Jou nal o Magne ic Resonance Open 14-15 (2023) 100095
A ailable online 20 Janua y 2023
2666-4410/© 2023 Published by Else ie Inc. 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/).
P obing diso de and dynamics in composi e elec oly es o an o ganic ionic
plas ic c ys al and li hium unc ionalised ac ylic polyme nanopa icles
Yady Ga cía
a
,
*
, Luca Po ca elli
a
,
b
, Haijin Zhu
a
, Ma ia Fo sy h
a
,
b
,
c
, Da id Mece eyes
b
,
c
,
Luke A. O’Dell
a
a
Ins i u e o F on ie Ma e ials and he ARC Cen e o Excellence o Elec oma e ials Science, Deakin Uni e si y, Geelong, VIC 3216, Aus alia
b
POLYMAT Uni e si y o he Basque Coun y UPV/EHU, Joxe Ma i Ko a Cen e , Donos ia−San Sebas ian 20018, Spain
c
Ike basque, Basque Founda ion o Science, Bilbao, Spain
ARTICLE INFO
Keywo ds:
Composi e elec oly e
Plas ic c ys al
Dynamics
Li ion mobili y
ABSTRACT
Solid composi e elec oly es combining an ionic molecula phase o acili a e ion anspo wi h a polyme ic
componen o p o ide mechanical s eng h a e p omising ma e ial o solid-s a e ba e ies. Howe e , he
s uc u e-p ope y ela ionships o hese complex composi es a e no ully unde s ood. He ein we s udy com-
posi es combining he non- lammabili y and he mal s abili y o he o ganic ionic plas ic c ys al (OIPC) N-
me hyl-N-e hylpy olidinium bis( i luo ome hanesul onyl) amide [C
2
mpy ][TFSI] wi h he mechanical s eng h
o ac ylic polyme nanopa icles unc ionalised wi h sulphonamide g oups ha ing li hium coun e -ca ions. The
e ec o he o ma ion o in e aces and in e acial egions be ween he OIPC and polyme nanopa icle on he
he mal s abili y, ion anspo , mo phology and ion dynamics we e s udied. I was ound ha he composi es
whe e an in e phase was o med by local mixing o he polyme wi h he OIPC upon hea ing showed highe local
diso de in he OIPC phase and enhanced ion anspo in compa ison wi h he as-p epa ed composi es. In
addi ion, doping he composi e wi h LiTFSI sal led o u he s uc u al diso de in he OIPC and a selec i e
inc ease in li hium-ion mobili y. Such an imp o ed undamen al unde s anding o s uc u e, dynamics and
in e acial egions in solid elec oly e composi es can in o m he design o OIPC-polyme nanopa icle com-
posi es wi h enhanced p ope ies o applica ion as solid elec oly e in ba e ies.
1. In oduc ion
The componen s o ene gy-s o age de ices, such as he elec oly e
and elec odes, in e ac ia in e aces and in e phases, which play a key
ole in egula ing he anspo o ma e and cha ge, and can de e mine
he ex insic ac i i y, s abili y and unc ionali y o a de ice [1,2]. Fo
example, composi e elec odes may con ain an ac i e ma e ial, poly-
me ic binde s ha p o ide mechanical s abili y and conduc i e diluen s
such as ca bon black, o acili a e cha ge anspo o he ac i e ma e ial
[3], while he o ma ion o he solid elec oly e in e phase (SEI) laye
plays a key ole in passi a ing he elec ode su ace. Whe e possible, i is
desi able o design in e aces and in e phases wi h speci ic p ope ies
such as enhanced ion anspo ha can con ibu e o he imp o ed
unc ionali y and eliabili y o he de ice [4]. He e we de ine an in e -
ace o be he poin a which wo di e en componen s mee , and an
in e phase o be a egion dis inc om he pu e componen s hemsel es
(e.g. a egion wi h enhanced s uc u al diso de o dynamics, o whe e
he componen s ha e mixed oge he ). Impo an ad ances owa ds
sa e ope a ional de ices ha e been achie ed h ough solid-s a e elec-
oly es. Thei inhe en mechanisms, such as hei low di usion o
ma e , allow o con ol o e he in e phase g ow h and o s abiliza-
ion o he elec odes (e.g. Li me al) [1,5]. Solid-s a e elec oly es can be
ino ganic (pe o ski e, ga ne , sulphide- ype ma e ials, e c.) o o ganic
(ionic plas ic c ys als (OIPCs), polyme s and composi e sys ems) and
ypically exhibi ionic conduc i i ies up o a ound he o de o 10
−3
S
cm
−1
a oom empe a u e [6].
Composi e solid elec oly es a e a e y p omising app oach as hey
can combine he ad an ageous p ope ies o hei componen s [7,8]. Fo
example, composi es be ween OIPCs and polyme nanopa icles ha e
ecen ly been de eloped ha combine he ionic conduc i i y,
non- lammabili y, non- ola ili y, plas ici y, elec ochemical, and he -
mal s abili y o OIPCs, while a he same ime o e ing he mechanical
s abili y (and po en ially also chemical unc ionali y) p o ided by he
polyme [9,10]. In hese elec oly e ma e ials he o ma ion o in e aces
* Co esponding au ho .
E-mail add esses: [email p o ec ed] (Y. Ga cía), [email p o ec ed] (L.A. O’Dell).
Con en s lis s a ailable a ScienceDi ec
Jou nal o Magne ic Resonance Open
jou nal homepage: www.sciencedi ec .com/jou nal/jou nal-o -magne ic- esonance-open
h ps://doi.o g/10.1016/j.jm o.2023.100095
Recei ed 30 No embe 2022; Recei ed in e ised o m 13 Janua y 2023; Accep ed 17 Janua y 2023
Jou nal o Magne ic Resonance Open 14-15 (2023) 100095
2
and in e phases has a c i ical unc ion in achie ing he desi ed p ope -
ies. A s uc u al model o desc ibe he kind o in e phases and in e a-
cial egions p esen in hese composi es has been p oposed by N i and
collabo a o s. This was based on he dis up ion o he o de ed (N-e hyl
N-me hyl py olidinium bis( luo osul onyl)imide ([C
2
mpy ][FSI]) OIPC
phase a e he addi ion o wo di e en polyme nanopa icles (poly-
inylidene luo ide (PVDF) and polys y ene (PS)) and an analysis o he
in e ac ion/a ini y be ween hose componen s [11].
