1
Tailo ed Silicon Nanos uc u es in Conduc i e-based Hyd ogel
Binde s: Role o Size, S uc u e, and Su ace Chemis y in
Enhancing Li-Ion Ba e y Pe o mance
Gab iela Soukupo á 1, Filip Ma ějka 1,2, Zuzana Vlčko á Ži co á 3, Abdelghani Laachachi 4,
Pa el Galář 2, Milosla Lho ka 5, O aka F ank 3, Jiří Če enka 2, Fa ima Hassouna 1*
(1) Facul y o Chemical Enginee ing, Uni e si y o Chemis y and Technology, P ague, 166 28
P ague 6, Czech Republic
(2) FZU - Ins i u e o Physics o he Czech Academy o Sciences, Cuk o a nická 10/112, P ague,
162 00 P ague 6, Czech Republic
(3) J. Hey o sky Ins i u e o Physical Chemis y, Czech Academy o Sciences, Dolejsko a 2155-
3, P ague 18223 8, Czech Republic
(4) Luxembou g Ins i u e o Science and Technology (LIST), 5, ue Bommel, L-4940 Hau cha age,
Luxembou g
(5) Facul y o Chemical Technology, Uni e si y o Chemis y and Technology, P ague, 166 28
P ague 6 , Czech Republic
Co esponding au ho :
E-mail add esses: [email p o ec ed] (Assoc. p o . Fa ima Hassouna)
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Abs ac
Silicon (Si) is a p omising high-capaci y anode ma e ial o Li-ion ba e ies (LIBs), bu i s p ac ical
applica ion is limi ed by se e e olume expansion du ing li hia ion/deli hia ion, leading o poo
cycling s abili y. While Si nanos uc u ing mi iga es his issue, i emains only a pa ial solu ion.
This s udy sys ema ically in es iga es he e ec s o Si pa icle size (6, 20, 55, and 100 nm), su ace
chemis y (oxide ype and deg ee), and solid-s a e p ope ies (amo phous s. c ys alline) on he
elec ochemical pe o mance o Si-based anodes using polypy ole (PPy) hyd ogel binde . In si u
PPy polyme iza ion a ound Si nanopa icles o ms a 3D in e connec ed conduc i e ne wo k wi hin
PPy/Si anodes, e ec i ely accommoda ing olume changes and main aining elec ical con ac
du ing he gal anos a ic cha ge-discha ge cycling. The pa icle size dependence shows ha la ge
Si nanopa icles p o ide highe ini ial cha ge capaci y (2975 mAh/g), whe eas smalle ones
imp o e cycling s abili y (85 % capaci y e en ion a e 100 cycles). Amo phous Si exhibi s lowe
speci ic capaci y bu supe io capaci y e en ion (~100% a e 100 cycles) compa ed o c ys alline
Si. Cyclic ol amme y and elec ochemical impedance spec oscopy demons a e ha in eg a ing
6 and 20 nm Si nanoc ys als in o he PPy ne wo k signi ican ly enhances anode pe o mance.
These indings highligh he impo ance o op imizing Si ma e ial p ope ies in designing
conduc i e hyd ogel-based anodes o high-pe o mance LIBs.
Keywo ds
Li-ion ba e y, Si nanopa icles, 3D ne wo k, elec ically conduc i e polyme , elec ochemical
p ope ies
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1 In oduc ion
In ecen yea s, he demand o cos -e ec i e, high-pe o mance echa geable ba e ies wi h
ex ended cycle li e has g own signi ican ly, d i en by hei applica ions in elec onic de ices,
elec ic ehicles, and la ge-scale ene gy s o age sys ems. Among all, Li-ion ba e ies (LIB) ha e
a ac ed signi ican a en ion due o hei excep ional ene gy densi y, high powe densi y, and long
cycle li e [1, 2]. The comme cially used g aphi ic anode o e s only limi ed heo e ical speci ic
capaci y (~370 mAh/g) [2, 3], which has p omp ed ex ensi e esea ch in o al e na i e anode
ma e ials. Si is conside ed one o he mos p omising anode ma e ials o LIB due o i s high
heo e ical speci ic li hia ion capaci y (~3579 mAh/g o Li15Si4), low discha ge po en ial (∼0.4 V
s Li/Li+), en i onmen al sus ainabili y, and high elemen al abundance [1, 4, 5]. Howe e , he
p ac ical applica ion o Si as an anode ma e ial in LIB is signi ican ly limi ed due o i s poo
elec ical conduc i i y and subs an ial olume expansion (~300 % o Li15Si4 [6]) du ing li hia ion.
This expansion leads o se e e issues such as ma e ial c acking, anode pul e iza ion, o e g ow h
o a solid elec oly e in e phase (SEI), and capaci y ading [4, 5, 7].
To add ess hese challenges, se e al s a egies ha e been explo ed. One p omising app oach is he
nanos uc u ing o Si (e.g., nanowi es o nanopa icles), which helps accommoda e he olume
changes, he eby enhancing he mechanical s abili y o he ma e ial and imp o ing i s cycling
pe o mance [8-10]. I has been epo ed ha when he pa icle size is educed below a c i ical
h eshold o 150 nm, he c acking o he ma e ial is signi ican ly educed [11-13]. Al hough
nanos uc u ing imp o es he mechanical p ope ies o Si anodes, se e al signi ican challenges
emain. These include he highe su ace ac i i y o Si, which can lead o pa icle agglome a ion,
he o ma ion o a hicke SEI laye , and he high cos associa ed wi h he p epa a ion p ocess [11,
14, 15]. To o e come he poo elec ical conduc i i y o nanos uc u ed Si and acili a e mo e
e icien Li-ions di usion, conduc i e ca bon (C) addi i es such as ca bon black (Supe P), ca bon
nano ubes, and g aphene a e commonly inco po a ed. The addi ion o hese C ma e ials no only
helps o bu e he olume expansion du ing li hia ion bu also imp o es he o e all conduc i i y,
he eby p o iding an e ec i e elec onic pa hway o elec on ans e [4, 14]. Gene ally, polyme
binde s such as ca boxyme hyl cellulose, polyamide imide, o poly(ac ylic acid) (PAA) a e
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inco po a ed in o Si/C o enhance mechanical s abili y and hence, he cycling pe o mance o he
anode ma e ial [4, 16].
