T acking S uc u al E olu ion in Li hium-ion Ba e ies ia In-Ope ando Scanning
Elec on Mic oscopy
Ondřej Kl ača,b*, Da id T och aa,b, Libo No áka, Pe e P iecela, Manuel Bo nhö a, and
Tomáš Kazdab, Zhao Liua*
a The mo Fishe Scien i ic, 5350 NE Dawson C eek D , Hillsbo o, OR 97124, USA
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, Technická 10, 616 00 B no, Czech
Republic
* Co esponding au ho
Abs ac :
The s udy o li hium-ion cells 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 mic os uc u e and mo phology o he cells. In-si u/ope ando
analyses a e in aluable as hey p o ide p ecise desc ip ions o he dynamic phenomena
and hei empo al e olu ion wi hin he ba e y. Howe e , he applica ion o SEM o in-
si u/ope ando analyses is hinde ed by he challenging p epa a ion o samples ha can
unc ion wi hin he SEM en i onmen . The e o e, we in oduces a uni e sally applicable
me hodology ha in eg a es sample p epa a ion using a b oad ion beam polishe wi h he
ans e o samples o he SEM in a specially designed holde unde an ine a mosphe e.
The e icacy o his sys em and wo k low is demons a ed on Nickel Manganese Cobal
Oxide (NMC) and Li hium Ti ana e Oxide (LTO) ba e y cells, e ealing g ain c acking and
expansion, as well as elec ode expansion and con ac ion. Addi ionally, a g aphi e-me al
li hium 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 o submic on
changes a he g anula le el and a he scale o en i e elec odes o la ge cell
componen s, applicable ac oss a ious chemis ies. We posi ha his wo k p o ides
signi ican insigh s o bo h undamen al esea ch o elec oac i e ma e ials and he
op imiza ion o he manu ac u ing p ocesses o comple e cells.
Keywo ds:
Li-ion ba e ies, elec ochemical cycling, SEM, BIB, in-si u, ope ando, s uc u al e olu ion
Highligh s:
• In eg a ion o b oad ion beam polishe and ope ando SEM
• Ope ando SEM analysis o c oss-sec ional elec ode ma e ials
• Examina ion o submic on and whole-cell changes
1. In oduc ion
Wi h ad ancemen s in he echnology ield, 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 amoun o aw ma e ials,
ising cos s, and en i onmen al impac s. Resea ch in his ield ocuses on enhancing cell
capaci y, li espan, and possible usage o elec oac i e ma e ials wi h a lowe
en i onmen al bu den.
Ope ando echniques o e eal- ime insigh s in o he kine ics o p ocesses and
mechanisms occu ing wi hin a ba e y du ing ope a ion. Unlike ex-si u o pos -mo em
me hods, hese echniques enable he p ecise iden i ica ion o when a phenomenon
occu s, leading o a clea e unde s anding o i s unde lying cause. A a ie y o ope ando
echniques a e a ailable, each sui ed o di e en ypes o analysis.[1][2][3][4]
X- ay echniques, such as compu ed omog aphy (CT)
[5][6][7][8][9][10][11][12][13][14][15], a e widely used in ope ando s udies o li hium-ion
ba e ies, enabling non-des uc i e 3D analysis du ing ope a ion. These me hods allow
da a collec ion ac oss a ious scales, om he en i e cell down o mic os uc u al de ails,
p o iding aluable insigh s in o elec ode aging and associa ed mo phological changes.
Howe e , a key d awback o CT analysis is i s lowe spa ial esolu ion compa ed o
elec on mic oscopy, as well as he ex ended ime equi ed o comple e each scan. To
o e come he esolu ion limi a ions o CT, X- ay di ac ion (XRD)
[16][17][18][19][20][21][22] can be employed. Unlike CT, XRD o e s esolu ion a he
in e -a omic scale, hough i s di ac ion da a s ill o igina es om a la ge sample egion.