Howe e , he ionic anspo mechanisms in OIPC-polyme com-
posi es a e s ill a ma e o s udy and i has been p oposed ha he in-
c ease in ionic conduc i i y obse ed in such composi es ( ela i e o he
pu e OIPC) is associa ed wi h he o ma ion o an in e phase be ween
he OIPCs and polyme nanopa icles [11]. This in e phase may ea u e
bo h inc eased s uc u al diso de and dynamics, esul ing in an
enhancemen in local ion anspo . I has been p oposed ha he highe
bulk ionic conduc i i y is a ained when his in e phase o ms a
con inuous ne wo k h ough he ma e ials, e med he pe cola ion
h eshold [8]. This highligh s he signi icance o unde s anding he e -
ec s o in e phase phenomena ha ake place in hese ma e ials.
The expe imen al cha ac e iza ion o composi e in e aces and in-
e phases can be challenging due o hei dimensions, complexi y,
mo phology and inhe en diso de , and his inc eases he di icul y o
unde s anding hei o ma ion and p ope ies in e ms o he in e acial
s uc u es and chemis ies [12,13]. Many echniques such as X- ay
di ac ion, elec on mic oscopy, and a ious o ms o spec oscopy ha e
been used o unde s and in e aces. Solid-s a e nuclea magne ic eso-
nance (SSNMR) is a powe ul echnique o s udying local diso de and
dynamics in ha d o so solids, amo phous, inhomogeneous o c ys al-
line ma e ials ha can co-exis in ene gy s o age ma e ials [14]. In solid
OIPCs, polyme s and composi es elec oly es,
7
Li,
19
F, and
1
H NMR ha e
been implemen ed o s udy he ion dynamics ia line wid h analysis.
NMR signals om solid powde samples a e gene ally b oadened by
in e ac ions de e mined by he igid-la ice a low empe a u es. As he
ion jump a es app oach o exceed he NMR in e ac ion equencies a
high empe a u es, peak na owing is obse ed. Thus, wo componen s
can o en be dis inguished, a na ow peak ep esen ing a mobile ion
ac ion in a diso de ed/dynamic egion such as an in e phase o a g ain
bounda y, and a b oad peak ep esen ing he less mobile ion ac ion in a
mo e o de ed egion in he ma e ial [15]. In p e ious s udies o
[C
2
mpy ][TFSI] and PVDF nanopa icle composi es i was sugges ed
ha he o ma ion o diso de ed in e phases led o an enhancemen in
ionic conduc i i y o a ound one o de o magni ude in he composi e
wi h 10 % o PVDF nanopa icles a 30 ∘C and his u he inc eased
wi h inc easing % o he polyme [16]. This was also con i med by he
na ow peaks obse ed in he
1
H and
19
F NMR spec a a e he addi ion
o PVDF o he composi e and sugges ed ha a ac ion o ions becomes
highly mobile.
Ion mo ions also in luence NMR elaxa ion p ocesses such as longi-
udinal elaxa ion (quan i ied by T
1
), o e ing an addi ional way o
p obe hei dynamics. Fo example,
7
Li T
1
alues a high magne ic ield
s eng hs a e sensi i e o mo ions on a imescale o ns, co esponding o
ib a ional mo ions o he Li ions and hei su ounding en i onmen
[17]. In he sys ems s udied by Meabe and co-wo ke s, whe e di e en
concen a ions o LiTFSI sal we e added o a polyme , he highes
conduc i i y o 3.2 ×10
−5
Scm
−1
a oom empe a u e was obse ed
a e adding 30 w % o LiTFSI. In addi ion, a iable empe a u e T
1
measu emen s enabled he calcula ion o he ac i a ion ene gies, co -
ela ion imes and quad upola cons an s o he sys ems. The analysis o
hese pa ame e s allowed he au ho s o conclude ha as he LiTFSI
con en was inc eased, he Li en i onmen became sligh ly mo e sym-
me ic due o Li ions coo dina ed by he TFSI anions a he han he
e he oxygens o he polyme . This end inc eases wi h he Li sal
con en and dec eases he li hium ionic conduc i i y [18].
The Li doping o he OIPC componen in polyme -based composi es
also has been s udied. Wang e al. p epa ed composi es by coa ing a Li
doped [C
2
mpy ][FSI] laye on comme cial PVDF nanopa icles [19].
They obse ed inc easing ion conduc i i y wi h mass loading con en
un il 30 w % o polyme , a e which i s a ed o dec ease. The con-
duc i i y was a ibu ed mainly o he conduc i e laye coa ed on he
polyme . They also s udied he composi e a e mel ing he OIPC
componen and obse ed a dec ease in he ionic conduc i i y. These
esul s we e suppo ed by
7
Li NMR linewid h analysis, i was concluded
ha an in e ac ion be ween he Li ions and he polyme slow down he Li
ion dynamics. C ys alline, Li- ich phases in Li-doped OIPCs can also
dec ease he ion conduc i i y. A ecen s udy pe o med by N i and
collabo a o s s udied he in e ac ions be ween he OIPC ie hyl
(me hyl)phosphonium e a luo obo a e [P
1222
][BF
4
] and PVDF nano-
pa icles as well as he doping o he OIPC. They obse ed he o ma ion
o Li- ich phases in he OIPC la ice a e he Li-doping o he OIPC. This
phase was associa ed wi h poo ion anspo p ope ies, bu could be
supp essed by he addi ion o PVDF nanopa icles, wi h he PVDF−OIPC
in e phase o med in he polyme -based composi e inc easing he local
diso de o he OIPC and leading o enhanced ionic conduc i i y [20].
The wo ks discussed abo e demons a e he ex ensi e e o s ha
ha e been made o unde s and he in e acial p ope ies ha enhance o
dec ease he desi ed p ope ies o solid elec oly es in composi es.
