T acking s uc u al e olu ion in li hium-ion ba e ies ia ope ando
scanning elec on mic oscopy
Ondˇ
ej Kl aˇ
c
a,b,*
, Da id T och a
a,b
, Libo No ´
ak
a
, Pe e P iecel
a
, Manuel Bo nh¨
o
a
,
Tom´
aˇ
s Kazda
b
, Zhao Liu
c,d,**
a
The mo Fishe Scien ic B no, Vlas imila Pecha 12, 627 00 B no, Czech Republic
b
Depa men o Elec ical and Elec onic Technology, Facul y o Elec ical Enginee ing and Communica ion, B no Uni e si y o Technology, Technick´
a 10, 616 00 B no,
Czech Republic
c
The mo Fishe Scien ic, 5350 NE Dawson C eek D , Hillsbo o, OR, 97124, USA
d
Ma e ials Science and Enginee ing Depa men , Uni e si y o Washing on, Sea le, WA, 98195, USA
ARTICLE INFO
Keywo ds:
Li-ion ba e ies
Ope ando SEM
S uc u al e olu ion
Ba e y R&D and manu ac u ing
ABSTRACT
The comp ehensi e unde s anding o s uc u al-pe o mance co ela ion o li hium-ion ba e ies is pa amoun o
op imizing hei pe o mance, sa e y, and longe i y, which a e c i ical o applica ions such as po able elec-
onics, elec ic ehicles, and enewable ene gy s o age sys ems. Scanning Elec on Mic oscopy (SEM) is
ins umen al in he examina ion o li hium-ion ba e ies, o e ing high- esolu ion imaging and de ailed insigh s
in o he ba e y mic os uc u e and mo phology. Ope ando SEM analyses a e in aluable as hey p o ide p ecise
desc ip ions o he dynamic phenomena and s uc u al empo al e olu ion wi hin he ba e y. Howe e , he
applica ion o SEM o ope ando analyses is hinde ed by he challenges in he p epa a ion o samples ha can
deli e p ac ical elec ochemical pe o mance wi hin he SEM en i onmen . In his manusc ip , we in oduce an
ope ando SEM wo kow ha enables high- esolu ion analysis o s uc u al e olu ion in li hium-ion ba e ies
om elec ode le el o pa icle le el. The e cacy o his sys em and wo kow is demons a ed on li hium nickel
manganese cobal oxide (NMC) and li hium i anium oxide (LTO) ba e y cells e ealing elec ode expansion and
con ac ion, as well as g ain c acking. Addi ionally, a g aphi e-li hium me al sys em is analyzed, whe e
expansion and c acking o g aphi e g ains we e obse ed. The s udy delinea es a p ocedu e enabling he
in es iga ion om en i e elec odes change a hund eds o mic on le el o e en la ge cell componen s o
submic on changes a he g anula le el, applicable ac oss a ious chemis ies. We p opose ha his wo kow
can o e aluable insigh s o bo h undamen al esea ch a he ma e ials de elopmen le el and cell s uc u e
op imiza ion in manu ac u ing en i onmen s.
1. In oduc ion
Wi h ad ancemen s in he echnology eld, deca boniza ion e o s,
and ecological demands, he need o ad anced elec ochemical powe
sou ces is inc easing. Howe e , la ge-scale p oduc ion aces challenges
connec ed wi h limi ed aw ma e ials esou ces, ising cos s, and en i-
onmen al impac s. Taking li hium-ion ba e y manu ac u ing as an
example, he p ocess aims o p oduce cells ha achie e high ene gy
densi y, long li espan, enhanced sa e y, and low cos , all while main-
aining consis en quali y [1]. Achie ing his goal elies on mul iple
c i ical ac o s, including cos -d i en undamen al esea ch o ma e ials
and p ocess inno a ion, a obus and esilien supply chain, as well as
ad anced me ology and cha ac e iza ion capabili ies [2,3]. Recen ly, as
ba e y designs ha e g own inc easingly complex ac oss mul iple leng h
scales o push he bounda ies o pe o mance, me ology echniques ha
o e deep insigh s in o physical, chemical, and elec ochemical p o-
cesses a hese scales ha e become c i ical [4]. They a e essen ial no
only o ad ancing esea ch and de elopmen (R&D) bu also o
ensu ing e ec i e quali y con ol and ailu e analysis wi hin
manu ac u ing en i onmen s.
Among all me ology echniques, in-si u/ope ando imaging ech-
niques o e insigh s in o he kine ics o p ocesses and mechanisms
* Co esponding au ho a : The mo Fishe Scien ic B no, Vlas imila Pecha 15; 627 00 B no, Czech Republic.
** Co esponding au ho a : The mo Fishe Scien ic, 5350 NE Dawson C eek D , Hillsbo o, OR 97124, USA.
E-mail add esses: ond ej.kl ac@ he moshe .com (O. Kl aˇ
c), zhao.liu@ he moshe .com (Z. Liu).
Con en s lis s a ailable a ScienceDi ec
Ene gy S o age Ma e ials
jou nal homepage: www.else ie .com/loca e/ensm
h ps://doi.o g/10.1016/j.ensm.2025.104516
Recei ed 2 May 2025; Recei ed in e ised o m 7 July 2025; Accep ed 2 Augus 2025
Ene gy S o age Ma e ials 81 (2025) 104516
A ailable online 5 Augus 2025
2405-8297/© 2025 The Au ho s. Published by Else ie B.V. This is an open access a icle unde he CC BY license ( h p://c ea i ecommons.o g/licenses/by/4.0/ ).
occu ing wi hin a ba e y du ing ope a ion by p obe s uc u e and
chemical in o ma ion in eal ime [5–9]. Unlike ex-si u o pos -mo em
me hods, whe e he s uc u al and chemical in o ma ion may ha e been
impac ed by sample handling o in insic cell elaxa ion p ocess, ope -
ando echniques enable he p ecise iden ica ion o s uc u al and
chemical s a es a he momen o occu ence, leading o a clea e un-
de s anding o i s unde lying mechanism [6,7]. Techniques wi h a ious
p obes, including elec on, X- ay, op ical, in a ed, and ul asound a e
nowadays applied in he ba e y eld [10–16]. Since each p obe p o-
ides a dis inc imaging esolu ion, hey collec i ely deli e in o ma ion
ac oss mul iple leng h scales, enabling - o -pu pose solu ions o mee
he me ology needs in ba e y R&D and manu ac u ing. In gene al,
elec on p obes and X- ay p obes o e s uc u al analysis om a omic
le el o cell le el wi h ocus co e ing bo h R&D and manu ac u ing [8,
17–20], while he op ical, in a ed, and ul asound p obes a e applied
mainly on he leng h scale om elec ode le el up o pack le el wi h
ocus and applica ion po en ial o ba e y quali y con ol and ailu e
analysis in manu ac u ing [21–26].
As he highes - esolu ion p obes, elec on p obes a e u ilized in
ansmission elec on mic oscopy (TEM) o scanning elec on mic o-
scopy (SEM), including ocused ion beam scanning elec on mic oscopy
(FIB-SEM), o obse e s uc u al e olu ion du ing ba e y eac ions in
eal ime wi h esolu ion down o a omic scale. TEM o e s highe es-
olu ion ha enables de ailed insigh in o eac ion p ocess wi hin elec-
ode pa icles, a he in e ace, o wi hin he elec oly e, such as
li hia ion/de-li hia ion s udy [27–32] o solid-liquid in e ace e-
ac ions analysis [33,34]. Because o he limi ed olume o he ma e ials
and deep le el o de ails TEM can access, i is commonly conside ed as a
powe ul ool o undamen al elec ochemical p ocesses and mecha-
nism unde s anding, making i well-sui ed o basic esea ch [35].
