ma e ial, causing complica ions in he quan i a i e analysis. As a esul , CP and
HETCOR canno be eliably used o de e mine he absolu e quan i ies o ela i e
concen a ions o di e en si es wi hin he sample. Fo applica ions equi ing p ecise
quan i a i e analysis, al e na i e NMR echniques o ca e ul calib a ions may be necessa y.
Addi ionally, al hough he co ela ions in HETCOR and CP depend on he in e nuclea
dis ances, o p ecise measu emen s o he dis ance be ween ce ain nuclei, o he NMR pulse
sequences such as Ro a ional-Echo Double-Resonance (REDOR) o T ans e -Echo Double-
Resonance NMR (TEDOR) a e employed.84
1.5.5 CP-spin di usion
In some EXSY expe imen s, i he in ensi y o he signal o in e es is oo low, o i selec i e
EXSY o ce ain signals is desi ed, a combina ion o CP and EXSY expe imen s may be used,
which he ein is e e ed o as “CP-spin di usion”. In his expe imen , a CP s ep is in oduced
a he beginning o he EXSY sequence o selec i ely enhance he signal in ensi y o he nuclei
ha a e spa ially close o he abundan nucleus. While his selec i e enhancemen limi s he
scope o he EXSY expe imen o egions ha a e close o he abundan nuclei, -which could
some imes be bene icial-, i signi ican ly boos s he in ensi y o he signals co esponding o
he co ela ed si es. As a esul , CP-spin di usion allows o sensi i e explo a ion o exchange
p ocesses in sys ems whe e he signals migh o he wise be oo weak o de ec . This app oach
is e y use ul in s udies o solid elec oly es, in which enhancing he in ensi y o ce ain signals
a he in e phase is c i ical o ob aining meaning ul insigh s in o he dynamics and
in e ac ions.
By omi ing he e olu ion s ep, CP-spin di usion expe imen s can be pe o med as one-
dimensional (1D) expe imen s. This modi ica ion esul s in a subs an ial educ ion in he
o e all expe imen ime, making i mo e e icien and less esou ce-in ensi e. Howe e , his
simpli ica ion comes a he cos o losing he addi ional in o ma ion p o ided by he second
dimension in a ypical 2D NMR expe imen . Consequen ly, 1D e sions o hese expe imen s
a e bes sui ed o sys ems whe e he molecula en i onmen and dynamics a e al eady well
esol ed. In addi ion, hese 1D measu emen s a e also e y bene icial when one o he signals
disappea s a e he CP s ep. In such cases, compa ing he CP-spin di usion spec um wi h CP
and di ec exci a ion spec a can yield aluable in o ma ion on he exchange p ocesses wi hin
he sample.
1.5.6 Iso ope-exchange expe imen s
These expe imen s a e speci ic o sys ems con aining elemen s wi h mul iple NMR-ac i e
iso opes, such as li hium (7Li and 6Li) and hyd ogen (1H and 2H). The main idea is o subs i u e
one iso ope o ano he and obse e he esul ing changes in he NMR spec a. This opens
oppo uni ies o inno a i e expe imen s ailo ed o he sys em in ques ion. Among se e al
possible combina ions, A common app oach in ol es in oducing a small quan i y o 6Li in o a
sys em p edominan ly composed o 7Li.85–87 Then, by acking he mo emen and in e ac ion
o he in oduced iso ope o e ime o du ing cell cycling, c i ical insigh s in o anspo
mechanisms, di usion a es, and he in e ac ions be ween di e en en i onmen s wi hin he
31
sample a e ob ained. This echnique is pa icula ly aluable o in es iga ing ion anspo in
complex, mul i-componen sys ems like solid-s a e ba e ies.87 Howe e , hese expe imen s
a e gene ally mo e cos ly and equi e special ca e in sample p epa a ion, measu emen , and
da a analysis.
1.5.7 Va iable Tempe a u e solid-s a e NMR
Va iable empe a u e NMR expe imen s used in his hesis ely on he p inciple ha he
linewid h o an NMR signal is in e sely p opo ional o he T2 elaxa ion ime. Thus, measu ing
he signal linewid h o e a b oad empe a u e ange can indi ec ly e eal he impac o
he mally ac i a ed mo ions on T2 elaxa ion.71
A e y low empe a u es, also known as igid la ice egime, he ion mo ions a e oo slow o
a e age ou he dipola in e ac ions, esul ing in b oadened NMR signals.88 Upon hea ing, he
ion o molecula mo ions a e inc eased, con inuously a e aging he dipola in e ac ions and
dec easing he signal linewid h, as demons a ed in Figu e 16. This p ocess is called mo ional
na owing, om which he Li+ jump a es can be oughly es ima ed.88 This can con inue un il
an ex eme na owing egime is achie ed, in which u he hea ing has no impac on he
linewid h.71,88
When plo ing he linewid h s empe a u e, bo h pla eaus a high and low empe a u es
should ideally be obse ed. Howe e , he onse empe a u es highly depend on he Li
dynamics o he sample. Fo ins ance, in a highly Li-conduc ing sample like Li6.6P0.4Ge0.6S5I,
p obing he ion-hopping p ocesses equi es NMR measu emen s a empe a u es as low as 9
K, hus needing a special se up.73 The a iable empe a u e measu emen s a e no mally
conduc ed in s a ic mode, i.e. wi hou MAS. This no only simpli ies he da a in e p e a ion
bu also allows o a signi ican ly b oade empe a u e ange.
Figu e 16 Schema ic ep esen a ion o a a iable empe a u e NMR expe imen and da a ep esen a ion o s udying
molecula o ion dynamics.
1.5.8 Pulse Field G adien NMR and Di usion Expe imen s
The di usion coe icien o a ious nuclei can be de e mined h ough Pulse Field G adien
(PFG) NMR expe imen s, in which as opposed o usual NMR expe imen s, he magne ic ield
is a ied in s eng h along a speci ic axis wi hin he sample. In hese expe imen s, he p esence
o a ield g adien causes he magne iza ion p ecession o nuclei o di e based on hei
posi ion wi hin he sample, leading o dephasing.71 As demons a ed in Figu e 17, he me hod
F M z
1 T -1
Mo ional
Na owing
Tempe a u e
7 i chemical shi ppm
32
in ol es applying wo ield g adien pulses o dephase and hen ephase he magne iza ion.
In he case o di usion du ing he delay ime be ween hese pulses (Δ), he magne iza ion
would no comple ely e ocus, esul ing in signal decay. By conduc ing hese expe imen s wi h
di e en g adien s eng hs and analyzing he signal in ensi y, he di usion coe icien is
de e mined.
Figu e 17 Pulse sequence o Pulse Field G adien S imula ed Echo expe imen . and he signal decay due o di usion.
1.5.9 In si u and ope ando NMR expe imen s
Reco ding NMR spec a o ba e y ma e ials du ing cell ope a ion, known as ope ando
measu emen s, enables eal- ime in es iga ion o ion dynamics, in e ac ions, and phase
e olu ion h oughou he cycling p ocess. This echnique, which is schema ically p esen ed in
Figu e 18, o e s aluable insigh s in o he chemical and s uc u al changes o he cell
componen s. In he case o solid-s a e ba e ies, i is especially use ul in s udying he Li
pla ing/s ipping and dend i e g ow h. In si u NMR is a g ea me hod o obse e and quan i y
he dead Li, a concep ha is pa icula ly impo an in anode- ee ba e ies.89,90 Ne e heless,
despi e all he ad an ages, his echnique comes wi h signi ican limi a ions. Fi s , due o
p ac ical challenges, ope ando measu emen s canno be combined wi h magic angle spinning,
es ic ing he analysis o a s a ic mode wi h lowe esolu ion. Addi ionally, cu en echnology
does no allow o s aigh o wa d measu emen s in s anda d cell con igu a ions such as coin
cells o Swageloks. Ins ead, specialized cell se ups a e equi ed which di e conside ably om
con en ional ones. Fo example, i is o en di icul o apply and main ain consis en s ack
p essu e in hese cells, causing signi ican challenges in s udying solid-s a e ba e ies.
GF
90
g adien
l ld d n m l d o
180
GF
GG adien eld s eng h
In ensi y
33
Figu e 18 Schema ic illus a ion o in si u NMR se up and i s applica ion in s udying Li pla ing, dend i e o ma ion, and
dead li hium quan i ica ion. Rep oduced wi h pe mission om Xiang e al.90
1.6 Scope and ield o esea ch
A e iew o he li e a u e highligh s ha despi e he p omising po en ial o he CPEs in solid-
s a e ba e ies, addi ional e o s a e needed o add ess he exis ing challenges. The main
a eas ha equi e imp o emen include hei oom- empe a u e ionic conduc i i y, in e ace
esis ance wi h he Li me al, and compa ibili y o he phases. Al hough CPEs ha e been
explo ed in se e al s udies and he concep is no en i ely new, he e emain knowledge gaps
abou se e al undamen al aspec s o hei p ope ies. Mos impo an ly, he mechanism o
ion anspo h ough he elec oly e, pa icula ly ac oss he in e phases, has no been
ho oughly in es iga ed. In addi ion, he impac o p ocessing condi ions such as humidi y o
empe a u e on he pe o mance o he CPEs emains unclea o poo ly unde s ood. Finally,
li le e o has been de o ed o in es iga ing he in e ac ions be ween he ino ganic ille s
and he polyme ma ix. This is while hese in e ac ions a e expec ed o play a c i ical ole in
mi iga ing he Li dend i e g ow h and hus signi ican ly enhance he a e pe o mance and
cyclabili y o he cells. Add essing hese gaps in knowledge is essen ial o d i ing inno a ion,
o e coming exis ing challenges, and ealizing he ull po en ial o CPE echnology in ad ancing
solid-s a e ba e ies.
o n o
NMR
40
in publica ion #2, i led: In luence o he LLZO-PEO in e ace on he mic o- and mac o-scale
p ope ies o composi e polyme elec oly es o solid-s a e ba e ies.
These s udies e ealed ha LLZO's ins abili y in ambien condi ions in oduces signi ican
complexi ies, impac ing bo h i s dynamics and su ace p ope ies. I was ealized ha hese
complexi ies a e gene ally no well unde s ood and ha he me hods commonly employed o
s udy he su ace laye s a e o en ine icien . Thus, o add ess his knowledge gap, hese issues
we e u he explo ed in publica ion #3, i led: A ision o LLZO Ca bona e Fo ma ion:
Pe spec i es on Su ace T ea men App oaches and Cha ac e iza ion Techniques.
Following he s udy o LLZO, he ion anspo p ope ies and phase in e ac ions we e
examined in a new CPE composed o LATP pa icles and a PEO-based polyme ma ix. These
CPEs demons a e a be e pe o mance, a ibu ed o he lowe ac ion o ino ganic pa icles
and he inclusion o plas icize s. Explo ing how LATP pa icles in e ac wi h a ious
componen s o he polyme ma ix, and how hese in e ac ions in luence he ion anspo
o med he basis o publica ion #4, i led: T anspo P ope ies and Local Ions Dynamics in
LATP-Based Hyb id Solid Elec oly es.
In he nex s ep, a CPE composed o Li₆PS₅Cl and PEO-LiTFSI was de eloped o examine hei
compa ibili y and po en ial in e acial eac ions. Solid-s a e NMR was employed o analyze he
eac ion p oduc s and hei in luence on ion anspo ac oss he in e phase. Fu he mo e,
he s udy explo ed how dopan -induced diso de in he a gy odi e c ys al s uc u e a ec s he
kine ics o hese in e acial eac ions. This s udy was discussed in publica ion #5, i led:
Un eiling he Reac i i y and he Li-Ion Exchange a he PEO-Li6PS5Cl In e phase: Insigh s om
Solid-S a e NMR.
Las ly, an all-ino ganic composi e elec oly e based on an a gy odi e (Li₆PS₅Cl) and a halide
(Li2.1Ga0.1Z 0.9Cl6) elec oly e was p epa ed o gain insigh in o he in e acial eac ions o hese
solid elec oly es. In his s udy, solid-s a e NMR, EIS, and DRT analysis we e used o in es iga e
hei chemical compa ibili y and o de e mine he ole o he in e phase species in he local
and long- ange ion anspo . The indings o his s udy a e p esen ed in publica ion #6, i led:
Insigh s in o he Compa ibili y and In e phases o LPSCl A gy odi es and Z -based Halide
Elec oly es o Solid-S a e Ba e ies.