He ein, we co ela e mac oscopic p ope ies such as ion conduc i i y
wi h he in e acial phenomena in a new chemical a chi ec u e o
composi es consis ing o he OIPC [C
2
mpy ][TFSI] and li hium unc-
ionalised ac ylic polyme nanopa icles (see Fig. 1). The polyme
nanopa icles consis o a c osslinked me hac ylic polyme chain
including a side chain ea u ing a unc ional co-monome li hium 1–(3–
(me hac yloyloxy)p opylsul onyl)–1–( i luo ome hylsul onyl)imide
(LiMTFSI), s uc u ally analogous o he TFSI anion and wi h li hium
ions as he ca ion [21,22]. These polyme nanopa icles exhibi a glass
ansi ion empe a u e o 122 ∘C, an a e age pa icle size o 95 nm and i
was es ima ed ha 80 mol% o he LiMTFSI monome esides a he
su ace o he nanopa icles. These composi es we e designed o ake
ad an age o he in insic p ope ies o he OIPC like plas ici y, wi h he
mechanical s eng h and Li ions con aining ionic unc ionalisa ion o he
polyme , and i is an icipa ed ha he o ma ion o in e aces and in-
e phases be ween hese componen s will p omo e he ion anspo o
he Li ca ions. Addi ionally, he e ec o doping one o he composi es
wi h LiTFSI was s udied. I was al eady obse ed ha he addi ion o Li
sal o he pu e OIPC inc eases he ionic conduc i i y by h ee o de s o
magni ude [9] and in hese composi es i may also p omo e he
compa ibili y be ween he polyme and he OIPC.
2. Expe imen al sec ion
2.1. P epa a ion o polyme pa icles: [C
2
mpy ][TFSI] composi es and
LiTFSI: [C
2
mpy ][TFSI]: polyme nanopa icle composi e
The [C
2
mpy ][TFSI] OIPC and polyme nanopa icles we e syn he-
sized ollowing p e iously es ablished p ocedu es [9,21]. Li hium bis
( i luo ome hanesul onyl) imide LiTFSI was pu chased om Sol ay and
used as ecei ed. The densi ies o [C
2
mpy ][TFSI] and he polyme
nanopa icles we e measu ed a 25 ∘C using a helium pycnome e and
co espond o 1.43 g/cm3 and 1.85 g/cm3, espec i ely. Fou
polyme -based composi es con aining di e en olume pe cen ages o
polyme nanopa icles (10, 15, 25 and 30 (±2) %) we e p epa ed by
dissol ing calcula ed amoun s o [C
2
mpy ][TFSI] and polyme nano-
pa icles in d y me hanol. Fo he p epa a ion o LiTFSI
0.1
[C
2
mpy ]
0.9
[TFSI]:polyme nanopa icle composi e elec oly e, LiTFSI
sal and [C
2
mpy ][TFSI], in [1:9] mola a io, we e also dissol ed in a
mix o d y me hanol and ace one, LiTFSI and [C
2
mpy ][TFSI] ep esen
12 and 63 (±2) % o he composi e, espec i ely. Then, 25 (±2) % o
polyme nanopa icles we e added in o he solu ion.
The esul ing solu ions we e sonica ed and s i ed o o m uni o m
suspensions. The suspensions we e cas on Pe i dishes, and he me h-
anol was quickly e apo a ed unde a gon low a oom empe a u e. The
Y. Ga cía e al.
Jou nal o Magne ic Resonance Open 14-15 (2023) 100095
3
samples we e hen packed in o glass ials and he esidual sol en was
emo ed on a Schlenk line a 50 ∘C o 24 h. A po ion o he composi es
wi h 25 % o polyme nanopa icles and doped wi h LiTFSI we e also
hea ed on a Schlenk a 90 ∘C while s i ing o 2 h. The as-p epa ed 25:75
% polyme nanopa icles: OIPC and doped composi es (unhea ed) a e
named as-p epa ed and as-p epa ed_doped, espec i ely, while he
samples hea ed a 90 ∘C (i.e., mel ing he OIPC componen ) a e named
mel ed and mel ed_doped, espec i ely, h oughou he discussion.
Finally, all samples we e ans e ed in o an a gon- illed glo e box o
s o age and p epa a ion o cha ac e iza ion.
2.2. Cha ac e isa ion
2.2.1. Di e en ial scanning calo ime y (DSC)
DSC measu emen s o he composi es we e ca ied ou using a Me -
le Toledo DSC1 ins umen equipped wi h STARTeV6.10 so wa e.
App oxima ely 7–12 mg o he composi es we e packed in aluminium
pans in an ine a mosphe e and es ed o e a empe a u e ange o
−120 o 140 ◦C a a scanning a e o 10 ◦C/min. To in es iga e he in-
luence o he mal his o y o he samples, h ee he mal cycles we e
pe o med o each sample. All samples we e held a an iso he mal
empe a u e o −120 ◦C o 30 min be o e hea ing.
2.2.2. Pola ised op ical mic oscopy
The OIPC and composi e samples we e i s p epa ed o op ical
mic oscopy by sol en cas ing he ma e ial di ec ly on o a mic oscope
slide, using he sol en s men ioned in Sec ion 2.1, o s udy he com-
posi es as p epa ed, and secondly by placing he samples on a mic o-
scope slide, and squeezed wi h a glass co e a e hea ing he ma e ials
abo e he mel ing poin o he OIPC in a ho s age. The empe a u e was
kep a 95 ∘C o 10 min be o e a cooling a e o 10 ◦C/min was used o
p omo e ec ys alliza ion. The polyme nanopa icles we e placed on a
mic oscope slide as p epa ed. The images we e cap u ed wi h a pola -
ised op ical mic oscope Nikon Eclipse Ti–U wi h 100x magni ica ion a
oom empe a u e.
2.2.3. Elec ochemical impedance spec oscopy (EIS)
The a e age ionic conduc i i ies o he composi es we e measu ed
using a biologic MTZ-35 d i en by MT-lab so wa e. The d ied powde
samples we e p essed be ween wo s ainless s eel discs in a sealed KB
die using a hyd aulic p ess unde 3 ons o p essu e o 5 min. Each pelle
o 3 mm hickness was inse ed in o a he me ically sealed ba el cell. A
equency ange o 10 MHz o 1 Hz was s udied using a ol age ampli-
ude o 0.01 V wi h empe a u e anging om 30 o 70 ∘C a 10 ∘C s eps.
Da a was acqui ed du ing h ee cycles, a hea ing scan om 30 o 70 ∘C, a
subsequen cooling scan (70 o 30 ∘C) and inally, ano he hea ing scan,
wi h he objec i e o obse e he ep oducibili y and any hys e esis ha
migh be p esen . Conduc i i y alues we e calcula ed om Nyquis
plo s in which he ouchdown poin o he semi-ci cle co esponds o he
bulk esis ance o he ionic conduc ing media. The Nyquis plo s o he
composi e as p epa ed and a e mel ing he OIPC componen a 30 ∘C
and 50 ∘C a e p esen ed in he suppo ing in o ma ion (Fig. S1).