Compa ed o TEM, SEM o e s he capabili y o access a much la ge a ea
and olume — om elec ode le el o indi idual pa icles — while
main aining capabili y o moni o nanome e -sized ea u es. This en-
ables he s udy o phenomena such as pa icle and elec ode s uc u al
e olu ion and dend i e o ma ion unde p ac ical ope a ion condi ions
possible, making he knowledge gained h ough ope ando SEM aluable
o bo h ba e y R&D as well as manu ac u ing applica ions. To da e,
i espec i e o he ba e y chemis y unde in es iga ion, h ee majo
ope ando SEM design app oaches ha e been de eloped, each accom-
panied by inhe en cons ain s ha limi hei lea ning o b oade
applicabili y [36–46]. The single-pa icle analysis app oach enables
de ailed s uc u al cha ac e iza ion wi hin an indi idual pa icle o
elucida e deg ada ion mechanisms; howe e , i lacks su cien s a is i-
cal ep esen a ion o ully cap u e he beha io o eal ba e y ope a ion
[36,37,46]. The liquid elec ochemical cell design o he cus omized cell
wi h ac i e ma e ials deposi ed on he mesh p o ide enough s a is ics
and elec ochemical pe o mance close o a p ac ical cell, while he
image esolu ion can be comp omised due o cell design ooded by
elec oly e as well as he equi emen o a long wo king dis ance in
SEM. In addi ion, only he su ace o he elec ode could be in es iga ed,
which lacks in o ma ion abou o he componen s, such as cu en col-
lec o s and sepa a o s [38–41]. The cell design wi h c oss-sec ion iew
geome y o e s oppo uni ies o obse e s uc u al e olu ion ac oss
mul iple laye s. Howe e , his congu a ion aces challenges in p e-
pa ing high-quali y c oss-sec ions o op imal SEM imaging (e.g. me-
chanical polishing esul s in su ace a i ac s o delamina ion), while
di ec FIB enching on ough su aces may es ic he eld o iew,
limi ing he abili y o ob ain su cien s a is ical da a [42–45].
To enable ope ando SEM be e ec i ely con ibu ing knowledge o
bo h ba e y R&D and manu ac u ing en i onmen , i shall sa is y
se e al c i e ia: (i) he se up p o ides access o la ge a ea and olumes
wi h mul iple componen s o ep esen a i e analysis, (ii) op imal su -
ace wi h minimized de ec allows o high esolu ion imaging o
de ailed s uc u al analysis, (iii) he sample ans e o handling p ocess
o SEM needs o be unde ine gas p o ec ion o acuum o a oid isk o
con amina ion and deg ada ion by exposu e o ai o mois u e, (i )
elec ochemical pe o mance is compa able wi h he eal ba e y cell
[47]. The challenges o p epa ing a smoo h su ace wi h minimized
a i ac s can be add essed ia b oad ion beam (BIB) polishing me hod,
which is commonly used in ba e y pos -mo em analysis [48,49]. As
shown in Fig. 1(a) and (b), he BIB me hod p epa es high quali y
c oss-sec ion wi h he egion o in e es a hund eds o mic on wid h o
ex-si u SEM imaging. Al hough pa icle c acking can be iden ied when
compa ing he elec ode be o e and a e cycling, in o ma ion may be
los as he samples a e no iden ical. In his s udy, by in eg a ing BIB
sample p epa a ion wi h ope ando bias SEM es ing, we p esen an
ope ando SEM wo kow ha enables high- esolu ion analysis o ack
s uc u al e olu ion in li hium-ion ba e ies om elec ode le el o
pa icle le el (Fig. 1(c)). Two elec ode pai s, namely li hium nickel
manganese cobal oxide–li hium i anium oxide (NMC-LTO) and
g aphi e –li hium me al (G -Li) pai s, we e selec ed o in es iga e he
s uc u al e olu ion o NMC and g aphi e du ing elec ochemical
cycling. Fo elec oly e selec ion, ac o s such as elec ochemical s a-
bili y, ionic kine ics, and acuum compa ibili y need o be conside ed.
Con en ional ca bona e-based elec oly es (e.g., EC:DMC wi h LiPF₆)
a e inhe en ly incompa ible wi h high- acuum condi ions, he eby
es ic ing hei use in cu en ope ando SEM wo kows. Mo eo e , hey
ypically induce he o ma ion o chemically uns able, he e ogeneous
o ganic/ino ganic in e phases ha a e p one o deg ada ion [50],
he eby complica ing he co ela ion be ween elec ochemical pe o -
mance loss and mic os uc u al obse a ions. In con as , he ionic liq-
uids (ILs), specically py olidinium-based ILs such as Py 13-TFSI and
Py 13-FSI, p omo e he o ma ion o p edominan ly ino ganic
solid-elec oly e in e phase (SEI) and ca hode-elec oly e in e phase
(CEI) laye s wi h enhanced chemical and mechanical obus ness [51],
ensu ing ha obse ed deg ada ion phenomena a he elec ode o
pa icle le el a e mo e di ec ly a ibu able o in insic elec ochemical
p ocesses. While he ela i ely high iscosi y and educed ionic con-
duc i i y o ILs may impede Li⁺ anspo and con ibu e o inc eased
pola iza ion, hey also se e o mode a e (de)li hia ion kine ics. Such
mode a e kine ics educe s ess accumula ion and mi iga e he o ma-
ion o concen a ion g adien s wi hin ac i e ma e ials, he eby
enhancing he spa ial and empo al esolu ion o s uc u al e olu ion
unde ope ando SEM [52]. Fu he mo e, he non- ola ile na u e o hese
ILs main ains s able elec ochemical en i onmen s du ing SEM ope a-
ion, minimizing elec oly e-induced imaging a i ac s and acili a ing
mo e accu a e a ibu ion o mo phological changes o undamen al
ma e ial beha io [53]. The e o e, o enable he demons a ion o he
ope ando SEM wo kow o in es iga ing elec ode mic os uc u al
dynamics, py olidinium-based ILs we e chosen as elec oly es o
in eg a ion in o bo h ba e y sys ems. The obse ed s uc u al e olu ion
is co ela ed wi h elec ochemical mechanisms o elucida e deg ada ion
pa hways and ma e ial beha io unde ope a ional condi ions.
2. Ma e ials and expe imen al me hods
2. Ma e ials
Comme cially a ailable elec ode shee s om Cus omCells we e
used in his s udy. Ca hode was made o NMC111 coa ed on an
aluminum cu en collec o o pai wi h anode ha was made o LTO
coa ed on an aluminum cu en collec o . The NMC ca hode composed
o NMC111, PVDF binde , and conduc i e ca bon was o mula ed in a
weigh a io o 86:7:7. G aphi e was coa ed on a cu en coppe collec o
o pai wi h Li-me al. The capaci y o he elec odes is specied in he
da ashee as 1 mAh/cm². Me allic li hium (99.9 %; Sigma-Ald ich) was
used as he coun e elec ode in G –Li me al s udy. A Wha man GF/C
glass be l e wi h a hickness o 260 µm was used as he sepa a o .
Di e en ILs elec oly es we e used o es NMC-LTO and G -Li sys-
em. Fo NMC - LTO sys ems, an ILs elec oly e was p epa ed using a
mix u e o 1-me hyl-1-p opylpy olidinium bis( iuo ome hylsul onyl)
imide (Py 13-TFSI, >99 %; Sigma-Ald ich) and li hium bis
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Ene gy S o age Ma e ials 81 (2025) 104516
2
( iuo ome hanesul onyl)imide sal (LiTFSI, >99 %; Sigma-Ald ich) a
a concen a ion o 0.5 M. Fo G -Li sys em, mix u e o LiTFSI: 1-p opyl-
1-me hylpy olidinium bis(uo osul onyl)imide (Py 13-FSI), 1:9 mol
(Sol ionic >99.5 %) was used.
2.2. Cells assembly and ope ando SEM se up
Fig. S1 shows he elec ochemical cell p epa a ion wo kow. To
p epa e o he cell assembly, elec ode pieces wi h app oxima ely 5 mm
x 8 mm in size we e s cu om he elec ode shee s wi h scisso s. The
elec ode o in e es (NMC and g aphi e) was hen mo ed o The mo
Scien ic CleanMill BIB polishe o p epa e a c oss-sec ion using A ion
beam. Fo he NMC elec ode, 16 kV and 3.5 mA (anode cu en ) we e
used o one hou ; o he g aphi e elec ode, 10 kV and 3.5 mA (anode
cu en ) we e used o 1.5 h. Sample ocking +/- 40◦was used o educe
cu aining a i ac . The esul ing a ea size o he comple ely polished
egion was abou 500 µm in wid h (Fig. S1(a)). Simila me hods can be
used o p epa e a c oss-sec ion o ei he elec ode indi idually o he
whole cell a once. A sligh ly la ge piece o app oxima ely 7 mm x 12
mm was cu om he sepa a o wi h a azo blade.
