Ceramic-Rich Composite Separators for High-Voltage Solid-State Batteries

Academic Edi o : Hao Liu
Recei ed: 19 Decembe 2024
Re ised: 14 Janua y 2025
Accep ed: 16 Janua y 2025
Published: 21 Janua y 2025
Ci a ion: Va appa a, K.;
Fins e busch, M.; Fa akho a-Rohl ing,
D.; U dampille a, I.; K asha, A.
Ce amic-Rich Composi e Sepa a o s
o High-Vol age Solid-S a e Ba e ies.
Ba e ies 2025,11, 42. h ps://doi.o g/
10.3390/ba e ies11020042
Copy igh : © 2025 by he au ho s.
Licensee MDPI, Basel, Swi ze land.
This a icle is an open access a icle
dis ibu ed unde he e ms and
condi ions o he C ea i e Commons
A ibu ion (CC BY) license
(h ps://c ea i ecommons.o g/
licenses/by/4.0/).
A icle
Ce amic-Rich Composi e Sepa a o s o High-Vol age
Solid-S a e Ba e ies
Ke in Va appa a 1,2,3 , Ma in Fins e busch 4, Dina Fa akho a-Rohl ing 2,3,4 , Idoia U dampille a 1
and And iy K asha 1,2,*
1CIDETEC, Basque Resea ch and Technology Alliance (BRTA), P. Mi amón 196,
20014 Donos ia-San Sebas ián, Spain; [email p o ec ed] (K.V.); [email p o ec ed] (I.U.)
2ALISTORE-Eu opean Resea ch Ins i u e, FR CNRS 3104, Hub de I’Ene gie, 15 Rue Baudelocque,
80039 Amiens, F ance; [email p o ec ed]
3
Facul y o Enginee ing and Cen e o Nanoin eg a ion Duisbu g-Essen CENIDE, Uni e si ä Duisbu g-Essen,
Lo ha s aße 1, 47057 Duisbu g, Ge many
4Ins i u e o Ene gy Ma e ials and De ices (IMD-2): Ma e ials Syn hesis and P ocessing, Fo schungszen um
Jülich GmbH, Wilhelm-Johnen-S aße, 52428 Jülich, Ge many; [email p o ec ed]
*Co espondence: [email p o ec ed]
Abs ac : Composi e solid elec oly es a e gaining in e es ega ding hei use in Li-me al
solid-s a e ba e ies. Al hough high ce amic con en imp o es he elec ochemical s a-
bili y o ce amic- ich composi e sepa a o s (C-SCE), he polyme ic ma ix also plays a
i al ole. In he i s gene a ion o C-SCE sepa a o s wi h a PEO-based ma ix, he ad-
di ion o 90–95 w % o Li
6.45
Al
0.05
La
3
Z
1.6
Ta
0.4
O
12
(LLZO) does no make C-SCE s able
o cell cycling wi h high- ol age (HV) ca hodes. Fo he nex i e a ion, he objec i e
was o ind an HV-s able polyme ic ma ix o C-SCEs. He ein, we epo esul s on
op imizing C-SCE sepa a o s wi h di e en ce amics and polyme s which can c a he
sys em owa ds be e s abili y wi h NMC622-based composi e ca hodes. Bo h LLZO and
Li
1.3
Al
0.3
Ti
1.7
(PO
4
)
3
(LATP) we e u ilized as ce amic componen s in C-SCE sepa a o s.
Poly(diallyldime hylammonium) bis( i luo ome hanesul onyl)imide (PDDA-TFSI) and
poly ( inylidene luo ide-co-hexa luo op opylene) (PVDF-HFP) we e used as polyme s in
he “polyme /LiTFSI/plas icize ”-based ma ix. The ini ial phase o he selec ion c i e ia
o he sepa a o ma ix in ol ed assessing mechanical s abili y and ionic conduc i i y.
Two op imized sepa a o o mula ions we e hen es ed o hei elec ochemical s abili y
wi h bo h Li me al and HV composi e ca hodes. The esul s showed ha Li/NMC622 cells
wi h LP70_PVDF_HFP and LZ70_PDDA-TFSI sepa a o s exhibi ed mo e s able cycling
pe o mance compa ed o hose wi h LZ90_PEO300k-based sepa a o s.
Keywo ds: solid-s a e elec oly e; solid-s a e ba e y; ce amic- ich composi e sepa a o ;
high ol age; composi e elec oly e
1. In oduc ion
Wi h he comme cializa ion o li hium-ion ba e ies (LIB) aking place in 1990s by
SONY Co po a ion, LIBs ha e been seen as he u u e o ene gy s o age [
1
,
2
]. The inc eased
in e es and awa eness o mo e en i onmen - iendly ene gy p oduc ion and s o age and
he boom in elec ic ehicles and sma g ids has led o de elopmen o nex -gene a ion
ba e ies [
2
,
3
]. Simila o o he ields, concu en esea ch is ongoing on u u e echnologies
such as de elopmen o solid-s a e ba e ies (SSB) [
4
,
5
], di e en cell designs such as
anode- ee ba e ies [6,7], o he conduc ing-ion sys ems such as sodium ion [8], e c.
Ba e ies 2025,11, 42 h ps://doi.o g/10.3390/ba e ies11020042
Ba e ies 2025,11, 42 2 o 24
Among upcoming echnologies, SSB ha e ga ne ed he mos in e es ecen ly [
9
]
and a e being in ensi ely esea ched o ad ance echnology in he ene gy s o age ield.
SSB looks a e ising LIB cell echnology in e ms o sa e y, accessible g a ime ic and
olume ic ene gy densi y, assembly p ocedu es, ope a ional condi ions such as p essu e,
e c. [
10
]. I also changes he en i e o ma o cells wi h espec o he elec oly e compo-
nen s, ansi ioning om LIBs, which consis o wo componen s—po ous sepa a o and
liquid elec oly e (LE)— o SSBs, which consis o a single componen —a solid elec oly e
(SE). Liquid elec oly es ha e se e al ad an ages, bu hey a e o ganic liquids wi h high
lammabili y. The e o e, he eplacemen o LE wi h he mally s able SEs con ibu es o
an inc ease in o e all sa e y in SSB [
11
,
12
]. SSB has also been en isioned o enable he
use o li hium (Li) me al as an anode o access highe he heo e ical capaci y in Li me al
(Q h o 3860 mAh/g) compa ed o ha o g aphi e (Q h o 372 mAh/g) o g aphi e/SiO
x
blends (Q h up o 700 mAh/g) usually used in he con en ional LIBs.
SE a e he co ne s one o making SSBs a comme cial success. Some o he equi e-
men s o make hem an a ac i e op ion a e as ollows: (i) high ionic conduc i i y,
(ii) mechanical s abili y o esis Li dend i es g ow h, (iii) cos -e ec i e p ecu so s,
(i ) acile p epa a ion, and ( ) wide elec ochemical s abili y window (ESW) [
13
]. The e o e,
i is e y impo an o e ec i ely and sa ely design SEs o achie e he expec ed pe o -
mances o SSBs in e ms o sa e y, longe cycle li e, e c. The classi ica ion o SEs is based
on he majo ma e ial class o hei indi idual cons i uen s. SEs can be classi ied in o wo
majo g oups: (a) solid polyme elec oly e (SPE) and (b) solid ino ganic elec oly e (SIE).
SPEs a e cha ac e ized by o ganic componen s such as polyme s, Li sal s, ionic liquids,
e c., o ming he ma ix. On he o he hand, SIE, as he name sugges s, consis s o Li ion
conduc i e ino ganics, di e en ce amics wi h unique c ys al s uc u es such as ga ne - ype
Li
7
La
3
Z
2
O
12
(LLZO) [
14
], NASICON- ype Li
1.3
Al
0.3
Ti
1.7
(PO
4
)
3
(LATP) [
15
], and sul ides
such as a gy odi e Li
6
PS
5
Cl [
16
] and Li
6
PSCl
5
(LPSCl) [
17
]. Bo h classi ica ions o SEs
di e on all abo e-men ioned p ope ies. SIE and SPE ha e di e en ionic conduc ion
mechanisms [
18
,
19
]. In e ms o he oxida i e elec ochemical s abili y limi o SEs [
20
,
21
],
SIEs such LLZO [
22
] and LATP [
23
] epo ed o ha e s abili y up o 6 V s. Li/Li
+
and
SPE sys ems based on polyme s such as poly( inylidene luo ide-co-hexa luo op opylene)
PVDF-HFP o <5.2 V s. Li/Li
+
[
24
], poly(
ε
-cap olac one) PCL o 4.6 V s. Li/Li
+
[
25
], and
poly(diallyldime hylammonium) PDDA-based o >5 V s. Li/Li
+
[
26
]. Bo h classes o SEs
also di e in hei p epa a ion me hodology and scalabili y, wi h each o hem being on he
opposi e ends o he di icul y scale o p epa a ion.
In he las wo decades, solid composi e elec oly es (SCE) as a class o solid elec-
oly es a e gaining ac ion in he esea ch communi y. The mo i a ion behind his class
o elec oly es is o combine so and lexible polyme ic ma ix om SPE and Li conduc-
i e ce amics om SIE in a singula ma ix o u ilize he ad an ages o bo h g oups o
solid elec oly es. Di e en ypes o SCEs a e classi ied based on he composi ions o
indi idual componen s mixed in he ma ix o SEs. Two popula classi ica ions o SCE
epo ed in he li e a u e a e quasi-solid SCE [
27
] and polyme -ce amic SCE [
28
]. The class
o polyme -ce amic-based SCEs can be u he ca ego ized based on he weigh ac ion
o indi idual componen s: (a) polyme - ich and (b) ce amic- ich (C-SCE). Ou o he
wo ca ego ies, polyme - ich sys ems a e mo e p e alen in he SSB communi y due
o hei ease o handling, adap abili y o polyme ic p ope ies, and o ma ion o be -
e in e aces wi h elec odes [
29
,
30
]. Recen ly, he e has been an inc eased ocus on
explo ing he segmen o composi e elec oly es wi h ce amic dominan ma ices [
31
].
Fo he sake o cla i y, om his poin in he a icle, we e e o elec oly es as “sepa a-
o s”. Fo he pu poses o his s udy in ou HV solid-s a e composi e ca hode, we ha e
conside ed LiNi
0.6
Co
0.2
Mn
0.2
O
2
(NMC622) as ca hode ma e ial. Since he majo i y o
Ba e ies 2025,11, 42 3 o 24
s udies on C-SCEs epo he gal anos a ic cha ge–discha ge (GCD) cycling in cells wi h
LiFePO4-based ca hodes.