2.2.4. Solid-s a e MAS NMR (SSNMR)
The s udy o he molecula -le el s uc u e o he pu e ma e ials and
selec ed composi es by solid-s a e MAS NMR expe imen s was ca ied
ou wi h a B uke A ance III 300 MHz wide-bo e spec ome e wi h a 4
mm H/F-X double esonance MAS p obe, a 12 kHz spinning equency,
and La mo equencies o 300.13, 75.468, 116.6 MHz o
1
H,
13
C and
7
Li, espec i ely. Samples we e packed and sealed in 4 mm NMR MAS
Fig. 1. Molecula s uc u es o (a) he OIPC, (N-me hyl N-e hyl py olidinium bis( i luo ome hanesul onyll)imide [C
2
mpy ][TFSI], (b) he Li sal , Li hium bis
( i luo ome hanesul onyl) imide and (c) he polyme .
Y. Ga cía e al.
Jou nal o Magne ic Resonance Open 14-15 (2023) 100095
4
o o s in an a gon- illed glo ebox.
19
F and
7
Li MAS NMR we e pe -
o med o a e age he chemical shi aniso opy (CSA) e ec s by spin-
ning he samples a 54.74∘ wi h espec o he ex e nal ield. A c oss
pola iza ion (CP) pulse sequence was pe o med wi h decoupling o
inc ease he sensi i i y o
13
C by ans e ing magne iza ion om
abundan nuclei like
1
H and
19
F. Then,
1
H–
13
C CPMAS (wi h
1
H
decoupling) spec a o he nea OIPC, polyme nanopa icles and
selec ed composi es we e acqui ed. Solid sodium luo ide (NaF), li hium
chlo ide (LiCl) and wa e we e used as chemical shi e e ences o
19
F
(−224.2 ppm),
7
Li (0.0 ppm) and
1
H (4.8 ppm), espec i ely.
S a ic (i.e., wi hou MAS) SSNMR expe imen s o s udy dynamics in
he pu e ma e ials and selec ed composi es we e ca ied ou wi h a
B uke A ance III 500 MHz wide-bo e spec ome e wi h La mo e-
quencies o 194.3 and 470.4 MHz, o
7
Li and
19
F, and using a 5 mm HX
s a ic p obe. Spec a we e acqui ed wi h a single pulse expe imen using
a 90∘ pulse in he case o
1
H and
7
Li and Hahn echo expe imen s o
19
F
wi h an echo ime o 5
μ
s. The sample empe a u es we e calib a ed
using he
207
Pb signal om lead ni a e [23]. Line wid hs epo ed
he ein, co espond o he ull wid h a hal o maximum in ensi y
(FWHM) o he spec al peak measu ed as a unc ion o empe a u e. The
sample empe a u e was equilib a ed a each empe a u e o 10 min.
The empe a u e a ia ion o he
7
Li and
19
F spin la ice elaxa ion imes
(T
1
) we e also measu ed o e he same empe a u e ange using a
sa u a ion eco e y pulse sequence. Six een elaxa ion delays we e used,
a ying om 0.1 ms o 60 s depending on he T
1
alue. The esul ing
da a we e i ed using a single exponen ial unc ion using he B uke
TopSpin so wa e.
The
19
F CSA pa e ns o he pu e OIPC we e also s udied using s a ic
Hahn echo expe imen s a −20 ∘C and 20 ∘C and echo delays om 5
μ
s o
0.5 s. These measu emen s we e pe o med in a B uke A ance III 500
MHz wide-bo e spec ome e wi h a 4 mm H/F-X-Y iple esonance
MAS p obe equipped which enabled he use o
1
H decoupling o emo e
he
1
H-
19
F dipola couplings.
3. Resul s and discussion
3.1. The mal analysis
3.1.1. Polyme nanopa icles: [C
2
mpy ][TFSI] composi es
The DSC he mal aces o pu e [C
2
mpy ][TFSI] and he polyme
nanopa icles: [C
2
mpy ][TFSI] composi es con aining 10, 15, 25 and 30
% o polyme nanopa icles a e p esen ed in Fig. 2. Du ing he i s
hea ing cycle, he pu e OIPC goes h ough h ee solid–solid endo he mic
phase ansi ions no ed as IV → III, III → II, and II → I wi h onse em-
pe a u es a app oxima ely −85, 16 and 45 ◦C, espec i ely, be o e
mel ing a 91 ◦C, as epo ed p e iously [9]. These phase ansi ions a e
Fig. 2. DSC o (a) i s and (b) second hea ing aces o he nea [C
2
mpy ][TFSI] and he polyme nanopa icles: [C
2
mpy ][TFSI] composi es as a unc ion o he
concen a ion o polyme pa icle (10, 15, 25 and 30 %), (c) i s and second hea ing aces o Li doped 25 % polyme nanopa icles: [C
2
mpy ][TFSI] composi e
no ed as-p epa ed_doped and mel ed_doped, espec i ely and (d) compa ison be ween he nea OIPC, 25 % polyme nanopa icles: [C
2
mpy ][TFSI] composi es (as-
p epa ed and mel ed) and Li doped 25 % polyme nanopa icles: [C
2
mpy ][TFSI] composi e (as-p epa ed_doped and mel ed_doped).
Y. Ga cía e al.
Jou nal o Magne ic Resonance Open 14-15 (2023) 100095
5
also obse ed in he composi es bu wi h a lowe en halpy (see Table S1
a). Mo eo e , he mel ing peak in he composi es is b oade and i s onse
empe a u e is shi ed om 91 o 88 ∘C. In he second hea ing cycle o
he nea OIPC, he peaks o he phase ansi ions ge na owe while he
mel ing peak ge s b oade which sugges s ha he c ys allini y o he
OIPC componen o hese composi es inc eased a e mel ing and sub-
sequen cooling (see Fig. 2b).
In he DSC aces o he composi es, he phase ansi ions o he OIPC
componen can s ill be obse ed du ing he second hea ing cycle bu
wi h a lowe in ensi y compa ed o he i s hea ing and shi ed o
sligh ly lowe empe a u es (see Fig. 2a and b). These peaks also become
b oade as he concen a ion o polyme nanopa icles inc eases,
e lec ing an inc easing le el o diso de in he OIPC componen .