41
4. Resul Summa y and Discussion
Publica ion #1:
The i s publica ion o his hesis ocuses on he eac ion o LLZO in ai and he o ma ion o
seconda y phases on i s su ace. The s udy e eals ha p is ine LLZO, e en when s o ed in a
glo ebox wi h an ine a mosphe e, con ains no iceable amoun s o seconda y phases,
pa icula ly Li2CO3 and LiOH laye s on i s su ace, and hyd ogens inside i s c ys al s uc u e.
Conside ing he well-es ablished nega i e impac o hese phases on he pe o mance o LLZO,
a hea ea men p ocess was p oposed o hei elimina ion. Based on he TGA p o ile, he
LLZO powde s we e hea ed a 350°C, 550°C, and 750°C o moni o he LLZO chemical and
phase e olu ion du ing his hea ea men , using XRD, solid-s a e NMR, and Raman
spec oscopy. The esul s demons a e ha hea ing a 750°C is highly e ec i e in emo ing
bo h he LiOH and Li2CO3 su ace laye s and he p o ons inside he s uc u e. Addi ionally,
a iable empe a u e NMR expe imen s e ealed ha his hea ea men signi ican ly
enhances he local Li dynamics o LLZO. Las ly, i was shown ha al hough he hea ea men
is no pa icula ly e ec i e as a p epa a o y s ep be o e sin e ing he ce amic pelle s, i
no ably imp o es he mo phology and in eg i y o he CPEs.
Publica ion #2:
In he nex s ep, he impac o hese in e phase species was explo ed by compa ing wo
ce amic- ich CPEs composed o p is ine and hea - ea ed LLZO. The indings indica ed ha
emo ing Li2CO3 and LiOH enhances he in e ac ions be ween PEO and LLZO, esul ing in a
mo e uni o m phase dis ibu ion and imp o ed mechanical p ope ies. Solid-s a e NMR
expe imen s showed ha emo ing hese su ace laye s educes he in e acial Li exchange
be ween LLZO and PEO. Fu he in es iga ion iden i ied LiOH as a key acili a o in his
exchange, aiding Li+ anspo ac oss he in e phase. Howe e , gi en ha he in e acial Li
exchange occu s ela i ely slowly (in he o de o hund eds o milliseconds), LLZO's
con ibu ion o ion conduc ion emains insigni ican . This conclusion was u he suppo ed
by he obse a ion ha he CPE con aining hea - ea ed LLZO exhibi ed an ionic conduc i i y
3 imes highe han i s p is ine coun e pa . Addi ionally, he hea ea men enhanced Li
pla ing kine ics and educed he solid elec oly e/elec ode in e ace esis ance by almos one
o de o magni ude. These imp o emen s we e also e lec ed in he educed o e po en ial
and p olonged cyclabili y o he CPEs in symme ic cells, ul ima ely demons a ing he
supe io pe o mance o hese CPEs in blocking Li dend i e g ow h h ough he elec oly e.
The p olonged cyclabili y o he CPE wi h hea - ea ed LLZO, likely due o he slowe a e o
li hium dend i e g ow h, encou aged a new p ojec o in es iga e he Li dend i e g ow h
h ough solid elec oly es using ope ando solid-s a e NMR. While ope ando NMR has been
success ully employed in Li-ion cells wi h liquid elec oly es, i s applica ion o solid elec oly es
emains limi ed. The main challenges o using his echnique in solid-s a e ba e ies a e:
1. S ack p essu e: E icien Li pla ing/s ipping es s in solid-s a e ba e ies equi e
consis en p essu e o ill he gene a ed oids and main ain a s able o e po en ial.
42
2. Ionic conduc i i y: The oom empe a u e ionic conduc i i y o CPEs and polyme
elec oly es is ela i ely low, making pla ing/s ipping a oom empe a u e easible
only a e y low cu en s.
The NMR ope ando cells, pu chased om eP obe, do no con ain a buil -in sp ing o
main aining s ack p essu e. On he o he hand, adding an i on-based sp ing is also no
possible, as i on is e omagne ic and unsui able o being used inside he NMR magne . Thus,
se e al laye s o Vi on ubbe we e included o mi iga e he p essu e issue. The second
challenge ega ding ionic conduc i i y was add essed by pe o ming he elec ochemical and
NMR expe imen s a high empe a u es. Howe e , i was ealized ha he cells a e no
pe ec ly ai igh a ele a ed empe a u es, causing he passi a ion o he Li me al. To
o e come his issue, pu e a gon as an ine gas was used o hea he sample inside he NMR
p obe. This app oach allows o cell ope a ion o abou 20 hou s o a 50-li e a gon cylinde .
Howe e , his pe iod is s ill insu icien o obse e he g ow h o Li dend i es. Addi ionally,
using a gon low o se e al days o weeks is no economically easible. Thus, ocusing mo e
on p ac icali y, ongoing e o s aim a imp o ing he oom empe a u e ionic conduc i i y and
inc easing he s ack p essu e by non-magne ic comp ession sp ings o enable he cell
ope a ion a oom empe a u e. This wo k is in p og ess and he solu ions a e an icipa ed o
he coming yea .
Publica ion #3:
A e iden i ying he nega i e impac o su ace laye s in LLZO in CPEs, a b ie concep
publica ion was de eloped o discuss and compa e se e al me hods o emo ing hese laye s.
In addi ion, his wo k p esen s he ad an ages and limi a ions o common cha ac e iza ion
echniques such as XRD, NMR, Raman, e c. in analyzing LLZO samples. Focusing on p ac ical
aspec s o LLZO handling, his guide aims o help esea che s be e unde s and he
complica ions o hese sys ems and conduc hei expe imen s mo e accu a ely.
Publica ion #4:
The nex wo k del ed in o ion anspo in a CPE composed o PEO-based polyme ma ix and
LATP pa icles. The sho - ange (local) and long- ange conduc i i y we e sepa a ely analyzed
in hyb id elec oly es con aining up o 20 ol% LATP o assess he pa icipa ion o LATP in ion
anspo . Sa u a ion eco e y and a iable empe a u e 19F NMR expe imen s demons a ed
ha he addi ion o LATP has minimal impac on he local ions’ dynamics. The indings om
6Li EXSY NMR and 6Li/7Li iso ope exchange expe imen s indica ed ha an in e acial Li+
exchange does occu be ween he phases a a local scale. Howe e , conduc i i y
measu emen s e ealed ha his exchange does no ansla e in o imp o ing long- ange
conduc i i ies, due o he high in e ace esis ance o Li+ anspo be ween he LATP and he
polyme phases. Ne e heless, by inc easing he empe a u e om 20°C o 60°C, he ime
cons an o his Li+ exchange dec eases by a ac o o 6, acili a ing he pa icipa ion o LATP in
long- ange anspo , obse ed by elec ochemical conduc i i y measu emen s. Combining
PFG-NMR and elec ochemical es s, i was e ealed ha a low o mode a e ac ions (10
ol%), LATP pa icles ha e li le o no impac on he ion anspo p ope ies o he CPEs.
43
Howe e , a his concen a ion, hey no ably imp o e he mechanical p ope ies o he
elec oly e memb anes, which esul ed in bo h imp o ed p ocessabili y and dend i e g ow h
esis ance.
Publica ion #5:
In he subsequen publica ion, he in e phases be ween Li6PS5Cl (LPSCl) and PEO-LiTFSI we e
in es iga ed, as unde s anding he na u e o hese in e phases and hei ole in ion anspo
is c ucial o bo h mul ilaye sys ems and CPEs. De ailed solid-s a e NMR analysis o his
sys em e ealed ha when highly diso de ed LPSCl is b ough in o con ac wi h highly pola
PEO, i s s uc u e deg ades o o m P(EO)3-LiCl and PEO-Li3PS4 complexes, as well as
polysul ides. 6Li EXSY and 1H-6Li Spin-di usion NMR expe imen s demons a ed a di ec Li
exchange be ween he PEO and LPSCl, which is no media ed by he species a he in e phase,
pa icula ly PEO-LiCl and PEO-Li3PS4. Fu he insigh s in o his sys em we e ob ained by
eplacing he LPSCl wi h a mo e diso de ed Li5.4PS4.6ClB 0.4 (LPSClB ), which eac ed mo e
in ensely wi h PEO and o med a highe con en o decomposi ion p oduc s a he in e phase.
The NMR analysis indica ed ha he men ioned in e phase species exhibi e y slow mobili y,
hinde ing he Li exchange be ween he phases. This s udy concluded ha he de ec chemis y
o a gy odi es g ea ly impac s hei s abili y agains highly pola polyme s like PEO, in luencing
he ion anspo ac oss he in e phase. The obse ed Li exchange and i s dependence on he
decomposi ion p oduc s sugges he signi ican po en ial o hese CPEs i he chemis y o he
polyme and he a gy odi e a e sligh ly modi ied o imp o e hei compa ibili y.
Publica ion #6:
The las publica ion in es iga es he chemical compa ibili y be ween Li6PS5Cl a gy odi e and a
Li2.1Ga0.1Z 0.9Cl6 (LGZC) halide elec oly e, as Li6PS5Cl is widely used as an in e laye be ween
he Li me al and halide elec oly es o mi iga e hei ins abili y. Solid-s a e NMR expe imen s
e ealed ha he chemical incompa ibili y be ween hese elec oly es d i es in e acial
eac ions, in ol ing pa ial decomposi ion o bo h halide and sul ide. The decomposi ion
p oduc s a he in e phase exhibi slowe dynamics han he main phases, hus inc easing he
esis ance o ion anspo h ough he in e phase. EIS, DRT, and solid-s a e NMR analysis
indica ed ha in e phase eaches s abili y a e a sho pe iod, al hough he decomposi ion
ad ances a ele a ed empe a u es. No ably, 6Li and 7Li EXSY NMR expe imen s e ealed he
spon aneous Li-ion exchange no only be ween he p ima y halide and a gy odi e phases bu
also be ween he decomposi ion p oduc s a he in e phase. These obse a ions explain why
inco po a ing a hin laye o Li6PS5Cl enhances cell pe o mance in mul ilaye sys ems.
Al hough his wo k ocused on LGZC/LPSCl in e ac ions, i s simple me hodology used o
examining he chemical compa ibili y and in e acial eac ions can be eadily applied o o he
halide/sul ide composi es wi h di e en chemical composi ions.
44
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6. Concluding Rema ks and Fu u e Impac s
In his hesis, solid-s a e NMR has been success ully employed as a powe ul ool o add ess
key challenges in designing composi e polyme elec oly es (CPEs) and in es iga ing in e acial
eac ions in solid-s a e ba e y ma e ials. This wo k con ibu es o a deepe unde s anding o
he ion anspo p ocesses a he in e phases, which a e c i ical o he de elopmen o
ad anced solid elec oly es. Th oughou he wo k, solid-s a e NMR played a c ucial ole in
p o iding deep insigh s in o he in e phases wi hin hese sys ems, pa icula ly he ion
anspo mechanisms and phase in e ac ions.
In he i s pa o he esea ch, NMR was used as a ool o he a ional design o CPEs,
in es iga ing bo h he s uc u e and Li dynamics o di e en phases, as well as he Li-ion
exchange p ocesses be ween he o ganic and ino ganic componen s. The in e phase was
shown o be a c i ical zone o ion anspo , impac ing no only he local ion exchange, bu
also he mic os uc u e, long- age ion anspo , and mechanical p ope ies o he CPEs. Using
solid-s a e NMR, aluable insigh s in o he dynamics a he in e aces we e ob ained,
demons a ing he ole o in e phase species such as passi a ion laye s o decomposi ion
p oduc s in acili a ing o impeding he Li-ion conduc ion in CPEs.
In he second pa , solid-s a e NMR was employed o in es iga e he compa ibili y and
in e acial eac ions be ween a ious solid elec oly es, using CPEs as model sys ems. This pa
ocused on unde s anding how di e en solid elec oly es, such as halides, polyme
elec oly es, and a gy odi es in e ac when b ough in o con ac . The wo k showed ha
in e acial eac ions, while some imes ine i able, can be managed and mi iga ed h ough
ca e ul ma e ial selec ion. Impo an ly, i was shown ha he chemical compa ibili y be ween
di e en elec oly es is highly in luenced by he s uc u al diso de and he chemical
composi ion o each phase, making i challenging o p opose gene al conclusions on he
compa ibili y be ween di e en amilies o ma e ials. Howe e , he me hods de eloped in his
s udy can be applied o a ious elec oly e sys ems o assess hei compa ibili y and iden i y
po en ial issues in hei design.
Al hough his hesis p ima ily ocused on he undamen al unde s anding o composi e
elec oly es, i was demons a ed ha high-pe o mance solid elec oly es wi h imp o ed
conduc i i y and cycling beha io can be de eloped by modi ying he in e phases be ween
he o ganic and ino ganic phases. Thus, he me hods used, pa icula ly solid-s a e NMR, a e
no only e ec i e o desc ibing he in e acial eac ions bu also aluable o add essing he
pe o mance limi a ions o hese sys ems.
The indings and me hodologies applied in his esea ch es ablish a ounda ion o u he
explo a ion o in e phases in solid-s a e ba e ies. By demons a ing how solid-s a e NMR can
e ec i ely de e mine ion exchange, moni o chemical e olu ion, and analyze in e phase
eac ions, his s udy pa es he way o e ining elec oly e designs. These insigh s will guide
u u e e o s in op imizing ma e ial compa ibili y and imp o ing he pe o mance o solid
elec oly es, d i ing ad ancemen s in eliable and e icien solid-s a e ba e y echnologies.
phases. Fig. 3 shows he iden ied phases o each sample and
he comple e emo al o Li
2
CO
3
ae hea ea ing a 750 °C.
While T-P is ine shows only a low empe a u e cubic phase, in
all he hea ea ed samples, he e agonal phase is p esen ,
coexis ing wi h he low empe a u e cubic phase in T-350, and
wi h he highly conduc i e cubic phase in T-550 and T-750.
Solid s a e NMR expe imen s we e conduc ed on he p is ine
and hea ea ed samples o u he de e mine he impac o
empe a u e on he composi ion and o cha ac e ize local Li
+
dynamics. The
1
H NMR spec um o T-P is ine is cha ac e ized
by h ee main signals (Fig. 4a) appea ing a −1.6 ppm, 0.9 ppm,
and 3.9 ppm. The signal a −1.6 ppm can be easily asc ibed o
LiOH in ag eemen wi h alues p e iously obse ed o his
compound o med as a seconda y p oduc o ga ne
p o ona ion.
33–37
The signal a 3.9 ppm was also p e iously
obse ed upon LLZO p o ona ion and is asc ibed o p o ons
inside he ga ne s uc u e.
33–35
The
1
H–
7
Li HETCOR co ela ion
expe imen pe o med o his sample (Fig. 4c) clea ly shows he
s ong co ela ion o
1
H signals a −1.6 and 3.9 wi h
7
Li, in
ag eemen wi h p o ons in LiOH and p o ons coexis ing wi h
li hium in Li
7−x
H
x
La
3
Z
2
O
12
. The signal a 0.9 ppm, which was
p e iously obse ed bu no specically assigned,
33,35
is ela-
i ely sha p in he
1
H spec um, bu does no show a clea
co ela ion wi h Li in he CP-based spec um o Fig. 4b. These
p o on signals could be a ibu ed o he p o ons o he wa e
molecules adso bed a he su ace o LLZO o included a i s
su ace de ec s, o ming LLZO$H
2
O h ough eac ion (4).
12
Li
7−x
H
x
La
3
Z
2
O
12
+xH
2
O/Li
7−x
H
x
La
3
Z
2
O
12
$nH
2
O(4)
To u he explo e he na u e and disposi ion o he
p o ona ed phases asc ibed o he obse ed p o on signals,
1
H–
1
H EXSY homonuclea co ela ions we e de e mined. This
expe imen was pe o med o T-P is ine wi h a mixing ime o
128 ms. The esul ing spec um shown in Fig. 4c is cha ac e -
ized by a diagonal wi h au oco ela ion signals obse ed in he
1D spec um and off-diagonal co ela ions be ween signals a
3.9 and 0.9 ppm as well as be ween signals a −1.6 and 0.9 ppm.
Since signals a 3.9 and −1.6 ppm a e assigned o p o ons inside
he ga ne s uc u e and LiOH a he su ace o he pa icles
espec i ely, he p o ons obse ed a 0.9 ppm should be placed
in close icini y o bo h phases. This is in ag eemen wi h wa e
molecules adso bed a he su ace o LLZO. The na owe
cha ac e o his signal a 0.9 ppm is also in ag eemen wi h he
as e local mobili y expec ed o a wa e molecule. Addi ional
1
H–
1
H EXSY NMR expe imen s pe o med wi h e y sho (0.1
ms) and long (256 ms) mixing imes p esen ed in Fig. S1,†
indica e ha off-diagonal co ela ions a e caused by chemical
exchange.
The
1
H and
7
Li NMR spec a as well as
7
Li T
1
imes o he
p is ine ga ne , T-350, T-550, and T-750 (Fig. 5a–c espec i ely)
we e eco ded and compa ed in o de o obse e he effec o
he hea ea men on he Li local mobili ies and s a es o
p o ona ion. F om he inspec ion o he
1
H NMR signal
Fig. 4 (a)
1
H NMR spec um, (b)
7
Li–
1
H 2D he e onuclea co ela ion, (c)
1
H–
1
H 2D co ela ion wi h a mixing ime o 128 ms and (d)
7
Li NMR
spec um o T-P is ine.
Fig. 5 (a)
1
H NMR spec a and (b)
7
Li NMR spec a and (c)
7
Li sa u a ion eco e y expe imen o T-P is ine, T-350, T-550 and T-750.
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e olu ion upon hea ea men (Fig. 5a), a signican educ ion
o in ensi y o he p o on signal is obse ed al eady o he
sample T-350. The educ ion o p o on in ensi y obse ed
in ol es he h ee signals p esen in he spec um o T-P is ine,
sugges ing he emo al o wa e molecules om LLZO$H
2
O,
p o ons om inside he s uc u e, and LiOH om he ga ne
su ace h ough eac ions (5)–(7) espec i ely.
Li
7−x
H
x
La
3
Z
2
O
12
$nH
2
O/Li
7−x
H
x
La
3
Z
2
O
12
+xH
2
O(5)
Li7xHxLa3Z 2O12/Li7xLa3Z 2O
12x
2
þx
2H2O(6)
Li
7−x
H
x
La
3
Z
2
O
12
+xLiOH /Li
7
La
3
Z
2
O
12
+xH
2
O(7)
Compa ing he
1
H–
1
H and
7
Li–
1
H co ela ions in T-P is ine
and T-350 (Fig. 6a and b), we can obse e ha LiOH is
comple ely emo ed, and only a small p o on popula ion
emains. As a esul , he signal in ensi ies a e low, and no
magne iza ion ans e can be obse ed be ween p o ons inside
he ga ne .
As can be obse ed in Fig. 5b, he
7
Li signal in bo h T-P is ine
and T-350 is b oad, al hough i is clea ha a leas o T-350, he
signal has mo e han one componen , p obably due o he
p esence o mo e han one Li compound. This is in ag eemen
wi h he clea ca bona e band in he Raman spec a (Fig. 3), as
well as
7
Li T
1
measu emen s (Fig. 5c and Table S1†), in which
he build-up cu es o bo h T-P is ine and T-350 can be  ed
only by a double exponen ial e m, indica ing he p esence o
wo Li ese oi s wi h conside ably diffe en elaxa ion imes. In
gene al, he p esence o as Li
+
dynamics esul s in sho e
elaxa ion imes in highly conduc i e ce amics as compa ed o
he long elaxa ion imes ypically obse ed o non-conduc i e
sal s like Li
2
CO
3
. By elimina ion o he p o ons inside he ga ne
s uc u e, he Li T
1
elaxa ion ime dec eases om 17 s o 3.9 s
(Table S1†).
When he hea ea men empe a u e was inc eased o 550 °
C and 750 °C, he
1
H signals a e u he educed, indica ing
addi ional p o on elimina ion h ough eac ion (6). No signals
we e obse ed o he he e onuclea
1
H–
7
Li and homonuclea
1
H–
1
H NMR co ela ions conduc ed on bo h samples T-550 and
T-750. This esul sugges s comple e elimina ion o p o ons in
he sample and ha he emaining p o on signals obse ed in
Fig. 5a a e due o backg ound p o on signals om he p obe o
he o o and he e o e ex e nal o he sample.
In gene al, he linewid h (FWHM) o
7
Li NMR signals is
di ec ly ela ed o ion dynamics, as as e ion mo ions can
effec i ely a e age ou he aniso opic in e ac ions p esen in
he solid s a e,
38,39
educing he obse ed linewid hs. Fig. 5b
shows a signican educ ion o he linewid h o
7
Li NMR
esonances om 691 Hz o 79 Hz ae hea ea men a 550 °C,
implying as e local dynamics o Li
+
in he T-550 sample. This
change can be explained by a phase ansi ion om e agonal
o highly conduc i e cubic, as well as by pa ial emo al o he
igid li hium ca bona es ( eac ion (8)) as shown p e iously by
Raman spec oscopy in Fig. 3.
Li7xLa3Z 2O
12x
2
þx
2Li2CO3/Li7La3Z 2O12 þx
2CO2(8)
By u he inc easing he hea ea men empe a u e o 750
°C, a u he na owing o he
7
Li NMR signal is obse ed om
79 Hz o 64 Hz. In addi ion, he build-up cu e o he sa u a ion
eco e y expe imen (Fig. 5c and Table S1†) can be  ed by
a single exponen ial e m only ae hea ea ing a 750 °C,
which indica es comple e emo al o Li
2
CO
3
and is consis en
wi h ou esul s om Raman measu emen s (Fig. 3). I is
no ewo hy ha acco ding o eac ion (8) and based on ou ICP
esul s (Table S2†), he Li om he ca bona e is no los and
a he e u ns o he ga ne s uc u e ae he Li
2
CO
3
decom-
posi ion. Fu he mo e, eac ion (8) implies he eco e y o he
oxygen acancies ha could be gene a ed a he LLZO su ace by
he p o on elimina ion h ough wa e e apo a ion desc ibed in
eac ion (6).
To pe o m a de ailed cha ac e iza ion o he Li dynamics in
he p is ine and T-750 hea ea ed samples, a iable empe a-
u e
7
Li Linewid h (LW) e olu ions we e measu ed and
compa ed wi h hose o sin e ed pelle s. The ansi ion om
b oad gaussian NMR signals obse ed a he igid la ice (low
empe a u es) o na ow Lo en zian peaks a he mally ac i-
a ed s a es is clea ly obse ed in all samples excep in T-
P is ine whe e he high empe a u es equi ed o as Li
+
dynamics could no be expe imen ally eached (Fig. 7a). The
mo ional na owing (MN) cu es (Fig. 7a) show ha unlike T-
P is ine, T-750 has a beha iou e y simila o he sin e ed
pelle s. The esul ing empe a u e-dependance o he
7
Li LW
we e  ed conside ing a Bol zmann unc ion (eqn (9)) o ob ain
he inec ion poin and linewid h o he igid la ice o each
sample.
y¼A1A2
1þeðxx0Þ=dxþA2(9)
Jump a es (a T
ip
) and he ac i a ion ene gy o mo ional
na owing (E
MN
a
) o each sample we e calcula ed h ough eqn
(10) ( e .
40
) and (11) ( e .
41
and
42
) espec i ely and a e p esen ed
in Table 1.
Fig. 6 (a)
1
H–
7
Li he e onuclea expe imen and (b)
1
H–
1
H homonu-
clea expe imen o T-P is ine (black) and T-350 ( ed).
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s
−1
MN
=2p$u
RL
(10)
uðTÞ¼uRL1þuRL
B1expEMN
a
KBT1
þD(11)
whe e u
RL
is he
7
Li linewid h in he igid la ice, K
B
is he
Bol zmann cons an and Dis a line-b oadening cons an o ake
he empe a u e-independen effec s such as magne ic eld
inhomogenei y in o accoun . Eqn (11) which assumes a simila
empe a u e dependency in he ac ion o acancies and he
ac ion o he mally ac i a ed ions is uninuenced by he
possible dis ibu ion o elaxa ion imes in he sys em and
he e o e can be applied in a wide ange o empe a u e.
41
Since he high empe a u e pa o he cu e could no be
achie ed o T-P is ine, i s ac i a ion ene gy is oughly es i-
ma ed by using eqn (12) known as he Waugh–Fedin
43
equa ion.
E
WF
a
=1.617 ×10
−3
$T
onse
(12)
whe e T
onse
is he empe a u e in which he mo ional na ow-
ing begins, and i is calcula ed by  ing he angen ial lines in
he MN cu e.
The E
MN
a
om solid s a e NMR akes bo h nonlocalized (long-
ange ion mo ions) and localized (dipola elaxa ions) conduc-
ion in o accoun and he e o e is lowe han he E
a
ob ained by
EIS. In ac , a ho ough calcula ion o E
a
by solid s a e NMR
would equi e addi ional T
1
,T
1
and T
2
elaxa ion ime
measu emen s, as well as impedance spec a eco ded in a wide
empe a u e and equency ange, which is ou o he scope o
his s udy.
44–48
Howe e , he E
MN
a
alues o T-750, Sin -P is ine and Sin -750
a e no iceably lowe han ha o T-P is ine and a e simila o
wha Buschmann e al.
49
epo ed o highly conduc i e cubic
LLZO wi h Al doping. A low empe a u es, he
7
Li NMR spec a
o T-750 seem o be composed o 2 o e lapping signals, showing
diffe en dynamics. The e o e, he spec a we e decon olu ed
conside ing Gaussian and Lo en zian unc ions. The a ea ac-
ion (A
) o he na ow componen calcula ed in he ange o −50
o −10 °C (Fig. 7b) indica es he ac ion o Li ions wi h as
jump a es (10
4
s
−1
). Fig. 7c shows ha he A
linea ly inc eases
upon hea ing, and al eady a −10 °C, abou 40% o he Li ions
a e subjec o as dynamics on he NMR imescale. This u he
con ms ou p e ious conclusion om
7
Li T
1
elaxa ion ime
measu emen s ha he hea ea men is no only su ace-
ela ed, bu a he affec s he dynamics o he Li a oms in he
bulk o he ga ne .
The effec o LiOH and Li
2
CO
3
emo al on he pelle 's ela i e
densi y and i s ionic conduc i i y was in es iga ed by p epa ing
sin e ed pelle s using T-P is ine and T-750 as s a ing ma e ials.
These pelle s, e e ed o as Sin -P is ine and Sin -750 espec-
i ely, showed no diffe ences in ela i e densi ies (92% in bo h
cases), and e y simila ac i a ion ene gies, p esen ed in Fig. 7a
and Table 1. The bulk ionic conduc i i ies we e calcula ed using
eqn (13), whe e Ais he su ace a ea and is he sample
hickness.
s= /RA (13)
Fu he mo e, he ac i a ion ene gy om ionic conduc i i ies
was ob ained h ough he ollowing A henius equa ion.
Fig. 7 (a) Tempe a u e dependency o he
7
Li linewid h o T-P is ine, T-750, Sin -P is ine, and Sin -750. Dashed lines indica e he fi wi h he
Bol zmann equa ion. (b)
7
Li NMR spec a o T-750 a −50 °C o −10 °C, and decon olu ion o he spec um a −30 °C. (c) Tempe a u e
dependency o he a ea ac ions o he na ow componen s ob ained om he decon olu ion o spec a wi h Gaussian and Lo en zian
unc ions.
Table 1 Tempe a u e o he inflec ion poin , ac i a ion ene gy o
mo ional na owing and he jump a es calcula ed om he a iable
empe a u e
7
Li LW analysis shown in Fig. 7a
Sample T
ip
(°C) E
MN
a
(eV) s
MN
−1
(kHz)
T-P is ine +116 0.49
a
51.2
T-750 −47 0.30 58.3
Sin -P is ine −49 0.28 56.9
Sin -750 −49 0.28 57.5
a
Calcula ed om eqn (11).
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s¼s0eEa
KBT(14)
Bo h Sin -P is ine and Sin -750 show iden ical ac i a ion
ene gies (0.43 eV) and compa able bulk ionic conduc i i ies a
25 and 70 °C, as p esen ed in Table 2 and Fig. S2.†
We can he e o e conclude ha hea ea ing he powde
p io o pelle izing and sin e ing shows no conside able
imp o emen in elec ochemical pe o mance. This esul
demons a es ha he high empe a u es used du ing he sin-
e ing p ocessing di ec ly p omo es p o on, hyd oxide, and
ca bona e emo al. Howe e , based on he signican inc ease
o local Li
+
mobili y obse ed om he p is ine o hea ea ed
powde , shown in Fig. 7a, hea ea ing LLZO a 750 °C is ex-
pec ed o ha e a s ong inuence in cases in which a sin e ing
s ep is no pe o med, as o composi e elec oly es o cold-
sin e ed pelle s in which ion anspo is highly sensi i e o
he in e acial p ope ies o g ains. To assess he possible
impac o he hea ea men on he Li ion anspo a he bulk
and he ou e mos su ace o LLZO g ains, T-P is ine and T-750
ga ne s we e added o he PEO-LiTFSI mix u e o p epa e
ga ne - ich solid composi e elec oly es (90 w % LLZO). The
memb anes we e cas in PTFE dishes and ca e ully emo ed
ae d ying in a acuum o en. Al hough he sample p epa a ion
was he same (as de ailed in he Expe imen al sec ion), he
memb anes show clea ly diffe en mechanical p ope ies as
shown in Fig. 8a and c. While he composi e made wi h T-
P is ine is highly agile and non-sel -s anding, he one
con aining T-750 has high in eg i y and is sel -s anding and
exible.
The SEM images (Fig. 8b and d) demons a e ha such be e
mechanical p ope ies could be ela ed o he ga ne –polyme
in e phase. In he composi e made o T-750, he ga ne pa icles
a e uni o mly coa ed wi h he polyme ma ix, whe eas in he
composi e wi h T-P is ine, many ga ne pa icles a e no
co e ed by PEO, which could be a ibu ed o a weak ga ne –
polyme in e ac ion as a esul o he p esence o su ace g oup
impu i ies, causing a phase seg ega ion and hus leading o low
mechanical p ope ies.
Despi e he non-sel -s anding na u e o he composi e wi h
T-P is ine, he impedance spec a o hese memb anes we e
eco ded (Fig. S3†) and he ionic conduc i i ies ob ained we e
4.3 ×10
−6
and 1.6 ×10
−5
Scm
−1
a 70 °C o composi es wi h
T-P is ine and T-750 espec i ely. The highe ionic conduc i i y
o he la e can be a ibu ed o i s mo e homogenous
mo phology and be e PEO–LLZO in e ace. The low ionic
conduc i i y o ga ne - ich composi es is no unp eceden ed
and has been p e iously epo ed and explained.
50,51
De ailed
cha ac e iza ion o he ga ne - ich composi es and de e mining
hei Li-ion pa hways a e ou o he scope o his a icle and
he e o e will be he subjec o ou u u e wo k.
I is well known ha diffe en dopan s and concen a ions
ha e an impo an effec on he Li conduc i i ies o LLZO,
24,30
al hough i has also been epo ed ha he p o ona ion and
o ma ion o LiOH and ca bona es a e p esen in ga ne s
ega dless o he dopan used.
14,17
The impac o hea ing on he
chemical and he modynamic p ocesses epo ed he e o a Nb
sample a e he e o e expec ed o be dopan -independen as
mainly su ace effec s a e in ol ed. Howe e , o con m his
hypo hesis, addi ional NMR expe imen s we e pe o med on
comme cial Al-doped LLZO. Fig. S4†clea ly shows he LiOH
o med on he Al-LLZO su ace, he adso bed wa e molecules
and LLZO p o ona ion h ough a H
+
/Li exchange eac ion. The
compa ison o he
1
H NMR spec a be o e and ae he hea
ea men a 750 °C (Fig. S5†) indica es he o al emo al o
LiOH and wa e molecules a he su ace, and a signican
educ ion o p o ons inside he LLZO s uc u e. The conside -
able educ ion o he 7Li T
1
elaxa ion imes upon hea ea -
men shown in Fig. S6†is a ibu ed o he LiOH and Li
2
CO
3
decomposi ion as well as o he inc eased Li dynamics upon
ga ne dep o ona ion. This con ms ha hea ea men a 750
°C is sufficien o comple e emo al o p o ons and seconda y
phases on he Al-LLZO su ace. Mo eo e , like o Nb-LLZO, he
hea ea men has a s ong impac on he
7
Li NMR linewid hs,
dec easing om 607 o 305 Hz upon hea ing a 750 °C in
ag eemen wi h as e local Li dynamics (Fig. S7†).
Concluding ema ks
In his wo k, he impac o hea ea men on he LLZO s uc-
u e, he seconda y p oduc s p esen on i s su ace, and he Li
dynamics inside he ga ne was in es iga ed. The cha ac e iza-
ion o he p is ine ga ne shows a signican deg ee o LLZO
p o ona ion as well as he p esence o wa e , LiOH and
ca bona es a he su ace. Hea ea men a 350 °C was ound
Table 2 Bulk ionic conduc i i y and ac i a ion ene gy o Sin -P is ine
and Sin -750 a 25 and 70 °C ob ained by using eqn (13) and (14)
Sample s
25 °C
(S cm
−1
)s
70 °C
(S cm
−1
)E
a
(eV)
Sin -P is ine 3.7 ×10
−4
3.5 ×10
−3
0.43
Sin -750 5.1 ×10
−4
4.2 ×10
−3
0.43
Fig. 8 Pho o and SEM mic og aphs o ga ne - ich composi e polyme
elec oly es con aining 90 w % (a and b) T-P is ine and (c and d) T-750.
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effec i e o comple ely elimina e he LiOH a he su ace and
educe he numbe o p o ons inside he LLZO s uc u e and
wa e a he su ace. Howe e , i doesn' suffice o emo e
ca bona es and cause he phase ansi ion o a highly Li
conduc i e cubic phase. To al elimina ion o ca bona es is
achie ed only ae hea ea ing a 750 °C. Mul iple phase
ansi ions om a low empe a u e cubic phase o a e agonal
phase and la e o a highly conduc i e cubic phase a e in ol ed
in his p ocess and oge he wi h Li
2
CO
3
emo al a e espon-
sible o a signican inc ease in he local Li mobili y inside he
ga ne s uc u e.
In he second pa o his wo k, he impac o hea ea men
a 750 °C as a p e- ea men s ep in he p epa a ion o sin e ed
pelle s was s udied. I was obse ed ha p e- ea men o LLZO
be o e sin e ing is no effec i e and has no big impac on he Li
dynamics and ionic conduc i i ies o sin e ed pelle s. Howe e ,
since he local mobili y o he ga ne ae hea ea men a 750
°C is alike he sin e ed pelle s and he seconda y phases a he
su ace a e emo ed, we expec his hea - ea men o g ea ly
enhance he ionic conduc i i y o LLZO in o he sys ems such as
ce amic-polyme composi e elec oly es in which ga ne lle s
a e no sin e ed. This imp o emen could be achie ed bo h by
as e Li mo ion in he bulk o LLZO and by be e p ocessabili y
o he ga ne - ich composi e solid elec oly es. These composi e
elec oly es will be ho oughly in es iga ed in ou u u e wo k.
Conside ing he simila obse a ions on he impac o hea
ea men on he in e acial and Li anspo p ope ies in Nb
and Al-doped LLZO, we belie e ha he gene al conclusion o
his wo k could be applied o LLZO ga ne s, ega dless o hei
doping composi ion.
Au ho con ibu ions
PG: in es iga ion, o mal analysis, w i ing-o iginal d a, and
w i ing- e iew & edi ing. AP: in es iga ion and w i ing- e iew &
edi ing. KG: in es iga ion. GA, PL, and DS: w i ing- e iew &
edi ing. JL: in es iga ion, supe ision, and w i ing- e iew &
edi ing.
Conflic s o in e es
The e a e no conic s o decla e.
Acknowledgemen s
P. G. as a pa o he DESTINY PhD p og amme acknowledges
unding om he Eu opean Union's Ho izon 2020 esea ch and
inno a ion p og amme unde he Ma ie Skłodowska-Cu ie
Ac ions COFUND –G an Ag eemen No: 945357. This wo k
was suppo ed by he “Minis e io de Ciencia e Inno aci´
on/
Agencia Es a al de In es igaci´
on”, unde he p ojec g an
TED2021-129663B-C52.
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In es iga ing he ole o in e phases in composi e elec oly es by solid-s a e NMR
62
7.2 Publica ion #2:
Ti le: In luence o he LLZO–PEO in e ace on he mic o- and mac o-scale p ope ies o
composi e polyme elec oly es o solid-s a e ba e ies
Au ho s: Ped am Gho banzade, G azia Acca do, Ke man Gómez, Ped o López-A angu en,
Shanmuka aj De a aj, Ca los Miguel Cos a, Senen xu Lance os-Mendez, and Juan Miguel
López del Amo
Jou nal: Ma e ials Today Ene gy
Jou nal impac ac o : 9.0
Jou nal qua ile: Q1 (Ma e ials Science)
Influence o he LLZOePEO in e ace on he mic o- and mac o-scale
p ope ies o composi e polyme elec oly es o solid-s a e ba e ies
Ped am Gho banzade
a
,
b
,
c
, G azia Acca do
a
, Ke man Gomez
a
, Ped o L
opez-A angu en
a
,
Shanmuka aj De a aj
a
, Ca los Miguel Cos a
d
, Senen xu Lance os-Mendez
d
,
e
,
,
Juan Miguel L
opez del Amo
a
,
*
a
Cen e o Coope a i e Resea ch on Al e na i e Ene gies (CIC ene giGUNE), Basque Resea ch and Technology Alliance (BRTA), Ala a Technology Pa k,
Albe Eins ein 48, 01510 Vi o ia-Gas eiz, Spain
b
Uni e si y o Basque Coun y (UPV/EHU), Ba io Sa iena, s/n, 48940 Leioa, Spain
c
ALISTORE-Eu opean Resea ch Ins i u e, 80039 Amiens, F ance
d
Cen e o Physics Uni e si ies o Minho and Po o (CFUM-UP) and Labo a o y o Physics o Ma e ials and Eme gen Technologies, LapMET, Uni e si y o
Minho, 4710-057 B aga, Po ugal
e
BCMa e ials, Basque Cen e o Ma e ials, Applica ions and Nanos uc u es, UPV/EHU Science Pa k, 48940 Leioa, Spain
Ike basque Basque Founda ion o Science, 48009 Bilbao, Spain
a icle in o
A icle his o y:
Recei ed 25 Augus 2023
Recei ed in e ised o m
9 Oc obe 2023
Accep ed 24 Oc obe 2023
A ailable online 31 Oc obe 2023
Keywo ds:
Solid-s a e elec oly es
Ga ne - ich composi e elec oly es
Hyb id elec oly es
Ga ne epolyme in e ace
abs ac
Li
7
La
3
Z
2
O
12
(LLZO) ga ne s o e ing high ionic conduc i i y and elec ochemical s abili y a e among he
mos p omising ce amic ma e ials o li hium me al solid-s a e ba e ies. Al hough hei applica ion in
composi e polyme elec oly es (CPEs) wi h poly(e hylene oxide) (PEO) has been widely s udied, hei
su ace chemis y which is influenced by hei hyg oscopic na u e is o en neglec ed. This wo k epo s
on how he he mal ea men and he consequen elimina ion o seconda y phases a he LLZOePEO
in e ace impac s he mic os uc u e o he ga ne - ich CPEs, which in u n a ec s hei mechanical
and ion- anspo p ope ies. I is shown ha LLZO hea ea men es ic s local polyme chain mo ions,
indica ing ein o cemen o PEO/LLZO in e ac ions which enhances he mechanical s eng h and ho-
mogenei y o he CPEs. These mic o-scale modifica ions o CPEs e en ually inc ease hei ionic con-
duc i i y and imp o e he solid elec oly e/li hium me al in e ace. Thus, he Li
þ
exchange a he PEO/
LLZO in e ace was s udied by using
7
Lie
7
Li exchange spec oscopyenuclea magne ic esonance , and i
was obse ed ha a e LLZO hea ea men , he in e acial Li
þ
exchange has significan ly dec eased, in
line wi h a lowe LiOH con en . This esul confi ms he ole o LiOH as an in e media e in he Li
þ
ex-
change eac ion and ha su ace chemis y plays a mo e impo an ole in he Li
þ
exchange han he
local Li mobili ies in he indi idual phases.
©2023 The Au ho s. Published by Else ie L d. This is an open access a icle unde he CC BY-NC-ND
license (h p://c ea i ecommons.o g/licenses/by-nc-nd/4.0/).
1. In oduc ion
Cu en Li-ion ba e ies (LIBs) based on liquid elec oly es and
in e cala ion elec odes o e nowadays high g a ime ic and
olume ic ene gy densi ies abo e 260 Wh/kg and 730 Wh/L a cell
le el, app oaching hei heo e ical ene gy densi y [1,2]. Howe e ,
he flammable na u e and low he mal s abili y o hei o ganic
sol en s aise se ious sa e y conce ns, pa icula ly o la ge-scale
applica ions such as elec ic ehicles [3,4]. The e o e, o mo e
owa d sa e ba e ies, solid-s a e elec oly es a e p omising al e -
na i es o subs i u e he flammable o ganic elec oly es in LIBs
[5,6]. In addi ion, solid elec oly es could a guably mi iga e he Li
dend i e g ow h, and in his way, hey could po en ially enable he
use o Li me al as he anode, which would significan ly inc ease he
g a ime ic ene gy densi y o he cell [7,8]. Fu he mo e, solid
elec oly es enable he applica ion o bipola elec odes, hus
dec easing he mass and olume o he package and inc easing he
cell ene gy densi y [5]. Solid elec oly es a e ypically di ided in o
h ee g oups: [9] i) polyme elec oly es, ha ing simple p ocess-
abili y and an accep able in e ace wi h he elec odes; ii) ino ganic
elec oly es, ha ing high he mal, mechanical, and elec ochemical
s abili y as well as high ionic conduc i i y; iii) composi e polyme
*Co esponding au ho .
E-mail add ess: [email p o ec ed] (J.M. L
opez del Amo).
Con en s lis s a ailable a ScienceDi ec
Ma e ials Today Ene gy
jou nal homepage: www.jou nals.else ie .com/ma e ials- oday-ene gy/
h ps://doi.o g/10.1016/j.m ene .2023.101448
2468-6069/©2023 The Au ho s. Published by Else ie L d. This is an open access a icle unde he CC BY-NC-ND license (h p://c ea i ecommons.o g/licenses/by-nc-nd/4.0/).
Ma e ials Today Ene gy 38 (2023) 101448
elec oly es (CPEs); combining he p e ious wo, o ideally combine
he high conduc i i y o ino ganics wi h he be e in e acial
p ope ies o polyme s.
poly(e hylene oxide) (PEO) is he mos widely used polyme in
CPEs [10]. Howe e , o he polyme s such as polye hylene ca bona e
and polycap olac one ha e also been success ully used [11].
Li hium bis( ifluo ome hanesul onyl)imide (LiTFSI) wi h i s bulky
anion s uc u e is he mos common Li sal in s udying CPEs,
al hough li hium pe chlo a e (LiClO
4
) and li hium i-
fluo ome hanesul ona e (LiTF) ha e also been in es iga ed [12e14].
Among Li
þ
conduc o s, Li
7
La
3
Z
2
O
12
, (LLZO) ga ne s a e he op
candida es, because hey o e a e y high ionic conduc i i y a
oom empe a u e [15], can e ec i ely inc ease he elec ochemical
s abili y o he composi es [16], and imp o e he in e ace wi h Li
me al [17]. The e o e, his s udy ocuses on CPEs made o PEO/
LiTFSI and LLZO.
Mos s udies on CPEs ocus on ce amic-in-polyme sys ems wi h
a low ac ion o he ino ganic phase. I has been shown ha he
addi ion o a small amoun o fille success ully imp o es he ionic
conduc i i y o he CPE. These imp o emen s a e usually associa ed
wi h he modifica ion o he polyme phase by dec easing i s
c ys allini y [18e20]. Howe e , Wieczo ek e al. [21] poin ed ou
ha he Lewis acid-base na u e o he in e ac ions be ween he
polye he hos and he ino ganic fille s a ec s he Li
þ
conduc i i y.
Fu he , Wang e al. [22] compa ed he e ec o Li-conduc ing
(ac i e) fille s wi h non-conduc ing (passi e) fille s and a ib-
u ed he imp o emen o he ionic conduc i i y o he fille /poly-
me in e ace. Zaman e al. [23] epo ed simila obse a ions in a
PEO/LLZO sys em wi h 15 ol% LLZO. Ne e heless, in all cases, he
ino ganic ac i e fille does no con ibu e o he ion anspo , due
o he fille ac ion being below i s pe cola ion h eshold and no
con inuous ne wo k is o med. Consequen ly, no long- ange Li-ion
conduc ion occu s h ough he ce amic phase [16]. An app oach
owa d imp o ing LLZO con ibu ion in ionic conduc i i y is
inc easing i s con en , and mo ing om ce amic-in-polyme o
polyme -in-ce amic elec oly es. These composi es, which ha e
ecen ly a ac ed huge a en ion, a e e y in e es ing om a
undamen al poin o iew, as la ge ac ions o LLZO inc ease he
ce amicepolyme in e aces and he Li
þ
anspo pa hway is mo e
complex. Fu he mo e, wi h he inco po a ion o a highe amoun
o LLZO, he mechanical and elec ochemical s abili y o he elec-
oly e can be imp o ed [16,18,24].
One o he majo d awbacks o LLZO is he e y as H
þ
/Li ex-
change eac ion a e exposu e o humidi y, o ming a laye o LiOH
which u ns in o Li
2
CO
3
upon eac ion wi h CO
2
[25e27]. Due o
hei hyg oscopic na u e, in mos cases, he LLZO su ace is co e ed
by seconda y phases such as LiOH and Li
2
CO
3
. In ou p e ious s udy
[28], we showed ha a hea ea men a 750