In compa ison o X- ay echniques, elec on mic oscopy allows in es iga ion o he
mic os uc u e down o he le el o indi idual a oms. Toge he wi h complemen a y
me hods such as ene gy-dispe si e X- ay spec oscopy (EDS), elec on backsca e
di ac ion (EBSD) and ocused ion beam (FIB) ha can be used o si e-speci ic sample
p epa a ion, he elec on mic oscopy can be used o in es iga e many o he impo an
phenomena in ba e y beha iou such as solid elec oly e in e phase (SEI) o ma ion, Li
pla ing, phase changes, o o ma ion o de ec s in he elec odes[1][2].
T ansmission elec on mic oscopy (TEM) p o ides a omic-scale esolu ion, enabling
de ailed insigh s in o elec ochemical p ocesses. Howe e , i s applica ion is limi ed by
challenging sample p epa a ion and he small olume o ma e ial ha can be analyzed.
As a esul , TEM s udies a e o en es ic ed o model sys ems, such as minia u ized
ba e y se ups o hal -cells c ea ed on dedica ed TEM biasing holde s [23][24][25].
Addi ionally, TEM s udies may be a ec ed by adia ion damage and local sample
o e hea ing. Despi e hese challenges, TEM emains a powe ul ool o in es iga ing
elec ochemical p ocesses a a undamen al le el, making i well-sui ed o basic
esea ch.[26][27][28][29][30][31][32]
The la ge specimen chambe o a Scanning Elec on Mic oscope o e s he possibili y o
ope ando s udies o whole ba e ies a he cos o lowe image esolu ion compa ed o
TEM, s ill eaching spa ial esolu ion o uni s o nanome e s on sample su ace. A he
same ime SEM allows us o moni o a eal-size ba e y in la ge-scale, cap u ing s uc u al
changes in all he pa s and in e aces. SEM ope ando s udies can be applied o ba e ies
a di e en le els o de elopmen , including quali y con ol o samples esul ing om he
manu ac u ing p ocess. [33]
Fo scanning elec on mic oscopy (SEM) imaging, he ba e y mus be pa ially opened
on one side o allow elec on access o he su ace o in e es . O e he pas decades,
a ious app oaches ha e been explo ed o achie e his geome y [25][34]. Addi ionally,
since he ba e y is exposed o he acuum o he SEM chambe , a acuum-compa ible
elec oly e is equi ed—one ha emains s able and does no e apo a e a p essu es as
low as 10-6 Pa.
One o he ea lies ope ando SEM expe imen s was conduc ed by Baud y in 1988 [35],
u ilizing a solid-s a e elec oly e. Since hen, a ious acuum-compa ible solid-s a e
elec oly es ha e been employed in subsequen ope ando SEM s udies
[35][36][37][38][39][40][41]. The lowe ionic conduc i i y o solid-s a e elec oly es can be
mi iga ed by hea ing he sample wi hin he SEM chambe [38][41][37][35]. Addi ionally,
he design o he SEM holde mus accoun o he comp ession o he solid-s a e ba e y
bo h du ing ope ando analysis and h oughou he ans e p ocess. Depending on he
ype and size o he solid-s a e ba e y, his can esul in high o ces o be handled by he
SEM biasing holde .
Va ious ypes o ionic liquids wi h low apo p essu e a e commonly used as elec oly es
in SEM ope ando s udies [42][43][44][45][46][47][48][49][50][51][52]. Howe e , eplacing
a con en ional elec oly e wi h an ionic liquid can al e ce ain ba e y p ope ies. Fo
ins ance, he composi ion o he solid elec oly e in e phase (SEI) laye may di e due o
he absence o o ganic componen s [53].