In ou p e ious s udy [
32
], we in es iga ed a model composi e sepa a o sys em
comp ising o 90 and 95 w % LLZO in a PEO-LiTFSI ma ix. The LLZO-PEO-LiTFSI-based
model composi e sepa a o s we e assessed o high- ol age (HV) s abili y in Li me al and
NMC622-based solid-s a e cells a 60
◦
C. Howe e , he in es iga ed Li/NMC622 cells
exhibi ed apid discha ge capaci y ading e en wi h a high con en o LLZO in he PEO-
LiTFSI ma ix. The esul was o p io i ize high oxida i e elec ochemical s abili y o
he polyme ic ma ix o he sepa a o o wa an mo e s able capaci y e en ion du ing
long- e m cycling. Thus, he mo i a ion o his wo k was o imp o e he o mula ion o
he polyme ic ma ix, which is essen ial o s able cyclabili y in solid-s a e li hium me al
cells wi h high- ol age ca hodes. Figu e 1depic s he s a egy u ilized o he selec ion o
di e en composi ions.
Ba e ies 2025, 11, x FOR PEER REVIEW 3 o 24
(NMC622) as ca hode ma e ial. Since he majo i y o s udies on C-SCEs epo he gal-
anos a ic cha ge–discha ge (GCD) cycling in cells wi h LiFePO4-based ca hodes.
In ou p e ious s udy [32], we in es iga ed a model composi e sepa a o sys em com-
p ising o 90 and 95 w % LLZO in a PEO-LiTFSI ma ix. The LLZO-PEO-LiTFSI-based
model composi e sepa a o s we e assessed o high- ol age (HV) s abili y in Li me al and
NMC622-based solid-s a e cells a 60 °C. Howe e , he in es iga ed Li/NMC622 cells ex-
hibi ed apid discha ge capaci y ading e en wi h a high con en o LLZO in he PEO-
LiTFSI ma ix. The esul was o p io i ize high oxida i e elec ochemical s abili y o he
polyme ic ma ix o he sepa a o o wa an mo e s able capaci y e en ion du ing long-
e m cycling. Thus, he mo i a ion o his wo k was o imp o e he o mula ion o he
polyme ic ma ix, which is essen ial o s able cyclabili y in solid-s a e li hium me al cells
wi h high- ol age ca hodes. Figu e 1 depic s he s a egy u ilized o he selec ion o di -
e en composi ions.
Figu e 1. Schema ic desc ip ion o s a egy employed o de elopmen o high- ol age s able ce-
amic- ich solid sepa a o s. No e: abb e ia ions used in he scheme: LLZO—
Li6.45Al0.05La3Z 1.6Ta0.4O12, LATP—Li1.3Al0.3Ti1.7(PO4)3, PVDF-HFP—poly ( inylidene luo ide-co-hex-
a luo op opylene), PDDA-TFSI—poly(diallyldime hylammonium)bis( i luo ome hanesul-
onyl)imide, PBA—poly (1,4-bu ylene adipa e), LiTFSI—li hium bis( i luo ome hanesul onyl)im-
ide, PYR14TFSI—1-bu yl-1-me hylpy olidinium bis( i luo ome hanesul onyl)imide, and SCN—
succinoni ile.
He ein, we epo he in luence o change in o mula ion om he e e ence LLZO-
PEO-LiTFSI sepa a o on physical–chemical and elec ochemical p ope ies including
ionic conduc i i y and long- e m cycling pe o mance in Li/NMC622 cell o C-SCE sepa-
a o s. C-SCE sepa a o s wi h diffe en weigh ac ions o ino ganic (70, 80, and 90 w %)
and o ganic componen s (30, 20, and 10 w %) we e p epa ed and es ed. LLZO and LATP
we e selec ed as he Li-ion conduc i e ino ganic ce amics due o hei con ibu ions o
high mechanical ionic conduc i i y and elec ochemical s abili y as ille s. In he o ganic
ma ix, h ee epo ed HV-s able polyme s, poly ( inylidene luo ide-co-hexa luo op o-
pylene), poly(diallyldime hylammonium)bis( i luo ome hanesul onyl)imide and poly
Figu e 1. Schema ic desc ip ion o s a egy employed o de elopmen o high- ol age s able ce amic-
ich solid sepa a o s. No e: abb e ia ions used in he scheme: LLZO—Li
6.45
Al
0.05
La
3
Z
1.6
Ta
0.4
O
12
,
LATP—Li
1.3
Al
0.3
Ti
1.7
(PO
4
)
3
, PVDF-HFP—poly ( inylidene luo ide-co-hexa luo op opylene),
PDDA-TFSI—poly(diallyldime hylammonium)bis( i luo ome hanesul onyl)imide, PBA—poly
(1,4-bu ylene adipa e), LiTFSI—li hium bis( i luo ome hanesul onyl)imide, PYR
14
TFSI—1-bu yl-1-
me hylpy olidinium bis( i luo ome hanesul onyl)imide, and SCN—succinoni ile.
He ein, we epo he in luence o change in o mula ion om he e e ence LLZO-
PEO-LiTFSI sepa a o on physical–chemical and elec ochemical p ope ies including ionic
conduc i i y and long- e m cycling pe o mance in Li/NMC622 cell o C-SCE sepa a o s.
C-SCE sepa a o s wi h di e en weigh ac ions o ino ganic (70, 80, and 90 w %) and
o ganic componen s (30, 20, and 10 w %) we e p epa ed and es ed. LLZO and LATP we e
selec ed as he Li-ion conduc i e ino ganic ce amics due o hei con ibu ions o high
mechanical ionic conduc i i y and elec ochemical s abili y as ille s. In he o ganic ma ix,
h ee epo ed HV-s able polyme s, poly ( inylidene luo ide-co-hexa luo op opylene),
poly(diallyldime hylammonium)bis( i luo ome hanesul onyl)imide and poly (1,4-bu ylene
adipa e), we e e alua ed as binding agen s in he ma ix. In polyme ic ma ix, he in lu-
ence o plas icize s such as ionic liquid and plas ic c ys als we e also e alua ed. Li hium
Ba e ies 2025,11, 42 4 o 24
bis( i luo ome hanesul onyl)imide sal was commonly added in all sepa a o composi-
ions. In his s udy, HV beha io o all op imized sepa a o s was es ed in solid-s a e
coin cells wi h Li me al anodes and NMC622-based solid-s a e composi e ca hodes. Thei
e alua ion also included he o ma ion o mechanically s able ilms, ionic conduc i i y,
and s abili y wi h Li me al. The pe o mance o p epa ed sepa a o s was compa ed wi h
GEN 1 e e ence sepa a o s con aining 90 and 95 w % o LLZO in he PEO-LiTFSI ma ix
in es iga ed in ou ea lie wo k [
32
]. This assessmen o e s insigh in o change in he
Li/NMC622 cells cycling s abili y wi h he eplacemen o PEO o mo e elec ochemically
s able polyme s.
2. Ma e ials and Me hods
2.1. Ma e ials
Li
6.45
Al
0.05
La
3
Z
1.6
Ta
0.4
O
12
(abb e ia ed as LLZO) and Li
1.3
Al
0.3
Ti
1.7
(PO
4
)
3
(abb e i-
a ed as LATP) we e syn hesized in-house ia SSR and SASSR ou es, espec i ely. LLZO
powde s we e syn hesized using a modi ied solid-s a e eac ion (SSR) me hod, wi h s oichio-
me ic mixing o p ecu so ma e ials and li hium excess. The p ocess in ol ed calcina ion
a 850
◦
C and 1000
◦
C, ollowed by sin e ing a 1175
◦
C. A e milling and sie ing, he
esul ing powde s we e p epa ed o C-SCE sepa a o applica ions. LATP powde s we e
syn hesized using a solu ion-assis ed solid-s a e eac ion (SASSR) me hod. The p ocess
in ol ed mixing and d ying p ecu so s, ollowed by calcina ion a 600
◦
C and sin e ing a
900
◦
C. The esul ing powde s we e milled, sie ed, and p epa ed o use in C-SCE sepa-
a o s. The de ails o bo h syn hesis me hods wi h he ma e ials used in espec i e hei
syn hesis ha e been discussed in he Suppo ing In o ma ion. The syn hesized ce amic
powde s we e sie ed wi h 25
µ
m sie e (CISA Sie ing Technologies, Ba celona, Spain)
o educe he pa icle size dis ibu ion be o e addi ion o C-SCE p epa a ion p ocedu e.
D50 pa icle sizes o LLZO and LATP used o p epa a ion we e 2
µ
m and 5.1
µ
m, espec-
i ely; mo e pa icle size de ails a e added in Figu e S1e, .
Poly ( inylidene luo ide-co-hexa luo op opylene), abb e ia ed as PVDF-HFP, wi h a
molecula weigh o 400 kg/mol, was pu chased om Sigma-Ald ich (Bu ling on, NJ, USA)
and used as ecei ed. Poly(diallyldime hylammonium)bis( i luo ome hanesul onyl)imide,
abb e ia ed as PDDA-TFSI, wi h a molecula weigh o 300 kg/mol, was pu chased om
Sol ionic (F ance) and used as ecei ed. Poly (1,4-bu ylene adipa e), abb e ia ed as PBA,
wi h a molecula weigh o 12 kg/mol, was pu chased om Sigma Ald ich (Bu ling on,
NJ, USA) and used as ecei ed. Poly (e hylene oxide) abb e ia ed as PEO300k, wi h a
molecula weigh o 300 kg/mol, was pu chased om Sigma Ald ich (Bu ling on, NJ, USA)
and used a e d ying a 55 ◦C unde acuum o 16 h.
Li hium bis( i luo ome hanesul onyl)imide (LiTFSI, 99.9%) was pu chased om
Sol ionic (F ance) and used as ecei ed. 1-Bu yl-1-me hylpy olidinium bis
( i luo ome hanesul onyl)imide (PYR
14
TFSI, 99.9%) was pu chased om Sol ionic
(Toulouse, F ance) and used as ecei ed. Succinoni ile (SN, 99%) was pu chased om
Sigma Ald ich (Bu ling on, NJ, USA) and used as ecei ed. Anhyd ous ace oni ile (ACN,
99.8%), used o he p epa a ion o PDDA-TFSI-based sepa a o and ca hode slu y, was
pu chased om Sigma Ald ich. Ex a-d y ace one (99.8%), used o p epa a ion o PVDF-
HFP-based sepa a o slu y, was pu chased om Fishe Scien i ic (Wal ham, MA, USA).
Ex a-d y dime hyl ca bona e (DMC, 99%), used o p epa a ion o PBA-based sepa a o
slu y, was pu chased om The mo Scien i ic Chemicals (Wal ham, MA, USA).
Single-c ys al NMC622 (comme cial g ade), pu chased om Ta g ay (Ki kland, QC,
Canada), was used as ca hode ac i e ma e ial. Polye hylene oxide wi h molecula weigh
o 400 kg/mol (PEO400k) was pu chased om Sigma Ald ich (Bu ling on, NJ, USA).