The elec ode o in e es was hen aligned oge he wi h coun e
elec ode and sepa a o . I has been ound o be ad isable o place he
elec ode o in e es o be a ew mic ome e s abo e he sepa a o o
a oid ooding he egion and elec ode o in e es wi h ILs elec oly e
du ing he ope ando SEM expe imen (Fig. S1(b)). The alignmen and
mechanical xa ion we e done in a cus omized clamping ool. I con-
ains wo clamping pla es, which can be p essed oge he using a sc ew.
In addi ion o mechanical clamping, hese pla es also se e as an elec-
ical con ac o he pins on he edge o he clamping ool (Fig. S2).
The p e-p epa ed cell was hen ans e ed o he A -lled glo ebox.
The specimen was le in he glo ebox an echambe o se e al hou s
unde acuum o d y all pa s o he sys em be o e subsequen appli-
ca ion o he elec oly e. The elec oly e was applied o he sepa a o
edges wi h a pipe e un il he cell was soaked p ope ly (Fig. S1(c)). The
Fig. 1. Compa ison o SEM analysis be ween ex-si u and ope ando analysis. Ex-si u SEM analysis o NMC ca hode c oss-sec ion p epa ed ia BIB polishing. I is no
possible o examine he same egion and i s changes o e ime o di ec ly compa e (a) p is ine and (b) cycled elec ode due o he des uc i e na u e o his analysis.
(c) Ope ando SEM analysis o selec ed NMC g ain c oss-sec ion a di e en cha ging s ages o show con inuous s uc u al e olu ion – obse a ion o c ack e olu ion
du ing s o ma ion cycle.
Fig. 2. Schema ic o ope ando SEM se up.
O. Kl aˇ
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Ene gy S o age Ma e ials 81 (2025) 104516
3
p epa ed cell was hen ans e ed o he SEM chambe in he A a -
mosphe e using he The mo Scien ic CleanConnec Sample T ans e
Sys em (Fig. S1(d)) o pe o m ope ando es ing in SEM (Fig. S1(e)).
Fig. 2 shows he schema ic o ope ando SEM analysis se up. In he
SEM chambe , a s age wi h he con ac pins was p e-ins alled, in o which
he pins on he clamping ool when inse ed (Fig. S2). These pins a e
wi ed h ough a acuum eed h ough o a po en ios a ou side he SEM
chambe . A BioLogic SP-150 po en ios a was used o elec ochemical
measu emen s. The capaci y o he sys em was es ima ed based on he
elec ode size, conside ing he da ashee alue o 1 mAh/cm
2
. The
desc ip ion o he po en ios a se ings and cycling p o ocol o each
sample is p o ided in he esul s and discussion sec ion.
2.3. Ope ando SEM imaging and da a p ocessing
The mo Scien ic Qua o ESEM was u ilized o pe o m ope ando
SEM imaging. An au oma ed con ol sc ip (The mo Scien ic Au o-
Sc ip 4 So wa e) was de eloped o manage SEM magnica ion and
s age mo emen s, enabling he imaging o mul iple a eas wi h di e en
ho izon al eld wid h (HFW) ha p o ided bo h de ailed and o e iew
SEM images du ing ba e y cycling. The acqui ed images we e hen
co ela ed wi h specic poin s on he elec ochemical cu e based on he
da a om po en ios a . By combing hese images, a ideo was gene a ed
whe e he cu en ame is indica ed by a cu so ( ed c oss, Fig. 2) on he
cu e.
Fu he image analysis was conduc ed using The mo Scien ic
Phenom Pa icleMe ic pa icle analysis so wa e and Py hon sc ip
au oma ic edge de ec ion o s uc u al quan ica ion. Fo elec ode
s uc u al analysis, elec ode bounda ies (edges) we e de ec ed using
Py hon sc ip o ack he whole elec ode hickness changes. Changes
a e exp essed as pe cen ages ela i e o he ini ial image aken a he
s a o he measu emen . Fo NMC pa icle s uc u al e olu ion anal-
ysis, he The mo Scien ic A izo so wa e iden ies g ain bounda ies
and calcula es he a ea o each g ain based on he ac ual SEM
magnica ion. The eal size o he pa icles and c acks can be calcula ed
om he known eld o iew o SEM images.
3. Resul s and discussion
3.1. Ope ando s udy o s uc u al e olu ion a elec ode le el
The NMC-LTO ba e y was p epa ed as desc ibed in Sec ion 2.2 and
connec ed o a po en ios a wi hin SEM as shown in Fig. 2. A e wo
ini ial o ma ion cycles conduc ed a 0.1C in a po en ial window o 1.3 –
2.8 V, 15 min es phase, he ba e y was u he cycled in cons an
cu en ollowed by cons an ol age (CCCV) mode a 1.0C wi h 5 min
es phase, and imaged. No ably, he cycling con inued a he po en ial
window o 0.8 – 3.3 V o accele a e and ampli y he s uc u al changes
on NMC elec ode o e alua ion.
The hickness o he elec ode was con inuously measu ed du ing
cycling (Fig. 3, co esponding ideo o eco d he ull cycling p ocess
can be ound in Video S1). The esul s show NMC elec ode hickness
oscilla ed wi h he cha ge/discha ge p ocess, namely expansion du ing
ba e y cha ging (NMC elec ode deli hia ion) and con ac ion du ing
ba e y discha ging (NMC elec ode li hia ion) (Fig. 3(a)). In e es ingly,
a e expansion du ing he ba e y cha ging phase, he elec ode does
no e u n o i s o iginal hickness du ing ba e y discha ging. Ins ead, i
g adually expands wi h each subsequen cycle, leading o i e e sible
expansion in he elec ode. In he s cycle, he hickness was
app oxima ely 37.9
μ
m in he ba e y cha ged s a e and 37.0
μ
m in he
discha ged s a e. By he end o he 13 h cycle, hese alues inc eased o
39.8
μ
m and 39.1
μ
m (Fig. 3(C)), espec i ely. P e ious s udies ha e
shown ha he changes in elec ode hickness du ing cycling canno be
simply de i ed om he olume ic changes o he uni cell o he ac i e
ma e ials [50]. Fo ins ance, in NMC ca hodes, he PVDF binde signi -
ican ly con ibu es o i e e sible elec ode expansion, owing o i s
plas ic de o ma ion beha io and weak an de Waals in e ac ions wi h
he ac i e ma e ial [51]. Ac ing as a s uc u al skele on, i p o ides
Fig. 3. Ope ando acking s uc u al e olu ion a elec ode scale; (a) Cha ge and discha ge cu e s. hickness change o e he cycling p ocess; SEM images o NMC
ca hode du ing he cycling be ween 0.8 – 3.3.V; Elec ode hickness compa ison be ween he (b) beginning o he expe imen and (c) a e 13 cycles.
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Ene gy S o age Ma e ials 81 (2025) 104516
4
mechanical s abili y and holds he ac i e ma e ial pa icles oge he .
Du ing ba e y cycling, he binde ma ix expe iences plas ic de o ma-
ion d i en by mechanical s esses, which o igina e om in e g anula
expansion du ing he li hia ion phase and mic oc ack p opaga ion
wi hin NMC seconda y pa icles du ing deli hia ion. Unlike
hyd ogen-bonded o co alen ly c osslinked binde s, he weak in e ac-
ion wi h he ac i e ma e ials and lack o s ong e oac i e o ces esul
in elec ode no ully eco e ing o i s o iginal s uc u e and he e o e
leading o i e e sible expansion o he elec ode o e en delamina ion
o e mul iple cycles [52,53]. In addi ion, he elec ode po osi y and
pa icle ea angemen also con ibu e o he obse ed hickness e o-
lu ion [54]. The elec ode po osi y allows local accommoda ion o s ess
and pe mi s pe manen displacemen o pa icles unde binde
de o ma ion. As he binde plas ically yields, addi ional oids o med
du ing con ac ion a e no always closed in he ollowing cycles, espe-
cially when he binde ails o eco e i s o iginal shape. This c ea es a
ne olume gain pe cycle, e en i he ac i e ma e ial i sel e u ns o i s
p e ious la ice s a e. O e all, he changes o elec ode hickness can be
a ibu ed o he syne gic in e ac ion among binde composi ion, me-
chanical p ope ies, ac i e ma e ials uni cell olume changes, and
elec ode po osi y. The ope ando expe imen al da a shows ha he
changes in he ma e ials s uc u e wi hin he elec ode, including he
beha io o he binde s, ha e a signican impac on he elec ode’s
pe o mance, and need o be conside ed when designing and op imizing
ba e y elec ode a chi ec u e.