C is highly e ec i e
in emo ing hese seconda y phases and imp o es he p ocess-
abili y o ga ne - ich composi es. In addi ion, i was shown ha his
hea ea men significan ly enhances Li
þ
dynamics in he LLZO,
which could eflec in hei ionic conduc i i y. In his wo k, we
in es iga e in mo e de ail he impac o he LLZO hea ea men on
he mo phological, mechanical, and Li anspo p ope ies o
ga ne - ich CPEs, as well as he impac o hea ea men on he Li
þ
exchange a PEO/LLZO in e ace. Finally, we assess he elec o-
chemical p ope ies and in e ace wi h Li me al o he symme ic
cells o demons a e he sui able pe o mance o he op imized
solid elec oly es.
2. Expe imen al sec ion
Comme cial LLZO (Li
6.75
La
3
Z
1.75
Nb
0.25
O
12
) pu chased om
Toshima was used in his wo k. The powde s we e fi s ball-milled
o educe he pa icle size. Pa o he powde s was placed in a
u nace a 750

C o 12 h o emo e he decomposi ion p oduc s
om hei su ace and ob ain hea - ea ed LLZO.
A so ball-milling p ocedu e was used o he p epa a ion o he
ga ne - ich composi e elec oly es. Poly(e hylene-oxide) (PEO,
110
6
g/mol, Sigma Ald ich) was mixed wi h li hium bis( i-
fluo ome hanesul onyl)imide (LiTFSI, Sol ionic), LLZO, and ace o-
ni ile (ACN, Sigma Ald ich). The EO:Li a io o 20:1 was kep
cons an in all samples. The mix u e was ball-milled o 25 min in
5-min in e als wi h a equency o 350 pm, and hen cas in 4 mm
Teflon e apo a ing dishes. The sol en was e apo a ed a oom
empe a u e unde con inuous a gon flow o e nigh . The mem-
b anes we e la e d ied a 50 C unde dynamic acuum o ensu e
comple e sol en e apo a ion. Finally, solid memb ane elec oly es
wi h a hickness o 120
m
m we e ca e ully emo ed om he
e apo a ing dish using a weeze . Excep o he ball-milling which
was pe o med inside ai - igh ja s, all he p epa a ion and
handling o he memb anes we e done in an A -filled glo e box. The
composi es made o 80 w % p is ine and hea - ea ed LLZO a e
e e ed o as CP80 and CA80 he eina e .
The mic og aphs we e ob ained using a scanning elec on mi-
c oscope (SEM Quan a FEG 250) by applying an accele a ion ol age
o 10 kV and u ilizing an E e ha -Tho nley de ec o . Pa icle size
dis ibu ion was analyzed using a Mas e size 3000 (Mal e n
Panaly ical).
The s esses ain cu es o he CPEs we e e alua ed a
oom empe a u e wi h a TST350 ensile de ice om
Linkam Scien ific Ins umen s a a s ain a e o 15
m
m/s. Fo
each sample, he mechanical cu es we e es ed in iplica e wi h
dimensions o 10 70.1 mm. Young modulus was ob ained
h ough he angen me hod in he elas ic egion a 3% o
de o ma ion.
All magic angle spinning nuclea magne ic esonance (MAS
NMR) spec a we e eco ded using a B uke A ance III 500 spec-
ome e , a 2.5 mm p obe and a MAS equency o 20 kHz.
1
H and
7
Li
chemical shi s we e e e enced o bulk wa e and 0.1 M LiCl
aqueous solu ion, espec i ely.
7
Li 1D spec a we e eco ded using
single exci a ion pulses o 2.4
m
s and a elaxa ion delay o 250 s. Fo
he
1
H 1D spec a, Hahn echo expe imen s we e used in which a
p
/
2 pulse (1.9
m
s) is ollowed by a
p
pulse (3.8
m
s), and he ecycle
delay is se o 5s.
1
He
7
Li He e onuclea co ela ion (HETCOR) ex-
pe imen s we e eco ded applying a c oss pola iza ion (CP)
1
He
7
Li
magne iza ion ans e s ep o 1 ms.
7
Lie
7
Li exchange spec oscopy
(EXSY) co ela ions we e ob ained using s anda d h ee
p
/2 pulse
expe imen s o 1.9
m
s.
The combined CP-EXSY expe imen shown in Fig. 5d was pe -
o med by using an ini ial
1
He
6
Li CP s ep ollowed by a
6
Lie
6
Li
EXSY, wi h a mixing ime o 1.6 ms and elaxa ion delay o 3 s.
The elec ochemical impedance spec a o he CPEs we e
eco ded using a Biologic VPM3 wi h AC in he equency ange
o 1 MHze1 Hz a an exci a ion ol age o 10 mV. The cells
we e p epa ed wi h s ainless s eeleblocking elec odes and he
spec a we e eco ded a he empe a u e ange o 30e80

Cwi h
10

C in e als. The ionic conduc i i ies we e calcula ed using
equa ion (1).
s
¼d
A$R(1)
whe e dis he elec oly e hickness, A is i s su ace a ea and R is he
elec oly e esis ance, ob ained om he impedance spec um.
Cyclic ol amme y was conduc ed using a Biologic VPM3 in a
po en ial ange o 0.5 o 2.5 V s. Li

/Li
þ
, a a scan a e o 10 mV/s
o 10 scans. The measu emen s we e pe o med on Li me al/CPE/
s ainless s eel cells a 70

C and he cells we e condi ioned o 2 h a
his empe a u e p io o measu emen .
P. Gho banzade, G. Acca do, K. Gomez e al. Ma e ials Today Ene gy 38 (2023) 101448
2
The Li pla ing/s ipping es s we e pe o med on Li symme ical
cells using a Macco Se ies 4000 a 70

C and a cu en densi y o
40
m
A/cm
2
. The cycling was s opped a e ~500 h, o collec he
elec ochemical impedance spec a, and esumed a 80
m
A/cm
2
.
The impedance spec a o Li symme ical cells bo h be o e and a e
cycling was eco ded a 70

C and wi h he same pa ame e s
men ioned abo e. The equi alen ci cui model used o fi ing he
impedance da a consis s o a esis ance elemen o ex e nal
esis ance in se ies wi h wo R//CPE blocks, co esponding o he
bulk and elec ode/elec oly e in e ace esis ance.
3. Resul s and discussions
To begin wi h, he impac o hea ea men on he pa icle size
dis ibu ion o he ball-milled LLZO powde s was s udied. As
demons a ed in Fig. S.1, i was obse ed ha o e all, he LLZO
pa icle size and agglome a ion we e dec eased, which could be
a ibu ed o he elimina ion o LiOH and Li
2
CO
3
laye s upon hea
ea men . In he nex s ep, ga ne - ich composi es wi h 80 w %
p is ine and hea - ea ed LLZO we e p epa ed o in es iga e he
impac o LLZO hea - ea men a 750

C as a p e-p ocessing s ep
on di e en p ope ies o CPEs.
To unde s and he mo phology and ga ne epolyme in e ace in
each sample, SEM analysis was pe o med. The mic og aph o CP80
(Fig. 1a and c) shows ha LLZO pa icles a e agglome a ed, and he
wo phases (polyme and ce amic) a e seg ega ed. On he o he
hand, in he case o CA80 (Fig. 1b and d), LLZO pa icles a e uni-
o mly dispe sed in he polyme ma ix. Almos all LLZO pa icles
a e homogenously co e ed by PEO and he polyme dis ibu ion is
a he uni o m. The imp o ed LLZO we ing by he polyme implies
s onge in e ac ions be ween PEO and LLZO a e he hea ea -
men . F om he compa ison o he SEM images, a be e LLZOePEO
in e ace in he memb ane wi h hea - ea ed LLZO is e iden , likely
due o he emo al o LiOH and Li
2
CO
3
om he LLZO su ace upon
hea ea men . When he ga ne ac ion is inc eased o 90 w %,
he hea ea men and he imp o emen o he in e ace will be
e en mo e ele an , due o he inc ease o he solid-solid in e aces.
Mo eo e , wi h a ac ion as high as 90 w % LLZO, he hea ea -
men becomes impe a i e o he success ul p ocessing o sel -
s anding memb anes [28].
In solid-s a e ba e ies, he e alua ion o he mechanical p op-
e ies o solid elec oly es is essen ial as hey a ec ba e y sa e y
and pe o mance [29,30]. The e o e, ensile es s we e pe o med
o e alua e he mechanical s eng h o CPEs and he LLZOe ee
PEO/LiTFSI memb anes desc ibed in Fig. 1.Fig. 2 shows he cha -
ac e is ic mechanical esponse o solid polyme elec oly es,
whe e a ypical he moplas ic beha io is obse ed, wi h wo
cha ac e is ic egions, he elas ic, and he plas ic egimes. I can be
obse ed ha he addi ion o LLZO imp o es he mechanical
p ope ies o he memb anes, in he sense ha he ce amic pa i-
cles ac as mechanical ein o cemen . Table 1 p esen s he Young's
modulus, yield s ess, and elonga ion a b eak o each sample. PEO/
LiTFSI memb ane shows he lowes yield s ess (0.41 MPa) bu he
highes elonga ion a b eak. CA80 on he o he hand, possesses he
highes yield s ess (0.91 MPa), wi h a Young's modulus simila o
CP80 (~35 MPa) bu conside ably highe han he one o PEO/LiTFSI
(2.1 MPa), indica ing ha he addi ion o LLZO inc eases he s i -
ness o he memb anes. CP80 shows a significan ly lowe elonga-
ion a b eak (42.7 %) compa ed o CA80 and PEO/LiTFSI (109.8 and
83.7%), which is in line wi h i s phase-seg ega ed mic os uc u e in
which LLZO pa icles a e agglome a ed and PEO ma ix is no
uni o mly dis ibu ed. The lowe yield s ess o CP80 can also be
explained by he poo PEO/LLZO in e ac ions, in ag eemen wi h
SEM mic og aphs. On he con a y, in CA80 he homogenous dis-
ibu ion o PEO and he s onge PEO/LLZO in e ac ions (we a-
bili y o he LLZO by he polyme ) no iceably inc ease he yield
s ess and he elonga ion a b eak. O e all, he mechanical p op-
e ies o CA80 a e sui able o solid-s a e ba e ies [31]. In any case,
Fig. 1. SEM mic og aphs o a, c) CP80 and b, d) CA80.
P. Gho banzade, G. Acca do, K. Gomez e al. Ma e ials Today Ene gy 38 (2023) 101448
3
In es iga ing he ole o in e phases in composi e elec oly es by solid-s a e NMR
72
7.3 Publica ion #3:
Ti le: A Vision o LLZO Ca bona e Fo ma ion: Pe spec i es on Su ace T ea men App oaches
and Cha ac e iza ion Techniques
Au ho s: Ped am Gho banzade, Ped o López-A angu en, and Juan Miguel López del Amo
Jou nal: ChemElec oChem
Jou nal impac ac o : 3.5
Jou nal qua ile: Q2 (Elec ochemis y)