Ba e ies 2025,11, 42 5 o 24
Conduc i e ca bon black C-ENERGY Supe C45 was pu chased om IMERYS Ca bon &
G aphi e (Bi onico, Swi ze land) and s o ed a 110 ◦C.
2.2. Sepa a o P epa a ion P ocedu e
C-SCEs in his wo k we e en i ely ab ica ed in a d y oom wi h a dew poin lowe
han
−
45
◦
C). The p epa a ion o ce amic- ich solid composi e sepa a o s ollows he
de ailed p ocedu e al eady epo ed in a p e ious s udy [32].
In he i s s ep o p epa a ion o all sepa a o s, he componen s o o ganic ma ix we e
weighed and mixed wi h espec i e sol en solu ions. The sol en s used o PVDF-HFP,
PBA and PDDA-TFSI-based ma ix we e selec ed as ace one, DMC, and ACN, espec i ely.
All polyme dissolu ions we e mixed o e nigh a 250 pm wi h mechanical mixe (Eu os a
60 digi al, IKA. S au en, Ge many). A e ob aining homogenous solu ion om o e nigh
mixing, ce amic powde s (LLZO and LATP) we e added o he polyme dissolu ion. The
syn hesis p ocedu e o LLZO and LATP is desc ibed in Suppo ing In o ma ion. The
sepa a o slu y was hen mixed o 2 h a 1100 pm. The o mula ions o all sepa a o s
p epa ed in his wo k a e lis ed in Table 1. To e alua e he in luence o change o com-
ponen s in he ma ix, e e ence sepa a o s wi h a PEO-based ma ix we e also p epa ed.
LZ90_PEO300k and LZ90_PEO300k wi h 90 and 95 w % o ce amic in he PEO-LiTFSI
ma ix we e p epa ed using he me hod al eady epo ed in Va appa a e al. [32].
Table 1. Lis o all C-SCEs e alua ed in his s udy wi h physical a ibu es a e pos -p ocessing.
C-SCE
Sample Name
Gene -
a ion o
Sepa a o s
Ce amic O ganic Pos -
P ocessing
Pa ame e s
Physical
Obse a ions
Ce amic
Type
Con en
(w %)
Polyme
Type
Polyme
Con en
(w %)
LiTFSI
Con en
(w %)
Plas icize
Con en
(w %)
Sol en
Used
LZ90_PEO300k *
GEN 1
LLZO 90 PEO
Mw-300
kg/mol 7.5 2.5
0.0
ACN 60 ◦C, 100
ba , 1 min Smoo h su ace
wi h less po es
LZ95_PEO300k * LLZO 95 PEO
Mw-300
kg/mol 3.8 1.2 ACN 60 ◦C, 100
ba , 1 min Smoo h su ace
wi h less po es
LZ70_PDDA-TFSI
GEN 2
LLZO 70 PDDA-TFSI
Mw-300
kg/mol 12 7.5 10.5 ACN 80 ◦C, 10
ba , 30 s Smoo h su ace
wi h less po es
LZ80_PDDA-TFSI LLZO 80 PDDA-TFSI
Mw-300
kg/mol 8 5 7 ACN 80 ◦C, 10
ba , 30 s Rough su ace
wi h less po es
LZ90_PDDA-TFSI LLZO 90 PDDA-TFSI
Mw-300
kg/mol 4 2.5 3.5 ACN 80 ◦C, 10
ba , 30 s Rough su ace
wi h lo o po es
LP70_PVDF-HFP LATP 70 PVDF-HFP
Mw-400
kg/mol 6.9 4.8 18.3
Ace one
80 ◦C, 10
ba , 30 s Smoo h su ace
wi h less po es
LP70_PVDF-HFP
wi hou SCN LATP 70 PVDF-HFP
Mw-400
kg/mol 9 7.5 13.5
Ace one
80 ◦C, 10
ba , 30 s Smoo h su ace
wi h less po es
LZ70_PBA LLZO 70 PBA
Mw-12
kg/mol 24.9 5.1 0.0 DMC 60 ◦C, 10
ba , 30 s
Su ace c acking
a e
pos -p ocessing
LZ80_PBA LLZO 80 PBA
Mw-12
kg/mol 16.6 3.4 0.0 DMC 60 ◦C, 10
ba , 30 s
Su ace c acking
a e
pos -p ocessing
No e: * The sepa a o s ha e been s udied in de ail in ou p e ious s udy [32].
Slu y cas ing was ca ied ou on a Te lon shee ixed on a glass subs a e o PDDA-
TFSI and PBA-based sepa a o s, and di ec ly on glass subs a es o PVDF-HFP-based
sepa a o s. The slu y was cas using a doc o -blade- ype applica o o achie e he equi ed
hickness using quad angula applica o (Nue ek, 60 mm wid h, Eiba , Spain). A e
cas ing, ilms we e le o d y a oom empe a u e in he d y oom and inally acuum
d ied unde ~10 mba a 60
◦
C o 40 h o emo e aces o sol en s om sepa a o s.

Ba e ies 2025,11, 42 6 o 24
A e wa ds, d ied sepa a o s we e subjec ed o pos -p ocessing s eps be o e ca ying ou
a ious cha ac e iza ions. Fo he i s s ep in pos -p ocessing, sepa a o s we e cu in disks
by Ø18.92 mm dies. Then, he sepa a o discs we e ho -p essed (Polys a 200T, Wus e ma k,
Ge many) a he pa ame e s lis ed in Table 1. A e he ho p essing, he sepa a o s we e cu
in o he inal equi ed diame e o 18.2 mm o be assembled in o 2025 coin cells o ca ying
ou a ious elec ochemical cha ac e iza ions wi h he coin cell p epa a ion p ocedu e
epo ed ea lie [32].
2.3. Ca hode P epa a ion P ocedu e
A solid-s a e composi e ca hode was p epa ed wi h e e ence o mula ion o compa a-
i e es ing o he p epa ed C-SCEs. The ca hode slu y was p epa ed using a DISPERMAT
LC30 mechanical mixe in he labo a o y a oom empe a u e. The ca hode o mula ion
consis s o NMC622 as a ca hode ac i e ma e ial (CAM), “PEO400k/PYR14TFSI/LiTFSI” as
a binding ca holy e, and C-ENERGY Supe C45 ca bon black as a ca bon addi i e (CA). The
composi e ca hode wi h ca holy e was p epa ed o imp o e he Li ion conduc ion h ough
he ac i e laye , o enhance plas ici y, and educe in e acial esis ance be ween ca hode
and sepa a o .
The p epa a ion o composi e ca hode also ollows he de ailed p ocedu e al eady
epo ed ea lie [
32
]. The i s s ep in ca hode p epa a ion was he mechanical dissolu ion o
PEO400k (10)-LiTFSI (1)/PYR
14
TFSI ca holy e mix u e (25 w %) o e nigh in ACN sol en
a 250 pm. Nex , CA (5 w %) was added wi h small amoun s o ACN sol en o ackle
slu y iscosi y change. In he inal s ep, NMC622 CAM (70 w %) powde was added in
mul iple se s wi h in e mi en addi ion o ACN sol en o ackle slu y iscosi y change.
The solid- o-sol en a io used in ca hode p epa a ion was 1:1.7. Slu y empe a u e was
main ained o be cons an du ing he en i e p epa a ion p ocess. A e mixing, slu y
was cas ed on o a 22
µ
m hick ca bon coa ed aluminum cu en collec o s (Gelon, Round
Rock, TX, USA) and using doc o -blade d ied in ambien a mosphe e a 55
◦
C o 3 h.
The ca hode shee s we e hen d ied a 55
◦
C o 16 h unde acuum (Memme VO400,
<10 mba ). A e d ying, cas shee s we e calende ed in hyd aulic calende machine
( om DPM Solu ions, Hebb ille, Canada) unde 400 psi a oom empe a u e. A e
calende ing, he ca hode shee was punched in o Ø16.6 mm discs using high-p ecision dies
(El-Cell, Hambu g, Ge many). The inal d ying o he ca hodes we e ca ied ou a 60
◦
C
o 40 h in a acuum o en (Memme VO400, <10 mba ) in he d y oom o p epa e o
2025 coin cell assembly. The a eal loading and densi y o he ca hodes we e calcula ed o be
1.0 ±0.1 mAh/cm2and 2.6 ±0.1 g/cm3, espec i ely.
2.4. Cha ac e iza ion
2.4.1. Physical–Chemical P ope ies
X-Ray di ac ion (XRD) measu emen s o LLZO and LATP powde s we e ca ied ou
using B uke D4 Endea ou wi h Cu-K
α
adia ion and da a was eco ded in he 2
θ
ange
o 10–80 deg ees wi h a scan a e o 0.02 deg ee/min. XRD measu emen s o p epa ed
C-SCEs we e ca ied ou using B uke AXS D8 Ad ance wi h Cu K
α
adia ion and da a was
eco ded in he 2
θ
ange o 10–80 deg ees wi h a scan a e o 0.01 deg ee/min. Su ace and
c oss-sec ional mo phologies o p epa ed C-SCEs we e analyzed using a Scanning Elec on
Mic oscope (SEM)—JEOL JSM-5500LV. Sample p epa a ion o SEM imaging included
moun ing o sepa a o agmen s using ca bon ape on Al pin-moun s and Au spu e -
coa ing (60 mA, 50 s, 1 mba ). Fo c oss-sec ional imaging, pos -p ocessed sepa a o s
we e imme sed in liquid N
2
and agmen ed o e eal c oss-sec ion o sepa a o s. The
pa icle size dis ibu ion (PSD) o LLZO powde (a e syn hesis and a e sie ing) was
ca ied ou using a lase -di ac ion-based Mas e size 3000 om Mal e n Ins umen s L d.
Ba e ies 2025,11, 42 7 o 24
(Wo ces e shi e, UK) wi h a Hyd o-EV we powde dispe sion a achmen . The PSD a
di e en olume dis ibu ions was calcula ed using Mas e size 3000 so wa e ( 3.40) om
he acqui ed ligh sca e ing pa e n using Mie and F aunho e heo y. The pa icle sizes
we e epo ed a 10% (D 10), 50% (D 50), and 90% (D 90) o he powde olume. The
measu emen s o each powde we e ca ied ou in quin uplica e. TGA measu emen s
we e eco ded unde ai a mosphe e om 40 ◦C o 600 ◦C a a hea ing a e o 10 ◦C/min.
2.4.2. Elec ochemical P ope ies
Ionic conduc i i y (
σ
) o ab ica ed sepa a o s was measu ed in symme ic cells wi h
s ainless s eel (SS) elec odes. Elec ochemical Impedance Spec oscopy (EIS) measu e-
men s we e pe o med using a 1455 FRA in e ace coupled wi h 1470E po en ios a (So-
la on Analy ical, UK). A sinusoidal signal wi h an ampli ude o 10 mV was applied in a
1 MHz–0.1 Hz equency ange. The coin cell was ini ially hea ed up o 80
◦
C and held a
he empe a u e o 2 h o comple ely emo e he mal o p ocessing his o y o he sample.