In addi ion, in he second hea ing ace o he composi es (wi hou
addi ional Li sal ) he appea ance o a new peak wi h an onse empe -
a u e a 60 ∘C can be obse ed o he le o he mel ing peak. This new
peak, which is no obse ed in he i s hea ing ace, becomes mo e
p ominen wi h he inc ease in polyme nanopa icle con en . The i s
hea ing aces o he composi es a e di e en o he second due o he
mel ing o he OIPC componen be ween each scan, which enables
ea angemen o he OIPC molecules and ec ys alliza ion o ake place.
P io o his, he in e ac ion o he OIPC and he polyme nanopa icles
c ea es a local diso de in he OIPC, close o he polyme nanopa icles,
as can be in e ed om he b oade mel ing peaks in Fig. 2a. This local
diso de close o he polyme nanopa icles is illus a ed schema ically
in Fig. 3a. The addi ional mel ing peak in he DSC (second hea ing) scans
o he composi es sugges s an addi ional componen , o med a e he
mel ing o he OIPC phase, wi h u he inc eased diso de ( ela i e o
he pu e OIPC) esul ing in a local dec ease in he OIPC mel ing em-
pe a u e [11,24]. This peak indica es he o ma ion o an in e phase
whe e he OIPC in e ac s wi h (and possibly mixes wi h) he polyme
chains du ing he mel ing o he OIPC componen (Fig. 3b). This egion
may also p omo e u he diso de in he local OIPC s uc u e as p o-
posed by N i and co-wo ke s [11]. The ac ha he in e phase mel ing
peak o e laps wi h he mel ing peak o he pu e OIPC componen in he
second hea ing ace o he composi es hinde s he calcula ion and
compa ison o he en opy and en halpy o hese wo componen s (peak
decon olu ion is ex emely di icul due o he asymme ic shape o
hese peaks). These obse a ions a e also suppo ed by a supp essing
e ec in he en halpy o he OIPC in he second hea ing in compa ison
wi h he i s hea ing and indica e ha he composi e sys ems become
mo e diso de ed (see Table S1 a).
3.1.2. Li sal – polyme nanopa icle composi e
The e ec s o he addi ion o 1 mol% LiTFSI sal in o he 25 %
polyme nanopa icles: [C
2
mpy ][TFSI] composi e was s udied du ing
he i s (as-p eap ed_doped) and second (mel ed_doped) hea ing, and
he DSC he mal aces o his sample a e p esen ed in Fig. 2c. This
concen a ion o Li sal was selec ed based on he inc ease o ionic
conduc i i y obse ed in a p e ious s udy o he pu e OIPC [9,25].
The solid-solid phase ansi ions a e obse ed in he composi e
doped wi h LiTFSI sal du ing he i s hea ing (as-p eap ed_doped), and
he addi ion o LiTFSI sal dec eases he en halpy o he OIPC u he
sugges ing ha he local en i onmen o he OIPC become mo e diso -
de ed (see Table S1 b). Fu he mo e, hese ansi ions a e b oadened
signi ican ly a e mel ing he OIPC componen and eco ding a second
hea ing scan (mel ed_doped) indica ing a high deg ee o s uc u al dis-
o de wi hin he OIPC; indeed, he nea comple e absence o he solid-
solid phase ansi ions in he second scan sugges s ha he OIPC e-
ains i s phase I cha ac e e en a lowe empe a u es and i is ollowed
by a cold c ys allisa ion be o e mel ing.
The mel ing peak o he OIPC in he Li-doped composi es show onse
Fig. 3. Schema ic ep esen a ions o (a) local diso de in he OIPC componen close o he polyme nanopa icles be o e he mel ing o he OIPC componen , (b) he
o ma ion o an in e phase (o ange egion) a e u he mixing o polyme nanopa icles and he OIPC a e mel ing he OIPC componen , wi h inc eased diso de in
he OIPC componen , and (c) doping o he composi e wi h LiTFSI. Schema ic ep esen a ions (d) o he dis ibu ion o Li ions in he polyme , he OIPC la ice
and LiTFSI.
Y. Ga cía e al.
Jou nal o Magne ic Resonance Open 14-15 (2023) 100095
6
empe a u es shi ed o a lowe empe a u e compa ed wi h he undo-
ped composi es (70 ∘C du ing he i s hea ing and a 65 ∘C du ing he
second hea ing) as shown in Fig. 2d. In addi ion, his peak is signi i-
can ly b oadened in he doped sys em. Thus, mo e s uc u al diso de
seems o be o med in he OIPC componen o he composi es a e
adding LiTFSI. I is accep ed ha in he LiTFSI doped [C
2
mpy ][TFSI] a
Li ich eu ec ic solu ion a g ain bounda ies o he OIPC is he leading
mechanism o conduc i i y [9]. As a esul o he OIPC ca ions
exchanging wi h Li on he su ace o he nanopa icle a u he Li doping
o he OIPC componen occu s. This will also c ea e g ea e local ee
olume, diso de , and dynamics.
Thus, we obse e he o ma ion o wo in e acial egions in he
composi es be o e and a e doping wi h Li sal . The i s one shows local
s uc u al diso de in he OIPC la ice, which is p esen in he composi es
as p epa ed, and will be e e ed h ough he documen as he “in e -
acial egion”. The second one is cha ac e ised by u he s uc u al
diso de in he OIPC la ice because o he deepe mixing o he com-
ponen s o he composi es ha occu s when he OIPC is mel ed, and his
will be e e ed o as he “in e phase”.
3.2. C ys alli e mo phology
O ganic ionic plas ic c ys als can be op ically aniso opic ma e ials
and p esen bi e ingence as a esul o he sho - ange diso de wi hin
hei long- ange o de ed c ys alline la ices [26]. On he o he hand,
comple ely amo phous ma e ials such as polyme s a e op ically
iso opic and do no exhibi s bi e ingence [27]. The mo phology o he
OIPC and composi es was s udied quali a i ely using an op ical mic o-
scope o ge insigh s abou he c ys alli e size, s uc u e, and dis ibu ion
(see Fig. 4). The images we e aken a oom empe a u e a e sol en
cas ing he samples o s udy he ma e ials as p epa ed and a e hea ing
he samples abo e he mel ing poin o he OIPC on a mic oscope
hea ing s age.