E ec i e binde s o Si-based anodes mus mee se e al c i ical equi emen s. They mus be
capable o o ming uni o m mix u es wi h Si and C, es ablishing s ong binding in e ac ions wi h
bo h Si and C o ensu e s able elec ical pa hways o he cu en collec o and demons a ing
elec ochemical s abili y wi hin he ope a ional po en ial window. Mo eo e , hey should exhibi
high elas ic modulus alues o accommoda e he signi ican olume expansion o Si, esis
excessi e swelling in he elec oly e, acili a e he o ma ion o a s able and hin SEI laye , and
ensu e a obus connec ion be ween he anode ma e ial and he cu en collec o h oughou
cycling. In addi ion o hese echnical cha ac e is ics, an ideal binde should also be economically
easible, s aigh o wa d o manu ac u e in la ge quan i ies, a o dable, and compa ible wi h
exis ing p oduc ion echniques [16]. The use o he a o emen ioned insula ing polyme binde s
may esul in a weak in e ace be ween Si and C, leading o con ac loss du ing cycling [16]. In
his con ex , eplacing he insula ing con en ional binde s wi h elec ically conduc i e polyme s
p esen s a p omising al e na i e, as i would elimina e he weak in e ace be ween Si and C. The
conduc i e polyme would no only se e as a binde bu also enhance he conduc i i y o he
anode ma e ial. The use o conduc i e polyme s, such as polyaniline, polypy ole (PPy), and
poly(3,4-e hylenedioxy hiophene), o e s se e al ad an ages, including mechanical lexibili y,
cos -e ec i eness, ease o syn hesis and p ocessing, en i onmen al iendliness, high elec ical
conduc i i y, and elec ochemical ac i i y [17-19].
Al hough conduc i e polyme s ha e ecei ed signi ican in e es o hei applica ion in LIB,
ela i ely limi ed esea ch has been conduc ed on in eg a ing hem wi h Si o de elop
comme cially iable anodes o LIB [1-3]. A iable and p omising s a egy o in eg a ing Si in o
conduc i e polyme binde s in ol es a hyd ogel-based p epa a ion echnique. In his app oach, in
si u polyme iza ion and c osslinking o he conduc i e polyme ake place in he p esence o Si,
o en accompanied by an addi ional elec ically conduc i e addi i e. The p ocess esul s in he
o ma ion o a h ee-dimensional (3D) ne wo k, whe ein Si is uni o mly coa ed and in e connec ed
by he conduc i e polyme ma ix [1-3, 5, 8, 16, 20, 21]. This 3D in e connec ed ne wo k imp o es
elec ochemical pe o mance h ough se e al bene icial ea u es. The hyd ogel amewo k
unc ions as bo h a conduc i i y enhance and a conduc i e binde , imp o ing he pa icle- o-
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pa icle con ac . I s po ous s uc u e helps bu e he olume changes o Si du ing li hia ion [21],
while he 3D conduc i e ne wo k acili a es imp o ed elec on and ion di usion [8]. Fu he mo e,
embedding Si wi hin he amewo k p omo es he o ma ion o a mo e s able SEI du ing li hia ion
by be e isola ing Si om he elec oly e [20]. Despi e hei impo ance, he impac o key ac o s
such as he size, su ace chemis y, and solid-s a e p ope ies o Si on he elec ochemical
pe o mance o esul ing anodes emains poo ly unde s ood and has no been sys ema ically
in es iga ed in Si/conduc i e polyme -based anodes, including hose p epa ed using hyd ogel-
based app oaches.
P e ious s udies in es iga ing he size e ec o Si in anode ma e ials ha e p ima ily ocused on
physical blending me hods, whe e Si pa icles o ca bonized co e-shell Si pa icles ( anging in size
om 30 nm o 5 μm) we e mechanically mixed wi h a binde and ca bon addi i e [12, 15, 22-24],
o p epa ed ia gas deposi ion echniques [25]. The s udies on Si anodes using conduc i e hyd ogel
binde s ha e used di e en ypes and sizes o Si, including nanopa icles wi h a e age diame e s
anging om 40 o 300 nm [1, 3, 5, 8, 16, 21, 26, 27], mic o-sized po ous Si pa icles [28], and Si
dend i es [20]. Howe e , he selec ion o Si ype and size has o en been a bi a y, lacking a
sys ema ic me hodology. Fu he mo e, hese s udies p edominan ly used comme cial Si ma e ials
wi h uncon olled su ace chemis y. This lack o sys ema ic in es iga ion ex ends o he p omising
po en ial o Si quan um do s (SiQD). Despi e hei ad an ages, such as high su ace a ea, sho e
di usion pa hways, and educed olume expansion, which make SiQD p omising o LIB, only a
limi ed numbe o s udies ha e ocused on hei applica ion [29-31]. These s udies ha e
demons a ed encou aging elec ochemical pe o mances [32-35]. Howe e , challenges pe sis in
syn hesizing monodispe se SiQD and in mi iga ing side eac ions ha a ise due o hei la ge ac i e
su ace a ea, which complica e hei p ac ical use.
To he bes o ou knowledge, no comp ehensi e s udy has sys ema ically examined he in luence
o Si pa icle size, su ace chemis y, and in insic solid-s a e p ope ies on he elec ochemical
pe o mance o Si-based anodes wi h conduc i e hyd ogel binde s in LIB. To add ess his
knowledge gap and de elop a undamen al unde s anding o s uc u e-p ope y ela ionships, his
s udy in es iga ed he pe o mance o Si-based anode ma e ials o LIB. These ma e ials we e
p epa ed ia he in si u polyme iza ion o a conduc i e PPy hyd ogel using an en i onmen ally
iendly, wa e bo ne app oach. Phy ic acid (PhA), a na u ally occu ing molecule, was employed
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as a c osslinking agen o he PPy chains, while PAA se ed as a s abilizing agen o he Si
nanopa icles. The PPy hyd ogel unc ioned as a high-pe o mance conduc i e binde , con o mally
coa ing he Si nanopa icles. The s udy examined he e ec s o size, su ace chemis y, and solid-
s a e p ope ies (amo phous e sus c ys alline) o bo h comme cial and lab-syn hesized Si
nanopa icles, including SiQD (pa icle size below 10 nm), on he s uc u al, mo phological, and
elec ochemical pe o mance o he Si-based anode ma e ials. These insigh s enabled he
op imiza ion o Si-based anodes o enhanced elec ochemical pe o mance. A clea co ela ion
was es ablished be ween Si nanopa icle size, su ace chemis y, solid-s a e p ope ies, and he
esul ing elec ochemical pe o mance o he de eloped anodes.