EIS measu emen s we e ca ied ou while cooling om 80
◦
C o 30
◦
C a a 10
◦
C in e al,
wi h cells s abilized a each empe a u e o 90 min. The ZView so wa e 3.5e (Sc ibne ,
Sou he n Pines, NC, USA) was used o i ob ained impedance spec a o equi alen ci cui
model (ECM).
All Li/Li and Li/NMC cells we e cycled a 60
◦
C using BaSyTec cell es ing sys em
(Ge many). Symme ic Li/Li cells we e also assembled and es ed o de e mining c i -
ical cu en densi y (CCD) alues and s udying long- e m cycling beha io o C-SCE
sepa a o s. Fo CCD measu emen s, Li/Li symme ic cells wi h C-SCE sepa a o s we e
cycled wi h 1 h s ep a di e en cu en densi y alues: 0.01, 0.02, 0.05, 0.10, 0.25, 0.50, 0.75,
1.00, 1.25, 1.50, 1.75, and 2.00 mA/cm
2
. Long- e m cycling o Li/Li symme ic cells we e
assessed a cu en densi y o 0.1 mA/cm2.
An elec ochemical loa ing es o “Li/sepa a o /NMC622” coin cells was pe o med
a 60
◦
C o assess he elec ochemical s abili y o he Li/NMC622 sys em assembled wi h
in es iga ed sepa a o s. The “Li/sepa a o /NMC622” cells we e ini ially cha ged o 4.2 V
a 0.05C. They we e p og ammed o be in cons an ol age (CV) mode om 4.2 V o 5.0 V,
a inc emen s o 0.1 V, and main ained a each ol age alue o 1 h wi h he cu en being
moni o ed. Gal anos a ic cha ge–discha ge cycling o assess discha ge C- a e pe o mance
and long- e m cycling s abili y o he Li/NMC622 cells wi h in es iga ed sepa a o s was
ca ied ou . The discha ge C- a e pe o mance es was ca ied ou a di e en discha ge
C- a es o 0.1C, 0.2C, 0.33C, 0.5C, 1C, and 2C. Howe e , he cha ging C- a e was kep
cons an a 0.05C. A e each a e es , cells unde go a eco e y cycle wi h a C- a e o
0.05C/0.1C. Long- e m cycling p o ocol o Li/NMC622-based solid-s a e coin cells was
selec ed as 0.05C o cha ge and 0.1C o discha ge wi hin he ol age ange o 3.0–4.3 V.
No ewo hy, as pa o es ing condi ions, no addi ional p essu e o he han coin cell
sp ing was applied du ing es ing o SS/SS, Li/Li and Li/NMC622 cells.
3. Resul s and Discussion
The o mula ion o ce amic- ich composi e sepa a o s plays an impo an ole in
de e mining he o e all pe o mance o SSB sys em. Di e en ac o s need o be consid-
e ed while selec ing componen s and composi ions o sepa a o s o SSBs. Some o he
ac o s men ioned abo e include mechanical s abili y, chemical s abili y be ween sepa a o
componen s, high oxida i e s abili y e sus high- ol age ca hode ma e ials, abili y o o m
s able in e ace wi h elec odes, e c. P e iously, we epo ed [
32
] ha ce amic- ich sepa-
a o s o med mechanically s able ilm and had s able in e ace wi h Li me al; howe e ,
he small con en o PEO in he ma ix con ibu ed o uns able long- e m cycling. The ob-
se ed lack o s abili y was due o a apid dec ease in discha ge capaci y du ing cycling a
Ba e ies 2025,11, 42 8 o 24
60
◦
C. Consequen ly, he selec ion o polyme ic hos s o unc ion as ma ix o C-SCEs was
pe o med based on hei elec ochemical s abili y du ing cycling in cells wi h high cha ge
cu -o ol ages.
3.1. Op imiza ion o Composi e Sepa a o Fo mula ion
The pu pose o his wo k is o add ess he high- ol age s abili y issues o LLZO-PEO-
LiTFSI-based GEN-1 C-SCEs [
32
]. To imp o e he elec ochemical pe o mance, he ini ial
a emp s made we e o eplace he PEO-based ma ix wi h a PVDF-HFP-based ma ix,
main aining he same con en o LLZO in he sys em. Howe e , i was obse ed ha
he p epa ed C-SCE would be discolo ed. I has been epo ed ha mixing LLZO wi h
PVDF-HFP causes discolo a ion o he sepa a o ma ix due o dehyd o luo ina ion o
PVDF-HFP which could a ec he long- e m cycling pe o mance in cells [33].
In his wo k, we elabo a ed on he ab ica ion and e alua ion o C-SCEs combining
di e en ypes o Li-ion conduc i e ce amic powde s and polyme ic ma ices. The il e ing
and op imiza ion p ocess o a ious sepa a o composi ions was ca ied ou based on hei
physical s abili y, mic os uc u e, and ionic conduc i i y. Fo op imizing he composi ion
o C-SCEs, a ious ials we e ca ied ou wi h di e en polyme -based o ganic ma ices
which a e lis ed in Table 1. The p epa a ion me hodology o all C-SCE composi ions was
kep analogous, as desc ibed in Sec ion 2.2. Howe e , one o he key di e ences in he
p epa a ion p ocedu e be ween he ab ica ed C-SCEs is he usage o di e en empe a u es
while ca ying ou pos -p ocessing s eps.
3.1.1. Mic os uc u al Analysis
The homogenized C-SCE slu ies consis ing o ce amic powde s and componen s
o polyme ic ma ix a e mechanical mixing we e cas on di e en subs a es, including
o PVDF-HFP-based sys ems and Te lon shee s o PDDA-TFSI and PBA-based sys ems.
The sepa a o memb anes we e d ied a 60
◦
C in a acuum o en o emo e any em-
nan s o sol en s. A e d ying, sepa a o memb anes in he o m o disks we e subjec ed
o pos -p ocessing condi ions, as ma ked in Table 1, o ob ain lexible and mechanically
s able sepa a o s. The ho p ess s ep, as pa o pos -p ocessing o all sepa a o s, has
been epo ed [
32
,
34
,
35
] o imp o e su ace mo phology, ela i e densi y, and he ionic
conduc i i y o SEs. Se e al ials we e ca ied ou o inalize he ho -p essing pa ame-
e s o he GEN 2 sepa a o s. The pa icle size con ol o bo h LLZO and LATP plays
an impo an ole in he o e all quali y o he sepa a o s. The sie ing o ce amic pow-
de s be o e hei addi ion o he sepa a o slu y plays an impo an ole du ing cas ing
o memb anes wi h homogenous mic os uc u e. Bo h LLZO and LATP powde s had
D90 alues o <25
µ
m (de ails on size and dis ibu ion a e a ailable in Suppo ing In o ma-
ion as Figu e S3).
The op imiza ion p ocess o sepa a o o mula ion o GEN 2 o C-SCEs consis ed
o a selec ion o polyme -based ma ix and sui able ce amic powde s o he ma ix. The
op imiza ion o he polyme ic ma ix included he selec ion o binding polyme , compa ible
plas icize s, and li hium sal . Wi h PVDF-HFP as he hos , wo di e en polyme ic ma ices
we e e alua ed. The i s combina ion o PVDF-HFP-based sepa a o ma ix consis ed o
PYR
14
TFSI and SCN as plas icize s and LiTFSI as Li sal . PYR
14
TFSI [
36
,
37
] and SCN [
38
,
39
]
we e chosen due o hei epo ed con ibu ions o imp o ing ionic conduc i i y, ion
mobili y, and elec ochemical pe o mance in solid polyme elec oly e sys ems. The
second combina ion consis ed o only PYR
14
TFSI as plas icizing agen and LiTFSI as he Li
sal . The wo ma ix combina ions we e e alua ed o unde s and he in luence o SCN on
he o e all pe o mance o PVDF-HFP-based C-SCEs. PDDA-TFSI-based sepa a o ma ix
consis ed o PYR
14
TFSI as plas icize along wi h LiTFSI as Li sal . The PBA-based sepa a o
Ba e ies 2025,11, 42 9 o 24
ma ix consis s o LiTFSI as Li sal , wi hou any plas icize s, due o he low molecula
weigh o PBA compa ed o ha o PVDF-HFP and PDDA-TFSI.
The second pa o he ma e ial selec ion p ocess was he choice o ce amic powde s in
C-SCEs, depending on hei p ocessing iabili y o o m s able and sel -s anding ilms. Fo
PVDF-HFP-based C-SCEs as esul o he dehyd o luo ina ion eac ion, LLZO was eplaced
by LATP. Sepa a o s p epa ed wi h 80 and 90 w % o LATP we e obse ed o ha e p oblems
in o ming sel -s anding sepa a o s due a lack o binding in LATP pa icles which leads o
deg ada ion o con ac wi h elec odes and inc eases in e acial esis ance du ing cycling.
In he PDDA-TFSI-based ma ix, he selec ion o LLZO con en was mo e lexible wi h
70 w % (LZ70_PDDA-TFSI), 80 w % (LZ80_PDDA-TFSI), and 90 w % (LZ90_PDDA-TFSI)
o LLZO powde s. Simila ly o PBA-based ma ix, LLZO was selec ed as he ce amic
componen wi h con en o 70 w % (LZ70_PBA) and 80 w % (LZ80_PBA).
Sel -s anding and mechanically s able sepa a o s we e ab ica ed wi h hickness be-
ween 100–250
µ
m wi h bo h LLZO and LATP as ce amic ille s and di e en polyme -based
ma ices. The di e en ma e ial conside a ions du ing he op imiza ion p ocess we e use ul
in p epa ing GEN 2 sepa a o s wi h PVDF-HFP-based, PDDA-TFSI-based, and PBA-based
ma ices. The p epa ed C-SCE sepa a o s we e labeled in Table 1acco ding o he ce amic
con en and polyme used in he ma ix, e.g., sample LP70_PVDF-HFP con ains 70 w %
sie ed LATP powde and PVDF-HFP as he polyme in he ma ix. The mechanical s abili y
o he sepa a o s was highly dependen on he o mula ions and he indi idual componen s
in he ma ix. Fo example, du ing ials o p epa ing PDDA-TFSI-based sepa a o s, i was
obse ed ha he addi ion o SCN o sepa a o ma ix had nega i e e ec on he s abili y o
sepa a o ilm. Howe e , he applica ions o addi ional s uc u al s abiliza ion echniques
such c oss-linking [
40
,
41
] and in-si u polyme iza ion [
42
,
43
] o he polyme ic ma ix was
ou o scope in his wo k.