A Vision o LLZO Ca bona e Fo ma ion: Pe spec i es on
Su ace T ea men App oaches and Cha ac e iza ion
Techniques
Ped am Gho banzade,*[a, b, c] Ped o López-A angu en,[a] and Juan Miguel López del Amo*[a]
Li7La3Z 2O12 ga ne s a e among he mos p omising ma e ials
o solid-s a e elec oly es hanks o hei high elec ochemical
s abili y and ionic conduc i i y. Howe e , hey a e uns able in
ai and easily unde go a Li+/H+exchange eac ion, o ming a
li hiophobic and poo ly Li-conduc ing su ace laye composed
o LiOH and Li2CO3upon u he eac ion wi h CO2. Despi e a
simple eac ion mechanism, p o ona ion o LLZO is a complex
phenomenon. The hickness and composi ion o he seconda y
phases on he su ace depend on many pa ame e s bo h in he
LLZO p ope ies and in he s o age a mosphe e. Due o his
complexi y, p oposing a uni e sal p ocedu e o emo ing he
seconda y phases is no simple. Howe e , unde s anding he
ole o di e en pa ame e s and a ional selec ion o cha ac e -
iza ion echniques makes i possible o ind he op imal
condi ions o emo ing he LiOH/Li2CO3laye and u he
p ocessing each ma e ial. This wo k compa es some o he main
app oaches o cleaning he LLZO su ace and desc ibes hei
ad an ages and sho comings. Addi ionally, he s eng hs and
limi a ions o he mos common cha ac e iza ion echniques o
analyzing he (de)p o ona ion o LLZO (XRD, XPS, Raman, NMR,
TGA) a e explained o help esea che s design hei expe imen s
mo e accu a ely.
1. In oduc ion
Among many di e en solid-s a e elec oly es (SSEs), ga ne
ype LLZO (Li7La3Z 2O12) is one o he op candida es, hanks o
i s b oad elec ochemical s abili y window which makes i
compa ible wi h high- ol age ca hodes,[1] high ionic conduc i -
i y (up o 1×103Scm1),[2,3] and chemical s abili y o i s in e -
ace wi h Li me al.[4,5] LLZO appea s in e agonal and cubic
phases, wi h only he la e o e ing high ionic conduc i i y. To
s abilize he cubic phase a oom empe a u e and achie e
highe ionic conduc i i ies, doping and alio alen subs i u ion
o Z 4+is a common app oach.[6,7]
The eac i i y o LLZO owa ds he humid ai and he
o ma ion o LiOH and Li2CO3on i s su ace is a well-known bu
non- i ial p ocess, wi h se e al pa ame e s playing a ole in he
con en and composi ion o his laye . This wo k e iews he
a ec ing pa ame e s in wo g oups o (i) LLZO p ope ies and
(ii) exposu e condi ions, and discusses he common me hods
o emo ing he LiOH/Li2CO3laye . As unde s anding and
ollowing he e ec s o (de)p o ona ion mechanisms o LLZO
equi es adequa e cha ac e iza ion ools, an o e iew o he
usual cha ac e iza ion echniques used in s udying he
(de)p o ona ion o LLZO and hei limi a ions is p esen ed o
be e design he expe imen s.
2. P o ona ion and A ec ing Pa ame e s
Ga ne s we e ini ially conside ed o be s able in ai .[8] Howe e ,
many wo ks la e e ealed ha LLZO is highly hyg oscopic and
can eac wi h mois u e o o m LiOH h ough a Li+/H+
exchange,[9,10] acco ding o eac ion 1.[11,12]
Li7La3Z 2O12 þx H2O!Li7xHxLa3Z 2O12 þx LiOH (1)
LiOH can hen eac wi h CO2 o o m Li2CO3acco ding o
eac ion 2.[11,12]
2 LiOH þCO2!Li2CO3þH2O(2)
Combining expe imen al and DFT calcula ions, Sha a i e al.
in es iga ed he eac ion mechanism and ound ou ha he
di ec hyd a ion and ca bona ion o LLZO a e he modynami-
cally un a o able and ha he LiOH can be o med only
h ough he Li+/H+exchange.[11] In e es ingly, his exchange
eac ion can expe imen ally go up o 60%, wi hou changing
he c ys al s uc u e o phase ansi ion.[13] In ac , p o ona ion
can s abilize he cubic phase a oom empe a u e.[14,15]
Howe e , he ionic conduc i i y o his low- empe a u e cubic
phase is much lowe han he highly Li-conduc i e phase.[16] In
addi ion, i was shown ha inse ed p o ons a e immobile
[a] P. Gho banzade, D . P. López-A angu en, D . J. M. López del Amo
Cen e o Coope a i e Resea ch on Al e na i e Ene gies (CIC ene giGUNE)
Basque Resea ch and Technology Alliance (BRTA)
Albe Eins ein 48, 01510 Vi o ia-Gas eiz, Spain
E-mail: [email p o ec ed]
[email p o ec ed]
[b] P. Gho banzade
Uni e si y o Basque Coun y (UPV/EHU)
Ba io Sa iena, s/n, 48940 Leioa, Spain
[c] P. Gho banzade
ALISTORE-Eu opean Resea ch Ins i u e
80039 Amiens, F ance
© 2024 The Au ho s. ChemElec oChem published by Wiley-VCH GmbH. This
is an open access a icle unde he e ms o he C ea i e Commons A i-
bu ion License, which pe mi s use, dis ibu ion and ep oduc ion in any
medium, p o ided he o iginal wo k is p ope ly ci ed.
Wiley VCH F ei ag, 24.05.2024
2411 / 347887 [S. 80/86] 1
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ChemElec oChem
www.chemelec ochem.o g
Concep
doi.o g/10.1002/celc.202400136
below 400 K, and do no compensa e o he loss in Li+
conduc i i y.[13,17] In gene al, p o ona ion o LLZO s ongly
depends on:
2.1. LLZO P ope ies
2.1.1. Fo m/Geome y
LLZO is gene ally pelle ized and sin e ed a empe a u es abo e
1100°C o achie e a dense pelle and educe he g ain
bounda ies. Al hough he acile and a he low-cos p epa a ion
o LLZO pelle s makes hem ideal o esea ch s udies, o he
o ms o LLZO solid elec oly es such as LLZO shee s, hin ilms,
o ce amic-polyme composi e elec oly es should no be
neglec ed. In ac , due o a highe su ace a ea in hese sys ems,
he p o ona ion would be mo e p onounced and he su ace
p ope ies o he LLZO will be o highe impo ance.[18,19]
2.1.2. Pelle Densi y and G ain Bounda ies
An app oach o educe he LLZO p o ona ion is maximizing he
pelle densi y o educe he in e ac ion wi h mois u e by
dec easing he e ec i e su ace a ea, and he a io o g ain
bounda ies which can accommoda e he LiOH and Li2CO3.[20,21]
Selec ing he p ope ype and con en o dopan s, c ucibles,
and sin e ing addi i es is impo an o ob ain a highly dense
pelle .[20,22–25] Fo ins ance, LiF can be used as a sin e ing aid, o
loca e a he su ace and he g ain bounda ies o he LLZO
pelle , o p e en he di usion o H2O and CO2in o he pelle ,
hus p o ec ing he LLZO.[26]
2.2. Exposu e Condi ions
As expec ed om eac ions 1 and 2, depending on he ela i e
humidi y (RH) and he amoun o CO2in he a mosphe e, he
a io o LiOH o Li2CO3in he decomposi ion laye can a y.[27]
Conside ing ha he di ec eac ion o LLZO wi h CO2is
minimal, he LiOH is he in e media e o Li2CO3 o ma ion, hus
ela i e humidi y is he key pa ame e o con ol. Al hough he
CO2con en is an impo an pa ame e which de ines he a io
o Li2CO3 o LiOH in he su ace laye , i is e y challenging o
p ecisely con ol, pa icula ly in d y ooms. The e o e, minimiz-
ing he ela i e humidi y is mo e c ucial om a p ac ical poin
o iew. I has been epo ed ha exposing LLZO o d y ai (RH
�0.5%) ins ead o ambien ai (RH�50%), signi ican ly educes
he o ma ion o Li2CO3.[11] I has also been shown ha he
g ow h o he con amina ion laye con inues when ex ending
he exposu e ime.[11] This implies ha he s o age condi ions
and he ime o exposu e a e highly decisi e o he handling.
Ne e heless, comple e p o ec ion o LLZO om Li2CO3 o ma-
ion is ex emely challenging because e en inside an a gon-
illed glo ebox, aces o H2O (<0.5 ppm) and CO2(<5 ppm)
can o m a 4–5 nm laye o LiOH/Li2CO3on he LLZO su ace in
less han 30 mins.[28,29]
Conside ing he longe s o age ime o comme cial ga ne s,
hey migh con ain a highe con en o seconda y phases
compa ed o powde s eshly calcined in he lab. While his will
Ped am Gho banzade ob ained his B.S deg ee
in Polyme Enginee ing om he Uni e si y o
Teh an in 2018. He hen s a ed his E asmus
Mundus Mas e s udies in Ma e ials o Ene gy
S o age and Con e sion (MESC+). Soon a e ,
he joined CIC Ene giGUNE o s a his doc o al
esea ch wi hin Ma ie Sklodowska-Cu ie CO-
FUND DESTINY Eu opean Doc o a e p o-
g amme unde he supe ision o D . López
del Amo. He is cu en ly a isi ing esea che
a he G ey g oup (Uni e si y o Camb idge).
His esea ch mainly ocuses on he design o
composi e polyme -ce amic elec oly es and
hei cha ac e iza ion by solid s a e NMR.
D . Ped o López-A angu en is esponsible o
he Ce amic Elec oly e esea ch line a CIC
Ene giGUNE in Vi o ia-Gas eiz, Spain. He ob-
ained his Ph.D. in ma e ials science om he
UAB in Ba celona, Spain, in 2014. In 2015 he
was awa ded wi h a Ma ie Cu ie ellowship.
He con ibu ed o he EU ECOSTORE p ojec ,
gaining unique expe ise in elec ochemis y
and on he new-gene a ion solid-s a e ba -
e ies. His main esea ch ocuses on add ess-
ing he challenges and bo lenecks in oxides,
sul ides, phospha es, halides and composi e
elec oly es o ad ancing solid-s a e ba e y
echnology.
D Juan Miguel López del Amo comple ed his
Ph.D. a he Chemis y Depa men o he F ee
Uni e si y o Be lin in 2006. His hesis was
dedica ed o he de elopmen and applica-
ions o solid-s a e NMR o he physicochem-
ical cha ac e iza ion o solid compounds.
F om 2007 o 2012, he joined he FMP cen e
o Be lin (Leibniz Ins i u e) and he Helmhol z
Ins i u e o S uc u al Biology (Munich), whe e
his esea ch was p ima ily ocused on bio-
solid-s a e NMR. Since 2012, he is he head o
he Solid S a e NMR depa men a CIC
ene giGUNE, whe e he in es iga es elec odes
and solid elec oly e ma e ials.
Wiley VCH F ei ag, 24.05.2024
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ChemElec oChem
Concep
doi.o g/10.1002/celc.202400136
21960216, 2024, 11, Downloaded om h ps://chemis y-eu ope.onlinelib a y.wiley.com/doi/10.1002/celc.202400136 by Readcube (Lab i a Inc.), Wiley Online Lib a y on [24/06/2024]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License
no make any huge di e ence o he pelle s o g een bodies
sin e ed a high empe a u es,[30] i mus be se iously conside ed
o applica ions such as manu ac u ing composi e elec oly es
o cold-sin e ing in which high sin e ing empe a u es a e no
in ol ed.[31] (see igu e 1). I should also be men ioned ha he
Li+/H+exchange o LLZO happens no only when exposed o
humid ai , bu also when in con ac wi h sol en s. Kun e al.
showed ha he Li+/H+exchange is mo e in ense in p o ic
sol en s wi h highe acidic cha ac e , ne e heless, i does occu
in ap o ic sol en s such as ACN and c-Hex.[17] This mus be
conside ed in we -p ocessing me hods o LLZO solid elec o-
ly es.
3. Su ace Cleaning
The p esence o LiOH and Li2CO3on he su ace o LLZO may
ha e a nega i e impac on he p ope ies and pe o mance o
LLZO elec oly es, pa icula ly on he in e acial esis ance wi h
he Li me al and he cell cyclabili y.[32] This is mainly due o he
li hiophobic and poo ly-conduc i e na u e o Li2CO3which
needs o be emo ed.[12,32] A success ul “cleaning” o he LLZO
su ace will esul in he educ ion o he a ea speci ic esis ance
(down o 2 Ωcm2), which can in u n inc ease he c i ical cu en
densi y (>0.3 mAcm2) and enhance he cycling pe o mance o
he cell.[32]
Despi e he highe ulne abili y o LLZO powde s o
p o ona ion and hei highe su ace a ea, emo ing he
seconda y phases om he LLZO su ace is usually neglec ed in
he case o LLZO-polyme composi e elec oly es. Ne e heless,
i was shown ha he emo al o LiOH/Li2CO3can e ec i ely
imp o e he LLZO-PEO in e ac ions and he we ing, esul ing
in imp o ed mechanical p ope ies, ionic conduc i i y, and
cyclabili y.[33] In addi ion, i is epo ed ha a polyme -LLZO
in e ace ee o Li2CO3can also inc ease he Li ans e ence
numbe , modi y he Li+ anspo pa hways, and supp ess he
Li dend i e g ow h.[12] He ein di e en me hods o “clean” he
LLZO su ace a e lis ed and hei ad an ages and sho comings
a e discussed.
3.1. Mechanical Polishing
Mechanical polishing, which can be done in d y o we o m, is
a simple and low-cos app oach o emo e he LiOH/Li2CO3
laye om he su ace o he LLZO. Upon polishing, he LLZO/Li
me al in e acial esis ance will dec ease signi ican ly.[32,34] How-
e e , i has he ollowing sho comings. (i) can only be applied
o pelle s, no powde s. (ii) no easy o scale up (iii) canno
comple ely emo e he LiOH and Li2CO3, as some will emain in
he g ain bounda ies.[26] (i ) canno dep o ona e and eco e
he LLZO.
3.2. Acid T ea men
Ano he low-cos and simple me hod o emo e he Li2CO3, is
h ough a chemical eac ion wi h acids such as HF, HCL, and
ci ic acid. Acco ding o eac ions 3 and 4, he Li2CO3will
decompose o o m a laye o LiCl and LiF, coa ing he LLZO
su ace.[35,36]
Li2CO3þ2 HF !2 LiF þCO2þH2O(3)
Li2CO3þ2 HCl !2 LiCl þCO2þH2O(4)
The acids can also eac wi h LiOH o o m Li sal s, acco ding
o eac ions 5 and 6.[37,38]
LiOH þ2 HF !2 LiF þH2O(5)
LiOH þ2 HCl !2 LiCl þH2O(6)
LiF and LiCl a e qui e li hiophilic and as a esul , hey
dec ease he in e acial esis ance wi h he Li me al.[35,39] In
addi ion, he coa ing laye can passi a e he LLZO and p e en
i s ehyd a ion.[26,40] Conside ing he low cos o acid ea men
and he passi a ion o LLZO which allows i s exposu e o ai o
some ime, his app oach seems a ac i e o he manu ac u -
ing scale up. Howe e , i comes wi h he ollowing d awbacks:
(i) A long ea men ime can co ode he LLZO.[36] (ii) Al hough
he Li2CO3is emo ed om he su ace, he p oduced H2O can
u he p o ona e he LLZO by Li+/H+subs i u ion.[41] (iii) The
LLZO is no eco e ed and he Li+o he Li2CO3 u ns in o low-
conduc ing LiCl o LiF, a he han o ming back he highly
conduc ing LLZO. (i ) Due o he possible ex a p o ona ion and
was e o Li, his app oach is no sui able o LLZO powde s,
whe e a high su ace a ea and high con en o Li2CO3exis .[12]
3.3. Hea T ea men
A e y s aigh o wa d app oach o elimina e he seconda y
phases is o hea he LLZO a empe a u es be ween 500–
Figu e 1. illus a ion o Li2CO3con en in eshly calcined and comme cial
LLZO powde s, and he impac o di e en p ocessing me hods on he inal
composi ion.
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900°C. By doing his, all he seconda y phases including he
LiOH, he adso bed wa e , p o ons inside he LLZO, and Li2CO3
will be g adually emo ed a di e en empe a u es, ollowing
eac ions 7–10.[14,30]
Li7xHxLa3Z 2O12:nH2O!Li7xHxLa3Z 2O12 þn H2O(7)
Li7xHxLa3Z 2O12 !Li7xLa3Z 2O12x
2þx=2 H2O(8)
Li7xHxLa3Z 2O12 þx LiOH !Li7La3Z 2O12 þx H2O(9)
Li7xLa3Z 2O12x
2þx
2Li2CO3!Li7La3Z 2O12 þx
2CO2(10)
The eco e y o LLZO h ough he decomposi ion o Li2CO3
(equa ion 8) is a e y impo an ea u e o his app oach,
making i especially sui able o cases wi h high su ace a ea
and high con en o Li2CO3, such as LLZO powde s and hin
ilms. In addi ion, hea ea men is he only me hod ha
elimina es he p o ons wi h low mobili y om he LLZO
s uc u e, esul ing in a dec ease in he ac i a ion ene gy o Li
jumps in LLZO.[30] These as e dynamics could lead o highe
ionic conduc i i ies, especially a low empe a u es a which
p o ons ha e lowe mobili y.
Despi e all he men ioned ad an ages, hea ea men
comes wi h he isk o o ma ion o he Li de icien La2Z 2O7
phase (py ochlo e) and Li loss, which can occu a empe a u es
abo e 600°C,[42] as depic ed in eac ion 11.[43]
Li7La3Z 2O12 $La2Z 2O7þLi2O(11)
Ne e heless, a su icien ly high empe a u es, LLZO can be
es o ed ei he h ough eac ion 9 in e e se di ec ion,[44] o
h ough eac ion o he py ochlo e wi h Li2CO3acco ding o
eac ion 12.[6,43]
Li2CO3þLa2Z 2O7!Li7La3Z 2O12 þCO2(12)
The empe a u e, du a ion, and he a mosphe e o he hea
ea men can s ongly in luence he o ma ion o py ochlo e,
hence he ionic conduc i i y o he LLZO.[42,45] I is epo ed ha
a sho e dwell ime and highe hea ing a es can e icien ly
supp ess he LLZO decomposi ion o achie e a ully li hia ed
LLZO phase.[6,42] Rega ding he gas low, hea ea men in
a mosphe es con aining oxygen is usually p e e ed, as i
p e en s bo h oxygen loss a ele a ed empe a u es, and
o ma ion o ca bona ed species on he su ace, ul ima ely
educing he in e acial esis ance.[30,45,46]
Unlike he acid ea men (whe e a passi a ion laye o LiF
o LiCl is o med), a e he hea ea men , he “cleaned”
su ace o LLZO is p one o ehyd a ion and ca bona ion.
The e o e, i is essen ial o pe o m he hea ea men a ine
a mosphe e o acuum and p o ec he LLZO a e wa d in an
ine a mosphe e.
The empe a u e and du a ion o he hea ea men
necessa y o emo e LiOH and Li2CO3depend on he ex en o
p o ona ion, composi ion o he LiOH/Li2CO3laye , and a mos-
phe e o he hea ea men , hus a ying om one sys em o
ano he . Such complexi y explains he disc epancies in he
li e a u e ega ding he op imal hea ea men empe a u e/
du a ion, anging om 500 o 900°C.[6,32,42,45] As a esul , i is
ex emely di icul o sugges a gene al hea ea men
p ocedu e o cleaning he su ace o all ypes o LLZO
elec oly es, wi hou i s deg ada ion o py ochlo e. Howe e ,
knowing he deciding pa ame e s and using he igh cha ac e -
iza ion echniques, i is possible o op imize he hea ea men
pa ame e s o achie e LLZO wi h clean su ace wi hou
deg ada ion. O e all, we sugges hea ea men as he mos
e ec i e app oach o dep o ona e he LLZO and emo e he
LiOH/Li2CO3laye om i s su ace.
4. Cha ac e iza ion Techniques
Fo selec ing he p ope se o cha ac e iza ion echniques o
assess he LLZO (de)p o ona ion and he (de) o ma ion o LiOH/
Li2CO3laye s; he s eng h and limi a ions o di e en es s,
hickness o he decomposi ion laye , and he speci ic loca ion
o di e en chemical species (whe he on he su ace o wi hin
he bulk) mus be ecognized. This ca e ul conside a ion
ensu es a comp ehensi e unde s anding o he ma e ials’
cha ac e is ics and con ibu es o he accu acy and eliabili y o
he analyses conduc ed. Fo ins ance, a hin laye o LiOH/Li2CO3
will be unde es ima ed when cha ac e ized using a bulk
echnique. Thus, a combina ion o echniques wi h di e en
p obing dep hs and sensi i i ies a e ecommended and will be
he e in discussed.
4.1. The mal G a ime y Analysis (TGA)
TGA is a simple me hod o ge an o e iew o he ex en o
p o ona ion. The sample is hea ed in a con olled a mosphe e
and he mass loss is co ela ed o di e en he mochemical
p ocesses such as dehyd a ion, deso p ion, and decomposi ion,
hus gi ing a quan i a i e es ima ion o di e en chemical
species in he sample, ega dless o being on he su ace o in
bulk.[47,48] TGA has no limi a ion o sample geome y bu is
especially use ul o powde s, as hey a e mo e p one o
p o ona ion.
4.2. Powde X- ay Di ac ion (PXRD)
XRD is a powe ul echnique o iden i y di e en phases o
LLZO and he p esence o py ochlo e, Li2CO3and LiOH.[6,49] As a
big ad an age, i can also ope a e in si u o obse e he
elimina ion o seconda y phases in eal ime.[42,45] Conside ing
he al e a ion o he la ice pa ame e by he Li+/H+subs i u-
ion, i can also e eal he s a e o p o ona ion o he LLZO.[17]
Howe e , a main d awback o con en ional powde -XRD is ha
in mos cases, he LiOH/Li2CO3laye is oo hin (<1μm) and
in il a i e o ob ain a clea di ac ion signal. In his case,
G azing Incidence X-Ray Di ac ion (GIXRD) is p e e ed o limi
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he pene a ion dep h o he inciden beam and a oid he
signals coming om he bulk. (see Figu e 2). In an in e es ing
wo k, Zhang e al.[42] epo ed ha using GIXRD, o ma ion o
py ochlo e was obse ed a empe a u es as low as 600 °C,
while i was no isible by con en ional PXRD. Thus, conclusions
om con en ional XRD mus be made wi h cau ion, pa icula ly
when he su ace decomposi ion laye is oo hin.
4.3. X- ay Pho oelec on Spec oscopy (XPS)
XPS is widely used o analyze he chemical composi ion o he
LLZO su ace. Using XPS, no only he Li2CO3, bu also he
hyd oca bons and g aphi ized ca bons adso bed on he su ace
can be obse ed.[45] Howe e , as a su ace cha ac e iza ion
echnique wi h limi ed p obing dep h, i canno easily de ec
he LiOH/Li2CO3loca ed in be ween he g ain bounda ies. As an
impo an ad an age, in-si u nea ambien p essu e XPS (NAP-
XPS) allows he eal- ime su ace analysis wi h inc easing
empe a u e up o a leas 500°C unde he low o di e en
gases.[45] Dep h p o iling XPS is an in e es ing ool o p obe
di e en su ace laye s in he nanome ic ange, ne e heless, i
is incon enien o cases whe e he LiOH/Li2CO3laye is mic o-
me e hick, and o powde s in gene al.[11,50,51] Examples o he
men ioned expe imen s a e shown in Figu e 3.
4.4. Solid S a e Nuclea Magne ic Resonance (NMR)
Being sensi i e o 1H, 7Li, and 6Li, solid s a e NMR is a powe ul
bu unde a ed echnique in analyzing he chemical e olu ion
o LLZO du ing de(p o ona ion). I is highly sensi i e o p o ons,
hus can show aces o HLLZO, H2O, and LiOH in he LLZO.
NMR can also be used o de ec he p esence o Li2CO3, hanks
o i s long T1 elaxa ion ime (unlike mobile Li a oms o
LLZO).[30] Finally, as NMR is an iso ope-speci ic echnique, he
mobili ies o H+and Li+in LLZO can be s udied sepa a ely, and
he nega i e impac o p o ona ion on he Li dynamics is
e ealed.[30] (see igu e 4). Solid s a e NMR is he ideal echnique