2 Expe imen al pa
2.1 Ma e ials
Two ypes o Si nanoc ys als (SiNC100 wi h 100 nm a e age diame e , s ock keeping uni
NG04CO28095; SiNC55 wi h 55 nm a e age diame e , s ock keeping uni NG04EO1804) we e
pu chased om Nanog a i. Two o he ypes o SiNC (SiNC6 wi h 6 nm a e age diame e ; SiNC20
wi h 20 nm a e age diame e ) and one ype o amo phous Si nanopa icles (SiNA20 wi h 20 nm
a e age diame e ) we e syn hesized in he ame o his s udy. Dilu ed silane (1% in a gon, Linde,
A 5.0, SiH4 5.0, UN1954), hyd ogen (H2 7.0, Linde, UN1049), a gon (A , A 6.0, UN1006), and
pu e silane (SiH4, UN2203) we e used o he Si syn hesis. Conduc i e ca bon ille Supe P (40
nm a e age diame e ) was kindly dona ed by Ime ys S.A. Py ole monome ( eagen g ade, 98 %,
Mw = 67.09), phy ic acid solu ion (PhA, 50 % (w/w) in H2O, Mw = 660.04), poly(ac ylic acid)
(PAA, Mw = 450,000), ammonium pe sul a e (APS, ≥98.0%, Mw = 228.20), li hium
hexa luo ophospha e solu ion in e hylene ca bona e and dime hyl ca bona e (1.0 M LiPF6 in
EC/DMC = 50/50 ( / ), ba e y g ade), and Li-me al oil ( hickness: 0.6 mm, 99.9 %) we e
pu chased om Me ck. Cu en collec o coppe oil ( hickness: 25 µm, 99.8 %) was pu chased
om The mo Fishe . Deionized (DI) wa e was used as an aqueous medium in all he expe imen s.
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2.2 Ma e ials P epa a ion
2.2.1 Syn hesis o SiNC
SiNC20, SiNC6, and SiNA20 we e syn hesized using a non-comme cial non- he mal plasma low-
h ough eac o ope a ed unde low p essu e. The sys em was c ea ed by adap ing he appa a us o
Ko s hagen e al [36]. The ope a ional p essu es we e wi hin 10 Pa in he s andby mode and lowe
han 500 Pa in he syn hesis mode. The plasma was gene a ed wi h a adio equency (RF) powe
sou ce (Coaxial Powe Sys ems) ope a ing a 13.56 MHz. Fo he syn hesis o 6 mm c ys alline
pa icles (SiNC6), a na ow glass ube eac o was used, wi h an in e nal diame e o 0.8 cm. The
plasma discha ge was gene a ed using plana elec odes (dimensions 5 o 12 cm). The ou pu RF
powe was 150 W, and he SiNC we e syn hesized using a 1% dilu ed silane ( low: 80 sccm) and
hyd ogen ( low: 10 sccm). Fo he syn hesis o he 20 nm c ys alline pa icles (SiNC20) glass
eac o wi h in e nal diame e o 2.1 cm a ached wi h ing elec odes (heigh 2.7 cm) was used.
The eac ion mix u e was composed o a gon ( low: 80 sccm) and pu e silane ( low: 2 sccm), and
he ou pu RF powe was se o 107 W. The 20 nm amo phous pa icles (SiNA20) we e syn hesized
using a wo-s age eac o . The i s s age consis ed o a na ow glass ube eac o wi h an in e nal
diame e o 0.8 cm and a leng h o 50 cm. Plana elec odes (measu ing 5 cm by 12 cm) we e
a ached o he eac o . A low o dilu ed silane (80 sccm) was in oduced in o his s age, and he
RF ou pu powe was se o 150 W. The second s age was implemen ed using a b oad glass ube
wi h an in e nal diame e o 2.1 cm and a leng h o 50 cm. Double-helix elec odes we e a ached
o he ube, wi h one elec ode g ounded, and he wi es spaced 1 cm apa . Du ing his s age, lows
o pu e silane ( low: 12 sccm) and a gon ( low: 48 sccm) we e in oduced, and he second RF
powe ou pu was se o 250 W.
2.2.2 Syn hesis o PPy hyd ogel-based Si composi es and anode p epa a ion
PPy hyd ogel-based composi es we e p epa ed ia in si u oxida i e polyme iza ion o py ole
monome using APS in he p esence o Si nanopa icles (SiNC o SiNA). The composi es we e
p epa ed acco ding o he ollowing p ocedu e. Fi s ly, 11 µl o py ole monome was ans e ed
o a small glass ial wi h 35.4 µl o PhA and DI wa e . The solu ion was mixed using a magne ic
s i e . Nex , 38.4 mg o Si nanopa icles we e g ounded in a mo a o 10 min. Subsequen ly,
15.9 mg o Supe P was added and mixed wi h he Si nanopa icles o an addi ional 10 min. Then,
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15.4 mg o PAA was inco po a ed in o he Si and Supe P mix u e and blended o ano he 10 min.