A scanning elec on mic oscope (SEM) was used o e alua e he mic os uc u e o
he p epa ed sepa a o s. Figu es 2and S3 show he c oss-sec ional and su ace SEM mi-
c og aphs o all C-SCE sepa a o s. Mic og aphs o he c oss-sec ion (Figu e 2a,b) and
su ace (Figu e S3a,b) o PEO-based sepa a o s [
32
] we e compa ed wi h he mic os uc u e
and mo phology o all o he C-SCE sepa a o s. The mic os uc u e o bo h PVDF-HFP-
and PDDA-TFSI-based sepa a o s wi h 70 w % o ce amic powde s (LP70_PVDF-HFP,
LP70_PVDF-HFP wi hou SCN and LZ70_PDDA-TFSI) a e shown in Figu e 2c, ,g, espec-
i ely. Upon compa ison wi h e e ence sepa a o s, LZ70_PDDA-TFSI in Figu e 2g is
seen o ha e a simila mic os uc u e o ha o LZ90_PEO300k sepa a o . The inc ease
o polyme ic con en in he LZ70_PDDA-TFSI ma ix helped he imp o ed coa ing o
LLZO pa icles along wi h educ ion o isible po es in he mic os uc u e. On he o he
hand, bo h LP70_PVDF-HFP and LP70_PVDF-HFP wi hou SCN a e obse ed o ha e
mic os uc u es like LZ95_PEO300k. This could be a ibu ed o hei inc eased olume
ac ion o ce amic pa icles compa ed o ha o LLZO-based LZ70_PDDA-TFSI sepa a-
o . None heless, all h ee sepa a o s we e seen o ha e dense mic os uc u e wi h no
isible po es.
Ba e ies 2025,11, 42 16 o 24
189.1 mAh/g, and LZ70_PDDA-TFSI—145.2 mAh/g, espec i ely. The capaci y ade o
cells wi h LZ90_PEO300k is e y as as epo ed ea lie [
32
], and as seen in he ol age
e sus capaci y plo in Figu e 7d. In he case o Li/NMC622 cells wi h GEN 2 sepa a o s,
we obse ed a much slowe capaci y ade compa ed o ha o cells wi h LZ90_PEO300k.
LP70_PVDF-HFP-based Li/NMC622 cells exhibi ed he highes alues in bo h discha ge
capaci y and coulombic e iciencies wi h LZ90_PEO300k-based cells ollowing closely be-
hind. The cells wi h LZ70_PDDA-TFSI showed lowe ini ial discha ge capaci y, bu o e
nex ew cycles he discha ge capaci y and he Coulombic e iciency alues inc eased o
he maximum alues o 155.3 mAh/g in he 3 d cycle. The slow inc ease in he discha ge
capaci y o cells wi h LZ70_PDDA-TFSI could be a ibu ed o he need o ac i a ion o
he “Li/sepa a o /NMC622” s ack.
Ba e ies 2025, 11, x FOR PEER REVIEW 16 o 24
Figu e 7. (a) Discha ge capaci y and (b) coulombic efficiency e sus cycle numbe o Li/NMC622
cells wi h all in es iga ed sepa a o s. (c) A e age ol age o bo h cha ge and discha ge s ep o
Li/NMC622 cells wi h diffe en sepa a o s. Vol age e sus capaci y cu es o Li/NMC622 cells wi h
GEN 1 and GEN 2 sepa a o s a e long- e m gal anos a ic cycling (d) LZ90_PEO300k o 35 cycles,
(e) LZ70_PDDA-TFSI o 50 cycles and ( ) LP70_PVDF-HFP o 50 cycles. dQ/dV e sus ol age
cu es o he 1s and 10 h cycles o Li/NMC622 cells wi h (g) LZ90_PEO300k, (h) LZ70_PDDA-
TFSI, and (i) LP70_PVDF-HFP sepa a o s ( ed ci cle ma king a peak wi h inc eased in ensi y).
Compa ing he cyclabili y o Li/NMC622 cells wi h GEN 2 sepa a o s as shown in
Table 2, in cells wi h LP70_PVDF-HFP, he discha ge capaci ies we e highe compa ed o
cells assembled wi h PDDA-TFSI-based sepa a o . On he o he hand, he capaci y e en-
ion o e he cycling pe iod was obse ed o be be e in he LZ70_PDDA-TFSI-based cell,
which was seen in Figu e 7a and he ol age e sus capaci y p o iles in Figu e 7e. How-
e e , in Li/NMC622 cells wi h LP70_PVDF-HFP, by he 22nd cycle ( ol age e sus capac-
i y p o iles in Figu e 7 ), he e we e p oblems wi h excessi e cha ge capaci y (>220
mAh/g), obse ed due o so sho -ci cui s du ing cha ging. Wi h he s a o so sho
ci cui s, bo h discha ge capaci y and coulombic efficiency alues dec eased apidly. The
capaci y ade in he cells is mo e se e e as he numbe o cycles inc eases. By he 30 h
cycle, he capaci ies ha e declined below ha o cell wi h LZ70_PDDA-TFSI. This diffe -
ence in he s abili y o he wo GEN 2 sepa a o s could be a ibu ed o he polyme s hem-
sel es and possible dehyd o luo ina ion o PVDF-HFP polyme in con ac wi h Li me al
[55,56]. This can be obse ed in cycling p o iles o symme ic Li/Li cells (Figu e 4b), whe e
he pola iza ion s ayed s able in he case o he LZ70_PDDA-TFSI-based cell, bu i was
seen o be inc easing in he case o he PVDF-HFP-based cell. The slow capaci y ade in
Figu e 7. (a) Discha ge capaci y and (b) coulombic e iciency e sus cycle numbe o Li/NMC622
cells wi h all in es iga ed sepa a o s. (c) A e age ol age o bo h cha ge and discha ge s ep o
Li/NMC622 cells wi h di e en sepa a o s. Vol age e sus capaci y cu es o Li/NMC622 cells wi h
GEN 1 and GEN 2 sepa a o s a e long- e m gal anos a ic cycling (d) LZ90_PEO300k o 35 cycles,
(e) LZ70_PDDA-TFSI o 50 cycles and ( ) LP70_PVDF-HFP o 50 cycles. dQ/dV e sus ol age
cu es o he 1s and 10 h cycles o Li/NMC622 cells wi h (g) LZ90_PEO300k, (h) LZ70_PDDA-TFSI,
and (i) LP70_PVDF-HFP sepa a o s ( ed ci cle ma king a peak wi h inc eased in ensi y).
Compa ing he cyclabili y o Li/NMC622 cells wi h GEN 2 sepa a o s as shown in
Table 2, in cells wi h LP70_PVDF-HFP, he discha ge capaci ies we e highe compa ed
o cells assembled wi h PDDA-TFSI-based sepa a o . On he o he hand, he capaci y
e en ion o e he cycling pe iod was obse ed o be be e in he LZ70_PDDA-TFSI-based
cell, which was seen in Figu e 7a and he ol age e sus capaci y p o iles in Figu e 7e.

Ba e ies 2025,11, 42 17 o 24
Howe e , in Li/NMC622 cells wi h LP70_PVDF-HFP, by he 22nd cycle ( ol age e -
sus capaci y p o iles in Figu e 7 ), he e we e p oblems wi h excessi e cha ge capaci y
(>220 mAh/g), obse ed due o so sho -ci cui s du ing cha ging. Wi h he s a o so
sho ci cui s, bo h discha ge capaci y and coulombic e iciency alues dec eased apidly.
The capaci y ade in he cells is mo e se e e as he numbe o cycles inc eases. By he 30 h
cycle, he capaci ies ha e declined below ha o cell wi h LZ70_PDDA-TFSI. This di e ence
in he s abili y o he wo GEN 2 sepa a o s could be a ibu ed o he polyme s hemsel es
and possible dehyd o luo ina ion o PVDF-HFP polyme in con ac wi h Li me al [
55
,
56
].
This can be obse ed in cycling p o iles o symme ic Li/Li cells (Figu e 4b), whe e he
pola iza ion s ayed s able in he case o he LZ70_PDDA-TFSI-based cell, bu i was seen
o be inc easing in he case o he PVDF-HFP-based cell. The slow capaci y ade in cells
wi h LZ70_PDDA-TFSI and LP70_PVDF-HFP could be also seen as he e ec o PEO-based
ca holy e in he composi e ca hode.
Table 2. Elec ochemical pe o mance indica o s o es ed Li/NMC622 cells wi h C-SCE sepa a o s a
key cycle numbe s.
C-SCE Sample Name Cycle
Numbe
Discha ge
Capaci y,
mAh/g
Capaci y
Re en ion,
%
Coulombic
E iciency,
%
A e age Vol age, V S a e o Cells
Cha ge Discha ge
Li/LZ90_PEO300k/NMC622
GEN 1
1 172.69 - 88.09 3.88 3.71 S a
10 111.79 64 96.64 3.94 3.51 Mid
35 6.6 3.8 106.82 ** 4.27 3.17 S op
Li/LZ70_PDDA-TFSI/NMC622
GEN 2
1 145.15 - 74.94 3.94 3.46 S a
10 147.07 94 97.31 3.94 3.51 Mid
50 101.87 61 97.18 4.0 3.48 S op
Li/LP70_PVDF-HFP/NMC622
GEN 2
1 189.07 - 91.59 3.87 3.75 S a
10 170.42 90 98.73 3.89 3.68 Mid
22 151.74 80 79.13 3.93 3.55
50 51.45 27 70.0 4.23 3.35 S op
** Coulombic e iciency (CE) was mo e han 100% in 35 h cycle due o cha ge (6.2 mAh/g) and discha ge
(6.6 mAh/g) capaci ies measu ed we e e y small because o inc ease in cell esis ance du ing long- e m cycling.
This inc eased CE alues has mino e ec on he cell because he o al summa ion o capaci ies shows ha he
discha ge capaci y is less han ha o cha ged capaci y.
The a e age ol ages o he Li/NMC622 cells wi h all h ee sepa a o s we e analyzed
using PROTEO™ Da a Analy ics V1 (CIDETEC) and shown in Figu e 7c. In he g aph,
he e a e indica ions owa ds deg ada ion in he Li/NMC622 cells wi h LZ90_PEO300k
and LP70_PVDF-HFP due o he inc easing di e ence be ween he a e age ol ages o
cha ge and discha ge. Howe e , in he Li/NMC622 cells wi h LZ70_PDDA-TFSI, i was
obse ed ha he di e ence be ween a e age ol age alues was la ge compa ed o o he
sys ems, which could be due o he highe esis ance o he “Li/sepa a o /NMC622” s ack
and may co obo a e he be e s abili y o cells du ing long- e m cycling.