o analyzing he p o ona ed phases. Mo eo e , i is a bulk
echnique and has no limi a ion o di e en o ms o LLZO, i.e.,
powde s, pelle s, o hin ilms.
4.5. Raman Spec oscopy
Raman spec oscopy is a simple ye powe ul echnique o
in es iga e he s uc u al p ope ies o LLZO as well as i s
su ace chemis y. CO3
2s e ching ib a ions shows a s ong
band a a ound 1100 cm1, allowing easy de ec ion o Li2CO3.
Mo eo e , using Raman mapping, he uni o mi y o Li2CO3
dis ibu ion can be s udied..[52,53] As shown in Figu e 5, besides
su ace mapping, Raman can be used o dep h p o iling and
p obe he g adien o CO3
2 ib a ions along he pelle dep h.
Due o he sensi i i y o Li2CO3and he simplici y o he
measu emen s, Raman is a g ea echnique o s udy Li2CO3
emo al.
4.6. Elec ochemical Impedance Spec oscopy (EIS)
Li2CO3is highly li hiophobic and o ms a poo in e ace wi h Li
me al.[32,36] This poo in e ace causes a high esis ance which
can be obse ed a low equencies in he Nyquis plo . Despi e
he inabili y o EIS o quan i ied analysis and i s incon enience
o powde s, eco ding an impedance spec um o a eshly
sin e ed LLZO pelle o hin ilm as a e e ence can be use ul in
ealizing he o ma ion o Li2CO3upon s o age.[11] In addi ion,
Figu e 2. Schema ic illus a ion o se up and p obing dep h o le ) con en-
ional XRD and igh ) G azing incidence XRD.
Figu e 3. a) O 1s XPS spec a o Al-LLZO eco ded a 500°C unde di e en gas en i onmen s. Rep oduced om Re . [45]. Copy igh 2023 The Au ho s.
Published by Ame ican Chemical Socie y, unde CC-BY-4.0 license. b,c) Analysis and schema ic illus a ion o XPS dep h p o iling, ep oduced om Re . [11]
wi h pe mission om he Royal Socie y o Chemis y.
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EIS con eys an imp ession o he elec oly e pe o mance. Thus,
i can be used o assess how de imen al he LiOH/Li2CO3laye
is om a p ac ical poin o iew. Fo ins ance, i LLZO
p ocessing in d y o ambien ai shows only a mino inc ease in
he bulk and in e ace esis ance, i will be well jus i ied o
la ge -scale p oduc ion.
5. Summa y and Ou look
Conside ing he eac i i y o LLZO owa ds ambien mois u e,
p o ona ion is p ac ically una oidable. Howe e , i can be
minimized i he ela i e humidi y and CO2con en o he
s o age a mosphe e a e p ecisely con olled. Mo eo e , special
cau ion in he selec ion o sol en and he mixing ime is
equi ed o he unc ionaliza ion and we p ocessing o LLZO.
Al hough su ace p ope ies a e o highe impo ance in
powde s, he p o ona ion o LLZO in composi e polyme
elec oly es is o en neglec ed o unde es ima ed. The su ace
p ope ies o LLZO pa icles can g ea ly impac he LLZO/PEO
in e ac ions, modi ying mic o- and mac o-scale p ope ies o
he elec oly es and he Li anspo .
The consequence o LLZO ins abili y is no only he
o ma ion o LiOH/Li2CO3laye on i s su ace, bu also he Li+/
H+exchange which plays a big ole in he Li dynamics,
especially when p o ona ion is signi ican . The e o e, besides
he LLZO/Li-me al in e ace esis ance, bulk conduc i i y and
he local ion dynamics should be ca e ully in es iga ed. To ill
he gap in he li e a u e, de ailed s udies on he dep o ona ion
o LLZO a e pa icula ly needed o powde s and hin ilms. In
addi ion, men ioning de ails o LLZO p ope ies ( o m, doping,
ela i e densi y) and s o age a mosphe e ( ela i e humidi y, CO2
con en , and exposu e ime) is necessa y o easie compa ison
o he esul s.
Acknowledgemen s
As a pa o he DESTINY PhD p og amme, his publica ion is
acknowledged by unding om he Eu opean Union’s Ho i-
zon2020 esea ch and inno a ion p og amme unde he Ma ie
Skłodowska Cu ie Ac ions COFUND e G an Ag eemen No:
945357.
Con lic o In e es s
The au ho s decla e no con lic o in e es .
Figu e 4. Di e en NMR expe imen s showing he impac o hea ea men
o LLZO in a) disappea ance o p o ona ed phases, b) emo al o Li2CO3wi h
long elaxa ion ime c) imp o ing he 7Li local dynamics in LLZO powde s.
Rep oduced om Re . [30] wi h pe mission om he Royal Socie y o
Chemis y.
Figu e 5. Top) Su ace Raman Mapping o Ta-LLZO pelle s aged in humid
ai , d y ai and a e polishing. Bo om) Raman mapping o Ta-LLZO pelle
along i s dep h a e exposu e in humid ai . Rep in om Re . [52] wi h
pe mission. Copy igh 2017 The Ame ican Ce amic socie y.
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Da a A ailabili y S a emen
The da a ha suppo he indings o his s udy a e a ailable
om The au ho s. Res ic ions apply o he a ailabili y o hese
da a, which we e used unde license o his s udy. Da a a e
a ailable om he au ho s wi h he pe mission o The au ho s.
Keywo ds: LLZO Ga ne ·Li hium Ca bona e ·P o ona ion ·ai
ins abili y ·Solid elec oly es
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Manusc ip ecei ed: Feb ua y 9, 2024
Re ised manusc ip ecei ed: Ma ch 14, 2024
Ve sion o eco d online: Ap il 15, 2024
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In es iga ing he ole o in e phases in composi e elec oly es by solid-s a e NMR
80
7.4 Publica ion #4:
Ti le: T anspo P ope ies and Local Ions Dynamics in LATP-Based Hyb id Solid Elec oly es
Au ho s: Nicola Boa e o, Ped am Gho banzade, Ha i z Pe ez-Fu unda ena, Lei e Meabe, Juan
Miguel López del Amo, Isu u E. Guna hilaka, Ma ia Fo sy h, Jö g Schuhmache , And eas
Ro e s, Se gey K achko skiy, Abdelbas Gue i, Michel A mand, and Ma ía Ma inez-Ibañez
Jou nal: Small
Jou nal impac ac o : 13
Jou nal qua ile: Q1 (Ma e ials Science)
RESEARCH ARTICLE
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T anspo P ope ies and Local Ions Dynamics in
LATP-Based Hyb id Solid Elec oly es
Nicola Boa e o,* Ped am Gho banzade, Ha i z Pe ez-Fu unda ena, Lei e Meabe,
Juan Miguel López del Amo, Isu u E. Guna hilaka, Ma ia Fo sy h, Jö g Schuhmache ,
And eas Ro e s, Se gey K achko skiy, Abdelbas Gue fi, Michel A mand,
and Ma ía Ma inez-Ibañez*
Hyb id solid elec oly es (HSEs), namely mix u es o polyme and ino ganic
elec oly es, ha e supposedly imp o ed p ope ies wi h espec o ino ganic
and polyme elec oly es. In p ac ice, HSEs o en show ionic conduc i i y
below expec a ions, as he high in e ace esis ance limi s he con ibu ion o
ino ganic elec oly e pa icles o he cha ge anspo p ocess. In his s udy,
he anspo p ope ies o a se ies o HSEs con aining Li(1+x)AlxTi(2–x)(PO4)3
(LATP) as Li+-conduc ing fille a e analyzed. The occu ence o Li+exchange
ac oss he wo phases is p o ed by iso ope exchange expe imen , coupled
wi h 6Li/7Li nuclea magne ic esonance (NMR), and by 2D 6Li exchange
spec oscopy (EXSY), which gi es a ime cons an o Li+exchange o abou
50 ms a 60 °C. Elec ochemical impedance spec oscopy (EIS) dis inguishes
a sho - ange and a long- ange conduc i i y, he la e dec easing wi h LATP
concen a ion. LATP pa icles con ibu e o he o e all conduc i i y only a
high empe a u es and a high LATP concen a ions. Pulsed field g adien
(PFG)-NMR sugges s a selec i e dec ease o he anions’ diffusi i y a high
empe a u es, ansla ing in o a ma ginal inc ease o he Li+ ans e ence
numbe . Al hough he anspo p ope ies a e only ma ginally affec ed,
addi ion o mode a e amoun s o LATP o polyme elec oly es enhances hei
mechanical p ope ies, hus imp o ing he pla ing/s ipping pe o mance and
p ocessabili y.
N. Boa e o, P. Gho banzade, H. Pe ez-Fu unda ena, L. Meabe,
J. M. López del Amo, M. A mand, M. Ma inez-Ibañez
Cen e o Coope a i e Resea ch on Al e na i e Ene gies
CIC ene giGUNE
Basque Resea ch and Technology Alliance (BRTA)
Ala a Technology Pa k
Albe Eins ein 48, Vi o ia-Gas eiz 01510, Spain
E-mail: [email p o ec ed]; [email p o ec ed]
The ORCID iden ifica ion numbe (s) o he au ho (s) o his a icle
can be ound unde h ps://doi.o g/10.1002/smll.202305769
© 2023 The Au ho s. Small published by Wiley-VCH GmbH. This is an
open access a icle unde he e ms o he C ea i e Commons A ibu ion
License, which pe mi s use, dis ibu ion and ep oduc ion in any
medium, p o ided he o iginal wo k is p ope ly ci ed.
DOI: 10.1002/smll.202305769
1. In oduc ion
Li hium-ion ba e ies (LIBs) a e he p in-
cipal elemen o elec ochemical ene gy
s o age in po able elec onics and au o-
mo i e applica ions. LIBs a e cha ac e -
ized by high ene gy densi y (260 Wh kg−1,
700 Wh L−1a cell le el),[1] which is,
howe e , s ill insufficien o mee he a -
ge s o d i ing ange in ull ba e y elec-
ic ehicles (>300 Wh kg−1,>800 Wh
L−1a cell le el).[2] Highe alues o en-
e gy densi y can be ob ained by subs i-
u ing he con en ional g aphi e anode
wi h a high-capaci y li hium me al an-
ode (372 mAh g−1 s 3860 mAh g−1 o
g aphi e and li hium me al, espec i ely).
This, in u n, leads o se ious sa e y con-
ce ns, owing o he g ow h o li hium
dend i es, which can cause sho ci cui s
and he mal unaway, and a e pa icula ly
dange ous in combina ion wi h common
flammable liquid ba e y elec oly es.[3] A
possible solu ion o his issue in ol es he
adop ion o nonflammable solid-s a e elec-
oly es (SSEs), such as ino ganic ce amic
P. Gho banzade
Uni e si y o Basque Coun y (UPV/EHU)
Ba io Sa iena, s/n, Leioa 48940, Spain
P. Gho banzade
ALISTORE-Eu opean Resea ch Ins i u e, CNRS, Hub de l’Ene gie
Amiens 80039, F ance
I. E. Guna hilaka, M. Fo sy h
Ins i u e o F on ie Ma e ials
Deakin Uni e si y
Geelong, VIC 3217, Aus alia
M. Fo sy h
Ike basque
Basque Founda ion o Science
Bilbao 48013, Spain
M. Fo sy h
POLYMAT
Uni e si y o he Basque Coun y UPV/EHU Joxe Ma i Ko a Cen e
Donos ia-San Sebas ián 200018, Spain
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Figu e 5. a) In e ace capaci ance, di ided by he elec odes a ea. Emp y do s a e mul iplied o he olume ac ion o LATP; b) ime cons an s 1( ull
do s) and 𝜏2(emp y do s), calcula ed by mul iplying Cin o R1andR2, espec i ely.
Fo HSE-05, 𝜎eff is la gely supe imposed o 𝜎 o , indica ing neg-
ligible LATP con ibu ion in he whole empe a u e ange. Wi h
HSE-10, 𝜎eff is close o 𝜎 o a low empe a u es, bu 𝜎 o inc eases
as e han 𝜎eff wi h he empe a u e, indica ing inc easing LATP
con ibu ion a high empe a u es o he long- ange conduc i -
i y. In HSE-20, 𝜎eff is lowe han 𝜎 o in he whole empe a u e
ange, and he sp ead be ween he wo alues inc eases wi h em-
pe a u e. The lowe alue o 𝜎eff, wi h espec o 𝜎 o , is possibly
caused by an unde es ima ion o 𝜎PE,20, bu he inc easing sp ead
is clea ly caused by he dec ease o he in e ace esis ance. Al-
oge he , he analysis e eals ha LATP con ibu ion o he con-
duc i i y inc eases wi h he empe a u e, and ha his effec be-
comes mo e in ense wi h inc easing LATP con en . This can be
easily obse ed by compa ing he conduc i i y a io 𝜌=𝜎 o /𝜎loc
(Figu e 4c). The conduc i i y a io is p ac ically cons an in HSE-
05 a 𝜌≈0.9, bu i inc eases wi h he empe a u e in bo h HSE-
10 and HSE-20. The inc ease is also mo e e iden in HSE-20, o
which 𝜌inc eases om 0.6 a 25 °C o 0.8 a 70 °C.
Fu he de ails on he in e ace esis ance can be ob ained
h ough he analysis o R2, and o he pa allel capaci ance
(Cin ). As no ed abo e, R2 inc eases wi h LATP concen a ion
(Figu e 4c). Mo e specifically, R2 is oughly p opo ional o he
olume ac iono LATP(Figu e4d).Thedependenceo R2 wi h
he empe a u e is o A henius ype, and he ac i a ion ene gy
is ≈0.55 eV, cons an wi h LATP concen a ion, hus e y close o
he ac i a ion ene gy o he ino ganic phase. R2 can be es ima ed
by combining Equa ions (4) and (6). The esul ing o mula is as
ollows
R2MG =9𝜎LATP LATP
2𝜎PE (1− LATP)
1
𝜎LATP +2𝜎PE +2(𝜎LATP −𝜎PE) LATP
L
A(7)
The alues o R2MG, calcula ed hough Equa ion (7), a e also
shown in Figu e 4d. The calcula ed alues a e oughly close o
he expe imen al ones (excep o HSE-20, o which 𝜎eff
LATP >0),
bu he Maxwell equa ion p edic s a VTF dependence o R2on
he empe a u e, whe eas he expe imen al dependence, as no ed
p e iously, is clea ly o A henius ype, wi h ac i a ion ene gy o
≈0.55 eV, cons an wi h LATP concen a ion. The a ea-specific
esis ance R2sp calcula ed by no malizing R2 on he LATP ol-
ume ac ion and mul iplying o he elec odes a ea, anges om
270Ωcm2inHSE-05 o450 Ωcm2in HSE-20,a 25 °C(Figu eS5,
Suppo ing In o ma ion). A 60 °C, R2sp a ies be ween 20 and
30 Ωcm2. Al hough R2sp is only indi ec ly ela ed o he in e ace
esis ance be ween he LATP pa icles and he polyme ma ix, i
is qui e in e es ing ha he alues o R2sp a e close o he alues
o in e ace esis ance p e iously epo ed o NASICON-based
mul ilaye ed model sys ems.[18,43,55]
The in e ace capaci ance, Cin , was calcula ed om he alues
o CPE2, R1, and R2 (see Figu e S4 in he Suppo ing In o ma-
ion), wi h he ollowing equa ion[56]
Cin =(1
R1+1
R2)(𝛼−1
𝛼)Q21
𝛼(8)
whe e Q2and𝛼a e he pseudocapaci ance and exponen o he
CPE2 elemen in Figu e S4 (Suppo ing In o ma ion), espec-
i ely. The alues o Cin di ided by he elec odes a ea, a e e-
po ed in Figu e 5a. In all samples, Cin is below 1 μFcm
−2,con-
fi ming ha his capaci ance is ela ed o an in e nal in e ace
and no o an elec odes in e ace. Fu he mo e, Cin dec eases
wi h he LATP concen a ion, hus u he confi ming ha i is e-
la ed o he LATP in e ace. Indeed, by di iding Cin o he LATP
olume ac ion, he alues o Cin all in o a single mas e cu e
(Figu e 5a), esembling he beha io o R2. In e es ingly, Cin in-
c eases wi h empe a u e a T>40 °C. This may be ela ed o he
dec easing in e ace esis ance.
By mul iplying Cin o R1andR2, wo ime cons an s can be
ob ained, namely 𝜏1and 𝜏2, espec i ely. The fi s one is he cha -
ac e is ic cha ging ime o he double laye a he LATP in e -
ace, whe eas he o igin o 𝜏2is mo e ambiguous, al hough i is
possibly ela ed o he conduc i i y o LATP and o he in e ace
esis ance. The alues o 𝜏1and 𝜏2a e shown in Figu e 5b. 𝜏1
a ies be ween 10−5and 10−6s, and i dec eases wi h inc easing
LATP concen a ion, owing o he dec easing alues o Cin .𝜏1
dec eases ini ially wi h inc easing empe a u e, bu i is app ox-
ima ely cons an a T>40 °C. This beha io , which is ela ed o
he inc easing alues o Cin , is possibly caused by he dec ease
o he in e ace esis ance and by he inc easing a e o Li+ ans-
e ac oss he in e ace. On he con a y, 𝜏2is p ac ically cons an
and gene ally lowe han 𝜏1, a ying om ≈2∙10−6s a oom em-
pe a u e o ≈5∙10−7sa 70°C. The cons an alues o 𝜏2sugges
ha R2 is s ongly co ela ed wi h Cin .
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Figu e 6. Sel -diffusion coefficien s and ans e ence numbe s by PFG-NMR: diffusion coefficien s o a) 7Li and b) 19F om20 o80°C; c) compa ison
o he diffusion coefficien s a 60 °C; d) ionic conduc i i y calcula ed om he diffusion coefficien s wi h he Ne ns –Eins ein equa ion; e) Ha en a ios
be ween 30 and 70 °C; ) li hium ans e ence numbe s, calcula ed om he diffusion coefficien s o 7Li and 19F, be ween 20 and 70 °C. The ed as e isk
indica es he ans e ence numbe calcula ed by po en ios a ic pola iza ion me hod.
2.2. Solid-S a e NMR Cha ac e iza ion
In o ma ion on he indi idual mobili y o anions and ca ions was
ob ained by PFG-NMR. The sel -diffusion coefficien s o 7Li (DLi)
and 19F(DF) be ween 20 and 80 °C a e depic ed in Figu e 6a,b, e-
spec i ely. Bo h diffusion coefficien s inc ease wi h empe a u e
be ween 10−12 o 10−11 m2s−1, bu he alues o DFa e gene ally
highe han hose o DLi, as could be expec ed o polyme elec-
oly es, since e hylene oxide uni s s ongly coo dina e wi h Li+
ca ions. The ac i a ion ene gies o he diffusion coefficien s we e
de e mined by fi ing wi h he A henius equa ion. The ac i a ion
ene gy is ≈0.3 eV o DLi, p ac ically cons an wi h LATP, and in
he case o DFis comp ised be ween 0.4 and 0.3 eV, dec easing
wi h LATP concen a ion.
In e es ingly, DFdec eases wi h LATP concen a ion, espe-
cially a high empe a u e (Figu e 6c), indica ing ha he mobili y
o TFSI−anions is nega i ely affec ed by he p esence o LATP.
On he con a y, DLiis almos cons an , sugges ing ha he di -
usi i y o Li+ca ions in he LATP pa icles is close o he diffu-
si i y in he polyme ma ix. I mus be no ed ha he fi ing o
he 7Li signals, o e ie e he diffusion coefficien s, was ca ied
ou wi h a single exponen ial unc ion. Fo compa ison, he fi -
ing was addi ionally pe o med wi h wo exponen ials, which e-
sul ed in qui e simila diffusion coefficien s. Howe e , since he
quali y o he fi ing was only ma ginally imp o ed by fi ing wi h
a wo-exponen ial unc ion, fi ing wi h one exponen ial was ul-
ima ely p e e ed. The difficul y in diffe en ia ing he diffusion
coefficien s o he wo phases is also ela ed o he imescale o
hePFG-NMRexpe imen . Thediffusion delay o 25 ms issignifi-
can ly la ge han he cha ac e is ic ime o ions accumula ion a
he LATP su ace which, as obse ed by EIS, is in he o de o 10−6
s. The diffusion leng h, gi en a diffusion coefficien o 5∙10−12 m2
s−1a 60 °C, is sligh ly lowe han 1 μm. This is la ge han he
a e age pa icles adius (≈0.7 μm), hus sufficien o mos Li+
wi hin he LATP pa icles o expe ience he pa icles bounda y.
Al hough his is no necessa ily ela ed o he cha ac e is ic ime
o he Li+exchange ac oss he in e ace, he esul s o EIS ex-
pe imen s sugges ha a imescale o 25 ms is sufficien o gi e
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a pic u e o he long- ange anspo p ope ies o he HSEs. To
confi m his assump ion, PFG-NMR expe imen s we e epea ed
a longe diffusion delay o 200 ms, on he samples HSE-00 and
HSE-20. The esul ing diffusion coefficien s (Figu e S6, Suppo -
ing In o ma ion) a e close o hose measu ed a 25 ms, excep
he fluo ine diffusion coefficien o fluo ine in HSE-20, which is
sligh ly highe han he one measu ed a 25 ms. In he ollowing
analysis, o sake o cohe ence, he alues ob ained a 25 ms will
be used. The diffusion coefficien s o 7Li, as de e mined by PFG-
NMR, should be unde s ood as he long- ange diffusi i y in he
HSEs, accoun ing also o he con ibu ion o he in e ace esis-
ance. Consequen ly, he esul s o he PFG-NMR expe imen can
be compa ed wi h he long- ange ionic conduc i i y, by applying
he Ne ns -Eins ein equa ion. This allows de e mining whe he
he e a e any ion pai ing effec s caused by he fille . To calcula e
he ionic conduc i i y om he diffusion coefficien s, he concen-
a ion o cha ge ca ie s is needed. The effec i e cha ge ca ie
concen a ion is no known, bu wo limi ing scena ios can be
concei ed. In he fi s case, he o al ions concen a ion is used,
includingalso he Li+in he LATP pa icles.[53] In hesecondcase,
only he sal concen a ion is conside ed. In he o me case, he
Ne ns -Eins ein equa ion assumes he ollowing o m[57]
𝜎NMR =e2
kBT(CLiDLi +CFDF)(9)
Wi h ebeing he elemen a y cha ge, kB he Bol zmann con-
s an , T he empe a u e, and CLi and CF he concen a ions o
Li+and TFSI−, espec i ely. The alues o 𝜎NMR , o HSE-00, a e
close o he expe imen al alues o 𝜎 o (compa e Figu e 4b and
Figu e 6d), wi h a Ha en a io HR( ha is, he a io be ween 𝜎NMR
and 𝜎 o ) anging be ween 1.2 and 1.3 (Figu e 6e). On he con-
a y, he conduc i i y o he LATP-con aining samples is o e es-
ima ed, app oaching 𝜎NMR o HSE-00 and hus close o he al-
ues o 𝜎loc. This is expec ed as he concen a ion o ca ions CLi
in Equa ion (9) conside s also he Li+in he ino ganic phase,
which a low empe a u es is essen ially confined owing o he
high in e ace esis ance. None heless, he Ha en a io dec eases
wi h he empe a u e (Figu e 6e), hus confi ming ha Li+plays
inc easingly a ole in he conduc ion p ocess. Fo compa ison,
we can calcula e again he conduc i i y, by conside ing only he
sal concen a ion. This is done by subs i u ing CLi and CFwi h
Csal in Equa ion (9). In his case, 𝜎NMR ≈𝜎 o also o he LATP-
con aining samples, and he Ha en a io is close o 1 in all sam-
ples (Figu e S7, Suppo ing In o ma ion). I he alues o HSE-
00 a e aken as a e e ence, lowe alues o HRa e obse ed, in
LATP-con aining samples, only a T≥60 °C. In his case, we
can assume ha he concen a ion o Li+is possibly unde es i-
ma ed. Despi e his, he use o he sal concen a ion alone, in he
Ne ns –Eins ein equa ion, gi es a good app oxima ion o he cal-
cula ion o he o al conduc i i y. The Ne ns –Eins ein equa ion
can also be applied e e sely o calcula e he sal diffusion coe -
ficien om he ionic conduc i i y. This can be compa ed wi h
he a e age sal diffusion coefficien by PFG-NMR. Again, he e
is a good ag eemen be ween he esul s o PFG-NMR and o he
conduc i i y measu emen s, wi h diffusi i y alues anging be-
ween 4∙10−12 m2s−1and 8∙10−12 m2s−1and dec easing be ween
HSE-00 and HSE-20 (Figu e S8, Suppo ing In o ma ion). The
alues a e close o hose ob ained by in e up ed cu en me hod