A cooled hyb id polyme -based elec oly e can also be used in SEM s udies [54]. When
employing an elec oly e wi h a apo p essu e exceeding he SEM acuum h eshold is
una oidable, encapsula ion wi hin an elec on- anspa en memb ane can p e en
e apo a ion. Silicon ni ide windows, ypically se e al ens o nanome e s hick, a e
commonly used o his pu pose[55]. Al e na i ely, sligh e apo a ion o a con en ional
elec oly e can be managed wi hou ull encapsula ion by u ilizing en i onmen al SEM
(ESEM) mode, whe e he chambe p essu e is main ained a se e al hund ed pascals
[56]. Howe e , bo h he memb ane encapsula ion and ESEM app oaches esul in
educed SEM esolu ion due o elec on sca e ing wi hin he memb ane, gas, o he
elec oly e laye ha may o m on he ba e y su ace.
In a quasi-in-si u app oach, he ba e y is cycled unde s anda d high-p essu e condi ions
and subsequen ly exposed o he elec on beam o imaging a selec ed s a es o he
cha ge-discha ge cycles [57]. Howe e , his me hod necessi a es epea ed ba e y
disassembly and eassembly, which can in oduce ep oducibili y challenges.
Fo di ec SEM imaging o he ba e y su ace, he ba e y can be opened om he side
o enable plana imaging o one elec ode. Al e na i ely, a pe pendicula c oss-sec ion
can be p epa ed, allowing SEM imaging o all in e nal in e aces wi hin he ba e y.
In a plana geome y ha enables imaging o he ou e su ace o one elec ode, an
elec on beam- anspa en cu en collec o is ypically used o allow SEM imaging o he
elec ochemically ac i e ma e ial h ough he modi ied collec o . This is mos commonly
achie ed by deposi ing he ac i e ma e ial on o a me al g id [56][42][43][44][46][48][52] o
by c ea ing a small hole in a me al oil se ing as he collec o [36]. Howe e , in his
con igu a ion, SEM imaging is limi ed o he ou e su ace o one elec ode and may no
accu a ely ep esen bulk beha io . Fo ins ance, i does no allow o he assessmen o
a ia ions in li hia ion dep h as a unc ion o dis ance om he coun e elec ode.
Fo he c oss-sec ional geome y p esen ed in his s udy, ca e ul su ace p epa a ion is
essen ial o p e en a i icial ea u es in SEM images caused by su ace opog aphy. The
ba e y can be opened and polished using a ious me hods, wi h mechanical cu ing
commonly employed as an ini ial s ep [54][37]. To enhance su ace quali y a e ough
cu ing, ion beam polishing echniques—such as b oad ion beam (BIB) polishing o FIB
milling in a FIB-SEM sys em—a e ypically used. Al e na i ely, c yomic o omy [47][41] o
lase milling [58] can be u ilized o c oss-sec ion p epa a ion. C oss-sec ioning mus be
pe o med ca e ully o a oid sho -ci cui ing o mechanically damaging he ba e y.
Addi ionally, special a en ion should be gi en o p e en ing he de achmen o indi idual
pa icles, pa icula ly om he elec ode laye s, du ing he cu ing and polishing p ocess.
FIB echnology can also be u ilized o addi ional plana - iew analysis [42][49][40], such
as cu ing h ough li hium dend i es o med du ing ope ando expe imen s in a FIB-SEM
sys em [43]. A speci ic case is he usage o he FIB oge he wi h a mic omanipula o . The
mic omanipula o can se e as a cu en collec o o small amoun s o elec oac i e
ma e ial ixed mechanically and elec ically by FIB-assis ed deposi ion o conduc i e
ma e ials [50][51]. In his case, a e y small amoun o ma e ial is su icien o
cha ac e iza ion, and i is assu ed ha measu ed elec ochemical da a co esponds o he
in es iga ed a ea. Howe e , his single a ea may no always show he same beha io o
a ious easons. Fo example, he cycling cu en s o such a sys em a e e y small, which
ca ies he isk o da a dis o ion by elec omagne ic in e e ence [59].
BIB polishing enables he p epa a ion o c oss-sec ions o en i e elec odes o e en ull
ba e y cells in a ela i ely sho ime. Compa ed o mechanical me hods, BIB polishing
in oduces minimal a i ac s; o ins ance, cu aining a i ac s can be signi ican ly educed
by ocking he sample du ing he milling p ocess [60][33].