Addi ionally, o unde s and he in luence o a ious ma ix componen s, PVDF-HFP-
based sepa a o s we e es ed in Li/NMC622 cells, including he LP70_PVDF-HFP sepa a o
wi hou SCN. Figu e S7 compa es he cycling pe o mance o Li/NMC622 cells wi h bo h
GEN 2 PVDF-HFP-based C-SCEs. The Li/NMC622 cells wi h bo h sepa a o s demons a e
ele an ini ial discha ge capaci ies. Figu e S7d,e illus a e apid capaci y decay in he
ol age e sus ime plo s o Li/NMC622 cells wi h bo h sepa a o s. Howe e , i was
obse ed ha om he 2nd cycle onwa ds ha he discha ge capaci y o Li/NMC622 cells
wi h LP70_PVDF-HFP wi hou SCN dec eased e y apidly o less han 50% o he ini ial
discha ge capaci y. One o he p obable easons o de ia ion in he cycling pe o mance
could be ela ed o he abili y o SCN (p esen ed in LP70_PVDF-HFP ma ix) o sepa a e
Ba e ies 2025,11, 42 18 o 24
cha ges in he elec oly e and he o a ional mo ion o SCN molecules. Bo h o which would
aid in he be e anspo o ions du ing cycling [46].
Figu e 7g–i depic he inc emen al capaci y cu es (dQ/dV) o Li/NMC622 cells wi h
LZ90_PEO300k, LP70_PVDF-HFP, and LZ70_PDDA-TFSI sepa a o s, espec i ely. The
dQ/dV analysis has been ca ied ou on he 1s (a—cha ge and b—discha ge) and 10 h
(a’—cha ge and b’—discha ge) cycle o Li/NMC622 cells. Compa ing all dQ/dV cu es in
he cha ging p ocess, in he 1s cycle o Li/NMC622 cell wi h LP70_PVDF-HFP, a mo e
p onounced peak (ma ked in ed ci cle) wi h inc eased in ensi y was obse ed. I has
been epo ed by S. Zhang and R. Jung e al. [
57
,
58
] ha he i s peak is usually ela ed
o hexagonal (H1) o monoclinic (M) ans o ma ion, which could be spli in some cases,
whe e i s peak ep esen s Ni
3+
/Ni
4+
oxida ion and second peak is a ibu ed o Co
3+
/Co
4+
oxida ion. The spli ing o H1 o M peak is obse ed in all Li/NMC622-based sys ems;
howe e , in Li/NMC622 cells wi h LZ90_PEO300k and LZ70_PDDA-TFSI sepa a o s, he
i s pa o he spli peak has e y low in ensi y. The inc eased in ensi y seen o he
p onounced i s peak (ma ked wi h ed ci cle in Figu e 7i) co esponds o he highe
capaci ies obse ed du ing cha ge in Li/NMC622 cell wi h LP70_PVDF-HFP and could be
a ibu ed o dec easing “sepa a o /ca hode” in e ace esis ance. On compa ing cha ging
p ocess peaks o cells wi h LLZO-based sepa a o s, he educ ion in he peak in ensi ies
o e bo h cycles is mo e p ominen in he case o cells wi h LZ90_PEO300k. This a iance
in he peak in ensi ies o he 10 h cycle be ween he wo sepa a o s demons a es he la ge
capaci y ade in Li/NMC622 cell wi h LZ90_PEO300k, which co obo a es he di e ences
in discha ge capaci ies as seen in Table 2. No u he phase ansi ion peaks we e obse ed
in NMC622 ma e ial due o he cha ging ol age no eaching 4.6 V [
57
]. The b oadening
and shi o discha ge p ocess peaks du ing he cycling could be seen due o an inc ease in
o e all cell esis ance [59].
3.3. Compa i i e Analysis
The wo k ca ied ou he e is pa o an ini ial a emp a op imiza ion o ce amic- ich
sepa a o s aimed a being used in li hium me al-based high- ol age solid-s a e ba e ies.
F om ou p e ious wo k [
32
], he key message abou PEO-based ce amic- ich sepa a o s
was abou he equi emen o modi ying he polyme hos in he ma ix o pai ing wi h
high- ol age ca hode ma e ials. Howe e , i has been obse ed ha he change in he
o mula ion o a polyme -based ma ix is no o simply eplace PEO wi h an HV-s able
polyme such as PDDA-TFSI o PVDF-HFP. The e o e, in his wo k, we we e ocused on
op imizing he ma ix in GEN 2 ce amic- ich composi e sepa a o s (C-SCEs) o imp o e
hei applicabili y in HV solid-s a e ba e ies wi h Li me al anode. The op imiza ion o he
sepa a o ma ix was done in wo pa s, wi h he i s pa conce ning ma e ial selec ion
and p epa a ion and he second pa conce ning he es ing o he sepa a o s. All GEN 2
sepa a o s we e compa ed wi h LLZO-PEO-LiTFSI-based e e ence sepa a o s du ing he
op imiza ion ials.
The i s pa o he op imiza ion p ocess consis ed o selec ing he componen s o
each ma ix and hei success ul ab ica ion a e modi ying he pos -p ocessing pa ame e s.
The in es iga ed sepa a o s we e es ed o hei ilm- o ming abili y, su ace mo phology,
c oss-sec ional mic os uc u e, and ionic conduc i i y a di e en empe a u es. All GEN
2 sepa a o s ha e been p epa ed ia a acile p ocess which can be easily scaled up o
la ge ba ch sizes. I is impo an o u ilize high-ene gy mixing solu ions o compensa e o
p oblems wi h agglome a ion o ce amic pa icles. The p ocessing o di e en sepa a o s
was highly dependen on he molecula weigh o he used polyme s, which was seen
om he lack o ilm o ma ion o LZ70_PBA and LZ80_PBA. An impo an pa ame e
o be moni o ed is he iscosi y o sepa a o slu y, which helps in achie ing desi ed
Ba e ies 2025,11, 42 19 o 24
hicknesses and p e en sedimen a ion o ce amic pa icles. The selec ion o sepa a o s o
he second pa has been done based on physical–chemical p ope y e alua ions and ionic
conduc i i y measu emen s.
In he second pa , selec ed GEN 2 sepa a o s ha e been e alua ed o hei s a-
bili y agains li hium me al and in high- ol age Li/NMC622 cells. In Li/Li cells wi h
LZ70_PDDA-TFSI and LP70_PVDF-HFP, bo h GEN 2 sepa a o s we e only able o endu e
CCD o 0.1 mA/cm
2
compa ed o ha o 0.25 mA/cm
2
[
32
] in LLZO-PEO-based GEN
1 sepa a o s. Du ing long- e m cycling o Li/Li cells wi h GEN 2 sepa a o s, ela i ely
poo cyclabili y has been demons a ed, wi h “Li/LZ70_PDDA-TFSI/Li” being s able up
o 300 h and “Li/LP70_PVDF-HFP/Li” being s able up o 350 h. Bo h GEN 2 sepa a o s
exhibi ed ela i ely poo s abili y wi h li hium me al compa ed o LZ90_PEO300k, which
emained s able, cycling o mo e han 800 h wi h a s able pola iza ion. Li/Li cells wi h
LZ70_PDDA-TFSI demons a ed s able and symme ic pola iza ion compa ed o uns able
and asymme ic pola iza ion in Li/Li cells wi h LP70_PVDF-HFP du ing long- e m cycling.
Howe e , when Li/NMC622 cells wi h GEN 2 sepa a o s we e e alua ed, i was seen
ha he oles we e e e sed, wi h Li/NMC622 cells wi h GEN 2 sepa a o s p o ing o be
mo e s able compa ed o hose o Li/NMC622 cells wi h LZ90_PEO300k du ing long- e m
gal anos a ic cycling. Compa ing he pe o mance o he selec ed GEN 2 sepa a o s, i was
seen ha LP70_PVDF-HFP demons a ed good discha ge C- a e pe o mance wi h ele an
discha ge capaci ies up o 0.5C compa ed o ha o 0.1C o LZ70_PDDA-TFSI. On he
o he hand, LZ70_PDDA-TFSI based cells exhibi ed s able cyclabili y wi h be e capaci y
e en ion o he wo GEN 2 sepa a o s o e 50 cycles. Fu he ad anced cha ac e iza ion
equi ed o shed ligh on he po en ial deg ada ion mechanisms o each o he sepa a o
sys ems will be pe o med as pa o u u e wo k.
Figu e 8summa ies he esul s om a ious indica o s e alua ed du ing his s udy.
I could be obse ed ha he PEO-based GEN 1 sepa a o shows good pe o mances in
ac o s which we e di ec ly a ec ed by con ac wi h Li me al, ha ing a good li hophilic
beha io . On he o he hand, GEN 2 sepa a o s exhibi be e pe o mance in indica o s
which di ec ly deal wi h high- ol age solid-s a e ba e ies. Thus, designing and op imizing
ce amic- ich composi e sepa a o s is no s aigh - o wa d and equi es mo e inpu s o
imp o e he pe o mance, especially o he s abili y wi h li hium me al and a high- ol age
s able ca hode.
Ba e ies 2025, 11, x FOR PEER REVIEW 19 o 24
s able, cycling o mo e han 800 h wi h a s able pola iza ion. Li/Li cells wi h LZ70_PDDA-
TFSI demons a ed s able and symme ic pola iza ion compa ed o uns able and asym-
me ic pola iza ion in Li/Li cells wi h LP70_PVDF-HFP du ing long- e m cycling.
Howe e , when Li/NMC622 cells wi h GEN 2 sepa a o s we e e alua ed, i was seen
ha he oles we e e e sed, wi h Li/NMC622 cells wi h GEN 2 sepa a o s p o ing o be
mo e s able compa ed o hose o Li/NMC622 cells wi h LZ90_PEO300k du ing long- e m
gal anos a ic cycling. Compa ing he pe o mance o he selec ed GEN 2 sepa a o s, i
was seen ha LP70_PVDF-HFP demons a ed good discha ge C- a e pe o mance wi h
ele an discha ge capaci ies up o 0.5C compa ed o ha o 0.1C o LZ70_PDDA-TFSI.
On he o he hand, LZ70_PDDA-TFSI based cells exhibi ed s able cyclabili y wi h be e
capaci y e en ion o he wo GEN 2 sepa a o s o e 50 cycles. Fu he ad anced cha ac-
e iza ion equi ed o shed ligh on he po en ial deg ada ion mechanisms o each o he
sepa a o sys ems will be pe o med as pa o u u e wo k.
Figu e 8 summa ies he esul s om a ious indica o s e alua ed du ing his s udy.
I could be obse ed ha he PEO-based GEN 1 sepa a o shows good pe o mances in
ac o s which we e di ec ly affec ed by con ac wi h Li me al, ha ing a good li hophilic
beha io . On he o he hand, GEN 2 sepa a o s exhibi be e pe o mance in indica o s
which di ec ly deal wi h high- ol age solid-s a e ba e ies. Thus, designing and op imiz-
ing ce amic- ich composi e sepa a o s is no s aigh - o wa d and equi es mo e inpu s o
imp o e he pe o mance, especially o he s abili y wi h li hium me al and a high- ol -
age s able ca hode.