The esul ing powde mix u e was ans e ed in o a small glass ial, and DI wa e was added. The
powde mix u e was dispe sed in DI wa e using a sonica ion ba h (PS 3000, Powe Sonic) and
u he mixed wi h a magne ic s i e o achie e a homogeneous dispe sion. Once he powde s
we e ully dispe sed and a uni o m ink was ob ained, he solu ion o py ole wi h PhA and DI
wa e was added o he ink. This mix u e was s i ed o 10 minu es wi h a magne ic s i e , and
he ial was labeled as solu ion A. In pa allel, an APS solu ion was p epa ed by dissol ing 11 mg
o APS in DI wa e . Bo h solu ions, solu ion A and APS solu ion, we e cooled sepa a ely in an ice
ba h o 10 minu es. Finally, he APS solu ion was pou ed in o solu ion A unde con inuous s i ing
in he ice ba h, ini ia ing he in si u polyme iza ion o he py ole monome . A e 4 hou s, he
esul ing ink was cas on o coppe oil and allowed o d y a oom empe a u e. The ob ained hin
ilms we e hen p essed o 1 min a 60 kPa and d ied in a acuum o en a 60°C o e nigh . The
p epa ed anodes we e labeled as PPy/Si, speci ying he ype o Si used, i.e., SiNC o SiNA.
2.3 Cha ac e iza ion me hods
The chemical s uc u e o all Si nanopa icles was analyzed by Raman spec oscopy (633 nm, 1.96
eV, objec i e 100x, He-Ne lase ; LabRAM HR spec ome e Ho iba Jobin-Y on in eg a ed wi h
an Olympus mic oscope), and Fou ie - ans o m in a ed spec oscopy (FTIR, Nicole iS50 ABX).
The su ace chemis y was examined using X- ay pho oelec on spec oscopy (XPS, X- ay beam
Al Kα wi h E = 1486.6 eV and powe o 60 W, pho oelec on emission ake-o angle o 0°;
The mo ishe Nexsa G2). The ob ained XPS spec a we e decon olu ed using he CasaXPS
so wa e. The mic o/nanos uc u e was isualized using scanning elec on mic oscopy (SEM,
Mi a3 LMH, Tescan, seconda y elec ons a 3 kV) and high- esolu ion ansmission elec on
mic oscopy (TEM, EFTEM Jeol 2200 FS, coppe mesh). The c ys allini y o he Si nanopa icles
was cha ac e ized using X- ay di ac ion (XRD, Cu lamp; PANaly ical X’Pe PRO wi h
PIXcel1D_1D de ec o ). The speci ic su ace a ea was analyzed using he ni ogen physiso p ion
echnique on a 3Flex analyze (Mic ome i ics, No c oss).
To assemble Li-ion hal -coin cell ba e ies, he anode ma e ials p epa ed in his wo k we e d ied
a 80°C in a acuum o en o 12 hou s and cu in o 1.5 cm diame e ci cles. Each cu ci cle was
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weighed and ans e ed o an A - illed glo ebox o he ba e y assembly. Li me al oil was used
as he e e ence and coun e elec ode, and 1.0 M LiPF6 in EC/DMC se ed as he elec oly e.
The elec ochemical pe o mance o hyd ogel-based anodes was e alua ed h ough gal anos a ic
cha ge/discha ge (GCD) cycling wi hin he po en ial ange o 0.05-1 V e sus Li/Li+. This was
pe o med using a ba e y es e (Newa e BTS-4008-5V50mA) a a cha ging a e o 0.1 C (0.4
A/g), calcula ed o each sample indi idually based on he mass o Si. Fu he cha ac e iza ion
in ol ed cyclic ol amme y (CV) using a po en ios a (µAu olab, Me ohm), and elec ochemical
impedance spec oscopy (EIS) in he discha ged s a e (0.05 V), wi h equencies anging om 80
kHz o 0.03 Hz (I ium Compac S a , I ium Technologi d B. V.).
3 Resul s and discussion
The PPy hyd ogel-based anodes we e syn hesized h ough a s aigh o wa d in si u oxida i e
polyme iza ion p ocess in an aqueous medium (Figu e 1). This me hod acili a es he o ma ion
o a 3D in e connec ed ne wo k, whe ein he conduc i e polyme embeds, connec s, and s abilizes
Si nanopa icles and Supe P. PPy was selec ed due o i s excellen elec ical conduc i i y,
mechanical lexibili y, and i s abili y o o m a conduc i e, 3D c osslinked ne wo k when
combined wi h a c osslinking agen such as PhA. Di e en ypes o Si nanopa icles wi h a ying
sizes and physicochemical p ope ies we e in eg a ed wi hin he anodes o examine he e ec o
Si pa icle size, su ace chemis y, and in insic solid-s a e p ope ies on he elec ochemical
pe o mance o Si-based anodes wi h conduc i e hyd ogel binde s in LIB.
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expe imen al p ocedu e. Al hough he measu ed capaci y (Figu e S4) was inhe en ly low, gi en
ha SiNC is he p ima y ac i e ma e ial in his sys em, no capaci y deg ada ion was obse ed o e
500 cycles. Ins ead, he capaci y g adually inc eased. This emphasizes he signi ican ole o SiNC
on he o e all capaci y decay. To u he con i m he bene icial ole o he 3D in e connec ed PPy
s uc u e in combina ion wi h SiNC, an anode ma e ial composed o non-c osslinked PPy and
SiNC20 (a ep esen a i e ype o SiNC) was p epa ed. The GCD cycling o he esul ing anode,
labeled as PPynon-c osslinked/SiNC20 (Figu e S5), e eals poo cycling s abili y, wi h he speci ic
capaci y d opping om app oxima ely 800 mAh/g o nea ly 0 mAh/g a e 300 cycles. These
indings highligh he impo ance o combining small SINC wi h a 3D c osslinked ne wo k o
achie e good capaci y e en ion.
The GCD p o iles we e measu ed a a ious cu en densi ies (Figu e S6) o 0.4, 0.7, 1.8, and 3.6
A/g and compa ed o wo selec ed ep esen a i e anodes, PPy/SiNC20 and PPy/SiNC100. The
cha ge capaci y o PPy/SiNC20 anges om ~1280 o 165 mAh/g, demons a ing good s abili y
and e e sibili y, especially a lowe cu en a es. A e e u ning o 0.4 A/g, i eco e s i s ini ial
capaci y alues. In con as , he cha ge capaci y o PPy/SiNC100 a ies om 2698 o 69 mAh/g.