Unde s anding and measu ing elec ode expansion du ing cycling
Fig. 4. Ope ando acking s uc u al e olu ion a pa icle le el wi h selec ed NMC pa icles. (a) ol age cu e o he cell and he co esponding g ain size changes o
Pa icle A and B; (b) SEM images o Pa icle A and (c) Pa icle B o wo deli hia ion/li hia ion cycles.
O. Kl aˇ
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Ene gy S o age Ma e ials 81 (2025) 104516
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can enhance knowledge o op imizing manu ac u ing p ocesses and
ba e y de elopmen . I is wo h no ing ha he cu en ope ando SEM
wo kow does no di ec ly measu e mechanical p ope ies o isola e he
binde ’s ole in deg ada ion. A mo e comp ehensi e unde s anding
could be achie ed by in eg a ing in-si u mechanical cha ac e iza ion
echniques, such as nanoinden a ion o AFM-based mechanical map-
ping, which enable di ec assessmen o local s i ness a ia ions, plas ic
de o ma ion, and ac u e beha io wi hin he elec ode composi e,
pa icula ly in binde -en iched egions [55,56] Complemen a y ap-
p oaches, such as Raman spec oscopy, could also help iden i y chemical
o s uc u al changes in he binde du ing cycling [57,58]. I is expec ed
ha he combina ion o eal- ime moni o ing on s uc u al acking wi h
in-si u mechanical es ing and complemen a y echniques such as
Raman spec oscopy can allow o in-dep h unde s anding he ole o
binde in he elec ode, whe e he lea ning can suppo s uc u al design
and p ocess op imiza ion o ensu e highe quali y and mo e eliable
ba e ies manu ac u ing.
3.2. Ope ando s udy o s uc u al e olu ion a pa icle le el
When acking s uc u al e olu ion a pa icle le el, imaging was
pe o med du ing s wo o ma ion cycles conduc ed a 0.1C in a
s anda d po en ial window o 1.3 – 2.8 V. Cycling was conduc ed in CC
mode wi h 15 min es phase. Fig. 4(a) illus a es he ol age cu e o he
cell and he co esponding g ain size changes. Poin s associa ed wi h
signican size changes we e selec ed om he cu es and ma ked wi h
lines, co esponding o he SEM images o Pa icle A (Fig. 4(b)) and
Pa icle B (Fig. 4(c)). The loca ion o Pa icle A and Pa icle B wi hin he
elec ode a e shown in Fig. S3 wi h Video S2 eco ding he p ocess o 2
ull cycles. Images labeled as "s a " ep esen he ini ial snapsho a he
beginning o he expe imen , while images labeled as “end” ep esen
he nal snapsho (no ma ked by lines in he g aph).
Obse a ions indica e ha a he onse o he s li hia ion ( s
NMC deli hia ion), pa icle sh inkage occu s in bo h obse ed cases.
App oxima ely hal way h ough he NMC deli hia ion pla eau, he pa -
icles each hei minimum size. P io o eaching he minimum (images
A1, B1), no signican changes in g ain in eg i y we e obse ed
compa ed o he "s a " images. Subsequen ly, he beha io o he pa -
icles di e ges. Image A2, aken sho ly a e he minimum size, shows
he ini ia ion o c ack o ma ion, which esul s in an inc ease in size.
This beha io is consis en wi h p e iously desc ibed obse a ions o
NMC 811 pa icles [59]. The g ow h o pa icle A eaches a maximum
upon comple ion o he NMC deli hia ion cycle (image A3), expanding
beyond i s o iginal size. A his poin , he c acks a e ully o med, and
he pa icle is mos ly expanded. In con as , pa icle B emains p ac i-
cally cons an in size a e eaching he minimum. Images B2 and B3
indica e minimal c ack o ma ion and p opaga ion compa ed o pa icle
A. Du ing he s NMC li hia ion cycle, a sh inkage o pa icle A was
obse ed oge he wi h signican disappea ance o mos c acks (images
A5). Pa icle B isibly g ew un il he end o he s NMC li hia ion
cycle, wi h a concu en disappea ance o c acks (images B4, B5).
Du ing he second deli hia ion/li hia ion cycle, pa icle A size
emained nea ly unchanged. The g aph sugges s he sign o po en ial
ini ial sh inkage in deli hia ion ollowed by expansion in he li hia ion
p ocess. Howe e , he well-de eloped c acks in he s cycle compen-
sa e o he size change due o he deli hia ion/li hia ion p ocess,
making he size change insignican compa ed o s cycle. Pa icle B,
du ing he second cycle, mimics he beha io o he s cycle. I sh inks
in he s hal and hen e u ns back o o iginal size un il he end. The
size changes a e smalle han s cycle also due o he compensa ion
om de eloped c acks. In he second li hia ion cycle, bo h pa icles
exhibi a e ac ion o c acks (images "end").
The obse a ions sugges ha syne gized e ec s o wo phenomena
a e esponsible o olume ic changes in pa icles: li hia ion and deli-
hia ion p ocess, and pa icle c acking. The li hia ion and deli hia ion
p ocess esul s in p ima y pa icles sh inkage and expansion due o he
expulsion and inse ion o li hium ions om and o hei s uc u e.
Howe e , signican c acking can lead o an inc ease in size du ing
deli hia ion while mi iga ing he pa icle u he inc ease du ing li h-
ia ion p ocess. Table S1 summa izes he quan i a i e analysis o pa icle
c acking and pa icle size o bo h pa icles a he co esponding cycling
s age du ing which SEM images we e acqui ed, p o iding quan i a i e
alida ion o he p oposed deg ada ion mechanism. In he case o
pa icle A, la ge c acks o ma ion esul ed in expansion beyond i s
o iginal size. Pa icle B exhibi ed minimal c acking and he e o e size
ollows deli hia ion/li hia ion p ocess mo e closely. The incomple e
eco e y o i s o iginal size may esul om capaci y loss du ing cycling,
whe e a po ion o li hium is no e u ned o he o iginal s uc u e.
Fu he mo e, i appea s ha once a pa icle has c acked, olume ic
changes a e mo e likely abso bed as he expansion/con ac ion o c acks
a he han o e all g ow h and con ac ion. This is obse able in pa icle
A. Pa icle B, which con ains only mino c acks, shows mo e signican
o e all size changes along cycling.
These obse ed phenomena may inuence elec ode design in
manu ac u ing p ocess, pa icula ly design o he binde s uc u e,
po osi y, size, and spa ial dis ibu ion o he ac i e ma e ial g ains. A
mo e exible binde could po en ially allow he pa icle o sh ink wi h
less c acking. Addi ionally, i is wo h conside ing whe he long- e m
cycling, which leads o he g ow h o he SEI laye , could cause "wo k-
ing" c acks o become clogged, po en ially leading o he o ma ion o
new c acks.
3.3. In ope ando s uc u al analysis in G -Li sys em
The ope ando SEM se up was also pe o med on G -Li sys em o
p o e i s b oade applicabili y in di e en ba e y sys ems. Obse a ion
was pe o med du ing s h ee o ma ion cycles conduc ed a 0.1C in a
po en ial window o 0.01 – 2.50 V. Cycling was conduc ed in CC mode
wi h 10 min es phase, wi hou he CV phase. Volume ic changes o he
pa icles and hei c acking we e obse ed a six selec ed poin s co e-
sponding o di e en s ages o li hia ion and deli hia ion, as well as a
he beginning and end o he cycling p ocess. The esul ing da a a e
depic ed in Fig. 5 (also see Video S3 o he eco ding o he elec o-
chemical cycling p ocess o G -Li sys em).
The s abili y and obus ness o he ope ando SEM wo kow was
p o ed based on he minimal capaci y loss du ing he cycles wi h
compa able cha ge/discha ge beha io wi h s anda d G -Li ba e y.
Al hough c acks and olume ic changes we e p esen , hei impac on
he o e all elec ode pe o mance was negligible, demons a ing sys em
esilien o s uc u al changes du ing he ini ial cycles.