Figu e 8. Compa a i e diag am o essen ial p ope ies o GEN 1 and GEN 2 ce amic- ich composi e
elec oly es.
4. Conclusions
To summa ize, his wo k is ocused on he op imiza ion and ab ica ion o ce amic-
ich composi e sepa a o s (GEN 2) o add ess high- ol age ins abili y o a polyme ic ma-
ix demons a ed by PEO-based composi e sepa a o s. The composi e sepa a o s we e
p epa ed using acile solu ion-cas ing me hod o s udy he in luence o diffe en ma ix
componen s and composi ions on he elec ochemical s abili y o Li/NMC622 cells wi h
ce amic- ich composi e sepa a o s.
The in es iga ed GEN 2 composi e sepa a o s wi h diffe en ce amic con en s and
polyme ma ices (PVDF-HFP, PDDA-TFSI, and PBA) ha e been explo ed in his s udy o
assess hei effec on he mechanical s abili y, mic os uc u e, and high- ol age s abili y
Figu e 8. Compa a i e diag am o essen ial p ope ies o GEN 1 and GEN 2 ce amic- ich composi e
elec oly es.
Ba e ies 2025,11, 42 20 o 24
4. Conclusions
To summa ize, his wo k is ocused on he op imiza ion and ab ica ion o ce amic-
ich composi e sepa a o s (GEN 2) o add ess high- ol age ins abili y o a polyme ic
ma ix demons a ed by PEO-based composi e sepa a o s. The composi e sepa a o s we e
p epa ed using acile solu ion-cas ing me hod o s udy he in luence o di e en ma ix
componen s and composi ions on he elec ochemical s abili y o Li/NMC622 cells wi h
ce amic- ich composi e sepa a o s.
The in es iga ed GEN 2 composi e sepa a o s wi h di e en ce amic con en s and
polyme ma ices (PVDF-HFP, PDDA-TFSI, and PBA) ha e been explo ed in his s udy o
assess hei e ec on he mechanical s abili y, mic os uc u e, and high- ol age s abili y o
he sepa a o s. PBA-based ce amic- ich composi e sepa a o s ha e been disca ded a an
ea ly s age due o poo mechanical p ope ies and low ionic conduc i i y. O he sepa a o s
based on 80 w % and 90 w % LLZO in PDDA-TFSI-based ma ix ha e been also ejec ed
due o low ionic conduc i i y and poo mechanical p ope ies.
The e o e, sepa a o s wi h 70 w % o he ce amic con en in PVDF, and PDDA-TFSI
polyme -based ma ices we e op imized and e alua ed u he . The LP70_PVDF-HFP sepa-
a o was seen o ha e he highes ionic conduc i i y a 60
◦
C, ollowed by he LZ70_PDDA-
TFSI and LZ90_PEO300k sepa a o s. Bo h LP70_PVDF-HFP and LZ70_PDDA-TFSI sepa a-
o s wi h dense mic os uc u e we e e alua ed o hei s abili y agains li hium me al and
high- ol age Li/NMC622 cells.
The di e ences be ween he PEO-based GEN 1 and PDDA-TFSI and PVDF-HFP-based
GEN 2 sepa a o s a e e y no iceable du ing he elec ochemical cha ac e iza ions in bo h
Li/Li and Li/NMC622 cells. In Li/Li cells es ing he s abili y agains Li me al, cells wi h
PEO-based GEN 1 sepa a o s had supe io pe o mance compa ed o cells wi h bo h GEN 2
sepa a o s. The supe io pe o mance o Li/Li cells wi h GEN 1 sepa a o s was ue in bo h
cases o c i ical cu en densi y and long- e m cycling es s. Con a y o he pe o mance o
Li/Li cells, Li/NMC622 cells wi h bo h GEN 2 sepa a o s showcased be e pe o mance
du ing long- e m cycling compa ed o he PEO-based GEN 1 sepa a o . Li/NMC622
cells wi h LP70_PVDF-HFP and LZ70_PDDA-TFSI ha e been obse ed o ha e highe
discha ge capaci y e en ion, as well as highe coulombic e iciency, signi ying imp o ed
elec ochemical s abili y o he high- ol age s able polyme s and mo e e e sible sys ems
du ing cycling.
Li/NMC622 cells wi h LP70_PVDF-HFP and LZ70_PDDA-TFSI exhibi ed be e pe -
o mances in discha ge C- a e pe o mance and long- e m cycling, espec i ely. The e o e,
i was seen ha when changing om a li hophilic polyme such as PEO in he ma ix,
some sac i ices need o be made o imp o e pe o mance a high ol age cycling condi ions
o he solid-s a e ba e ies. Ne e heless, despi e imp o emen in high- ol age s abili y
du ing cycling a e changing he polyme ype in he ma ix, he deg ada ion obse ed is
signi ican and needs o be u he cha ac e ized o be e unde s anding.
As pa o u u e wo k, i is ecommended ha he GEN 2 sepa a o s be es ed in cells
wi h a composi e ca hode ha ing a high- ol age s able ca holy e o compa e he changes in
cyclabili y and capaci y e en ion wi h he eplacemen o he PEO-based ca holy e. GEN 2
sepa a o s in combina ion wi h high- ol age s able ca hodes would also be e alua ed o
cycling pe o mance a a lowe ope a ing empe a u e o 25 ◦C.
Supplemen a y Ma e ials: The ollowing suppo ing in o ma ion can be downloaded a : www.
mdpi.com/xxx/s1, Figu e S1 Scheme o LATP syn hesis p ocess ia solu ion assis ed solid-s a e
eac ion ou e; Figu e S2 XRD di ac og ams o (a) cubic—LLZO and (b) hombohed al LATP
powde wi h (
Ba e ies 2025, 11, x FOR PEER REVIEW 20 o 24
o he sepa a o s. PBA-based ce amic- ich composi e sepa a o s ha e been disca ded a
an ea ly s age due o poo mechanical p ope ies and low ionic conduc i i y. O he sepa-
a o s based on 80 w % and 90 w % LLZO in PDDA-TFSI-based ma ix ha e been also
ejec ed due o low ionic conduc i i y and poo mechanical p ope ies.
The e o e, sepa a o s wi h 70 w % o he ce amic con en in PVDF, and PDDA-TFSI
polyme -based ma ices we e op imized and e alua ed u he . The LP70_PVDF-HFP
sepa a o was seen o ha e he highes ionic conduc i i y a 60 °C, ollowed by he
LZ70_PDDA-TFSI and LZ90_PEO300k sepa a o s. Bo h LP70_PVDF-HFP and
LZ70_PDDA-TFSI sepa a o s wi h dense mic os uc u e we e e alua ed o hei s abili y
agains li hium me al and high- ol age Li/NMC622 cells.
The diffe ences be ween he PEO-based GEN 1 and PDDA-TFSI and PVDF-HFP-
based GEN 2 sepa a o s a e e y no iceable du ing he elec ochemical cha ac e iza ions
in bo h Li/Li and Li/NMC622 cells. In Li/Li cells es ing he s abili y agains Li me al, cells
wi h PEO-based GEN 1 sepa a o s had supe io pe o mance compa ed o cells wi h bo h
GEN 2 sepa a o s. The supe io pe o mance o Li/Li cells wi h GEN 1 sepa a o s was ue
in bo h cases o c i ical cu en densi y and long- e m cycling es s. Con a y o he pe -
o mance o Li/Li cells, Li/NMC622 cells wi h bo h GEN 2 sepa a o s showcased be e
pe o mance du ing long- e m cycling compa ed o he PEO-based GEN 1 sepa a o .
Li/NMC622 cells wi h LP70_PVDF-HFP and LZ70_PDDA-TFSI ha e been obse ed o
ha e highe discha ge capaci y e en ion, as well as highe coulombic efficiency, signi y-
ing imp o ed elec ochemical s abili y o he high- ol age s able polyme s and mo e e-
e sible sys ems du ing cycling.
Li/NMC622 cells wi h LP70_PVDF-HFP and LZ70_PDDA-TFSI exhibi ed be e pe -
o mances in discha ge C- a e pe o mance and long- e m cycling, espec i ely. The e-
o e, i was seen ha when changing om a li hophilic polyme such as PEO in he ma ix,
some sac i ices need o be made o imp o e pe o mance a high ol age cycling condi-
ions o he solid-s a e ba e ies. Ne e heless, despi e imp o emen in high- ol age s a-
bili y du ing cycling a e changing he polyme ype in he ma ix, he deg ada ion ob-
se ed is signi ican and needs o be u he cha ac e ized o be e unde s anding.
As pa o u u e wo k, i is ecommended ha he GEN 2 sepa a o s be es ed in cells
wi h a composi e ca hode ha ing a high- ol age s able ca holy e o compa e he changes
in cyclabili y and capaci y e en ion wi h he eplacemen o he PEO-based ca holy e.
GEN 2 sepa a o s in combina ion wi h high- ol age s able ca hodes would also be e alu-
a ed o cycling pe o mance a a lowe ope a ing empe a u e o 25 °C.
Supplemen a y Ma e ials: The ollowing suppo ing in o ma ion can be downloaded a :
www.mdpi.com/xxx/s1, Figu e S1 Scheme o LATP syn hesis p ocess ia solu ion assis ed solid-
s a e eac ion ou e; Figu e S2 XRD diff ac og ams o (a) cubic—LLZO and (b) hombohed al LATP
powde wi h ( ) ma king addi ional o ho hombic phase and ( ) ma king addi ional ma king ad-
di ional LiTiPO5 phase; SEM mic og aphs o (c) LLZO powde pa icles and (d) LATP powde pa -
icles. Powde pa icle size dis ibu ion g aph o (e) LLZO and ( ) LATP; Figu e S3 C oss-sec ional
SEM images o ab ica ed C-SCEs compa ing mic os uc u es o diffe en polyme ic ma ix g oups,
s a ing om PEO-ma ix-based sepa a o s [2]: (a) LZ90_PEO300k- and (b) LZ95_PEO300k-, PVDF-
HFP-ma ix-based sepa a o s (c) LP70_PVDF-HFP and ( ) LP70_PVDF-HFP wi hou SN, PBA-ma-
ix-based sepa a o s (d) LZ70_PBA and (e) LZ80_PBA- and PDDA-TFSI-ma ix-based sepa a o s
(g) LZ70_PDDA-TFSI (h) LZ80_PDDA-TFSI and (i) LZ90_PDDA-TFSI; Figu e S4 TGA he mo-
g aphs o (a) LZ70_PDDA-TFSI and (b) LP70_PVDF-HFP; Figu e S5 O iginal and i ed EIS spec a
o (a) Li/LZ70_PDDA-TFSI/Li and (d) Li/ LP70_PVDF-HFP /Li cell be o e and a e pola iza ion;
Inse - Ch onoampe ome y p o ile (I s. ime) o (b) Li/LZ70_PDDA-TFSI/Li and (e) Li/ LP70_PVDF-
HFP /Li symme ic cell; (c) and ( ) Equi alen ci cui used o i he (be o e and a e pola iza ion)
impedance p o iles o ans e ence numbe .; Figu e S6 Vol age e sus ime p o iles o long- e m
) ma king addi ional o ho hombic phase and (
Ba e ies 2025, 11, x FOR PEER REVIEW 20 o 24
o he sepa a o s. PBA-based ce amic- ich composi e sepa a o s ha e been disca ded a
an ea ly s age due o poo mechanical p ope ies and low ionic conduc i i y. O he sepa-
a o s based on 80 w % and 90 w % LLZO in PDDA-TFSI-based ma ix ha e been also
ejec ed due o low ionic conduc i i y and poo mechanical p ope ies.