In e es ingly, his anode does no show he same le el o e e sibili y and s abili y as he one wi h
a smalle SiNC20. While he e e sibili y o PPy/SiNC100 emains ai ly high, i does no ully
eco e i s ini ial capaci y upon e u ning o 0.4 A/g. This obse a ion u he emphasizes he
bene icial ole o small-sized nanos uc u ed SiNC (20 nm) in enhancing cycling s abili y and
capaci y e en ion.
The elec ochemical pe o mance o PPy/SiNC20 and PPy/SiNA20, bo h con aining Si
nanopa icles o he same size (Figu e S7) was examined o e alua e he in luence o Si solid-s a e
p ope ies (c ys alline s. amo phous) on elec ochemical beha io . Al hough PPy/SiNA20 exhibi s
ema kable capaci y e en ion (78 % a e 500 cycles), i s speci ic capaci y is signi ican ly lowe
han ha o PPy/SiNC20. This indica es he impo ance o Si c ys allini y in achie ing highe
speci ic capaci ies. No ably, wi h p olonged cycling, he capaci y o PPy/SiNC20 g adually
app oaches ha o PPy/SiNA20, likely due o p og essi e amo phiza ion.
To in es iga e he s uc u al and mo phological e olu ion o he anode ma e ials a e he GCD
cycling, ep esen a i e anodes we e analyzed by Raman spec oscopy and SEM be o e and a e
cycling. SEM images (Figu e S8) o anode ma e ials on hei c oss-sec ions be o e and a e he
cycling show a loss o he s uc u e. The Raman spec a o PPy/SiNC100 and PPy/SiNC20 be o e
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and a e he cycling a e compa ed o hose o PPy/SiNA20 (Figu e S9). All anodes display
cha ac e is ic peaks o PPy [59, 60] along wi h he dis inc Si peak. P io o cycling, he Si peak
appea s a 515 cm-1 o bo h PPy/SiNC100 and PPy/SiNC20, co esponding o he c ys alline Si.
Howe e , a e cycling, a no iceable shi o he SiNC peak o lowe wa enumbe s (~472 cm-1) is
obse ed, aligning wi h he peak posi ion o PPy/SiNA20. These shi s con i m he amo phiza ion
o SiNC a e cycling.
Table S3 p esen s he elec ochemical pe o mance o ou de eloped anodes con aining SiNC6
and SiNC20 (i.e., PPy/SiNC6 and PPy/SiNC20) in compa ison wi h he mos ele an hyd ogel-
based conduc ing polyme /Si anodes epo ed in he li e a u e. I is wo h men ioning ha wo key
ac o s mus be conside ed be o e making any di ec compa ison. Fi s o all, he Si used in hose
s udies a ies signi ican ly in e ms o pa icle size and su ace chemis y. In many cases,
p ope ies such as c ys allini y and su ace chemis y a e nei he analyzed no discussed. O en,
comme cially a ailable Si is selec ed wi hou ho ough examina ion and used as is, which can
in oduce signi ican a iabili y in he esul s. As demons a ed in ou s udy, any su ace
modi ica ion, p onounced oxida ion, o al e a ion in he c ys alline s uc u e can ha e a
emendous impac on he esul ing elec ochemical p ope ies. Secondly, he condi ions unde
which he elec ochemical measu emen s a e pe o med, such as he po en ial window, cu en
a e, elec oly e used, and he numbe o cycles, also a y ac oss s udies. In addi ion, impo an
de ails, such as whe he he epo ed ini ial speci ic capaci y e e s o discha ge o cha ge capaci y
o whe he he s a ed capaci y e en ion is ela ed o he 1s , 2nd, o la e cycles, a e no always
clea ly speci ied. The e o e, di ec compa isons o hese esul s should be made wi h cau ion, as
hey may conceal se e al po en ial pi alls. Bo h anodes (PPy/SiNC6 and PPy/SiNC20) p esen ed
in his s udy exhibi p omising cha ac e is ics and p ope ies ac oss a ious pa ame e s. The
p epa a ion p ocedu e was conduc ed in an aqueous medium using a conduc ing polyme as a
binde , bo h o which a e en i onmen ally iendly. As shown in Table S3, hese anodes achie ed
ini ial discha ge capaci ies o 3291 mAh/g o PPy/SiNC6 and 2978 mAh/g o PPy/SiNC20, which
a e among he highes alues epo ed o hyd ogel-based conduc ing polyme /Si anode ma e ials.
Al hough hei ini ial cha ge capaci ies a e ela i ely modes (1014 mAh/g o PPy/SiNC6 and
1273 mAh/g o PPy/SiNC20), hey emain signi ican and a e compa able o hose epo ed in he
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18
li e a u e [3, 5, 21]. Fu he mo e, he ob ained capaci y e en ions o his wo k a e sa is ac o y and
compa able wi h p e iously epo ed esul s (Table S3).
Figu e 4: Elec ochemical pe o mance in po en ial window 0.05-1 V a cu en densi y 0.4 A/g
o PPy hyd ogel-based anodes con aining SiNC: a) GCD cycling o 500 cycles, b) zoom o he
GCD cycling up o 100 cycles, c) gal anos a ic ol age p o iles om 1s cycle, d) coulombic
0 100 200 300 400 500
0
1000
2000
3000
4000
5000
0 20 40 60 80 100
0
1000
2000
3000
4000
5000
0 1000 2000 3000 4000 5000
0,0
0,5
1,0
1,5
2,0
2,5
3,0
0 100 200 300 400 500
0
20
40
60
80
100
120
SiNC100 SiNC55 SiNC20 SiNC6
0
20
40
60
80
100
Speci ic capaci y (mAh/g)
Numbe o cycles
PPy/SiNC100
PPy/SiNC55
PPy/SiNC20
PPy/SiNC6
a) b)
c) d)
e) )
Speci ic capaci y (mAh/g)
Numbe o cycles
PPy/SiNC100
PPy/SiNC55
PPy/SiNC20
PPy/SiNC6
Po en ial (V)
Speci ic capaci y (mAh/g)
PPy/SiNC100
PPy/SiNC55
PPy/SiNC20
PPy/SiNC6
Coulombic e iciency (%)
Numbe o cycles
PPy/SiNC100
PPy/SiNC55
PPy/SiNC20
PPy/SiNC6
SiNC100 SiNC55 SiNC20 SiNC6
20
30
40
50
60
70
80
90 Capaci y e en ion a e 100 cycles
2nd cycle
PPy/SiNC
Capaci y e en ion a e 100 cycles (%)
1000
1500
2000
2500
3000
Speci ic capaci y (2nd cycle) (mAh/g)
Capaci y e en ion a e 100 cycles (%)
PPy/SiNC
Capaci y e en ion
A e 100 cycles
A e 200 cycles
A e 500 cycles
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e iciency, e) capaci y e en ion a e 100 cycles and ini ial speci ic capaci y (in 2nd cycle), and )
e olu ion o capaci y e en ion du ing he cycling o each anode ma e ial. The emp y squa es in
e) and ) ep esen he capaci y e en ion o PPy/SiNC55 calcula ed based on he highes speci ic
capaci y achie ed a he 10 h cycle.