We p opose a wo k low o ope ando ba e y cha ac e iza ion in SEM ha combines he
ad an ages o he p e iously discussed app oaches. This me hod p o ides a obus
es ing en i onmen , ensu ing epea able esul s while minimizing he ime and e o
equi ed o ba e y sample p epa a ion p io o SEM analysis. The c oss-sec ional iew
is achie ed by placing he ba e y in a biasing holde wi hin he SEM. The sample su ace
is p epa ed using a b oad ion beam polishe [61] o ensu e smoo h c oss-sec ions. To
main ain sample in eg i y, all ans e s eps—be ween he glo e box and he CleanMill
polishe , as well as be ween he glo e box and he SEM—a e acili a ed by he
CleanConnec (CC) ans e de ice [62]. The wo k low is demons a ed on an examples
o li hium nickel manganese cobal oxide (NMC) – li hium- i ana e oxide (LTO) and
g aphi e – me allic li hium sys ems wi h a acuum compa ible ionic liquid elec oly e and
can be applied o a ious acuum compa ible ba e y ma e ials.
Mo eo e , apa om ex-si u echniques ypically analyzing p is ine and cycled elec odes
sepa a ely (Figu e 1a), ou echnique can examine he same loca ion con inuously,
p o iding a mo e consis en and de ailed obse a ion o he p ocesses (Figu e 1a).
Da a pos -p ocessing co ela ing he SEM image in o ma ion wi h ba e y cha ge s a e in
ime allows o sys ema ic cha ac e iza ion and di ec compa ison o indi idual ba e y
samples.
Figu e 1: Compa ison o da a ob ained du ing ex-si u (a) and in-si u (b) analysis. Ex-si u SEM analysis o NMC ca hode
c oss-sec ion, p is ine and cycled elec ode - due o he des uc i e na u e o his analysis, i is no possible o examine
he same egion and i s changes o e ime; Ope ando SEM analysis o selec ed NMC g ain c oss-sec ion a di e en
cha ging s ages – obse a ion o c ack e olu ion du ing i s o ma ion cycle
5 μm
20 μm
p is ine cycled
0.13 V 2.31 V 2.32 V 2.80 V
a
b
2. .Expe imen al me hod
2. 1 Ma e ials
Comme cially a ailable elec ode shee s om Cus omCells we e used in his s udy. We
used NMC 111 coa ed on an aluminum cu en collec o , LTO coa ed on an aluminum
cu en collec o , and g aphi e on a coppe cu en collec o . The capaci y o he
elec odes is speci ied in he da ashee as 1 mAh/cm². In he supplemen a y expe imen ,
me allic li hium (99.9%; Sigma-Ald ich) was used as he coun e elec ode. A Wha man
GF/C glass ibe il e wi h a hickness o 260 µm was used as he sepa a o .
Fo NMC – LTO sys ems, an ionic liquid elec oly e was p epa ed using a mix u e o 1-
me hyl-1-p opylpy olidinium bis( i luo ome hylsul onyl)imide (Py ₁₃-TFSI, >99%; Sigma-
Ald ich) and li hium bis( i luo ome hanesul onyl)imide sal (LiTFSI, >99%; Sigma-Ald ich)
a a concen a ion o 0.5 M.
Fo g aphi e – Li me al sys em, mix u e o LiTFSI: 1-p opyl-1-me hylpy olidinium
bis( luo osul onyl)imide (PYR13FSI), 1:9 mol (Sol ionic >99.5%) was used.
2.2. Cells assembly and placemen in o SEM
In his publica ion, he esul s o h ee expe imen s a e p esen ed. In he i s expe imen ,
he hickness o he en i e NMC elec ode in he NMC-LTO sys em (deno ed as sample 1)
was measu ed. In he second expe imen , he expansion and mo phological changes o
indi idual NMC g ains in a newly cons uc ed NMC-LTO sys em (sample 2) we e analyzed.