(5–6∙10−12 m2s−1a 60 °C), al hough in his case no effec o
LATP is obse ed.
Al oge he , i appea s ha , a leas a high empe a u es, he
obse ed dec ease o ionic conduc i i y is caused by a dec ease
o he anions’ diffusi i y. This is a ibu ed o he anions-specific
blocking effec exe cised by he LATP pa icles. On he con a y,
Li+diffusion is unhinde ed by LATP pa icles, a leas a high
empe a u es. The la ge Ha en a io a low empe a u es is a -
ibu ed o he high in e ace esis ance blocking he ans e
o Li+. O e all, his esul s in a sligh inc ease o he Li+ ans-
e ence numbe a high empe a u es: The la e was calcula ed
om he diffusi i y alues[58]
+=DLi
DLi +DF
(10)
I mus be no ed ha he ans e ence numbe calcula ed in
his way assumes an equal concen a ion o ca ions and anions,
and hus is possibly unde es ima ed, as he Li+concen a ion in
he LATP pa icles is no conside ed. Howe e , as no ed abo e,
he use o he sal concen a ion is a good app oxima ion when
conside ing he long- ange cha ge anspo . A oom empe a-
u e, he ou HSEs ha e simila ans e ence numbe s o 0.38
(Figu e 6 ). Howe e , he alues s a o di e ge a ≈50 °C. A
60 °C, he sample HSE-20 has ans e ence numbe o o e 0.41,
whe eas HSE-00 has ans e ence numbe sligh ly below 0.3. I
mus be no ed ha his diffe ence is qui e low. Indeed, ans-
e ence numbe T+, de e mined by po en ios a ic pola iza ion
me hod, is equal o T+=0.35 in all samples (ch onoampe o-
me ic p ofiles and impedance spec a a e shown in Figu e S9
in he Suppo ing In o ma ion). The alue is close o he one de-
e mined by PFG-NMR, bu no effec is obse ed due o LATP.
Al oge he , he expe imen al esul s do no confi m a signifi-
can inc ease o he ans e ence numbe due o LATP. On he
o he hand, he close alues ob ained by po en ios a ic pola iza-
ion me hod and PFG-NMR sugges he absence o ion pai ing
effec s. This is confi med by solid-s a e NMR measu emen s (see
la e discussion in his sec ion) and is expec ed owing o he high
dissocia ion deg ee o LiTFSI.[59]
Finally, he li hium ans e ence numbe s, ob ained by PFG-
NMR, we e combined wi h he o al ionic conduc i i y, o calcu-
la e he ca ionic conduc i i y 𝜎Li+(Figu e 7). Owing o he in-
c ease o he ans e ence numbe , he ca ionic conduc i i y e-
mains cons an up o 10% LATP. A 60 °C, he ca ionic conduc-
i i y is ≈1.6∙10−4Scm
−1, up o 10% LATP. A 20% LATP, a sligh
dec ease is obse ed, wi h 𝜎Li+=1.1∙10−4Scm
−1. To summa ize,
a mode a e LATP con en , since he dec ease o he ionic conduc-
i i y is mos ly caused by he blocking o anions, i has almos no
effec on he ca ionic conduc i i y. This sugges s ha he elec o-
chemical pe o mances should no be comp omised by he de-
c ease o he o al conduc i i y, a leas a mode a e con en s o
LATP. This, combined wi h he esul s o he mechanical mea-
su emen s, sugges s ha he o e all cycling pe o mance should
be enhanced by he addi ion o mode a e amoun s o LATP.
Elec ochemical cha ac e iza ion sugges s ha , a 60 °C, LATP
pa icles pa icipa e in he long- ange Li+ anspo p ocess. To
assess his hypo hesis, a 6Li–7Li iso ope exchange expe imen
was ca ied ou . This ype o expe imen , which combines elec o-
chemical 6Li–7Li iso ope exchange wi h NMR, has been used o
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Figu e 7. a) Li+ionic conduc i i y as a unc ion o empe a u e, and b) a 60 °C, compa ed o he o al ionic conduc i i y.
p obing he pa icipa ion o ac i e fille s in he conduc ion p o-
cess o HSEs.[14,40,41] Iso ope subs i u ion o 7Li by 6Li in a HSE-10
elec oly e was o ced by cycling gal anos a ically he elec oly e
be ween 99% en iched 6Li me al elec odes, as desc ibed in he
Expe imen al Sec ion. The possible 7Li–6Li exchange in LATP
and he polyme ma ix was subsequen ly assessed by 7Li and
6Li 1D NMR measu emen s, pe o med ex si u on he eco e ed
elec oly e. F om his expe imen , he Li-ions s emming om he
LATP pa icles and om he Li hium sal can be dis inguished
om he Li-ions coming om he me al oil by solid-s a e NMR,
by eco ding samples o HSE-10 be o e and a e pla ing e sus
6Li me al.
7Li and 6Li NMR spec a we e collec ed on he p is ine
HSE-10 memb ane, as a e e ence (Figu e 8a,b, espec i ely).
The 7Li spec um o HSE-10 be o e pla ing (HES-10-P is ine
in Figu e 8a) shows wo highly o e lapped signals a a ound
−1.3 and −1.1 ppm. F om he decon olu ion o he 7Li spec-
a o HSE-10 and i s compa ison wi h he one o HSE-00
(Figu e S10, Suppo ing In o ma ion), hese wo signals can be
assigned o he Li+ions in he polyme ma ix and he LATP,
espec i ely.
The compa ison o he NMR spec a be o e and a e pla -
ing, Figu e 8a, clea ly shows ha , a e he 6Li pla ing, he in-
ensi y o he 7Li signal o he HSE-10 sample did almos disap-
pea . The signal educ ion clea ly in ol es Li NMR signals om
bo h he LATP and he polyme phases. Pa allelly, he 6Li signal
inc eases d as ically, gi ing an in ense asymme ic peak, as ex-
pec ed a e homogeneous 7Li o 6Li exchange in bo h he poly-
me and LATP phases. This esul clea ly demons a es ha Li+
ions a he polyme and LATP phases mus be in e changing.
The spec a shown in Figu e 8b also shows ha he 6Li NMR
signal linewid h inc eases a e he pla ing. This phenomenon,
which could be a ibu ed o he inc eased he e ogenei y o he
memb ane,[44] makes he decon olu ion complica ed. Howe e ,
since he al e a ion o 7Li signal in ensi ies is homogeneous, i
can be concluded ha he Li+ions in bo h he polyme and ce-
amic phases a e mobile and a e accessible o ion anspo . This
sugges s he occu ence o Li+ion exchange be ween he polyme
ma ix and he LATP pa icles. The esul s also show ha his ex-
change is no limi ed o he Li a oms on he su ace o LATP, bu
a he all he Li a oms in he bulk o LATP can be subs i u ed by
he ones om he me al oil.
6Li EXSY expe imen s ha e been ca ied ou wi h he p is ine
HSE-20 sample o unequi ocally demons a e ion exchange in
he ce amic-polyme in e ace, he same way as in ou p e ious
wo ks ega ding LLZO-PEO elec oly es.[14,47] In hese spec a,
he diagonal peaks (iden ical chemical shi s in bo h dimensions)
co espond o egula signals o he iden ified componen s o he
sample, while he off-diagonal esponses (c oss-peaks) ep esen
magne iza ion ans e be ween he componen s ei he ia chem-
ical exchange o h ough dipola in e ac ion be ween neighbo -
ing spins sepa a ed in space by less han 5 Å. Taking in o ac-
coun ha na u al abundance o 6Li is less han 8%, he p oba-
bili y o obse ing se e al 6Li iso opes a a close dis ance om
each o he is negligible. Mo eo e , he low dipola momen o
6Li would make spin diffusion h ough dipola in e ac ions e en
mo e unlikely. I means ha he appea ance o c oss-peaks in ou
spec a clea ly demons a es he p esence o dynamic physical ex-
change p ocesses o Li+ions be ween he wo phases in he HSE.
In ensi y o c oss-peaks depends on a mixing ime – ime delay in
he EXSY expe imen , du ing which magne iza ion ans e oc-
cu s (Figu e 8c and Figu e S11, Suppo ing In o ma ion). By un-
ning he expe imen mul iple imes wi h diffe en mixing ime,
one can quan i y he exchange a e. In he analyzed sample a
20 °C, he ime cons an o he exchange is abou 300 ms, wi h
he pla eau obse ed a a ound 1 s, while a 60 °C he cons an de-
c eases o 50 ms and he pla eau is eached a 400 ms (Figu e 8d).
Beside p obing he pa icipa ion o he LATP pa icles in he
long- ange cha ge anspo , solid-s a e NMR can be used also
o in es iga e he local ions dynamics, which may be affec ed by
chemical in e ac ions be ween he ions and polyme ma ix and
he fille pa icles. Fo ins ance, possible chemical in e ac ions o
he anions wi h he pa icles su ace may gi e ise o a dec ease o
he anion’s mobili y, p omp ing an inc ease o he ca ion ans e -
ence numbe and o he oxida i e s abili y in HSEs.[29] To s udy
he possible TFSI−agg ega ion a he LATP su ace, 19FNMRex-
pe imen s we e conduc ed and T1 elaxa ion imes we e in es i-
ga ed. The longi udinal elaxa ion imes o he nuclea magne-
iza ions in NMR depend s ongly on he local mobili ies and
ime fluc ua ions o he chemical en i onmen s. In his line,
he a achmen o anions o he su ace o a fille would esul
in diffe en anion en i onmen s wi h dis inc elaxa ion imes
and line shapes.[60] Since in he 19F 1D spec a o all samples
(HES-00, HSE-10, and HSE-20) only single lines we e obse ed,
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Figu e 8. Solid-s a e NMR cha ac e iza ion o LATP-based HSEs. a) 7Li NMR spec a o HSE-10, p is ine (black line) and a e elec ochemically d i en
iso ope exchange ( ed line); b) 6Li NMR spec a o HSE-10, p is ine (black line) and a e iso ope exchange ( ed line); c) 6Li 2D EXSY spec a o HSE-20
a 60 °C, a mixing imes o 10 ms ( ed con ou ) and 600 ms (blue con ou ); d) no malized in ensi y o he off-diagonal peaks in he 6Li 2D EXSY spec a
o HSE-20 a 20 and 60 °C, as a unc ion o he mixing ime; e) 19F NMR sa u a ion eco e y expe imen s o HSEs wi h diffe en LATP concen a ions.
Fi ing line was ob ained conside ing a single exponen ial; ) 19F linewid h a a iable empe a u e, wi h and wi hou LATP.
complemen a y T1sa u a ion- eco e y expe imen s we e con-
duc ed o examine he possible o e lapping o esonances. As
shown in Figu e 8e, he da a could be pe ec ly fi ed in all cases
wi h a single exponen ial e m, and simila 19F elaxa ion imes
(T1=0.76 s) we e ob ained, indica ing no anion immobiliza ion
upon he addi ion o LATP. I his we e he case, diffe en 19F
NMR esonances and/o mul iexponen ial beha io in T1would
be expec ed.
To compa e he anion dynamics in he HSE-00 and HSE-10
in mo e de ail, a iable empe a u e NMR expe imen s we e pe -
o med and he linewid hs (FWHM) as a unc ion o empe a-
u e we e plo ed in Figu e 8 . The mo ional na owing cu e
shows simila beha io o he 19F signals o he TFSI−anions
be ween hese wo hyb id elec oly e memb anes. Fo bo h HSE-
00 and HSE-10, he mo ional na owing is comple ed a a ound
20 °C, and he linewid h o he igid la ice is a leas 32 kHz,
which would esul in jump a es (1/𝜏NMR) abo e 2∙105s−1a
he empe a u e o inflec ion poin (−31 °C). A simila expe i-
men o ollow 7Li local dynamics by NMR was no easible due o
he o e lapping be ween 7Li signals om he polyme and LATP
phases. The esul s ag ee wi h he T1 elaxa ion ime measu e-
men s, and u he p o e ha fille inco po a ion keeps he anion
local dynamics a he unaffec ed. I mus be no ed ha his esul
is no in conflic wi h he p e ious esul s o impedance spec-
oscopy and PFG-NMR expe imen s. Indeed, impedance spec-
oscopy showed ha he local mola conduc i i y is no affec ed
by he in oduc ion o LATP, which ag ees well wi h he esul s
o he NMR linewid h expe imen s. On he o he hand, as no ed
abo e, he diffusion coefficien s de e mined by PFG-NMR a e e-
la ed o he long- ange anspo , and hus a e pa ially decoupled
om he local mobili y, owing o he p esence o he high in e -
ace esis ance.
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Figu e 9. Pla ing/s ipping p ofiles o he ou HSEs, a 60 °C. Tes s we e pe o med a fixed capaci y (1 mAh cm−2) and inc easing cu en densi y. The
cu en densi y is indica ed as C- a e, whe e 1C (o C/1) is 1 mA cm−2. The ed as e isk indica es he minimum C- a e a which ol age ins abili y o
sho ci cui is obse ed. a) HSE-00; b) HSE-05; c) HSE-10; d) HSE-20.
2.3. Pla ing/S ipping Tes
Pla ing/s ipping es s we e ca ied ou o es he esis ance o
he ou elec oly es agains dend i es g ow h, and hus o e -
i y he combined effec o LATP on he mechanical and ans-
po p ope ies o he elec oly es. The es s we e pe o med
a 60°C, wi h fixed capaci y o 1 mAh cm−2and a inc eas-
ing cu en densi y, o de e mine he maximum cu en den-
si y a which s able pla ing/s ipping can be achie ed. Thus, his
es gi es an indica ion o he limi ing cu en densi y a which
he hyb id elec oly es can be cycled. The pla ing/s ipping p o-
files a e shown in Figu e 9. HSE-00 shows s able cycling only
up o 0.1 mA cm−2(C/10), whe eas ol age ins abili ies (so
sho s) and a clea sho ci cui a e obse ed a 0.2 mA cm−2
(C/5) and 0.33 mA cm−2(C/3), espec i ely. HSE-05 and HSE-
10 show be e pla ing/s ipping pe o mance, wi h s able cy-
cling a 0.2 mA cm−2(C/5) and ol age ins abili ies s a ing om
0.33 mA cm−2(C/3). In bo h cases, no clea sho ci cui is ob-
se ed. HSE-20, on he con a y, shows a sho ci cui al eady a
0.2 mA cm−2(C/5).
The enhanced pla ing/s ipping pe o mance ob ained wi h
HSE-05 and HSE-10 esul s om he combina ion o im-
p o ed mechanical p ope ies and e ained anspo p ope -
ies, whe eas he dec ease o he pe o mance a HSE-20 is a -
ibu ed o he dec ease o he ionic conduc i i y a high LATP
concen a ions. These esul s possibly confi m he combined
esul s ob ained by mechanical, conduc i i y and PFG-NMR
measu emen s, which is ha addi ion o mode a e amoun s
o LATP can enhance he cycling pe o mance o he polyme
elec oly es.
3. Conclusions
The anspo p ope ies and local ions dynamics o LATP-
con aining HSEs we e analyzed by means o impedance spec-
oscopy and solid-s a e NMR. The analysis o he admi -
ance/impedance spec a allowed disce ning wo conduc i i ies,
a local conduc i i y, a imescales so sho ha no ions accumu-
la ion no Li+ ans e ac oss he in e phase bounda y occu , and
a long- ange conduc i i y, a longe imescales, accoun ing o
he con ibu ion o in e ace esis ance and Li+ ans e ac oss
he pa icles in e ace. The o me co esponds o he effec i e
conduc i i y o he HSE, modeled h ough he Maxwell-Ga ne
mixing ule, wi hou he con ibu ion o he in e ace esis ance.
O e all, his local conduc i i y is negligibly affec ed by LATP, ow-
ing o he high in insic conduc i i y o he amo phous and plas-
icized polyme ma ix. On he con a y, he long- ange conduc-
i i y dec eases wi h inc easing olume ac ion o LATP, owing
o he high in e ace esis ance o Li+ ans e be ween he wo
phases. Up o 10 ol% LATP, he d op in he long- ange ionic
conduc i i y can be modeled wi h he Maxwell-Ga ne mixing
ule, by conside ing LATP pa icles as insula ing. None heless,
he con ibu ion o LATP pa icles o he o e all cha ge anspo
p ocess inc eases wi h LATP con en and wi h inc easing em-
pe a u e. Indeed, he addi ional pola iza ion esponsible o he
conduc i i y d op dec eases wi h inc easing empe a u e, espe-
cially a high LATP con en . In o he wo ds, a high empe a u es
he long- ange conduc i i y app oaches he local conduc i i y.
Ions’ diffusi i y was s udied by PFG-NMR. Resul s show a
sligh dec ease o he anions’ diffusion coefficien wi h inc eas-
ing LATP concen a ion, whe eas he ca ions’ diffusi i y, a leas
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a high empe a u es, is unaffec ed. This was a ibu ed o he
blocking effec o LATP pa icles owa ds he anions. Al oge he ,
his esul s in a mode a e inc ease o he Li+ ans e ence num-
be , which compensa es o he dec ease o he o al conduc i i y
up o 10 ol% LATP. None heless, his inc ease o ans e ence
numbe is small and was no confi med by po en ios a ic pola -
iza ion me hod.
The occu ence o Li+exchange be ween he wo phases was
u he p o ed by 6Li 2D EXSY NMR, which p o ided an ex-
change ime cons an o 50 ms a 60 °C and 20 ol% LATP, and by
iso ope exchange expe imen , coupled wi h 6Li/7Li NMR, show-
ing almos comple e iso ope subs i u ion in he elec oly e a e
gal anos a ic cycling be ween 6Li-en iched Li discs. Finally, elax-
ome y expe imen s and a iable empe a u e NMR expe imen s
indica e negligible a ia ion in he local ions’ dynamics, confi m-
ing ha he local mo ion is unhinde ed by he LATP pa icles and
ha no anions agg ega ion occu s on he LATP su ace.
Rega ding a possible applica ion o he HSEs in Li me al ba -
e ies, esul s o PFG-NMR and conduc i i y measu emen s sug-
ges ha he anspo p ope ies a e no affec ed by addi ion o
mode a e amoun s o LATP (up o 10% LATP). Mechanical mea-
su emen s, on he o he hand, indica e a clea enhancemen o
he oughness and Young modulus o he memb anes wi h LATP
concen a ion. The combined esul s sugges ha HSEs wi h low
concen a ion o LATP (up o 10 ol%) should ha e imp o ed p o-
cessabili y and esis ance o dend i es g ow h. Indeed, his las
conclusion was la e confi med by pla ing/s ipping es s in Li||Li
symme ic cells.
4. Expe imen al Sec ion
Hyb id Solid Elec oly es P epa a ion:LATP-based HSEs we e p epa ed
by mixing mic ome e -sized LATP pa icles (Scho ) wi h an e hylene oxide-
based polyme ma ix. LiTFSI (sol ionic, 99.9%) was used as li hium sal .
The composi ion o he polyme phase was kep cons an , wi h a mole a-
io o e hylene oxide uni s o Li+(EO:Li+)fixeda EO:Li
+=16, whe eas he
con en o LATP was a ied be ween 0 and 20 ol% (0, 5, 10 and 20 ol%,
co esponding o 0, 12, 22, and 39 w % o he o al HSE mass). The poly-
me elec oly e ma ix was composed o an e hylene oxide-p opylene oxide
copolyme (p(EO-PO), Mw≈800 000), poly(e hylene glycol)dime hyl e he
(PEGDME, Mn≈500, Sigma Ald ich) as plas icize , and poly(e hylene gly-
col)diac yla e (PEGDA, Mn≈700, Sigma Ald ich) as c oss-linke . PEGDME
wi h molecula weigh o 500 g mol−1was chosen, o e lowe molecula
weigh analogues, o enhance he he mal s abili y o he elec oly es. All
HSE componen s we e d ied unde high acuum be o e use, and all p epa-
a ion s eps we e ca ied ou in an a gon-filled glo e box. Fi s , he poly-
me ma ix componen s, LiTFSI, and he LATP we e mixed o e nigh in
ace oni ile (ACN) unde igo ous s i ing. In a ypical p epa a ion, 24 mL
o ACN, 1.26 g o p(EO-PO) (25.3 w % wi h espec o he o al mass o he
polyme elec oly e phase), 1.38 g o LiTFSI (27.7 w %), 0.9 g o PEGDA
(18.1 w %), and 1.44 g o PEGDME (28.9 w %) we e used. Second, AIBN
(≈20 mg) was added o he solu ion. The solu ion was hen milled wi h
a Mic o Pul e ise e 7 p emium plane a y (F i sch). He me ically sealed
45 mL zi conium flasks we e used, which we e loaded and sealed in a gon
a mosphe e wi h 5 mm diame e Z O2beads (70 g). The o al we milling
ime was 20 min a 250 pm, in e up ed by a 10 min pause o a oid o e -
hea ing o he sys em. The homogeneous solu ions we e cas on a Myla
film, wi h a a ge d y hickness o 140 μm. The ACN was fi s e apo a ed
o 3 h a oom empe a u e. Then, he empe a u e was inc eased o 70°C
o one hou (hal acuum was applied) o he c oss-linking s ep, o ming
an in e pene a ing ac ylic polyme ne wo k. P io o cha ac e iza ion, he
memb anes we e d ied unde acuum o e nigh . The cas ing was ca ied
ou on a minicoa e (TOC sheen) in a glo e box, unde A a mosphe e,
and he d ying s eps we e ca ied ou in a hea ed glo ebox an echambe .
The memb anes we e finally s o ed in he same glo ebox o u he use.
The memb anes densi y was measu ed by weighing discs wi h diame e
o 16 mm and by measu ing hei hickness wi h a mic ome e .
Cha ac e iza ion Me hods:The mo phology o he HSEs was s udied
by SEM, wi h a FEI Quan a 250. C oss sec ions we e p epa ed by cu ing
he memb anes a oom empe a u e in an a gon glo ebox. Images we e
collec ed wi h a ol age accele a ion o 10 keV and wi h a backsca e ed
elec on de ec o (BSED) and wi h a seconda y elec on de ec o . The mo-
g a ime ic analysis (TGA) was ca ied ou unde a gon (60 mL min−1),
om oom empe a u e up o 600 °C, a a hea ing a e o 10 °Cmin
−1,
wi h a TGA 209 F1 Lib a (Ne zsch). Diffe en ial scanning calo ime y mea-
su emen s (DSC) we e pe o med wi h a DSC 2500 diffe en ial calo ime e
(TA Ins umen s). The measu emen s we e ca ied ou by placing sam-
ples o 5–10 mg in sealed aluminum pans unde a gon a mosphe e, in
he empe a u e ange be ween −80 and 100 °C, and wi h a hea ing a e o
2°Cmin
−1. Each sample was cycled wice be ween −80 and 100 °C, and
he second hea ing scan was used o he analysis. The mechanical p ope -
ies o he hyb id elec oly es we e cha ac e ized by ensile es , wi h a sin-
gle column uni e sal es ing machine (Ins om, 34SC-5). The s a ic load
cell (100 N 2519 Se ies S-beam) had a displacemen speed o 20 cm min−1.
The samples had an app oxima e leng h o 4 cm and a wid h o 10 mm,
whe eas he sepa a ion be ween he ensile clamps was o ≈10 mm.
Ionic conduc i i y measu emen s we e pe o med wi h a Sola on
1260A Impedance/Gain-Phase Analyze , in he equency ange be ween
32 MHz and 1 Hz (20 poin s pe decade), wi h a signal ampli ude o 20 mV,
and in he empe a u e ange be ween 25 and 70 °C(wi h10°C s ep). The
measu emen s we e ca ied ou by placing he memb anes in coin cells
CR2032, wi h h ee s ainless s eel pla es o 0.5 mm hickness. The em-
pe a u e was con olled wi h a Binde KB23 Cooling incuba o . The ionic