Fo deepe unde s anding o he elec ochemical pe o mance, CV was conduc ed on coin hal -
cell ba e ies con aining PPy hyd ogel-based anodes (Figu e 5 and Figu e S10). Measu emen s
we e pe o med in he po en ial window o 0.05-1 V a a scan a e o 0.1 mV/s. Figu e 5a-c
compa es 1s , 3 d, and 10 h cycles o all he anodes and Figu e S10 p esen s CV o each anode
sepa a ely. In he 1s cycle, a educ ion peak appea s a 0.4 V o PPy/SiNC20 and PPy/SiNA20, 0.5
V o PPy/SiNC6, and app oxima ely 0.6 V o PPy/SiNC100 and PPy/SiNC55. This peak disappea s
in subsequen cycles and co esponds o he i e e sible eac ion o elec oly e decomposi ion on
he anode su ace, and o he o ma ion o he SEI laye [61-63]. In e es ingly, PPy/SiNC55 exhibi s
a b oad educ ion peak a a ound 0.9 V, which is signi ican ly mo e in ense han he peak a 0.6 V,
sugges ing he occu ence o ano he i e e sible eac ion. This peak (a ound 0.9 V and highe )
has been p e iously connec ed wi h he i e e sible eac ion be ween SiO2 and Li+, esul ing in he
con e sion o SiO2 o Si [64, 65]. This obse a ion aligns well wi h he ea lie analysis o SiNC55,
which showed a highe SiO2 con en . Du ing con inued CV cycling, ou peaks eme ged.
Reduc ion ca hodic peaks a 0.17 V and 0.05 V a e linked o he con e sion o c ys alline Si o
amo phous Li-Si phases (a-LixSi) du ing he li hia ion and he subsequen c ys alliza ion and
o ma ion o c-Li3.75Si [4, 62]. Oxida ion anodic peaks a 0.35 V (a-Li3.5Si o a-Li2Si) and 0.5 V
(a-Li2Si o a-Si) co espond o he ansi ion o c ys alline o an amo phous phase, ollowed by a
dealloying eac ion [4, 66, 67]. Howe e , PPy/SiNC6 and PPy/SiNA20 (Figu e S10d) ini ially
showed only one educ ion and one oxida ion peak. This beha io can be expec ed o PPy/SiNA20
as i con ains amo phous Si, meaning he e is no ansi ion om c ys alline o amo phous Si, and
only alloying and dealloying p ocesses occu . As CV cycling con inues, a educ ion peak a ound
0.1 V s a s o appea , indica ing a g adual ac i a ion o li hia ion si es. In he case o PPy/SiNC6,
only one educ ion and one oxida ion peak a e obse ed un il he 7 h cycle, when he educ ion
peak a 0.17 V i s appea s. The anodic peak a 0.35 V emains ba ely no iceable h oughou he
10 cycles. These obse a ions sugges ha he li hia ion connec ed wi h phase ans o ma ion o
bo h PPy/SiNC6 and PPy/SiNA20 is slowe compa ed o hose o PPy/SiNC20.
The posi ions o bo h educ ion and oxida ion peaks emain s able h oughou cycling o all he
s udied anodes, indica ing good e e sibili y o he Si-Li eac ions [66]. CV cycling es s o
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PPy/SiNC20, PPy/SiNC6, and PPy/SiNC55 e eal inc easing peak in ensi ies o e ime, a
phenomenon p e iously epo ed in he li e a u e and asc ibed o he ac i a ion p ocess o he
anode ma e ial [66]. This ac i a ion p ocess is acili a ed by he amo phiza ion o Si, which
enhances li hia ion capaci y wi h each cycle [68]. No ably, his e ec is less p onounced o
PPy/SiNC100, whe e peak in ensi ies ini ially inc ease bu begin o decline a e 5 cycles. This
beha iou can be a ibu ed o he la ge size o SiNC100 due o a limi ed li hia ion ime, which
es ic s he dep h o li hia ion and s ess buildup o he sub-su ace egions in he la ge
nanopa icles. This localized s ess can cause nanopa icle ac u e, deac i a ion, and a subsequen
dec ease in peak in ensi y [68]. In con as , he peak in ensi ies o PPy/SiNC55 (Figu e S10b)
inc ease sligh ly o e cycling, as a esul o he smalle size o SiNC55. Among all he anodes,
PPy/SiNC20 demons a es he bes CV pe o mance, which can be linked o he op imal size o he
SiNC20. In e es ingly, PPy/SiNC6 does no each simila ly high peak in ensi ies, indica ing lowe
elec ochemical ac i i y ha aligns wi h i s ini ial lowe speci ic capaci y alues (Figu e 4a). This
beha iou may be due o nanopa icle agglome a ion, which diminishes he s abilizing ad an ages
ypically associa ed wi h smalle pa icle sizes (< 20 nm)[69]. Indeed, as p e iously obse ed,
SEM images o PPy/SiNC6 (Fig ue 3i) e eal signi ican agglome a ion o SiNC6, a ea u e unique
o his anode.
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Figu e 5: CV measu emen s a a scan a e 0.1 mV/s o all he anodes in a) 1s , b) 3 d cycle, and c)
10 h cycles.