3.4. Me hod applicabili y and u u e di ec ions
The wo kow p esen ed in his s udy o e s high- esolu ion insigh
in o he mo phological e olu ion om elec ode le el o pa icle le el
unde nea ope a ional condi ions. These insigh s can in o m op imi-
za ion du ing R&D and pilo -scale p oduc ion, acili a ing mo e e ec i e
scaling o high- olume manu ac u ing condi ions. While his app oach
enables di ec isualiza ion o deg ada ion mechanisms wi h spa ial and
empo al p ecision, i is impo an o dene i s scope o applicabili y and
acknowledge cu en limi a ions, pa icula ly ega ding manu ac u ing
ele ance, complemen a y analy ical echniques and s a is ical
signicance.
This wo kow is ully compa ible wi h bo h ull-cell and hal -cell
congu a ions, allowing exible in es iga ion o a wide ange o ba -
e y chemis ies, including solid-s a e ba e ies. Howe e , gi en ha he
p oposed wo kow is undamen ally based on SEM echnology, i is no
di ec ly compa ible wi h in-line o high- h oughpu me ology sys ems
commonly u ilized in manu ac u ing se ings o eal- ime eedback and
p ocess op imiza ion. I s alue o ba e y manu ac u ing lies in he
mechanis ic insigh s ob ained om obse ing s uc u al e olu ion o he
ba e y sample du ing ope ando cycling. By isualizing i e e sible
O. Kl aˇ
c e al.
Ene gy S o age Ma e ials 81 (2025) 104516
6
changes such as elec ode expansion, pa icle c acking, o cu en col-
lec o de achmen , i p o ides aluable in o ma ion on how ma e ials
selec ion and cell design pa ame e s, including binde o mula ion,
po osi y, and coa ing hickness, inuence mechanical s abili y and
elec ochemical pe o mance.
Fu he mo e, he wo kow is compa ible wi h analy ical echniques
in SEM, such as ene gy-dispe si e X- ay spec oscopy (EDS) and elec on
backsca e di ac ion (EBSD), which p o ide composi ional and c ys-
allog aphic in o ma ion o mo e in-dep h mechanis ic unde s anding.
Fo example, in his s udy, he c acks end o o m in he cen e o he
pa icles, which is consis en wi h p e ious s udies [60,61]. Mo e
mechanis ic unde s anding could be achie ed by he in eg a ion o
analy ical capabili y such as EBSD o unde s and he co ela ion be-
ween g ain s uc u e and c acking pa hway. Howe e , i is impo an o
no e ha implemen ing hese echniques in an ope ando amewo k also
in oduces specic challenges. EDS and EBSD ypically equi e highe
beam cu en s, longe acquisi ion imes, and highe accele a ing ol -
ages, which inc ease chances o beam-induced damage, esolu ion loss,
o sample con amina ion, pa icula ly when wo king wi h sensi i e
ba e y ma e ials. While con inuous eal- ime mapping wi h EDS o
EBSD is imp ac ical unde ope ando cycling condi ions, a ge ed mea-
su emen s can be pe o med a selec ed s ages o cycling, o example
du ing es phases o a e dened cycling s eps. In such cases, spa ial o
empo al esolu ion mus be aded o addi ional composi ional o
s uc u al in o ma ion.
Finally, al hough wo pa icles wi h high- esolu ion images a e
selec ed and discussed, hey a e selec ed as he ep esen a i e pa icles
sc eening om a ound 30 pa icles om he ull elec ode shown in
Fig. S3. Fu he s a is ical signicance can be achie ed by applying he
ope ando SEM wo kow in a wide elec ode (sub mm) wi h mo e
pa icles o in es iga e (Fig. S4). Howe e , di e en imaging s a egies
need o be de eloped o enable bo h high esolu ion o accu acy and a
la ge eld o iew o s a is ics. Addi ionally, he cycling a e mus be
op imized o align wi h imaging h oughpu , ensu ing ha s uc u al
changes emain negligible du ing he acquisi ion o la ge eld-o - iew
images.
4. Conclusion
In his s udy, we p esen an ope ando SEM wo kow o in es i-
ga ing ba e y s uc u al e olu ion, which in eg a es high-quali y elec-
ode c oss-sec ion p epa a ion using a b oad ion beam polishe , ine
sample ans e o a glo ebox, and SEM imaging, ollowed by semi-
au oma ed imaging and quan i a i e s uc u al analysis. I sa ises
ou majo c i e ia iden ied as c i ical o adop ing his echnology o
bo h ba e y R&D and manu ac u ing.
In elec ode s uc u al acking s udy, expansion o he whole NMC
elec ode du ing cell cha ging (NMC deli hia ion) and con ac ion du -
ing cell discha ging (NMC li hia ion) we e obse ed. The esul s sugges
ha he binde plays a key ole in elec ode le el s uc u al changes in
addi ion o changes in he c ys allog aphic s uc u e o he ac i e ma-
e ial. Fo pa icle le el s uc u al acking, wo ac o s ha de e mine
size changes we e obse ed – deli hia ion/li hia ion and c acking. The
c acks a e de eloped om deli hia ion p ocess. Subsequen size changes
associa ed wi h di e en li hia ion le els mani es ed p ima ily as
expansion and con ac ion o c acks wi hin he pa icles, a he han as
ex e nal bulk de o ma ion. Finally, G -Li sys em was used o e i y ha
he unc ionali y o he ope ando SEM wo kow can be applied o
b oade ba e y sys ems wi h a di e en chemical composi ion. In
pa icula , i s po en ial applica ion o li hium me al sys ems holds
p omise o ad ancing nex -gene a ion ba e y de elopmen . The esul s
also showed expansion and c acking o g aphi e pa icles du ing li h-
ia ion and con ac ion du ing deli hia ion.
In conclusion, he p esen ed me hod enables a deepe unde s anding
o ba e y cycling p ocesses, p o iding insigh s ha can d i e he op i-
miza ion o pe o mance and li e ime. I is impo an o no e ha ,
Fig. 5. Ope ando s uc u al analysis in G -Li sys em, he c acking (indica ed by yellow a ow) and expansion we e obse ed du ing cycling.
O. Kl aˇ
c e al.
Ene gy S o age Ma e ials 81 (2025) 104516
7
al hough ILs elec oly es a e used o demons a e i s capabili y in Li-ion
ba e y, his me hod is also applicable o nex -gen ba e y de elopmen ,
such as solid-s a e ba e y and Li-me al ba e ies, which can acili a e
inno a ion and esea ch in o new ma e ials, ul ima ely con ibu ing o
he de elopmen o mo e ad anced ba e y sys ems.
CRediT au ho ship con ibu ion s a emen
Ondˇ
ej Kl aˇ
c: W i ing – o iginal d a , So wa e, Me hodology,
In es iga ion, Visualiza ion. Da id T och a: W i ing – o iginal d a ,
Visualiza ion, Valida ion, So wa e, Me hodology, In es iga ion. Libo
No ´
ak: W i ing – o iginal d a , Resou ces, P ojec adminis a ion,
Me hodology, Funding acquisi ion. Pe e P iecel: W i ing – e iew &
edi ing, Valida ion. Manuel Bo nh¨
o : So wa e, Fo mal analysis.
Tom´
aˇ
s Kazda: W i ing – e iew & edi ing, Supe ision, Me hodology,
In es iga ion, Funding acquisi ion. Zhao Liu: W i ing – o iginal d a ,
Supe ision, W i ing – e iew & edi ing.
Decla a ion o compe ing in e es
The au ho s decla e he ollowing nancial in e es s/pe sonal e-
la ionships which may be conside ed as po en ial compe ing in e es s:
This wo k was conduc ed as pa o a collabo a ion be ween The mo
Fishe Scien ic and B no Uni e si y o Technology unde he Na ional
Compe ence Cen e (NCK) p ojec . Se e al au ho s a e employees o
The mo Fishe Scien ic, a p o ide o elec on mic oscopy solu ions.
The wo kow p esen ed in his publica ion may be u he de eloped
in o a comme cial p oduc in he u u e. The emaining au ho s, who a e
no a lia ed wi h The mo Fishe Scien ic, decla e no known
compe ing nancial in e es s o pe sonal ela ionships ha could ha e
inuenced he esea ch epo ed in his pape .