conduc i i y was calcula ed wi h he ollowing o mula
𝜎i=1
Ri
L
A(11)
whe e 𝜎iis he local o long- ange conduc i i y, Riis he co esponden e-
sis ance, as de e mined by EIS, Ais he elec odes su ace a ea, and Lis he
memb ane hickness. The la e was measu ed wi h a digi al mic ome e ,
a e he expe imen . The measu emen was epea ed on h ee diffe en
cells o each composi ion, and he alues o esis ance and conduc i i y
used in he analysis a e he a e age alues o he h ee measu emen s.
Li hium ans e ence numbe T+and sal es ic ed diffusion coefficien
D es we e measu ed in Li||Li coin cells, on a Biologic VMP3 po en ios a ,
a 60 °C. The li hium ans e ence numbe was de e mined by po en io-
s a ic pola iza ion me hod, by combining a ch onoampe ome y wi h he
measu emen o he impedance spec a, collec ed be o e and a e he
ch onoampe ome y. Fo he ch onoampe ome y, a cons an ol age o
±10 mV was applied o a du a ion o 20 min, and he esul ing cu en was
egis e ed wi h a equency o 10 poin s s−1du ing he fi s minu e, and
o one poin pe second du ing he es o he ch onoampe ome y. The
impedance spec a we e collec ed in he equency ange be ween 1 MHz
and 100 mHz and wi h po en ial ampli ude o 10 mV. The expe imen was
epea ed on h ee cells pe sample and six imes on each cell, by al e na ing
posi i e and nega i e po en ios a ic pola iza ion. The cells we e allowed o
elax o one hou a e each ch onoampe ome ic s ep, and o 10 min a -
e he EIS. The ans e ence numbe was hen calcula ed using he usual
o malism[61]
T+
1=ISS
I0(ΔV−Rin ,0I0)
(ΔV−Rin ,SSI0)(12)
whe e I0and ISS a e he ini ial and s eady-s a e cu en , espec i ely, ΔV
is he applied po en ial and Rin ,0 and Rin ,SS a e he in e ace esis ances
Small 2024,20, 2305769 © 2023 The Au ho s. Small published by Wiley-VCH GmbH
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be o e and a e he ch onoampe ome ic s ep, espec i ely. The alues o
T+we e u he con olled wi h he ollowing equa ion[62]
T+
2=Rb,0
(ΔV∕ISS −Rin ,SS)(13)
whe e Rb,0 is he bulk esis ance be o e he ch onoampe ome y. The wo
calcula ion me hods ga e simila esul s, and he ans e ence numbe s
epo ed in he esul s sec ion a e he ones calcula ed wi h Equa ion (12).
The sal es ic ed diffusion coefficien , D es, was de e mined using he
ollowing equa ion[63]
D es =−
BL2
𝜋2(14)
whe e Bis he slope o he na u al loga i hm o he cell ol age e sus
ime, du ing he es s ep ollowing he ch onoampe ome y, and Lis he
memb ane hickness.
Magic angle spinning NMR spec oscopy (MAS NMR) expe imen s
we e pe o med on hyb id solid elec oly es using a B uke A ance III 500
spec ome e equipped wi h a 2.5 mm p obe. The MAS equency was se
o 20 kHz o all measu emen s excep a iable empe a u e s udies ha
we e ca ied ou in s a ic samples. 7Li and 6Li chemical shi s we e e -
e enced o a 1 m LiCl wa e solu ion and 19F was e e enced indi ec ly o
solid LiF esona ing a −204 ppm. 1D expe imen s we e eco ded using
single exci a ion pulses (2.4, 3, and 3.7 μs) and elaxa ion delays o 10, 3,
and8s o 7Li, 6Li, and 19F espec i ely. These spec a we e eco ded o
quali a i e pu poses. Sa u a ion eco e y expe imen s we e pe o med o
ob ain he 19F elaxa ion imes wi h he elaxa ion delay a ying om 1 ms
o 180 s. Va iable empe a u e expe imen s we e conduc ed in he empe -
a u e ange o −80 o 110 °C in a s a ic p obe, and he 19F 1D expe imen s
we e eco ded using a single 3 μs exci a ion pulse wi h a single scan.
In he Li iso ope subs i u ion expe imen , a HSE-10 elec oly e wi h a
na u al 6Li abundance (7.5%) was used as elec oly e in a symme ic Li||Li
cell, wi h 99% en iched 6Li me al. A cons an cu en densi y o 32 μAcm
−2
was applied o he cell, o 20 h, o o ce iso ope subs i u ion in he elec-
oly e. The cha ge passed was calcula ed o be sufficien o displace all he
Li a oms con ained in he elec oly e. A e he pla ing, he cell was opened
in he glo ebox and he elec oly e memb ane was ca e ully emo ed and
packed in o a o o o pe o m he 7Li and 6Li 1D NMR measu emen s.
Pulsed-field g adien nuclea magne ic esonance (PFG-NMR) was
used o de e mine he diffusion coefficien s o 7Li and 19F o all he elec-
oly es a a iable empe a u e ( anging om 80 o 20 °C) using a B uke
A ance III 300 MHz wide bo e NMR spec ome e equipped wi h a 5 mm
diff50 p obe. S imula ed Echo was used o all nuclei diffusion measu e-
men s. Typical diffusion ime o bo h nuclei was 25 ms, g adien pulse
du a ion was 2 ms. The maximum field s eng h was 7.05 T on a log scale.
7Li and 19F PFG-NMR expe imen s we e epea ed o 0 and 20 ol%
LATP con aining samples o e i y whe he he ob ained diffusion coeffi-
cien s depend on diffusion ime. B uke A ance NEO 500 MHz wide bo e
NMR spec ome e equipped wi h double esonance (7Li/19F) 8 mm Diff
50 p obe has been used o hese expe imen s. Diffusion ime was se o
200 ms, while g adien delay, and he maximum field s eng h we e kep
he same as in p e ious expe imen s: 2 ms and 7.05 T, espec i ely.
The same B uke A ance NEO 500 MHz wide bo e NMR spec ome e
bu wi h 4 mm MAS p obe (maximum spinning speed o 15 kHz) has been
used o ca y ou 6Li–6Li 2D EXSY expe imen s o 20 ol% LATP sample
a 20 and 60 °C. A s anda d h ee-pulse sequence wi h mixing imes om
10 ms o 1.6 s and a elaxa ion delay o 80 s was applied o quan i a i e
cha ac e iza ion o ca ion exchange be ween LATP pa icles and polyme
ma ix. 16 scans we e collec ed o each o he 64 da a poin s in indi ec
dimension wi h he o al acquisi ion ime o 23 h pe spec um.
Li hium pla ing/s ipping es s we e ca ied ou in symme ical Li||Li
coin cells, a 60 °C. Be o e each measu emen , he cells we e kep a
70 °C o 12 h, o ensu e s abiliza ion o he li hium in e ace. The cells
we e cycled gal anos a ically wi h a fixed pla ing/s ipping capaci y o
1mAhcm
−2, and wi h p og essi ely inc easing cu en densi ies o 0.05,
0.1, 0.2, 0.33, 0.5, 1 mA cm−2(C/10, C/5, C/3, C/2, C/1), plus one final
con ol cycle a 0.1 mA cm−2(C/10). One cycle was pe o med a each
cu en densi y. The measu emen s we e pe o med in a Newa e ba e y
es e .
Suppo ing In o ma ion
Suppo ing In o ma ion is a ailable om he Wiley Online Lib a y o om
he au ho .
Acknowledgemen s
The au ho s a e g a e ul o he Eu opean Commission o he suppo o
he wo k pe o med wi hin SAFELiMOVE. The p ojec has ecei ed und-
ing om he Eu opean Union’s Ho izon 2020 esea ch and inno a ion
p og amme unde G an ag eemen no. 875189. The in o ma ion and
iews se ou on his pape do no necessa ily eflec he official opin-
ion o he Eu opean Commission. Nei he he Eu opean Union ins i u-
ions and bodies no any pe son ac ing on hei behal , may be held e-
sponsible o he use o he in o ma ion con ained he ein. P.G. as a pa
o he DESTINY PhD p og amme acknowledges unding om he Eu o-
pean Union’s Ho izon2020 esea ch and inno a ion p og amme unde
he Ma ie Skłodowska-Cu ie Ac ions COFUND – G an Ag eemen No:
945357. The au ho s acknowledge Ma ia E xeba ia and Ma ia Campos
Te on o collec ing he c oss-sec ion SEM images.
Conflic o In e es
The au ho s decla e no conflic o in e es .
Da a A ailabili y S a emen
The da a ha suppo he findings o his s udy a e a ailable om he co -
esponding au ho upon easonable eques .
Keywo ds
composi e polyme elec oly es, conduc ion mechanism, hyb id solid elec-
oly es, LATP, NASICON, solid-s a e ba e ies, anspo p ope ies
Recei ed: July 10, 2023
Re ised: Sep embe 18, 2023
Published online: Oc obe 24, 2023
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Small 2024,20, 2305769 © 2023 The Au ho s. Small published by Wiley-VCH GmbH
2305769 (16 o 16)
16136829, 2024, 10, Downloaded om h ps://onlinelib a y.wiley.com/doi/10.1002/smll.202305769 by Uni e sidad Del Pais Vasco, Wiley Online Lib a y on [10/03/2024]. See he Te ms and Condi ions (h ps://onlinelib a y.wiley.com/ e ms-and-condi ions) on Wiley Online Lib a y o ules o use; OA a icles a e go e ned by he applicable C ea i e Commons License
In es iga ing he ole o in e phases in composi e elec oly es by solid-s a e NMR
97
7.5 Publica ion #5:
Ti le: Un eiling he Reac i i y and he Li-Ion Exchange a he PEO-Li6PS5Cl In e phase: Insigh s
om Solid-S a e NMR
Au ho s: Ped am Gho banzade, A ianna Pesce, Michel A mand, Ke man Gómez, Shanmuka aj
De a aj, Ped o López-A angu en, and Juan Miguel López del Amo
Jou nal: Small S uc u es
Jou nal impac ac o : 13.9
Jou nal qua ile: Q1 (Ma e ials Science, Mul idisciplina y)
quan i y di e en decomposi ion p oduc s in he in e phase, i is
e iden ha he o al amoun o hese p oduc s is significan ly
highe in he composi e made wi h B -doped LPSCl.
Compa ing he
7
Li–
7
Li 2D EXSY NMR expe imen s in hese
wo samples indica ed ha he chemical species in he in e phase
es ic he Li ion exchange be ween he wo phases, and do no
play an in e media e ole in he exchange.
In gene al, he in e phase species a e ound o be undesi able.
Thus, o limi he in e acial eac ion one should a ge ei he he
Li a fini y o he polyme by dec easing i s complexing abili y, o
he diso de o he LPSCl c ys al s uc u e. The addi ion o side
chains o he PEO o educing he numbe and con en o dop-
an s a e among possible app oaches o minimize he in e acial
eac ion. Conside ing he obse ed Li exchange be ween he wo
phases, we belie e ha i he in e acial eac ion is p e en ed and
he ac i a ion ene gy o he Li exchange is educed, a con inuous
Li pa hway h ough bo h phases could be o med, and he objec-
i e o combining he high ionic conduc i i y o he LPSCl wi h
he p ocessabili y o polyme s could be achie ed.
4. Expe imen al Sec ion
Solid S a e NMR Expe imen s: All NMR expe imen s we e eco ded
using a B ucke A ance III 500 MHz spec ome e . Samples we e packed
inside 2.5 mm o o s and magic angle spinning speed was fixed a 20 kHz
in all expe imen s. The o o s we e spun in a ni ogen a mosphe e, o
a oid possible eac ions wi h mois u e du ing he expe imen . The
7
Li,
6
Li, and
31
P spec a we e eco ded using one pulse exci a ion and pulse
leng hs o 2.4, 3, and 2.5 μs o
7
Li,
6
Li, and
31
P espec i ely. Fo he
19
F
and
1
H expe imen s, o o -synch onized Hahn-echo pulse sequences we e
used wi h he 90° pulse leng h se o 3 and 2.1 μs o
19
F and
1
H, espec-
i ely. The mixing imes o he
7
Li–
7
Li and
6
Li–
6
Li EXSY expe imen s we e
se o 400 ms and he con ac ime o 1000 and 1200 μs we e espec i ely
selec ed o he
1
H–
7
Li and
1
H–
31
P CP HETCOR expe imen s.
The
1
H,
19
F,
31
P,
7
Li, and
6
Li 1D spec a we e eco ded wi h ecycle
delays o 5, 5, 30, 60, and 120 s, espec i ely (unless men ioned o he -
wise), while he ecycle delay was se o 3 s o
1
H–
31
P and
1
H–
7
Li CP
expe imen s, and 10 s o he
19
F–
7
Li HETCOR. The signal decon olu ions
o
6
Li 1D spec a we e pe o med using DM-Fi p og am.
[46]
Powde X- ay Di ac ion: X- ay di ac ion o he syn he ized powde was
ca ied ou a BL04-MSPD beamline a ALBA synch o on. The powde s
we e packed in a 0.7 mm diame e bo osilica e glass capilla y. The pa e n
was eco ded a 15 keV.
LPSClB and LPSCl Syn hesis: S oichiome ic amoun s o Li
2
S, P
2
S
5
,
LiCl, and LiB we e ball-milled in a Pul e ise e 7 o 20 h o ob ain
LPSClB acco ding o eac ion 1.
4.2 Li2SþP2S5þ2 LiCl þ0.8 LiB !2Li
5.6PS4.6ClB 0.4 (1)
The composi ion and he c ys al s uc u e o he LPSClB was
confi med by synch o on XRD expe imen s as shown in Figu e S8,
Suppo ing In o ma ion.
Comme cial Li
6
PS
5
Cl was pu chased om NEI co po a ion and was
used wi h no u he modifica ion.
Composi e Polyme Elec oly e P epa a ion: Composi e elec oly es we e
p epa ed by mixing 70 w % poly(e hylene-oxide) (PEO, 1 106 g mol
1
,
Sigma Ald ich), li hium bis( ifluo ome hanesul onyl)imide (LiTFSI,
Sol ionic) (EO:Li =20), and 30 w % a gy odi e (LPSCl o LPSClB ) pow-
de s in ai igh g inding bowls inside an A -filled glo ebox. The ball-milling
was conduc ed using a Plane a y Mic o Mill Pul e ise e 7 ou side he glo-
ebox o 30 min (six in e als o 5 min a 500 pm wi h 10 min pauses in
be ween o p e en o e hea ing). A e being ans e ed back o he glo e-
box, he mix u e was p essed in o 6 mm pelle s using a hyd aulic p ess
applying 1.5 ons o weigh . Each pelle was placed be ween wo plas ic
films, sealed inside a co ee bag, and subsequen ly ho -p essed a 80 °C
o 2 min ou side he glo ebox. The co ee bags we e hen ans e ed
and opened inside he glo ebox. The PEO-a gy odi e sel -s anding films
appea ed isually homogeneous and had a hickness o ≈70 μm. This
me hod a oids unce ain ies ega ding possible in e ace modifica ion
by sol en while ensu ing su ficien con ac be ween he wo phases o
o m he in e ace. Bo h LPSCl and LPSClB composi es we e p epa ed
ollowing he same p ocedu e o allow o ai compa ison.
Addi ionally, he ep oducibili y o he composi es was e ified by solid-
s a e NMR expe imen s pe o med on di e en ba ches o composi es.
Digi al pho og aphs o he di e en p ocessing s eps o he PEO-LPSCl
composi e a e shown in Figu e S9, Suppo ing In o ma ion.
Solid S a e NMR Sample P epa a ion: The composi e memb anes we e
cu in o hin ibbon-like shapes and packed inside 2.5 mm NMR o o s.
A e he fi s se o measu emen s, he same o o was placed inside a
glo ebox an echambe unde dynamic acuum and hea ed a 70 °C o e -
nigh o p omo e mo e eac ions a he in e phase. A e cooling down o
oom empe a u e, he sample was ans e ed back o he spec ome e
o u he NMR expe imen s. Fo he ime e olu ion expe imen s, he
same o o was s o ed inside he glo ebox a e he fi s se o measu e-
men s and he es s we e epea ed a e 10 days. Repea ing he expe i-
men s on he same samples a e hea ing o a pe iod o ime allows
us o clea ly obse e signal e olu ions and elimina es o he pa ame e s
ha could cause unce ain y in he conclusions.
Suppo ing In o ma ion
Suppo ing In o ma ion is a ailable om he Wiley Online Lib a y o om
he au ho .
Acknowledgemen s
As a pa o he DESTINY PhD p og amme, his publica ion is acknowl-
edged by unding om he Eu opean Union’s Ho izon2020 esea ch and
inno a ion p og amme unde he Ma ie Skłodowska-Cu ie Ac ions
COFUND (G an ag eemen #945357). The au ho s also acknowledge
Rosalia Cid o ui ul discussion. The XRD expe imen s we e pe o med
a BL04-MSPD. beamline a ALBA Synch o on wi h he collabo a ion o
ALBA. This p ojec has ecei ed unding om he Eu opean Union h ough
he H2020 p og am unde G an ag eemen numbe 875028 (SUBLIME
P ojec ).
Conflic o In e es
The au ho s decla e no conflic o in e es .
Da a A ailabili y S a emen
The da a ha suppo he findings o his s udy a e a ailable on eques
om he co esponding au ho . The da a a e no publicly a ailable due o
p i acy o e hical es ic ions.
Keywo ds
a gy odi e ion conduc o s, ba e ies, composi e polyme elec oly es,
in e phases, solid s a e NMR
Recei ed: Ma ch 26, 2024
Re ised: July 12, 2024
Published online: July 28, 2024
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Small S uc . 2024,5, 2400139 2400139 (8 o 8) © 2024 The Au ho (s). Small S uc u es published by Wiley-VCH GmbH
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In es iga ing he ole o in e phases in composi e elec oly es by solid-s a e NMR
106
7.6 Publica ion #6:
* The manusc ip is submi ed o he Jou nal o Ma e ials Chemis y A and is unde e iew.
Ti le: Insigh s in o he Compa ibili y and In e phases o LPSCl A gy odi es and Z -based Halide
Elec oly es o All-Solid-S a e Ba e ies
Au ho s: Ped am Gho banzade, A ianna Pesce, Ke man Gómez, Ped o López-A angu en, and
Juan Miguel López del Amo
Jou nal: ---
Jou nal impac ac o : ---
Jou nal qua ile: ---
ARTICLE
Please do no adjus ma gins
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Recei ed 00 h Janua y 20xx,
Accep ed 00 h Janua y 20xx
DOI: 10.1039/x0xx00000x
Insigh s in o he Compa ibili y and In e phases o Li6PS5Cl
A gy odi es and Z -based Halide (LGZC) Elec oly es o All-Solid-
S a e Ba e ies
Ped am Gho banzade a,b,c, A ianna Pesce a, Ke man Gomez a, Ped o López-A angu en a and Juan
Miguel López del Amo *a
Cos -e ec i e Li2.1Ga0.1Z 0.9Cl6 (LGZC) halides wi h high ionic conduc i i y (> 0.4 mS/cm a 25°C) a e conside ed p omising
solid elec oly es o beyond Li-ion ba e ies. Howe e , hey su e om low s abili y agains Li me al, o ming a solid
elec oly e in e phase (SEI) ha causes con inuous deg ada ion, and limi s hei long- e m cyclabili y. Inco po a ing Li6PS5Cl
(LPSCl) elec oly es as an in e laye be ween LGZC and Li me al is a common app oach o add ess his issue and imp o e
cyclabili y. Ne e heless, e y ew s udies assessed he compa ibili y o halides and sul ides, epo ing con adic ing esul s.
Thus, his wo k used solid-s a e NMR and impedance spec oscopy o in es iga e in e acial eac ions and compa ibili y
be ween hese phases. The esul s show ha LPSCl and LGZC a e chemically incompa ible, and hei in e acial eac ions
in ol e hei decomposi ion o species wi h slowe ionic mobili y, dec easing he cell pe o mance. Al hough hei in e ace
eaches s abili y wi h ime, he decomposi ion eac ions a e accele a ed a high empe a u es. 6Li-6Li EXSY expe imen s
demons a e spon aneous Li-ion exchange be ween LGZC and LPSCl, despi e hei incompa ibili y. In e es ingly he
decomposed p oduc s pa icipa e in his exchange, explaining why hese bilaye sys ems can success ully enhance he cell
pe o mance. Ou s udy sheds ligh on he complex in e acial in e ac ion be ween halides and sul ides, p o iding insigh s
o a mo e op imal design o solid elec oly es o he new gene a ion o elec ochemical de ices.
In oduc ion
All-solid-s a e ba e y (ASSB) is conside ed a p omising
echnology able o inc ease bo h he ene gy densi y and sa e y
o he de ice.1,2 In con as o con en ional li hium-ion ba e ies
which use a liquid elec oly e and a sepa a o , ASSBs employ a
solid sepa a o ha pe o ms bo h unc ions. Thanks o hei
high mechanical p ope ies, solid elec oly es could enable he
use o Li me al as he anode which o e s a conside ably highe
heo e ical ene gy densi y han adi ional g aphi e anodes.3,4
In addi ion, since solid elec oly es do no con ain any ola ile
and lammable o ganic sol en s, hey could add ess some
sa e y issues o li hium-ion ba e ies.5
Sul ides and halides a e highly p omising and as -eme ging
g oups o solid elec oly es o ASSBs. They bo h o e a high
oom- empe a u e ionic conduc i i y, allowing apid cha ge and
discha ge.6,7 In addi ion, hey a e bo h so and easy o p ocess,
and unlike oxides, hey do no equi e any high- empe a u e
sin e ing.8 This impo an ea u e makes sul ides and halides
pa icula ly well-sui ed o la ge-scale manu ac u ing and
comme cializa ion8,9.
The a gy odi e ype Li6PS5X (X=Cl, B , I) a e among he mos
p omising sul ide elec oly es, owing o hei high ionic
conduc i i y, a ibu ed o hei highly diso de ed c ys al
s uc u e. The oom- empe a u e ionic conduc i i y o Li-
a gy odi es eaches 7 mS.cm-1,10 close o he Li mobili y in liquid
elec oly es. Wi hin his amily, Li6PS5Cl is pa icula ly popula
as i o e s a mo e s able in e ace wi h Li me al.11
Halides ha e he gene al o mula o Li3MX6 (M= i alen me als,
X=halogen elemen ), wi h Li3InCl6 and Li3YCl6 being among he
mos common composi ions, o e ing ionic conduc i i ies as
high as 1.49 mS.cm-1.12 Subs i u ion o elemen s wi h di e en
ionic adii o alences is a ypical app oach o al e he
p ope ies o he halide by inducing diso de and acancy in he
ca ion/anion subla ices.13 Fo ins ance, he pa ial o o al
subs i u ion o i alen me al wi h e a alen zi conium (Z )
leads o Li3-xZ xIn1-xCl6 o Li2Z Cl6 which a e highly conduc ing,
mo e ole an o humidi y, and mo e cos -e ec i e.13
Al hough halide elec oly es o e a g ea oxida i e s abili y
po en ial ( eaching 6 V s Li+/Li in some composi ions) and a e
compa ible wi h mos high- ol age ca hode ma e ials like
LiNixMnyCo1-x-yO2 (NMC), hei educ i e s abili y po en ial is
a he high,14 causing hei deg ada ion in con ac wi h Li me al.
This eac ion, which was obse ed in se e al s udies,15,16
in ol es he educ ion o he ansi ion me al o i s educed
s a e acco ding o eac ion 1.14
a.
Cen e o Coope a i e Resea ch on Al e na i e Ene gies (CIC ene giGUNE)
Basque Resea ch and Technology Alliance (BRTA), Albe Eins ein 48, 01510
Vi o ia-Gas eiz, Spain.
E-mail: jmlopez@cicene gigune.com
b.
Uni e si y o Basque Coun y (UPV/EHU), Ba io Sa iena, s/n, 48940 Leioa, Spain.
c.
ALISTORE-Eu opean Resea ch Ins i u e, 80039 Amiens, F ance.
Supplemen a y In o ma ion a ailable: See DOI: 10.1039/x0xx00000x
ARTICLE Jou nal Name
2 | J. Name., 2012, 00, 1-3 This jou nal is © The Royal Socie y o Chemis y 20xx
Please do no adjus ma gins
Please do no adjus ma gins
Li