Pu e [C
2
mpy ][TFSI] in he as p epa ed s a e displays a poly-
c ys alline s uc u e o c ys al domains la ge han 500 µm (Fig. 4a and
b). The colo s in Fig. 4 ep esen di e en o ien a ions o he c ys alli es
delimi ed by g ain bounda ies. A e adding he polyme nanopa icles
some egions wi h much smalle c ys als (<50 µm) a e obse ed (see
Fig. 4c). The image o he as p epa ed composi e wi h LiTFSI (Fig. 4d)
Fig. 4. Pola ised op ical mic og aphs o (a) and (b) pu e OIPC as p epa ed, (c) he 25 % polyme nanopa icles: [C
2
mpy ][TFSI] composi e as p epa ed, (d) Li doped
composi e wi h LiTFSI as p epa ed, (e) he OIPC a e mel ing he OIPC componen , ( ) 25 % polyme nanopa icles: [C
2
mpy ][TFSI] composi e a e mel ing he
OIPC componen , and (g) doped wi h LiTFSI a e mel ing he OIPC componen .
Y. Ga cía e al.
Jou nal o Magne ic Resonance Open 14-15 (2023) 100095
7
shows mo e a ia ion in colou indica ing di e en c ys al o ien a ions,
sugges i e o an inc eased le el o diso de in his ma e ial han in he as
p epa ed polyme -based composi e.
A e mel ing and ec ys allisa ion, he nea OIPC shows smalle
c ys als on he o de o 100 µm wi h di e en o ien a ions (see Fig. 4e)
indica ing ha mo e g ain bounda ies a e o med a e mel ing he OIPC
in compa ison wi h he as-p epa ed sample. A e mel ing he OIPC
componen in he composi e wi h 25 % o polyme nanopa icles,
polyc ys alline sphe uli e-like domains g ea e han 100 µm in size a e
obse ed wi h a inc eased amoun o g ain bounda ies han he as-
p epa ed sample (Fig. 4 ). This is a ibu ed o he in luence o he
polyme nanopa icles on he ec ys allisa ion o he OIPC, which may
ac as nuclea ion si es and di ec he c ys al g ow h. Doping he com-
posi e wi h LiTFSI also leads o he o ma ion o smalle sphe uli es han
hose obse ed a e mel ing he OIPC componen in he polyme -based
composi e hus leading o u he educed domain sizes as seen in
Fig. 4g, indica ing mo e s uc u al diso de a e doping he composi e
wi h Li. These obse a ions again suppo he inc easing diso de
obse ed in he DSC hea ing aces a e mel ing he OIPC componen in
he composi e wi h li hium doping.
These images a e consis en wi h he DSC esul s discussed in he
p e ious sec ion, wi h smalle c ys alli es being accompanied by a
g ea e o e all le el o diso de ed g ain bounda y egions. Simila ob-
se a ions ha e p e iously been made by Ramos and collabo a o s in he
s udy o poly(e hylene oxide) (PEO) and OIPCs memb ane composi es
[28], who p oposed ha he OIPC migh be con ined by he polyme
componen du ing he ec ys allisa ion, u he inc easing he s uc u al
diso de .
3.3. Ionic conduc i i y measu emen s
The ionic conduc i i ies o he pu e OIPC and a selec ed composi e
wi h 25 % o polyme nanopa icles as p epa ed (i.e., as-p epa ed) and
a e mel ing he OIPC componen (i.e., mel ed) and he Li doped
composi e as p epa ed (i.e., as-p epa ed_doped) and a e mel ing he
OIPC componen (i.e., mel ed_doped) we e measu ed as a unc ion o
empe a u e h ough EIS expe imen s and he esul s a e p esen ed in
Fig. 5a. The expe imen s we e pe o med om 20 o 60 ∘C o a oid he
mel ing empe a u e o he OIPC componen . The obse a ion o a single
well-de ined semici cle in he Nyquis plo s o all samples (Fig. S1)
sugges s a single conduc i i y mechanism is p esen in all samples.
A gene al end o inc eased conduc i i y wi h empe a u e can be
obse ed o he samples measu ed. I is also obse ed ha he ionic
conduc i i y o he composi e (whe e he OIPC componen is mo e
diso de ed as obse ed in he DSC hea ing aces) is highe han he pu e
[C
2
mpy ][TFSI] du ing he i s hea ing (see Fig. 2a). The e is no
obse ed jump in conduc i i y du ing he ansi ion om phase II o I,
implying ha his phase ansi ion does no signi ican ly a ec he ion
conduc i i y mechanism.
A u he inc ease in ion conduc i i y in he composi e is obse ed
du ing he second hea ing (mel ed, Fig. 5a). This inc ease in conduc-
i i y can be a ibu ed o he o ma ion o he diso de ed in e phase
egion be ween he OIPC and polyme componen s as sugges ed by DSC
esul s, as well as he la ge amoun o OIPC g ain bounda ies obse ed
in he mo phology s udy o he composi es (Fig. 4). The in e phase and
g ain bounda ies a e bo h expec ed o ea u e inc eased diso de , dy-
namics, and ee olume. Addi ionally, he [C
2
mpy ] ca ions may un-
de go exchange wi h he Li on he polyme nanopa icles su ace, he e
may be a Li doping e ec on he OIPC ( u he discussed h ough he
s uc u al NMR analysis in Sec ion 3.5), ha acili a es he ion
conduc i i y.
The as-p epa ed_doped composi e shows simila conduc i i ies a
lowe empe a u es o he pu e OIPC sugges ing ha he in e acial e-
gion be ween he OIPC, polyme nanopa icles and LiTFSI does no
imp o e he a e age ion mobili y un il phase I is eached. Con e sely,
a e mel ing he OIPC componen in he doped composi e he conduc-
i i y is obse ed o inc ease signi ican ly (by mo e han one o de o
magni ude a 60 ∘C in compa ison wi h he OIPC). This can be a ibu ed
o an inc ease in he mobili y o he ions loca ed in he diso de ed
in e phase o med be ween he OIPC and polyme nanopa icles as a
esul o he ini ial exchange be ween OIPC ca ions and Li on he poly-
me nanopa icles ha c ea e a pa ial doping o he OIPC and he
u he doping o he OIPC a e adding LiTFSI leading o a highe
conduc i i y in mel ed_doped compa ed o mel ed (Fig. 5). These ob-
se a ions suppo he DSC and mo phology analysis whe e mo e
s uc u al diso de is obse ed in he doped composi e a e mel ing he
OIPC componen in compa ison wi h he as-p epa ed doped composi e.
Howe e , he mel ed_doped showed lowe conduc i i y han he OIPC
doped wi h 0.9 mol% o LiTFSI s udied p e iously [9], which showed
conduc i i y o almos wo o de o magni ude (i.e., om 10
-8
o 10
-6
S
cm
-1
) la ge han he OIPC a 27 ∘C indica ing ha he polyme nano-
pa icles es ic he mobili y o he ions in he composi e in compa ison
wi h he doped OIPC.