To gain deepe insigh s in o he p ocesses occu ing a he anode-elec oly e in e ace, EIS was
ca ied ou on ou PPy hyd ogel-based anodes. Figu e 6 and Figu e S11 show Nyquis plo s
measu ed a he discha ged s a e (0.05 V) o 5 cycles. The da a we e i ed using an equi alen
ci cui (Figu e S12), which accoun s o he con ibu ions o a ious componen s. The i ing
p ocedu e is based on he obse ed shape o Nyquis plo s, which ea u e wo dis inc semici cles
and a linea egion a high equencies. The cell esis ance (RS) is ep esen ed by he high-
equency in e cep and co esponds o he o e all esis ance o he ba e y sys em, including he
elec oly e, cu en collec o , and sepa a o [1, 70]. The i s semici cle, obse ed a high o
medium equencies, is a ibu ed o he o ma ion o he SEI laye . This is modeled by a pa allel
ci cui comp ising he SEI esis ance RSEI and a cons an phase elemen CPESEI [4, 70], which
accoun s o he non-ideal capaci i e beha io a he han an ideal capaci o . The second
semici cle, appea ing a in e media e equencies, is associa ed wi h cha ge ans e p ocesses and
is ep esen ed by he cha ge ans e esis ance RCT in pa allel wi h a cons an phase elemen CPECT
[2, 4]. Repo edly, his semici cle is in luenced by changes in he su ace coa ing and pa icle size,
0,0 0,2 0,4 0,6 0,8 1,0
-1,4
-1,2
-1,0
-0,8
-0,6
-0,4
-0,2
0,0
0,2
0,0 0,2 0,4 0,6 0,8 1,0
-1,2
-1,0
-0,8
-0,6
-0,4
-0,2
0,0
0,2
0,4
0,0 0,2 0,4 0,6 0,8 1,0
-2,0
-1,6
-1,2
-0,8
-0,4
0,0
0,4
0,8
1,2
Cu en densi y (A/g)
Po en ial s. Li/Li+ (V)
1s cycle o anode con aining
SiNC100
SiNC55
SiNC20
SiNC6
Cu en densi y (A/g)
Po en ial s. Li/Li+ (V)
3 d cycle o anode con aining
SiNC100
SiNC55
SiNC20
SiNC6
Cu en densi y (A/g)
Po en ial s. Li/Li+ (V)
10 h cycle o anode con aining
SiNC100
SiNC55
SiNC20
SiNC6
a) b)
c)
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making i a use ul indica o o unde s anding he eac ion p ocesses occu ing wi hin he anode
[70]. The linea egion a low equencies co esponds o he Wa bu g impedance, which
ep esen s he di usion o Li ions in he anode [2, 71].
To compa e he elec ochemical p ocesses in di e en PPy/SiNC anodes, Nyquis diag ams we e
plo ed, and he e olu ion o RS, RSEI, and RCT was analyzed (Figu e 6 and Figu e S11). One can
obse e ha RS emains s able in all anodes a e y simila alues, consis en ly anging be ween
6-12 Ω. This s abili y likely e lec s he use o he same hal -cell se up o each ba e y [72]. In he
1s cycle o each anode, ele a ed RSEI alues a e obse ed, which can be a ibu ed o he o ma ion
o he SEI laye . The eco ded alues o PPy/SiNC100 (121 Ω), PPy/SiNC55 (134 Ω), PPy/SiNC20
(159 Ω), and PPy/SiNC6 (133 Ω) ollow he end o dec easing Si pa icle size, wi h he excep ion
o PPy/SiNC6. The obse ed inc ease in RSEI wi h dec easing Si size sugges s enhanced SEI laye
o ma ion due o a highe speci ic su ace a ea, aligning wi h he GCD esul s discussed ea lie .
The lowe RSEI obse ed in he 1s cycle o PPy/SiNC6 can be asc ibed o i s agglome a ed inne
s uc u e, as discussed abo e (Figu e 3i), whe e Si clus e s a e embedded wi hin he o med PPy
hyd ogel. In he subsequen cycles o all he anodes, RSEI alues dec ease, sugges ing he o ma ion
o a ela i ely s able SEI laye . This could be explained by a a o able e ec o PPy, which
p omo es he de elopmen o a mo e s able SEI laye [72]. In e es ingly, PPy/SiNC100 shows he
lowes RSEI (16 Ω) in he 3 d cycle, a e which g adually inc eased ( o 35 and 48 Ω). This sugges s
he ongoing o ma ion o he uns able SEI laye du ing cycling, mos likely due o he c acking o
la ge SiNC, which exposes esh SiNC su aces o he elec oly e. This obse a ion suppo s he
p e iously p esen ed GCD and CV esul s in his s udy, sugges ing ha he e is an incomple e
li hia ion o la ge SiNC, which p oceeds o only shallow dep hs and leads o pa icle b eakage in
he la e cycling s ages [68]. Mo eo e , his anode shows he leas s abili y ac oss all
elec ochemical me hods p esen ed, which may be connec ed o he pa icle agmen a ion and he
po en ial o ma ion o a hicke SEI laye in la e cycles. A simila beha io is exhibi ed by
PPy/SiNC55, whe e a sligh inc ease in RSEI is no iced in he 5 h cycle (up o 96 Ω). The slowe
inc ease in subsequen cycles can be a ibu ed o imp o ed s abili y as SiNC size dec eases.
Howe e , i is impo an o conside ha he epo ed 55 nm diame e ep esen s an a e age alue
o his comme cial SiNC, meaning he e a e la ge pa icles p esen , which could con ibu e o
as e ma e ial deg ada ion. The smalle SiNC (6-20 nm) and SiNA exhibi be e s abili y in e ms
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o RSEI, showing a con inuous dec ease o e all 5 cycles. By he 5 h cycle, he alues each 89 Ω
o PPy/SiNC20, 67 Ω o PPy/SiNC6, and 32 Ω o PPy/SiNA20.