MCl

+ 3 Li → 6 LiCl + M

(M = In, Y)
eac ion (1)
This decomposi ion eac ion may cause a signi ican inc ease in
he solid elec oly e/Li me al in e ace esis ance,16 due o he
poo ionic conduc i i y o he byp oduc s p esen a he
in e phase. As epo ed in se e al s udies, he in e phase
species ha e mixed ionic and elec onic conduc i i y, which
causes he eac ion o p oceed o se e al days be o e eaching
s abili y.16,17
Common app oaches applied o deal wi h his issue include
modi ying he halide chemis y,17 using Li-me al alloys ins ead
o pu e Li me al,9,18 o inco po a ing in e laye s.19,20 These hin
in e laye s, which physically sepa a e he halide and Li me al,
ha e been ound o e ec i ely p e en in e acial eac ions and
imp o e cell cyclabili y.21 Keeping he in e ace esis ance a a
minimum equi es he in e laye o be as hin and conduc i e
as possible. Thus, sul ide a gy odi e elec oly es, wi h hei high
ionic conduc i i y and ease o p ocessabili y, a e p oposed and
in es iga ed in a ious s udies. I mus be no ed ha
a gy odi es a e also uns able agains he Li me al.22,23 Howe e ,
he p oduc s o hei deg ada ion eac ion, ypically Li2S, LiCl,
and Li3P o m a s able solid elec oly e in e phase (SEI) ha
passi a es he elec oly e om u he decomposi ion, hus
allowing long cycling o he cell.21,23,24 Ji e al.20 demons a ed
ha inco po a ing an a gy odi e LPSCl bu e laye p e en s he
undesi ed educ ion o Li3YCl6 and signi ican ly imp o es he cell
cyclabili y, enabling a s able pla ing/s ipping o e 1000 h a 0.2
mA/cm2. In he same line, Wang e al.23 showed ha he LPSCl
in e laye s abilizes he solid elec oly e/Li me al in e ace and
ema kably dec eases he cell o e po en ial du ing
pla ing/s ipping. Zhang e al.21 epo ed a simila enhancemen
in a Li2Z Cl6-based sys em. This mul ilaye design enabled ASSBs
wi h high coulombic e iciency and supe io cycling beha io .21
While in es iga ing he pe o mance imp o emen o hese
mul ilaye sys ems has been he subjec o se e al s udies, li le
e o has been de o ed o in es iga ing he chemical
compa ibili y and he in e phases be ween he halides and
a gy odi es. Mo eo e , he ew a ailable wo ks on he li e a u e
epo con adic ing esul s. While Janek e al.18 claim ha he
in e acial eac ions be ween halides and a gy odi es a e
negligible, Ta ascon e al.25 epo hei incompa ibili y and
ques ion he he e o-s uc u al cell design, in which hese
phases come in o con ac . Kwak e al.26 also demons a ed ha
Li2Z Cl6 and LPSCl a e incompa ible, bu hese in e acial
eac ions a e d i en elec ochemically a high empe a u es.
The e o e, u he esea ch on his opic and cla i ica ion o he
eac i i y is equi ed. In addi ion, a deepe unde s anding o he
undamen als o ion anspo be ween hese phases and i s
con olling pa ame e s is necessa y o designing cells wi h
imp o ed pe o mance.
This wo k ocuses on he in e ac ion o halide and a gy odi e
elec oly es, aiming o in es iga e he ole o he in e phase
species in he local Li+ exchange be ween halides and
a gy odi es. Unde s anding he anspo p ope ies o he
in e phase species is c ucial in all cell con igu a ions in which
hese ma e ials a e in con ac . This also applies o he ele an
wo ks om Kim e al.27 and Ye e al.28 in which hey p oposed
coa ing he ca hode ma e ials wi h a hin halide laye o p e en
he oxida ion o he a gy odi e elec oly es s high- ol age
ca hodes.
In a p e ious s udy, solid-s a e NMR p o ed o be an e ec i e
ool o in es iga ing he compa ibili y o elec oly e ma e ials
and examining he composi ion and p ope ies o in e phase
species.29 Howe e , his me hod equi es he o ma ion and
p esence o a su icien ly high amoun o in e phases. Thus, a
composi e elec oly e design was used as a model sys em o
inc ease he e ec i e su ace a ea and o gene a e mo e
in e phase species compa ed o a bilaye con igu a ion. The
same app oach is applied in he cu en wo k as i enables a
mo e in-dep h in es iga ion o he in e acial chemis y
be ween halides and a gy odi es, e en hough hese ma e ials
a e o en used in bilaye con igu a ions in p ac ical applica ions.
The cen al ole o solid-s a e NMR in his s udy s ems om i s
sensi i i y o he chemical en i onmen , making i ideal o
dis inguishing be ween di e en li hium en i onmen s in halide
and sul ide phases. Mo eo e , he in e acial Li-ion exchange
be ween he wo phases can be s udied by applying Exchange
Spec oscopy (EXSY) NMR expe imen s.30,31 These wo-
dimensional NMR expe imen s allow o p obing he exchange
p ocesses be ween wo di e en si es wi hin a ce ain ime
ame. Such local sho - ange in e acial exchanges a e c i ical
in composi e o mul ilaye solid elec oly es as hey could
impac he long- ange ion anspo p ope ies, ul ima ely
a ec ing he o e all cell pe o mance.
In addi ion o EXSY, moni o ing he spec um e olu ion o e
ime can p o ide impo an insigh s in o po en ial
decomposi ion eac ions a ising om phase incompa ibili y. Fo
ins ance, in he case o decomposi ion eac ions, a dec ease in
he signal in ensi y and he eme gence o new signals
co esponding o decomposi ion p oduc s is expec ed. These
spec al changes p o ide a di ec indica ion o chemical
ins abili y a he in e phase. The in e acial eac ions can also
in luence he ull wid h a hal -maximum (FWHM) o he NMR
signals, commonly e e ed o as signal linewid h. The linewid h
gene ally co ela es wi h local ion dynamics32 and can e eal
how he in e ace in e ac ions impac he local ion mo ions in
indi idual phases. Combining hese measu emen s wi h EXSY
o ms a mo e comple e pic u e o bo h chemical and dynamic
p ocesses occu ing a he halide-a gy odi e in e ace, leading
o a mo e comp ehensi e unde s anding o he unde lying
mechanisms ha go e n sho and long- ange ionic
conduc i i y in solid-s a e elec oly es.
The halide ma e ial in es iga ed in his wo k co esponds o he
chemical o mula Li2.1Ga0.1Z 0.9Cl6 (LGZC). Using Z as he
ansi ion me al makes his halide mo e sus ainable and lowe s
he cos compa ed o Y- o In-based halides. Howe e , he bulk
ionic conduc i i y o he dopan - ee Li2Z Cl6 is conside ably
lowe han i s Y- and In-based compe i o s. This issue is
commonly add essed by he addi ion o alio alen dopan s such
as Ga o Fe. Fo ins ance, Kwak e al.33 epo ed a maximum
ionic conduc i i y o
∼
1 mS.cm-1 upon 25% doping wi h Fe3+.
Simila ly, we obse ed ha 10% Ga doping has inc eased he
oom empe a u e ionic conduc i i y o he halide up o 0.44
mS.cm-1, compa ed o 0.103 mS.cm-1 p e iously epo ed o
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dopan - ee LZC.
34
This imp o emen could be a ibu ed o he
induced diso de in he halide s uc u e, as well as he inc eased
Li con en .
Expe imen al sec ion
Ma e ials and syn hesis p ocedu e
The LGZC halide ma e ials we e syn hesized by mixing
s oichiome ic amoun s o LiCl, GaCl
3
, and Z Cl
4
and applying a
so ball-milling p ocess a 600 pm o 8 cycles o 40 minu es,
including 10 minu es o pause a e e e y cycle o p e en
o e hea ing. The c ys al s uc u e and he composi ion o he
syn hesized halide ma e ial we e con i med by synch o on XRD
analysis pe o med a he Alba synch o on. These s uc u al
analyses a e p esen ed in Figu e S.1 and show no aces o he
p ecu so s and a c ys al s uc u e co esponding o he doped
Li
2
Z Cl
6
.
Comme cial Li
6
PS
5
Cl a gy odi es (LPSCl) we e pu chased om
NEI manu ac u ing. The analysis o hei XRD pa e n shown in
Figu e S.2 con i ms he phase pu i y.
The syn hesized halides and comme cial Li
6
PS
5
Cl a gy odi es
we e mixed in a 3:1 a io and we e hand-milled o 5 mins. The
mix u e was p essed a 700 MPa o ob ain dense pelle s wi h 6
mm diame e . Fo he NMR measu emen s, he pelle s we e
c ushed in o powde s o ill he NMR o o . The main pu pose
o he p essing s ep is o ensu e good con ac be ween he
halide and a gy odi e pa icles and acili a e he in e ac ions
and o ma ion o in e phases. To obse e he impac o
empe a u e on he in e acial eac ions, he o o s we e
hea ed a 70°C in a acuum a mosphe e.
All he ma e ials we e handled and p ocessed in an A - illed
glo ebox o a oid mois u e abso p ion and deg ada ion.
Solid S a e NMR
Magic angle spinning nuclea magne ic esonance (MAS NMR)
spec a we e eco ded u ilizing a B uke A ance III 500
spec ome e , a 2.5 mm p obe, and a MAS equency o 20 kHz.
1
H and
6
Li chemical shi s we e e e enced o 0.1 M LiCl aqueous
solu ion.
6
Li 1D NMR spec a we e eco ded using single
exci a ion π/2 pulses o 3 µs and a elaxa ion delay o 30 s. The
1
H 1D NMR spec a we e eco ded by he Hahnecho pulse
sequence in which he π/2 and π pulses a e 2.1 and 4.2 µs, and
he elaxa ion delay was se o 5 seconds. The
6
Li-
6
Li and
7
Li-
7
Li
EXSY NMR expe imen s we e eco ded by s anda d h ee π/2
pulses o 3 and 2.4 µs o
6
Li and
7
Li espec i ely, wi h mixing
ime being se o 256 ms o bo h expe imen s.
Elec ochemical Impedance Spec oscopy (EIS)
The Elec ochemical Impedance spec oscopy (EIS) expe imen s
we e pe o med on a mul ilaye pelle in which LGZC is
sandwiched be ween wo LPSCl laye s and ca bon-coa ed
aluminum disks we e p essed oge he wi h he powde s o
imp o e he in e ace con ac . The esul ing pelle s we e placed
in a Swagelok cell wi h s ainless s eel plunge s wi hou u he
modi ica ion. The impedance measu emen s we e conduc ed
using a Sola on 1260 FRA module, applying a bias ol age o
20 mV om 32 MHz o 10 Hz. Finally, he spec a we e analyzed
using ZView® so wa e om Sc ibne . All impedance spec a
we e eco ded a oom empe a u e. Dis ibu ion o elaxa ion
imes (DRT) analyses we e applied o he eco ded impedance
spec a, using he pyDRT ools in he MATLAB oolbox o esol e
he o e lapping anspo p ocesses in he EIS equency
domain.
35
PyDRT is a Py hon-based g aphic use in e ace (GUI)
based on Bayesian idge eg ession (also known as Tikhono
egula iza ion).
36,37
The sui abili y o he EIS spec a o he DRT
analyses was e i ied by he K ame -K onig alidi y es me hod
using he Lin-KK so wa e de eloped by Ka ls uhe Ins i u e o
Technology (KIT).
38
Resul s and discussion
NMR Cha ac e iza ion o pu e LGZC
In he i s s ep and be o e he cha ac e iza ion o he
composi e elec oly es, he LGZC halides we e analyzed by
solid-s a e NMR. This cha ac e iza ion is conduc ed i s ly o
con i m he absence o seconda y species o e s o age ime,
bu also o use as a e e ence when analyzing he NMR
spec um o he composi e elec oly es. The
6
Li spec um
displayed in Figu e 1.a shows a s ong, na ow signal a
app oxima ely -0.85 ppm, wi h a linewid h o 2.8 Hz,
co esponding o he highly mobile Li-ions in he halide
s uc u e. No ably, a mino shoulde appea s a -0.9 ppm, which
may be a ibu ed o p o ona ed phases o he halide, as
indica ed by measu emen s on an aged halide sample (Figu e
S.3). I is challenging o iden i y hese species solely based on
NMR expe imen s. Howe e , i has been p e iously epo ed
ha Li
3
InCl
6
can u n in o Li
3
InCl
6
.xH
2
O upon exposu e o
mois u e.
39,40
Thus, he o ma ion o a simila compound such
as Li
2.1
G
0.1
Z
0.9
Cl
6
.xH
2
O could be expec ed. The b oade na u e
o his shoulde signal sugges s educed Li
+
mobili y, aligning
wi h his in e p e a ion. Howe e , he low in ensi y o he
shoulde and he na ow linewid h o he main signal imply ha
p o ona ion is minimal, indica ing ha he syn hesized halides
a e in good condi ion. To u he alida e his, he
1
H spec um
o he halide was eco ded and analyzed. As seen in Figu e 1.b,
he
1
H spec um e eals se e al b oad signals. Ye , he low
Figu e 1 a)
6
Li and b)
1
H NMR spec a o LGZC halide elec oly e

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in ensi y o hese signals, despi e he high sensi i i y o NMR o
he
1
H nucleus, con i ms ha p o ona ion is indeed minimal.
Mo eo e , he s a k con as be ween he
1
H spec a o he
esh and aged halide samples p esen ed in Figu e S.4 suppo s
he conclusion ha he syn hesized LGZC powde s a e
adequa ely d y.
I mus be no ed ha high sensi i i y o
1
H -owing o he high
na u al abundance and gy omagne ic a io o
1
H- makes solid-
s a e NMR an excellen ool o moni o ing he p o ona ed
phases. Since he p o ona ed phases migh be amo phous o
oo hin, hey migh no be easily de ec ed by o he
cha ac e iza ion echniques such as powde X- ay Di ac ion
(PXRD). This is simila o he case o LLZO ga ne s whe e
p o ona ed phases a e some imes unde es ima ed due o
inaccu a e ma e ial cha ac e iza ion.
41
This is highly impo an
because he p o ona ed phases o he decomposi ion p oduc s
o he p o ona ion a e known o be undesi able, dec ease he
ionic conduc i i y o he halides, and in gene al, nega i ely
impac hei pe o mance.
39,40
Thus, u he esea ch in o he
p o ona ion and dep o ona ion mechanisms o halide ma e ials
is needed.
NMR Cha ac e iza ion o LPSCl/LGZC Composi es
In he nex s ep, halide/sul ide composi e elec oly es we e
p epa ed by hand milling and p essing, as desc ibed in he
expe imen al sec ion. Subsequen ly, NMR measu emen s we e
conduc ed o in es iga e hei po en ial in e acial eac i i y
along wi h anspo p ope ies o he o med species. In he
6
Li
NMR spec um o he composi e, shown in Figu e 2, wo se s o
signals a posi i e (1.8 o 0.8 ppm) and nega i e (-0.5 o -1.3
ppm) chemical shi s a e obse ed which a e a ibu ed o he
sul ide and halide phases espec i ely. While he
6
Li signals o
he LPSCl sul ide a 1.5 ppm and i s shoulde a 1.4 ppm a e
simila o i s pu e o m, he less in ense signal a 1.1 ppm only
appea s a he composi e elec oly e, al eady sugges ing he
eac i i y be ween sul ide and halide. This in e phase could be
due o he in e ace eac ions be ween he halide and sul ide,
possibly in ol ing hei decomposi ion. Simila ly, he signal a -
1.1 ppm is also a ibu ed o he p oduc s o halide
decomposi ion, as i was absen in he pu e halide
6
Li spec um,
shown in Figu e 1.
The assignmen o he signals a 1.1 and -1.1 ppm o he
in e acial eac ion p oduc s was u he alida ed by hea ing
he samples o e nigh and subsequen ly epea ing he NMR
measu emen s. The hea ing is expec ed o acili a e he
eac ions be ween he LGZC and LPSCl, inc easing he eac ion
p oduc s. Indeed, he e olu ion o he
6
Li NMR spec a
demons a ed in Figu e 3 e eals a ma ked inc ease in he
in ensi y o he Li signals a 1.1 and -1.1 ppm a e hea ing,
con i ming ha hese signals a e di ec ly co ela ed wi h he
ex en o he in e acial eac ions. Addi ionally, his inc ease in
signal in ensi y is accompanied by a co esponding dec ease in
he in ensi y o he Li signals a 1.4 and -0.85 ppm, indica ing
ha he obse ed eac ions in ol e he decomposi ion o bo h
he halide and sul ide phases. This spec um e olu ion p o ides
s ong e idence o he chemical eac ions occu ing a he
in e ace and highligh s he dynamic na u e o he in e phase as
he eac ion p og esses.
As shown in Figu e S.5, his spec um e olu ion was also
accompanied by an inc ease in he
7
Li T
1
elaxa ion ime. This
indica es ha he in e phase species ha e slowe local Li
dynamics compa ed o he main a gy odi e and halide phases.
Thus, hese eac ions a e expec ed o be de imen al o he
composi e elec oly e's pe o mance, and hey mus be
minimized.
Figu e 2
6
Li NMR spec um o LPSCl/LGZC composi e elec oly e. Figu e 3
6
Li spec um o p is ine and hea - ea ed LPSCl-LGZC composi e.
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EIS and DRT analysis
To be e unde s and he impac o his eac i i y on he cell
pe o mance, EIS expe imen s we e conduc ed and he
e olu ion o he impedance spec a wi h ime was moni o ed.
As demons a ed in Figu e 4, he esis ance o he mul ilaye
elec oly e wi h blocking elec odes inc eases wi h ime bu
eaches s abili y in less han 9 hou s. This inc ease in esis ance
can be a ibu ed o he ins abili y o he wo phases and he
o ma ion o less conduc i e phases h ough in e acial
eac ions be ween he LGZC and LPSCl, as was sugges ed by
NMR esul s. Since he NMR expe imen s e ealed he impac
o high empe a u es on he in e acial eac ions be ween LPSCl
and LGZC, he mul ilaye pelle s we e hea ed a 70°C o 64
hou s and e u ned o oom empe a u e o impedance
measu emen s. The esul s show a signi ican inc ease in he
cell impedance, implying in e acial eac ions and
decomposi ion o highly conduc i e halide and sul ide phases.
This can be u he alida ed by he dis ibu ion o elaxa ion
imes (DRT) analysis (Figu e 4.b) which shows di e en ion
dynamics and hei co esponding imescale. In he DRT
spec um o he mul ilaye pelle s, 3 main esis i e p ocesses
a e obse ed labeled as R1, R2, and R3, which a e ypically
assigned o ion anspo a bulk, g ain bounda ies, and
passi a ion laye /elec oly e in e ace espec i ely.
42,43
Compa ing he DRT spec a a 0.5 and 18 h e eals a mino
inc ease in he esis ance o he medium- equency R3 p ocess
(1-6 kHz) while he high- equency R1 peak (5-13 MHz) exhibi s
almos no change du ing his pe iod. In con as , a e hea ing,
he DRT spec um shows a clea change in he high- equency
egion and a shi o he R1 peak o lowe equencies. This shi
sugges s a deg ada ion in he bulk ion anspo p ope ies,
consis en wi h he pa ial decomposi ion o he highly
conduc ing halide and sul ide phases, as con i med by NMR
analysis. Mo eo e , he subs an ial inc ease in esis ance a
low- equency R3 a e hea ing can be explained by he
o ma ion o decomposi ion p oduc s a he in e phase, which
exhibi slowe ion dynamics. These obse a ions con i m ha
highe empe a u es acili a e he in e acial eac ions be ween
LPSCl and LGZC, leading o he o ma ion o seconda y phases
wi h slowe dynamics, as p e iously sugges ed by NMR.
Figu e 5 a)
6
Li-
6
Li and b)
7
Li-
7
Li EXSY NMR spec a o LPSCl-LGZC composi e
elec oly es
Figu e 4 a) Nyquis plo and b) DRT analysis o LPSCl/LGZC composi e
elec oly es and hei e olu ion wi h ime and empe a u e
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Finally, while i migh seem ha hese eac ions ha e less
impac on he R2 peak, wi h ca e ul analysis, an inc ease in he
in ensi y o his peak a e hea ing is obse ed. Again, his is
explained by he decomposi ion o he main phase, nega i ely
a ec ing he ion anspo in g ain bounda ies. O e all, he DRT
and EIS analyses align well wi h he NMR indings, p o iding a
comp ehensi e pic u e o he in e acial deg ada ion and he
esul ing impac on ion anspo p ocesses.
In e acial Li Exchange
In he nex s ep, he ole o hese species in he in e acial Li
exchange be ween he wo phases is in es iga ed by EXchange
Spec oscopY (EXSY) expe imen s, p esen ed in Figu e 5. This
wo-dimensional NMR expe imen allows o obse ing he
magne iza ion ans e be ween wo di e en si es wi hin a
limi ed pe iod, called mixing ime. The double Fou ie
ans o ma ion gene a es a 2D g aph ypically demons a ed
wi h con ou le els. The signals appea ing on he diagonal line
co espond o he Li ions ha emained in hei ini ial
en i onmen . In con as , he o -diagonal signals, also called
c oss-peaks, ep esen he Li ions ha ha e exchanged hei
en i onmen . I he in e phase species blocked he in e acial
ion exchange be ween he halide and a gy odi e, no c oss-peak
could be obse ed. Simila ly, i he exchange is oo slow and i s
ime cons an is longe han he mixing ime, no exchange
would be isible.
The esul s om ou 6Li-6Li EXSY measu emen s demons a ed
in Figu e 5.a show clea exchange be ween he a gy odi e
signals (1.1 and 0.8 ppm) and he main halide signal (-0.85 ppm).
Addi ionally, a weak c oss-peak be ween he wo halide signals
a -0.85 and -1.1 ppm is obse ed. In heo y, c oss-peaks migh
also appea due o spin di usion be ween wo neighbo ing
nuclei, a phenomenon ha s ongly depends on he
in e nuclea dis ance. Howe e , conside ing he na u al
abundance o he 6Li (a ound 7%), he spin di usion be ween
wo neighbo ing 6Li is a he unlikely and canno cause such
clea signals. Thus, he obse ed c oss-peaks unambiguously
ep esen he physical exchange be ween he halide and
a gy odi e. This implies ha e en i he in e phase species ha e
slowe dynamics, hey a e no blocking he Li-ion exchange
be ween he halide and sul ides. To be e obse e he
exchange be ween he mino phases, i.e. decomposed sul ide
(1.1 ppm) and decomposed halide (-1.1 ppm), 7Li-7Li
expe imen s (Figu e 5.b) we e conduc ed. Thanks o he highe
na u al abundance and gy omagne ic a io o 7Li, his
expe imen o e s a highe signal in ensi y, al hough his comes
a he cos o dec eased esolu ion. Despi e he a he low
in ensi y o he c oss-peak signals, he esul s show an exchange
be ween decomposed a gy odi e (1.1 ppm) and decomposed
halide (-1.1 ppm). Combining his obse a ion wi h
he p e iously men ioned exchanges be ween he es o he
signals, i can be concluded ha hese mino species indeed
pa icipa e in he complex ion dynamics o he sys em. This
con as s wi h he LPSCl and PEO-LiTFSI composi e, in which he
decomposi ion p oduc s a he in e phase we e ound o
impede he in e acial exchange.29
This in e acial Li exchange and i s a e a e o high impo ance,
as hey can impac and con ol he ion anspo mechanism a
a la ge scale. Fo ins ance, in a halide-a gy odi e mul ilaye
se up, i his exchange does no occu as enough, he
in e phase could be he bo leneck o he ion anspo , and
he o e all ionic conduc i i y o he cell is comp omised.
Concluding Rema ks
In his s udy i was shown ha LGZC and LPSCl a e chemically
incompa ible, d i ing o wa d an in e acial eac ion ha causes
hei pa ial decomposi ion in o less conduc i e phases. While
p ecise iden i ica ion o hese decomposi ion p oduc s emains
challenging and equi es u he in es iga ion, i was shown
ha hese p oduc s a e de imen al o cell pe o mance and
dec ease he ionic conduc i i y o he cells. Bo h NMR and
Impedance spec oscopy e ealed ha despi e hei
occu ence, hese in e acial eac ions s abilize a he apidly.
Ne e heless, he eac ions may con inue o p og ess a highe
empe a u es, indica ing ha he mal condi ions could
exace ba e in e acial deg ada ion. In addi ion, using EXSY NMR
expe imen s, he in e acial Li+ exchange be ween LGZC and
LPSCl was obse ed. I was shown ha his exchange, which is
essen ial o as ion anspo h ough he in e phase, di ec ly
in ol es he decomposed phases p esen a he in e phase.
I mus be emphasized ha his s udy in composi e design
in ol ing hea ing highligh s he in e acial eac ions o a be e
undamen al unde s anding o he sys em. In a bilaye design
which is he se up o choice in p ac ical applica ions, he con ac
a ea be ween he phases is conside ably smalle , hus he
ex en o hese eac ions is expec ed o be lowe .
Finally, while he esul s p esen ed in his wo k con i m he
in e acial eac ions be ween he LGZC and LPSCl solid
elec oly es, i mus be no ed ha he in e ac ions be ween
halides and a gy odi es highly depend on hei chemis ies and
hese conclusions canno be ex ended o he whole amily o
halides wi h di e en chemical composi ions. Howe e , he
me hods used in his s udy can be applied o o he sys ems wi h
ela i e ease o de e mine he compa ibili y o di e en halides
and a gy odi es.
Au ho con ibu ions
PG: in es iga ion, o mal analysis, w i ing-o iginal d a , and w i ing-
e iew & edi ing. AP: in es iga ion and w i ing- e iew & edi ing. KG:
in es iga ion. PL: w i ing- e iew & edi ing. JL: in es iga ion,
supe ision, and w i ing- e iew & edi ing.
Con lic s o in e es
The au ho s decla e ha hey ha e no known compe ing
inancial in e es s o pe sonal ela ionships ha could ha e
appea ed o in luence he wo k epo ed in his pape .
Jou nal Name ARTICLE
This jou nal is © The Royal Socie y o Chemis y 20xx J. Name., 2013, 00, 1-3 | 7
Please do no adjus ma gins
Please do no adjus ma gins
Da a a ailabili y
The da a ha suppo he indings o his s udy a e a ailable on
eques om he co esponding au ho .
Acknowledgmen s
As a pa o he DESTINY PhD p og amme, his publica ion is
acknowledged by unding om he Eu opean Union's
Ho izon2020 esea ch and inno a ion p og amme unde he
Ma ie Skłodowska-Cu ie Ac ions COFUND (G an Ag eemen
#945357). These expe imen s we e pe o med a BL04-MSPD
beamline a ALBA Synch o on wi h he collabo a ion o ALBA
s a . This p ojec has ecei ed unding om he Eu opean
Union’s Ho izon 2020 esea ch and inno a ion p og am unde
g an ag eemen No 101069726 (SEATBELT P ojec ).
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