Decla a ion o gene a i e AI and AI-assis ed echnologies in he w i ing
p ocess
Du ing he p epa a ion o his wo k he au ho s used GPT-4o
(OpenAI), No ebookLM (Google), and DeepL T ansla e in o de o
enhance ex quali y, x g amma e o s, and imp o e eadabili y. A e
using hese ools, he au ho s e iewed and edi ed he con en as needed
and ook ull esponsibili y o he con en o he published a icle.
Acknowledgemen s
This wo k was suppo ed by he p ojec The Ene gy Con e sion and
S o age (P ojec no CZ.02.01.01/00/22_008/0004617), unded unde
he Excellen Resea ch call o he Johannes Amos Comenius P og amme.
Addi ional suppo was p o ided by he B no Uni e si y o Technology
h ough he specic g adua e esea ch g an FEKT-S-23-8286 and also
was conanced by he Technology Agency o he Czech Republic wi hin
he Cen e o Elec on and Pho onic Op ics p og amme TN02000020.
The au ho s also acknowledge unding om he Eu opean Union’s Ho-
izon Eu ope esea ch and inno a ion p og amme unde g an ag ee-
men no 101192848 (FULL-MAP).
Supplemen a y ma e ials
Supplemen a y ma e ial associa ed wi h his a icle can be ound, in
he online e sion, a doi:10.1016/j.ensm.2025.104516.
Da a a ailabili y
Da a will be made a ailable on eques .
Re e ences
[1] V. E ache i, R. Ma om, R. Elaza i, G. Sali a, D. Au bach, Challenges in he
de elopmen o ad anced Li-ion ba e ies: a e iew, Ene gy En i on. Sci. 4 (2011),
h ps://doi.o g/10.1039/c1ee01598b.
[2] J. Xiao, X. Cao, B. G idley, W. Golden, Y. Ji, S. Johnson, D. Lu, F. Lin, J. Liu, Y. Liu,
Z. Liu, H.N. Ramesh, F. Shi, J. Sch oo en, M.J. Sims, S. Sun, Y. Shao, A. Vaisman,
J. Yang, M.S. Whi ingham, F om mining o manu ac u ing: scien ic challenges
and oppo uni ies behind ba e y p oduc ion, Chem. Re . (2025), h ps://doi.o g/
10.1021/acs.chem e .4c00980.
[3] J. Xiao, F. Shi, T. Glossmann, C. Bu ne , Z. Liu, F om labo a o y inno a ions o
ma e ials manu ac u ing o li hium-based ba e ies, Na . Ene gy 8 (2023), h ps://
doi.o g/10.1038/s41560-023-01221-y.
[4] X. Liu, L. Zhang, H. Yu, J. Wang, J. Li, K. Yang, Y. Zhao, H. Wang, B. Wu, N.
P. B andon, S. Yang, B idging mul iscale cha ac e iza ion echnologies and digi al
modeling o e alua e li hium ba e y ull li ecycle, Ad . Ene gy Ma e . 12 (2022),
h ps://doi.o g/10.1002/aenm.202200889.
[5] H. Yang, P. Tang, N. Piao, J. Li, X. Shan, K. Tai, J. Tan, H.-M. Cheng, F. Li, In-si u
imaging echniques o ad anced ba e y de elopmen , Ma e . Today 57 (2022)
279–294, h ps://doi.o g/10.1016/j.ma od.2022.05.021.
[6] D. Liu, Z. Shadike, R. Lin, K. Qian, H. Li, K. Li, S. Wang, Q. Yu, M. Liu,
S. Ganapa hy, X. Qin, Q. Yang, M. Wagemake , F. Kang, X. Yang, B. Li, Re iew o
ecen de elopmen o In si u/ope ando cha ac e iza ion echniques o li hium
ba e y esea ch, Ad . Ma e . (2019) 31, h ps://doi.o g/10.1002/
adma.201806620.
[7] P.P.R.M.L. Ha ks, F.M. Mulde , P.H.L. No en, In si u me hods o Li-ion ba e y
esea ch: a e iew o ecen de elopmen s, J. Powe Sou ce. 288 (2015) 92–105,
h ps://doi.o g/10.1016/j.jpowsou .2015.04.084.
[8] S.-M. Bak, Z. Shadike, R. Lin, X. Yu, X.-Q. Yang, In si u/ope ando synch o on-
based X- ay echniques o li hium-ion ba e y esea ch, NPG Asia Ma e . 10 (2018)
563–580, h ps://doi.o g/10.1038/s41427-018-0056-z.
[9] M. Pin, J. Choi, J.H. Chang, A.S. Schenk, J. Han, S. Wacławek, Y. Kim, J.Y. Cheong,
In si u X- ay based analysis o anode ma e ials o li hium-ion ba e ies: cu en
s a us and u u e implica ions, Ene gy S o age Ma e . 73 (2024), h ps://doi.o g/
10.1016/j.ensm.2024.103798.
[10] G. Qian, S. Kuppan, A. Gallo, J. Zhou, Z. Liu, Y. Liu, F om in-si u expe imen a ion
o in-line me ology: ad anced imaging cha ac e iza ion o ba e y esea ch and
manu ac u ing, Ene gy S o age Ma e . 73 (2024), h ps://doi.o g/10.1016/j.
ensm.2024.103819.
[11] M. Goloza , R. Gau in, K. Zaghib, In si u and In ope ando echniques o s udy Li-
ion and solid-S a e ba e ies: mic o o a omic le el, Ino gan. (Basel) (2021) 9,
h ps://doi.o g/10.3390/ino ganics9110085.
[12] W. Du, R.E. Owen, A. Jnawali, T.P. Ne ille, F. Iaco iello, Z. Zhang, S. Lia a d, D.J.
L. B e , P.R. Shea ing, In-si u X- ay omog aphic imaging s udy o gas and
s uc u al e olu ion in a comme cial Li-ion pouch cell, J. Powe Sou ce. 520
(2022), h ps://doi.o g/10.1016/j.jpowsou .2021.230818.
[13] P. Blazek, P. Wes enbe ge , S. E ke , A. B inek, T. Zikmund, D. Re enwande , N.
P. Wagne , J. Keckes, J. Kaise , T. Kazda, P. Vy oubal, M. Macak, J. Tod , Axially
and adially inhomogeneous swelling in comme cial 18650 Li-ion ba e y cells,
J. Ene gy S o age. 52 (2022), h ps://doi.o g/10.1016/j.es .2022.104563.
[14] L. Willenbe g, P. Dechen , G. Fuchs, M. Teube , M. Ecke , M. G a , N. Kü en, D.
U. Saue , E. Figgemeie , The de elopmen o jelly oll de o ma ion in 18650
li hium-ion ba e ies a low S a e o cha ge, J. Elec ochem. Soc. 167 (2020),
h ps://doi.o g/10.1149/1945-7111/aba96d.
[15] P. Pie sch, V. Wood, X- ay omog aphy o li hium ion ba e y esea ch: a p ac ical
guide, Annu. Re . Ma e . Res. 47 (2017) 451–479, h ps://doi.o g/10.1146/
annu e -ma sci-070616-123957.
[16] Z. S a o a, O. Kl ac, J. Bana, B. Ano humakkool, T. Zikmund, P. Blazek, J. Kaise ,
T. Kazda, Comp ehensi e s udy o apid capaci y ade in p isma ic Li-ion cells wi h
exible packaging, Sci. Rep. 14 (2024), h ps://doi.o g/10.1038/s41598-024-
77673-3.
[17] S. Zhou, K. Liu, Y. Ying, L. Chen, G. Meng, Q. Zheng, S.-G. Sun, H.-G. Liao,
Pe spec i e o ope ando/in si u scanning elec on mic oscope in echa geable
ba e ies, Cu . Opin. Elec ochem. 41 (2023), h ps://doi.o g/10.1016/j.
coelec.2023.101374.
[18] A. P ang, A. Ke sys, A. K is on, D.U. Saue , C. Rahe, S. K¨
abi z, E. Figgemeie ,
Geome ical inhomogenei ies as cause o mechanical ailu e in comme cial 18650
li hium ion cells, J. Elec ochem. Soc. 166 (2019) A3745–A3752, h ps://doi.o g/
10.1149/2.0551914jes.