The mos signi ican di e ences be ween he small and la ge Si nanopa icles a e obse ed when
compa ing he e olu ion o RCT. Anodes con aining la ge SiNC (PPy/SiNC100 and PPy/SiNC55)
show an inc ease in RCT wi h con inuous cycling. A e 5 cycles, RCT inc eases om 38 o 101 Ω
in PPy/SiNC100 and om 100 o 260 Ω in PPy/SiNC55. This indica es he ins abili y o o med SEI
ollowed wi h a p og essi e loss o elec ical con ac be ween he SiNC and he cu en collec o
[2], likely due o ma e ial c acking, deg ada ion, and pul e iza ion associa ed wi h he use o la ge
SiNC pa icles. This was u he suppo ed by he e olu ion o RSEI. In con as , smalle SiNC (6-
20 nm) show a simila end o RCT as obse ed o RSEI, wi h he highes alue in he 1s cycle,
ollowed by a con inuous dec ease in he subsequen cycles. The RCT o PPy/SiNC20 dec eases
om 420 o 71 Ω, while he alues o PPy/SiNC6 dec ease om 150 o 65 Ω. In e es ingly, RCT
o PPy/SiNA20 shows huge inc ease om he 1s cycle (184 Ω) o he 2nd cycle (706 Ω) indica ing
SEI laye o ma ion and slow cha ge ans e . Bu , in subsequen cycles, RCT is dec easing ( o 375
Ω in he 5 h cycle), which migh be asc ibed o he SEI laye s abiliza ion and po en ially o he
o ma ion o mo e ac i e si es (as showed by CV). This sugges s ha he PPy ne wo k coa ing
could be mo e e ec i e when applied o smalle SiNC, likely o he ollowing easons, i.e.,
enhanced s abili y du ing cycling and a highe speci ic su ace a ea, which acili a es cha ge
ans e . Thus, smalle SiNC may in e ac mo e e ec i ely wi h he c osslinked PPy ma ix,
p omo ing e icien cha ge ans e . This syne gis ic combina ion ul ima ely leads o imp o ed
cha ge kine ics [72].
0 100 200 300
0
50
100
150
200
250
300
1 2 3 4 5
0
50
100
150
200
-Z'' (Ω)
Z' (Ω)
1s cycle
2nd cycle
3 d cycle
4 h cycle
5 h cycle
PPy/SiNC100 PPy/SiNC100 RS
RSEI
RCT
Resis ance (Ω)
Cycle
a)
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Figu e 6: Nyquis plo s (le cha s) om EIS a he discha ged s a e (0.05 V) wi h i ing (solid
line) o he equi alen ci cui (Figu e S12) and he e olu ion o esis ance RS, RSEI, RCT ( igh
cha s) du ing 5 cycles o a) PPy/SiNC100, b) PPy/SiNC55, c) PPy/SiNC20, and d) PPy/SiNC6.
0 100 200 300 400 500 600
0
50
100
150
200
250
300
1 2 3 4 5
0
100
200
300
400
-Z'' (Ω)
Z' (Ω)
1s cycle
2nd cycle
3 d cycle
4 h cycle
5 h cycle
PPy/SiNC55 PPy/SiNC55
b) RS
RSEI
RCT
Resis ance (Ω)
Cycle
0 100 200 300 400 500 600
0
50
100
150
200
250
300
1 2 3 4 5
0
100
200
300
400
500
-Z'' (Ω)
Z' (Ω)
1s cycle
2nd cycle
3 d cycle
4 h cycle
5 h cycle
c) PPy/SiNC20 PPy/SiNC20 RS
RSEI
RCT
Resis ance (Ω)
Cycle
0 100 200 300 400 500 600 700
0
50
100
150
200
250
300
350
400
1 2 3 4 5
0
50
100
150
200
-Z'' (Ω)
Z' (Ω)
1s cycle
2nd cycle
3 d cycle
4 h cycle
5 h cycle
PPy/SiNC6RS
RSEI
RCT
Resis ance (Ω)
Cycle
d) PPy/SiNC6
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4 Conclusions
In his s udy, he elec ochemical p ope ies o PPy/Si anodes we e in es iga ed. These anodes a e
composed o Si nanopa icles wi h a ying cha ac e is ics, including pa icle size (6, 20, 55, and
100 nm), ex u al ea u es, solid-s a e p ope ies (amo phous and c ys alline), and su ace
chemis y (deg ee and ype o su ace oxide), in combina ion wi h PPy hyd ogel, which ac s as an
elec ically conduc i e binde . The PPy/Si anodes we e ab ica ed using in si u polyme ized PPy
hyd ogel, c osslinked wi h phy ic acid, i.e., a na u ally occu ing c osslinking agen , and
inco po a ed wi h Si nanopa icles. The PPy hyd ogel o med a conduc i e ne wo k ha
con o mally coa s he Si su ace and p o ides po ous space o accommoda e he olume expansion
o Si nanopa icles. The GCD cycling o e 500 cycles in he po en ial window 0.05-1 V a a cu en
densi y o 0.4 A/g showed ha , ega dless o he Si nanopa icle ype, in eg a ion in o he 3D
conduc i e ne wo k signi ican ly imp o ed elec ochemical pe o mance by accommoda ing Si
olume expansion and main aining conduc i e con ac be ween pa icles. GCD esul s u he
e ealed ha la ge Si nanopa icles con ibu ed o highe ini ial cha ge capaci y (e.g., 2975 mAh/g
o PPy/SiNC100 and 1013 mAh/g o PPy/SiNC6), whe eas smalle Si nanopa icles enhanced
cycling s abili y and capaci y e en ion (e.g., 24 % o PPy/SiNC100 s. 85 % o PPy/SiNC6 a e
100 cycles). The impo ance o Si c ys allini y in achie ing highe speci ic capaci ies was also
demons a ed, wi h PPy/SiNC20 exhibi ing signi ican ly highe speci ic capaci y h oughou he
en i e cycling ange compa ed o PPy/SiNA20. All he GCD, CV, and EIS analyses highligh ed he
ad an ages o in eg a ing SiNC wi h a e age sizes lowe han 55 nm (i.e., SiNC20 and SiNC6) in o
he PPy c osslinked ma ix. This pa icula dual combina ion p o ides enhanced elec ochemical
pe o mance o he anode. Mo e gene ally, i es ablishes a new ounda ion o u u e s udies on
SiNC and conduc i e polyme binde s, aiming o mi iga e he challenges associa ed wi h he
subs an ial olume changes o Si anodes in LIB.
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