The hi d expe imen (sample 3) se es as a supplemen a y e i ica ion o he unc ionali y
o sys em wi h di e en ma e ials. G aphi e s Li me al was used.
Fi s ly, pieces o app oxima ely 5 mm x 8 mm we e cu om he elec ode shee s wi h
scisso s. 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 in es iga ed elec ode was consequen ly mo ed o CleanMill polishe and a c oss-
sec ion was p epa ed using A ion beam. Fo he NMC elec ode, 16 kV and 3.5 mA we e
used o one hou ; o he g aphi e elec ode, 10 kV and 3.5 mA we e used o 1.5 hou s.
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 um. The simila me hod can be used o
p epa e a c oss-sec ion o bo h elec odes indi idually o he whole cell a once.
The in es iga ed elec ode was hen aligned oge he wi h coun e elec ode and
sepa a o . F om ou expe ience, i has been ound o be ad isable o place he
in es iga ed elec ode in a ew mic ome e s o e lap abo e he sepa a o o a oid looding
he inspec ed a ea wi h elec oly e du ing he SEM ope ando expe imen . The alignmen
and mechanical ixa ion was done in ou designed 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.
The p e-p epa ed cell was hen ans e ed o he A - illed 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 applica 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. The p epa ed cell
was hen ans e ed o he SEM chambe in he A a mosphe e using he CleanConnec
Sample T ans e Sys em.
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 i when inse ed. These pins a e wi ed h ough a acuum
eed h ough o a po en ios a ou side he SEM chambe (Figu e 2).
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/cm2.
Expe imen al wo k low scheme and clamping ool images a e in ol ed in supplemen a y
da a.
2.3 Sample imaging and da a p ocessing
Fo sample imaging, a Qua o ESEM (The mo Fishe Scien i ic) was u ilized. An
au oma ed con ol sc ip (The mo Scien i ic Au oSc ip 4 So wa e) was de eloped o
manage SEM imaging and s age mo emen s, enabling he imaging mul iple a eas +
di e en ho izon al ield wid h (HFW)/magni ica ion/image g ab se ings ha allowed us
o ake bo h de ailed and o e iew images. The acqui ed images we e hen co ela ed
wi h speci ic poin s on he elec ochemical cu e based on he da a om po en ios a . By
composi ing hese images, a ideo was p oduced, whe e he cu en ame is indica ed
by a cu so ( ed c oss) on he cu e.
Fu he analysis o he images was conduc ed using Phenom Pa icleMe ic pa icle
analysis so wa e and Py hon au oma ic edge de ec ion. Fo selec ed NMC g ains,
changes in size we e examined. The Phenom so wa e iden i ies g ain bounda ies and
calcula es he a ea o each g ain. The eal size o he pa icles can be calcula ed om he
known ield o iew o SEM images.
In he simila way elec ode bounda ies (edges) was de ec ed using Py hon sc ip o ack
whole elec ode hickness changes. Fo bo h, 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 .
Figu e 2: Ope ando SEM expe imen al scheme
3. Resul s and discussion
3.1 Sample 1 – moni o ing NMC elec ode hickness
The NMC-LTO ba e y was p epa ed as desc ibed in chap e 2, mo ed o SEM, and
connec ed o a po en ios a . 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, 5 min es phase,
and imaged. No ably, he cycling con inued beyond he usual ope a ional window (0.8 –
3.3 V) o ampli y he obse ed phenomena and e alua e he expansion o he en i e NMC
elec ode (Figu e 3).
The hickness o he elec oac i e laye was con inuously measu ed du ing cycling (Figu e
3). This da a indica es elec ode 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).
Mo eo e , 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 changes in he elec ode. In he i s
cycle, he hickness was app oxima ely 37.9 μm in he ba e y cha ged s a e and 37.0 μm
in he discha ged s a e. By he end o he 13 h cycle, hese alues inc eased o 39.8 μm
and 39.1 μm, espec i ely.
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, ix 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 ake ull esponsibili y o he con en o he published a icle.
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