The e o e, sepa a o s wi h 70 w % o he ce amic con en in PVDF, and PDDA-TFSI
polyme -based ma ices we e op imized and e alua ed u he . The LP70_PVDF-HFP
sepa a o was seen o ha e he highes ionic conduc i i y a 60 °C, ollowed by he
LZ70_PDDA-TFSI and LZ90_PEO300k sepa a o s. Bo h LP70_PVDF-HFP and
LZ70_PDDA-TFSI sepa a o s wi h dense mic os uc u e we e e alua ed o hei s abili y
agains li hium me al and high- ol age Li/NMC622 cells.
The diffe ences be ween he PEO-based GEN 1 and PDDA-TFSI and PVDF-HFP-
based GEN 2 sepa a o s a e e y no iceable du ing he elec ochemical cha ac e iza ions
in bo h Li/Li and Li/NMC622 cells. In Li/Li cells es ing he s abili y agains Li me al, cells
wi h PEO-based GEN 1 sepa a o s had supe io pe o mance compa ed o cells wi h bo h
GEN 2 sepa a o s. The supe io pe o mance o Li/Li cells wi h GEN 1 sepa a o s was ue
in bo h cases o c i ical cu en densi y and long- e m cycling es s. Con a y o he pe -
o mance o Li/Li cells, Li/NMC622 cells wi h bo h GEN 2 sepa a o s showcased be e
pe o mance du ing long- e m cycling compa ed o he PEO-based GEN 1 sepa a o .
Li/NMC622 cells wi h LP70_PVDF-HFP and LZ70_PDDA-TFSI ha e been obse ed o
ha e highe discha ge capaci y e en ion, as well as highe coulombic efficiency, signi y-
ing imp o ed elec ochemical s abili y o he high- ol age s able polyme s and mo e e-
e sible sys ems du ing cycling.
Li/NMC622 cells wi h LP70_PVDF-HFP and LZ70_PDDA-TFSI exhibi ed be e pe -
o mances in discha ge C- a e pe o mance and long- e m cycling, espec i ely. The e-
o e, i was seen ha when changing om a li hophilic polyme such as PEO in he ma ix,
some sac i ices need o be made o imp o e pe o mance a high ol age cycling condi-
ions o he solid-s a e ba e ies. Ne e heless, despi e imp o emen in high- ol age s a-
bili y du ing cycling a e changing he polyme ype in he ma ix, he deg ada ion ob-
se ed is signi ican and needs o be u he cha ac e ized o be e unde s anding.
As pa o u u e wo k, i is ecommended ha he GEN 2 sepa a o s be es ed in cells
wi h a composi e ca hode ha ing a high- ol age s able ca holy e o compa e he changes
in cyclabili y and capaci y e en ion wi h he eplacemen o he PEO-based ca holy e.
GEN 2 sepa a o s in combina ion wi h high- ol age s able ca hodes would also be e alu-
a ed o cycling pe o mance a a lowe ope a ing empe a u e o 25 °C.
Supplemen a y Ma e ials: The ollowing suppo ing in o ma ion can be downloaded a :
www.mdpi.com/xxx/s1, Figu e S1 Scheme o LATP syn hesis p ocess ia solu ion assis ed solid-
s a e eac ion ou e; Figu e S2 XRD diff ac og ams o (a) cubic—LLZO and (b) hombohed al LATP
powde wi h ( ) ma king addi ional o ho hombic phase and ( ) ma king addi ional ma king ad-
di ional LiTiPO5 phase; SEM mic og aphs o (c) LLZO powde pa icles and (d) LATP powde pa -
icles. Powde pa icle size dis ibu ion g aph o (e) LLZO and ( ) LATP; Figu e S3 C oss-sec ional
SEM images o ab ica ed C-SCEs compa ing mic os uc u es o diffe en polyme ic ma ix g oups,
s a ing om PEO-ma ix-based sepa a o s [2]: (a) LZ90_PEO300k- and (b) LZ95_PEO300k-, PVDF-
HFP-ma ix-based sepa a o s (c) LP70_PVDF-HFP and ( ) LP70_PVDF-HFP wi hou SN, PBA-ma-
ix-based sepa a o s (d) LZ70_PBA and (e) LZ80_PBA- and PDDA-TFSI-ma ix-based sepa a o s
(g) LZ70_PDDA-TFSI (h) LZ80_PDDA-TFSI and (i) LZ90_PDDA-TFSI; Figu e S4 TGA he mo-
g aphs o (a) LZ70_PDDA-TFSI and (b) LP70_PVDF-HFP; Figu e S5 O iginal and i ed EIS spec a
o (a) Li/LZ70_PDDA-TFSI/Li and (d) Li/ LP70_PVDF-HFP /Li cell be o e and a e pola iza ion;
Inse - Ch onoampe ome y p o ile (I s. ime) o (b) Li/LZ70_PDDA-TFSI/Li and (e) Li/ LP70_PVDF-
HFP /Li symme ic cell; (c) and ( ) Equi alen ci cui used o i he (be o e and a e pola iza ion)
impedance p o iles o ans e ence numbe .; Figu e S6 Vol age e sus ime p o iles o long- e m
) ma king addi ional ma king ad-
di ional LiTiPO
5
phase; SEM mic og aphs o (c) LLZO powde pa icles and (d) LATP powde
Ba e ies 2025,11, 42 21 o 24
pa icles. Powde pa icle size dis ibu ion g aph o (e) LLZO and ( ) LATP; Figu e S3 C oss-
sec ional SEM images o ab ica ed C-SCEs compa ing mic os uc u es o di e en polyme ic ma ix
g oups, s a ing om PEO-ma ix-based sepa a o s [
2
]: (a) LZ90_PEO300k- and (b) LZ95_PEO300k-,
PVDF-HFP-ma ix-based sepa a o s (c) LP70_PVDF-HFP and ( ) LP70_PVDF-HFP wi hou SN, PBA-
ma ix-based sepa a o s (d) LZ70_PBA and (e) LZ80_PBA- and PDDA-TFSI-ma ix-based sepa a o s
(g) LZ70_PDDA-TFSI (h) LZ80_PDDA-TFSI and (i) LZ90_PDDA-TFSI; Figu e S4 TGA he mog aphs
o (a) LZ70_PDDA-TFSI and (b) LP70_PVDF-HFP; Figu e S5 O iginal and i ed EIS spec a o
(a) Li/LZ70_PDDA-TFSI/Li and (d) Li/ LP70_PVDF-HFP /Li cell be o e and a e pola iza ion; Inse -
Ch onoampe ome y p o ile (I s. ime) o (b) Li/LZ70_PDDA-TFSI/Li and (e) Li/ LP70_PVDF-
HFP /Li symme ic cell; (c) and ( ) Equi alen ci cui used o i he (be o e and a e pola iza ion)
impedance p o iles o ans e ence numbe .; Figu e S6 Vol age e sus ime p o iles o long- e m
gal anos a ic cycling o Li/Li cells wi h LP70_PVDF-HFP. Cycling condi ions: cu en densi y
0.1 mA/cm
2
, hal cycle s ep o 1 h, 60
◦
C.; Figu e S7 Discha ge capaci y and (b) coulombic e icien-
cies e iciency and (c) a e age ol age o bo h cha ge and discha ge s ep o Li/NMC622 cells wi h
LP70_PVDF-HFP and LP70_PVDF-HFP wi hou SCN. Vol age e sus capaci y cu es o Li/NMC622
cells wi h GEN 2 sepa a o s a e long- e m cycling (d) LP70_PVDF-HFP wi hou SCN and
(e) LP70_PVDF-HFP. All compa isons we e made a e cycling o 20 cycles. dQ/dV e sus ol age
cu es o he 1s and 10 h cycles o Li/NMC622 cells wi h (g) LP70_PVDF-HFP wi hou SCN,
(h) LP70_PVDF-HFP; Table S1 T ans e ence numbe o GEN 2 sepa a o s [14,32,60–63].
Au ho Con ibu ions: Concep ualiza ion, K.V., D.F.-R. and A.K.; me hodology, K.V., M.F., D.F.-R.
and A.K.; alida ion, K.V. and A.K.; o mal analysis, K.V. and A.K.; in es iga ion, K.V.; esou ces,
M.F., D.F.-R., I.U. and A.K.; da a cu a ion, K.V. and A.K.; w i ing—o iginal d a p epa a ion, K.V.;
w i ing— e iew and edi ing, K.V., M.F., D.F.-R., I.U. and A.K.; isualiza ion, D.F.-R. and A.K.;
supe ision, D.F.-R. and A.K.; p ojec adminis a ion, D.F.-R. and A.K.; unding acquisi ion, D.F.-R.,
I.U. and A.K. All au ho s ha e ead and ag eed o he published e sion o he manusc ip .
Funding: Funding om Fundación CIDETEC, DESTINY COFUND PhD P og amme unde Ma ie
Sklodowska-Cu ie g an (G.A. No 945357), and Ge man “Fede al Minis y o Educa ion and Resea ch”
(BMBF) unde g an numbe s 13XP0434A (Fes Ba 2—Oxid) and 13XP0428A (Fes Ba 2—Hyb ide).
Da a A ailabili y S a emen : The da a ha suppo he indings o his s udy a e a ailable om he
co esponding au ho upon easonable eques .
Acknowledgmen s: K.V. acknowledges he unding om he DESTINY COFUND PhD P og amme
which has ecei ed unding om he Eu opean Union’s Ho izon 2020 esea ch and inno a ion p o-
g amme unde he Ma ie Sklodowska-Cu ie (g an ag eemen No 945357) and Fundación CIDETEC.
Financial suppo om he Ge man “Fede al Minis y o Educa ion and Resea ch” (BMBF) unde
g an numbe s 13XP0434A (Fes Ba 2—Oxid) and 13XP0428A (Fes Ba 2—Hyb ide) is g a e ully
acknowledged. The au ho s also g a e ully acknowledge G i Häuschen and Philipp Hecke om
Fo schungszen um Jülich GmbH o help wi h he syn hesis o LLZO and LATP powde s used in
his wo k.
Con lic s o In e es : The au ho s decla e no con lic s o in e es .
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