3.4. Solid-s a e NMR analysis: s uc u e
The pu e [C
2
mpy ][TFSI], polyme nanopa icles, and composi es
wi h 25:75 % polyme nanopa icles: [C
2
mpy ][TFSI] as p epa ed (as-
p epa ed) and a e mel ing he OIPC componen (mel ed), as well as he
same composi e wi h 1 mol% LiTFSI sal inco po a ed as p epa ed (as-
Fig. 5. Ion conduc i i y as a unc ion o he empe a u e o (a) he composi es wi h polyme nanopa icles concen a ion o 25 % as p epa ed (as-p epa ed) and
a e mel ing he OIPC componen (mel ed), and (b) he LiTFSI doped composi e as p epa ed (as-p epa ed_doped) and a e mel ing he OIPC componen (mel-
ed_doped) agains he ion conduc i i y o [C
2
mpy ][TFSI].
Y. Ga cía e al.
Jou nal o Magne ic Resonance Open 14-15 (2023) 100095
8
p epa ed_doped) and a e mel ing he OIPC componen (mel ed_doped)
we e s udied by
13
C CPMAS and
19
F and
7
Li MAS NMR expe imen s. The
1
H–
13
C CPMAS NMR spec a o hese samples and he assignmen o
ca bon esonances o he OIPC and he polyme nanopa icles a e
p esen ed in Fig. 6.
The c ys alline s uc u e o he OIPC esul s in na owe
13
C peaks
han he signals om he polyme whe e he ca bon si es exis in a
locally diso de ed s uc u e. The as-p epa ed composi e spec um e-
sembles he pu e OIPC, and polyme signals supe imposed wi h sligh ly
b oade OIPC peaks shi ed o a lowe chemical shi , sugges ing ha he
chemical en i onmen o he ca bons in he OIPC is al e ed o some
ex en by he addi ion o polyme nanopa icles and ha he OIPC and
polyme ha e mixed in he in e acial egion. On he o he hand, in he
mel ed composi e some changes can be obse ed in he shape and in-
ensi y o some o he polyme signals and in he OIPC linewid h o he
13
C peaks whe e he na owe
13
C peaks e lec s he inc ease o he local
dynamics o he OIPC ca ions (i.e., o a ions) in his composi e. In
addi ion, hese signals a e shi ed o a lowe chemical shi han in
mel ed composi e and sugges ha he chemical en i onmen o he
OIPC ca ions was al e ed a e he addi ion o he polyme nanopa icles,
consis en wi h some mixing wi h he OIPC componen in he mel s a e.
In he composi e doped wi h he Li sal as p epa ed, changes in he
in ensi y and b oad signals o he ca bon en i onmen s ha come om
he polyme a e also obse ed in a simila magni ude o mel ed_doped
composi e. The
13
C peaks om he OIPC componen show simila line-
wid hs han he pu e OIPC bu a e shi ed o lowe chemical shi s han
he as-p epa ed and mel ed composi es (see Fig. S2), sugges ing ha he
addi ion o LiTFSI u he changes he local en i onmen a ound he
OIPC ca ions. In addi ion, a new peak a 180 ppm is obse ed in bo h
doped composi es. This is a ibu ed o an in e ac ion be ween he Li
ca ion o he Li sal wi h he elec onega i e oxygen o he ca bonyl
g oups a he su ace o he polyme nanopa icles.
The changes in he chemical en i onmen o he OIPC ca ion signals
indica ed by he lowe chemical shi s sugges an exchange o hese
ca ions wi h he Li ions on he polyme nanopa icles, as will be dis-
cussed la e , ha allows an ini ial Li doping o he OIPC in he com-
posi es as-p epa ed and mel ed and a u he doping a e adding LiTFSI.
These doping e ec s no only inc eased local diso de bu also local
dynamics o he OIPC ca ions. I should be no ed ha he
13
C signals
om he CF
3
g oups o he polyme nanopa icles and OIPC a e no
obse ed in hese spec a due o he use o c oss pola isa ion om
1
H.
Changes in he a e age chemical en i onmen o he Li ions we e
obse ed in he composi es wi h espec o he polyme nanopa icles as
can be seem in Fig. 7. A b oad
7
Li MAS NMR peak is obse ed o he
polyme nanopa icles as was expec ed due o he inhe en s uc u al
diso de in his ma e ial.
In gene al, he composi es showed asymme ic
7
Li peak wid hs wi h
a no iceable shi o lowe chemical shi s wi h espec o he polyme ,
indica ing a change in he su ounding s uc u al en i onmen o he Li
ions. In he case o he as-p epa ed composi e, he peak was shi ed as a
esul o he in e ac ion o he Li ions wi h he su ounding OIPC. Once
he OIPC is mel ed in he composi e, he OIPC and polyme componen s
become mo e in ima ely mixed and as a esul a u he shi and b oade
peak is obse ed o mel ed composi e, indica i e o mo e s uc u al
diso de a ound he Li ions in he in e phase. A e doping he composi e
Fig. 6. (a)
1
H–
13
C CPMAS NMR o [C
2
mpy ][TFSI], polyme , 25:75 % polyme nanopa icles: [C
2
mpy ][TFSI] composi es as p epa ed (as-p epa ed) and a e
mel ing he OIPC componen (mel ed), and Li doped composi es as p epa ed (as-p epa ed_doped) and a e mel ing he OIPC componen (mel ed_doped). Molecula
s uc u es o (b) [C
2
mpy ][TFSI] and c) polyme wi h pa ial assignmen o he
13
C peaks o ce ain s uc u al si es.
Fig. 7.
7
Li MAS NMR spec a o polyme nanopa icles, 25:75 % polyme
nanopa icles: [C
2
mpy ][TFSI] composi es as p epa ed (as-p epa ed) and a e
mel ing he OIPC componen (mel ed), and Li doped composi es as p epa ed
(as-p epa ed_doped) and a e mel ing he OIPC componen (mel ed_doped).