[19] O.O. Taiwo, D.P. Finegan, J.M. Paz-Ga cia, D.S. Eas wood, A.J. Bodey, C. Rau, S.
A. Hall, D.J.L. B e , P.D. Lee, P.R. Shea ing, In es iga ing he e ol ing
mic os uc u e o li hium me al elec odes in 3D using X- ay compu ed
omog aphy, Phys. Chem. Chem. Phys. 19 (2017) 22111–22120, h ps://doi.o g/
10.1039/C7CP02872E.
[20] J. Gonzalez, K. Sun, M. Huang, J. Lamb os, S. Dillon, I. Chasio is, Th ee
dimensional s udies o pa icle ailu e in silicon based composi e elec odes o
li hium ion ba e ies, J. Powe Sou ce. 269 (2014) 334–343, h ps://doi.o g/
10.1016/j.jpowsou .2014.07.001.
[21] A. Schoo, R. Moschne , J. Hülsmann, A. Kwade, Coa ing de ec s o li hium-ion
ba e y elec odes and hei inline de ec ion and acking, Ba e ies 9 (2023),
h ps://doi.o g/10.3390/ba e ies9020111.
[22] S. Wang, K. Li, Y. Tian, J. Wang, Y. Wu, S. Ji, In a ed imaging in es iga ion o
empe a u e uc ua ion and spa ial dis ibu ion o a la ge lamina ed li hium–ion
powe ba e y, Appl. The m. Eng. 152 (2019) 204–214, h ps://doi.o g/10.1016/j.
appl he maleng.2019.02.096.
O. Kl aˇ
c e al.
Ene gy S o age Ma e ials 81 (2025) 104516
8
[23] Z. Deng, Z. Huang, Y. Shen, Y. Huang, H. Ding, A. Luscombe, M. Johnson, J.
E. Ha low, R. Gau hie , J.R. Dahn, Ul asonic scanning o obse e we ing and
“unwe ing” in Li-ion pouch cells, Joule 4 (2020) 2017–2029, h ps://doi.o g/
10.1016/j.joule.2020.07.014.
[24] C. Hog e e, T. Waldmann, M.B. Moline o, L. Wildne , P. Axmann, M. Wohl ah -
Meh ens, C oss-sec ional In si u op ical mic oscopy wi h simul aneous
elec ochemical measu emen s o li hium-ion ull cells, J. Elec ochem. Soc. 169
(2022), h ps://doi.o g/10.1149/1945-7111/ac6c57.
[25] J. S eige , D. K ame , R. M¨
onig, Mechanisms o dend i ic g ow h in es iga ed by in
si u ligh mic oscopy du ing elec odeposi ion and dissolu ion o li hium, J. Powe
Sou ce. 261 (2014) 112–119, h ps://doi.o g/10.1016/j.jpowsou .2014.03.029.
[26] H. Li, S. Guo, H. Zhou, In-si u/ope ando cha ac e iza ion echniques in li hium-ion
ba e ies and beyond, J. Ene gy Chem. 59 (2021) 191–211, h ps://doi.o g/
10.1016/j.jechem.2020.11.020.
[27] M.T. McDowell, S.W. Lee, J.T. Ha is, B.A. Ko gel, C. Wang, W.D. Nix, Y. Cui, In
si u TEM o wo-phase li hia ion o amo phous silicon nanosphe es, Nano. Le . 13
(2013) 758–764, h ps://doi.o g/10.1021/nl3044508.
[28] J.M. Yuk, H.K. Seo, J.W. Choi, J.Y. Lee, Aniso opic li hia ion onse in silicon
nanopa icle anode e ealed by in si u g aphene liquid cell elec on mic oscopy,
ACS Nano 8 (2014) 7478–7485, h ps://doi.o g/10.1021/nn502779n.
[29] S.-W. Lee, D.-H. Jang, J.-B. Yoon, Y.-H. Cho, Y.-S. Lee, D.-H. Kim, W.-S. Kim, W.-
S. Yoon, C ys al s uc u e changes o LiNi
0.5
Co
0.2
Mn
0.3
O
2
ca hode ma e ials
du ing he s cha ge in es iga ed by in si u XRD, J. Elec ochem. Sci. Technol. 3
(2012) 29–34, h ps://doi.o g/10.5229/JECST.2012.3.1.29.
[30] H. Asayesh-A dakani, W. Yao, Y. Yuan, A. Nie, K. Amine, J. Lu, R. Shahbazian-
Yassa , In si u TEM in es iga ion o ZnO nanowi es du ing sodia ion and li hia ion
cycling, Small Me hod. 1 (2017), h ps://doi.o g/10.1002/sm d.201700202.
[31] X.H. Liu, L.Q. Zhang, L. Zhong, Y. Liu, H. Zheng, J.W. Wang, J.-H. Cho, S.A. Dayeh,
S.T. Pic aux, J.P. Sulli an, S.X. Mao, Z.Z. Ye, J.Y. Huang, Ul a as elec ochemical
li hia ion o indi idual Si nanowi e anodes, Nano Le . 11 (2011) 2251–2258,
h ps://doi.o g/10.1021/nl200412p.
[32] J.Y. Huang, L. Zhong, C.M. Wang, J.P. Sulli an, W. Xu, L.Q. Zhang, S.X. Mao, N.
S. Hudak, X.H. Liu, A. Sub amanian, H. Fan, L. Qi, A. Kushima, J. Li, In si u
obse a ion o he elec ochemical li hia ion o a single SnO
2
nanowi e elec ode,
Science 330 (1979) (2010) 1515–1520, h ps://doi.o g/10.1126/science.1195628.
[33] Q. Zhang, Z. Song, X. Sun, Y. Liu, J. Wan, S.B. Be zle , Q. Zheng, J. Shangguan, K.
C. Bus illo, P. E cius, P. Na ang, Y. Huang, H. Zheng, A omic dynamics o
elec ied solid–liquid in e aces in liquid-cell TEM, Na u e 630 (2024) 643–647,
h ps://doi.o g/10.1038/s41586-024-07479-w.
[34] Z. Zeng, W.-I. Liang, H.-G. Liao, H.L. Xin, Y.-H. Chu, H. Zheng, Visualiza ion o
elec ode–Elec oly e in e aces in LiPF
6
/EC/DEC elec oly e o li hium ion
ba e ies ia in si u TEM, Nano. Le . 14 (2014) 1745–1750, h ps://doi.o g/
10.1021/nl403922u.
[35] D. Cheng, J. Hong, D. Lee, S.-Y. Lee, H. Zheng, In si u TEM cha ac e iza ion o
ba e y ma e ials, Chem. Re . 125 (2025) 1840–1896, h ps://doi.o g/10.1021/
acs.chem e .4c00507.
[36] X. Zhou, T. Li, Y. Cui, Y. Fu, Y. Liu, L. Zhu, Si u ocused ion beam scanning elec on
mic oscope s udy o mic os uc u al e olu ion o single in pa icle anode o Li-ion
ba e ies, ACS Appl. Ma e . In e ace. 11 (2019) 1733–1738, h ps://doi.o g/
10.1021/acsami.8b13981.
[37] D.J. Mille , C. P o , J.G. Wen, D.P. Ab aham, J. Ba e˜
no, Obse a ion o
mic os uc u al e olu ion in Li ba e y ca hode oxide pa icles by In si u elec on
mic oscopy, Ad . Ene gy Ma e . 3 (2013) 1098–1103, h ps://doi.o g/10.1002/
aenm.201300015.
[38] C.-Y. Chen, T. Sano, T. Tsuda, K. Ui, Y. Oshima, M. Yamaga a, M. Ishikawa,
M. Ha u a, T. Doi, M. Inaba, S. Kuwaba a, si u scanning elec on mic oscopy o
silicon anode eac ions in li hium-ion ba e ies du ing cha ge/discha ge p ocesses,
Sci. Rep. 6 (2016), h ps://doi.o g/10.1038/s ep36153.
[39] T. Tsuda, K. Hosoya, T. Sano, S. Kuwaba a, In-si u scanning elec on mic oscope
obse a ion o elec ode eac ions ela ed o ba e y ma e ial, Elec ochim. Ac a
319 (2019) 158–163, h ps://doi.o g/10.1016/j.elec ac a.2019.06.165.