Y. Ga cía e al.
Jou nal o Magne ic Resonance Open 14-15 (2023) 100095
9
wi h he Li sal he
7
Li signals in as-p epa ed_doped and mel ed_doped
appea e y sligh ly u he shi ed o he igh , bu a e qui e simila o
he spec um o mel ed composi e. The changes obse ed in he shape,
linewid h and chemical shi in he composi es sugges some ype o
complexa ion o exchange o he li hium on he polyme nanopa icles
wi h o he anions, in his case wi h he OIPC ca ions. This exchange is
g ea e in he composi es a e mel ing he OIPC componen (i.e., mel ed
and mel ed_doped) and esul s in in e phases wi h inc eased diso de
ha acili a e he ion conduc i i y as discussed in Sec ions 3.1–3.3.
19
F MAS NMR spec a we e also acqui ed om he OIPC, polyme
nanopa icles and composi es, and a e shown in Fig. 8. A single
19
F
iso opic chemical shi is obse ed o he pu e OIPC, polyme nano-
pa icles and all ou composi es. Howe e , he
19
F signal o he polyme
is much b oade han ha o he OIPC and composi es due o he highe
le el o local s uc u al diso de a ound he polyme anionic g oups.
The
19
F spec a o he composi es appea e y simila o ha o he
OIPC and his is due o he dominance o he OIPC TFSI signal. Howe e ,
a sligh b oadening o he signal obse ed in he doped composi es
sugges s some inc eased s uc u al diso de a e he addi ion o LiTFSI.
Due o he composi ion, he b oade signal om he anionic polyme
g oups will show a much lowe in ensi y and is hus somewha hidden
unde he sha pe TFSI signal (see peak decon olu ion in Fig. S3).
In e ac ions such as chemical shi aniso opy (CSA) a e inhe en o
s a ic
19
F NMR spec a and a e ela ed o he chemical en i onmen , so
can p o ide in o ma ion bo h on he s uc u e (e.g. con o ma ion) and
molecula dynamics such as o a ions o eo ien a ions o TFSI anions
[29]. The e o e, s a ic
19
F NMR spec a we e also acqui ed om hese
samples using a Hahn echo pulse sequence. Addi ionally,
1
H decoupling
was used o emo e he he e onuclea dipola in e ac ions wi h he
p o ons p esen on he [C
2
mpy ] ca ion, p o iding sha pe
19
F CSA
pa e ns. In e es ingly, he i ing o he [C
2
mpy ][TFSI] s a ic Hahn
echo NMR spec um wi h a sho echo delay ime a 20 ∘C equi ed h ee
dis inc CSA pa e ns (Fig. 9 and Table S2) despi e only a single iso opic
19
F signal being obse ed by MAS NMR (Fig. 8).
These CSA pa e ns a e pos ula ed o a ise om di e en con o -
ma ions o he TFSI anion (i.e., ans, cis and gauche). P e iously, hese
h ee di e en con o ma ions o he TFSI ion we e obse ed in liquid
LiTFSI-ace amide elec oly es wi h mola a ios o 1:2, 1:4, and 1:6 using
DFT simula ions [30]. I was obse ed ha he gauche con o ma ion was
p e e ed when he concen a ion o ace amide molecules was low (i.e.,
elec oly e wi h mola a io o 1:2) because i can help o educe he
epulsion be ween Li ca ions in close con ac in he elec oly e.
Howe e , a highe ac ion o TFSI anions adop ed he cis con o ma ion
in he elec oly e wi h high ace amide concen a ion whe e s ong in-
e ac ions be ween he TFSI anions and Li ca ions wi h ace amide occu .
Finally, he au ho s obse ed ha TFSI anions adop ed p e e en ially he
ans con o ma ion wi h lowe ene gy in he elec oly e wi h mola a io
o 1:4. The cis and ans con o ma ions ha e also been obse ed by
solid-s a e NMR, showing di e en iso opic chemical shi s [31].
The single iso opic signal we ha e obse ed in he MAS spec um
indica es ha hese h ee con o ma ions mus unde go exchange on he
imescale o he MAS NMR signal acquisi ion (a ound 5 ms). The
assignmen o hese dis inc CSA pa e ns o speci ic con o ma ions
would equi e he pa ame e s o be calcula ed om he di e en
s uc u es, which is beyond he scope o his a icle. Fu he e idence o
he exchange be ween hese si es is p o ided by he e olu ion o he
spec al line shapes as he empe a u e and echo ime a e a ied
(Fig. S4).
3.5. Solid-s a e NMR analysis: dynamics
The analysis o SSNMR line wid hs and T
1
elaxa ion imes we e
employed in his s udy. These expe imen s a e sensi i e o o a ional
and ansla ional dynamics, and quan i a i e and quali a i e in o ma-
ion on dynamics can be ex ac ed om hese pa ame e s based on hei
empe a u e dependence. The ion dynamics in he OIPC, polyme
nanopa icles and composi es we e s udied using solid-s a e
19
F,
1
H and
7
Li NMR ca ied ou on s a ic samples.
3.5.1. Line wid h analysis
Polyme nanopa icles. The e ec o empe a u e on he li hium en i-
onmen and dynamics in he pu e polyme nanopa icles was s udied by
7
Li single pulse s a ic NMR expe imen s wi h he sample hea ed om 20
o 160 ∘C, ollowed by cooling (Fig. 10). Du ing hea ing om 20 o 100
∘C, he
7
Li line wid h dec eases om a ound 2000 o 1200 Hz, e lec ing
inc eased dynamics o he Li ca ions such as as e ion jumps ha esul
in mo ional a e aging [17,32]. A d ama ic inc ease in he
7
Li line wid hs
is hen seen abo e 100 ◦C, eaching a ound 3400 Hz a 160 ◦C. When he
sample is cooled om 160 ∘C a u he inc ease o he line wid h alues is
obse ed.
This beha iou is ela ed o he eo ganiza ion o he polyme
s uc u e. Ini ially, he li hium ions a e loca ed p ima ily on he su ace
o polyme nanopa icles associa ed wi h he anion o he side chain, and
Fig. 8.
19
F MAS NMR spec a o [C
2
mpy ][TFSI], polyme , 25:75 % polyme
nanopa icles:[C
2
mpy ][TFSI] composi es as p epa ed (as-p epa ed) and a e
mel ing he OIPC componen (mel ed), and Li doped composi es as p epa ed
(as-p epa ed_doped) and a e mel ing he OIPC componen (mel ed_doped).
Side bands a e indica ed wi h (*) in each spec um.
Fig. 9. Fi ing s a ic
19
F NMR CSA pa e ns o [C
2
mpy ][TFSI] a 20◦C o h ee
di e en con o ma ions o he TFSI anion.
Y. Ga cía e al.