[40] D. Chen, S. Ind is, M. Schulz, B. Game , R. M¨
onig, In si u scanning elec on
mic oscopy on li hium-ion ba e y elec odes using an ionic liquid, J. Powe
Sou ce. 196 (2011) 6382–6387, h ps://doi.o g/10.1016/j.jpowsou .2011.04.009.
[41] G. Rong, X. Zhang, W. Zhao, Y. Qiu, M. Liu, F. Ye, Y. Xu, J. Chen, Y. Hou, W. Li,
W. Duan, Y. Zhang, Liquid-phase elec ochemical scanning elec on mic oscopy o
In si u in es iga ion o li hium dend i e g ow h and dissolu ion, Ad . Ma e . 29
(2017), h ps://doi.o g/10.1002/adma.201606187.
[42] S. Kaboli, H. Deme s, A. Paolella, A. Da wiche, M. Don igny, D. Cl´
emen , A. Gue ,
M.L. T udeau, J.B. Goodenough, K. Zaghib, Beha io o solid elec oly e in Li-
polyme ba e y wi h NMC ca hode ia in-si u scanning elec on mic oscopy, Nano
Le . 20 (2020) 1607–1613, h ps://doi.o g/10.1021/acs.nanole .9b04452.
[43] P. Ho ing on, M. Don igny, A. Gue , J. T o ie , M. Lagac´
e, A. Mauge , C.
M. Julien, K. Zaghib, In si u scanning elec on mic oscope s udy and
mic os uc u al e olu ion o nano silicon anode o high ene gy Li-ion ba e ies,
J. Powe Sou ce. 248 (2014) 457–464, h ps://doi.o g/10.1016/j.
jpowsou .2013.09.069.
[44] F. O sini, A. Du Pasquie , B. Beaudoin, J.M. Ta ascon, M. T en in,
N. Langenhuizen, E. De Bee , P. No en, In si u Scanning elec on mic oscopy
(SEM) obse a ion o in e aces wi hin plas ic li hium ba e ies, J. Powe Sou ce.
76 (1998) 19–29, h ps://doi.o g/10.1016/S0378-7753(98)00128-1.
[45] P. Pe eno , P. Bayle-Guillemaud, P.-H. Jouneau, A. Boulineau, C. Ville ieille,
Ope ando ocused ion beam–Scanning elec on mic oscope (FIB-SEM) e ealing
mic os uc u al and mo phological e olu ion in a solid-S a e ba e y, ACS Ene gy
Le . 9 (2024) 3835–3840, h ps://doi.o g/10.1021/acsene gyle .4c01750.
[46] L. No ak, P. Glajc, O. Kl ac, Ba e y in si u elec ical es ing in FIB-SEM, Mic osc.
Mic oanaly. 28 (2022) 834–835, h ps://doi.o g/10.1017/S1431927622003737.
[47] K.K. Neelise y, J. S e ina, J. Vond uˇ
ska, M. T enz, T. Kazda, M. H ouzek,
P. Wand ol, T ans e o li hium oil unde ine condi ions using CleanConnec
ine gas ans e sys em, Mic osc. Mic oanaly. 27 (2021) 2508–2509, h ps://doi.
o g/10.1017/S1431927621008941.
[48] T. Waldmann, A. I u ondobei ia, M. Kaspe , N. Ghanba i, F. Aguesse, E. Bekae ,
L. Daniel, S. Genies, I.J. Go don, M.W. L¨
oble, E. De Vi o, M. Wohl ah -Meh ens,
Re iew—pos -mo em analysis o aged li hium-ion ba e ies: disassembly
me hodology and physico-chemical analysis echniques, J. Elec ochem. Soc. 163
(2016) A2149–A2164, h ps://doi.o g/10.1149/2.1211609jes.
[49] W. Hau e, S. Menzel, T. G¨
obel, Ad an ages o b oad ion beam (BIB) p ocessing
compa ed wi h ocused ion beam (FIB) echnology o 3D in es iga ion o
he e ogeneous solids, Mic osc. Mic oanaly. 9 (2003) 148–149, h ps://doi.o g/
10.1017/S1431927603016106.
[50] F.B. Spingle , S. Küche , R. Phillips, E. Moyassa i, A. Jossen, Elec ochemically
s able In si u dila ome y o NMC, NCA and g aphi e elec odes o li hium-ion cells
compa ed o XRD measu emen s, J. Elec ochem. Soc. 168 (2021), h ps://doi.o g/
10.1149/1945-7111/ab 262.
[51] M. S i as a a, A. Kuma M.R., K. Zaghib, Binde s o Li-ion ba e y echnologies
and beyond: a comp ehensi e e iew, Ba e ies 10 (2024) 268, h ps://doi.o g/
10.3390/ba e ies10080268.
[52] J.M. Fos e , X. Huang, M. Jiang, S.J. Chapman, B. P o as, G. Richa dson, Causes o
binde damage in po ous ba e y elec odes and s a egies o p e en i , J. Powe
Sou ce. 350 (2017) 140–151, h ps://doi.o g/10.1016/j.jpowsou .2017.03.035.
[53] D.-H. Yoon, M. Ma ina o, P. Axmann, M. Wohl ah -Meh ens, S udy o he binde
inuence on expansion/con ac ion beha io o silicon alloy nega i e elec odes
o li hium-ion ba e ies, J. Elec ochem. Soc. 167 (2020) 160537, h ps://doi.o g/
10.1149/1945-7111/abc 4 .
[54] T. Beuse, M. Finge le, C. Wagne , M. Win e , M. B¨
o ne , Comp ehensi e insigh s
in o he po osi y o li hium-ion ba e y elec odes: a compa a i e s udy on posi i e
elec odes based on LiNi0.6Mn0.2Co0.2O2 (NMC622), Ba e ies 7 (2021) 70,
h ps://doi.o g/10.3390/ba e ies7040070.
[55] L.S. de Vasconcelos, N. Sha ma, R. Xu, K. Zhao, In-si u nanoinden a ion
measu emen o local mechanical beha io o a Li-ion ba e y ca hode in liquid
elec oly e, Exp. Mech. 59 (2019) 337–347, h ps://doi.o g/10.1007/s11340-018-
00451-6.
[56] H. Sakai, Y. Taniguchi, K. Uosaki, T. Masuda, Quan i a i e c oss-sec ional mapping
o nanomechanical p ope ies o composi e lms o li hium ion ba e ies using
bimodal mode a omic o ce mic oscopy, J. Powe Sou ce. 413 (2019) 29–33,
h ps://doi.o g/10.1016/j.jpowsou .2018.12.003.
[57] B. Becca d, S.N. Ka a ad a, S. Dahal, Li hium-ion ba e y manu ac u ing and
Quali y con ol: aman spec oscopy, an analy ical echnique o choice,
Spec oscopy (2022) 46–53, h ps://doi.o g/10.56530/spec oscopy.sx2271c5.
[58] V. S anco ski, S. Badilescu, In si u Raman spec oscopic–elec ochemical s udies o
li hium-ion ba e y ma e ials: a his o ical o e iew, J. Appl. Elec ochem. 44
(2014) 23–43, h ps://doi.o g/10.1007/s10800-013-0628-0.
[59] S.S. Shish an, N.A. Fleck, R.M. McMeeking, V.S. Deshpande, C acking and
associa ed olume ic expansion o NMC811 seconda y pa icles, J. Powe Sou ce.
588 (2023), h ps://doi.o g/10.1016/j.jpowsou .2023.233745.
[60] X. Zhu, Y. Chen, H. Chen, W. Luan, The di usion induced s ess and c acking
beha iou o p ima y pa icle o Li-ion ba e y elec ode, In . J. Mech. Sci. 178
(2020) 105608, h ps://doi.o g/10.1016/j.ijmecsci.2020.105608.
[61] H.C.W. Pa ks, A.M. Boyce, A. Wade, T.M.M. Heenan, C. Tan, E. Ma ínez-Pa˜
neda,
P.R. Shea ing, D.J.L. B e , R. Je is, Di ec obse a ions o elec ochemically
induced in e g anula c acking in polyc ys alline NMC811 pa icles, J. Ma e .
Chem. A. Ma e . 11 (2023) 21322–21332, h ps://doi.o g/10.1039/D3TA03057A.
O. Kl aˇ
c e al.
Ene gy S o age Ma e ials 81 (2025) 104516
9
