1
Comp ehensi e analysis o deg ada ion
mechanisms in 18650 Li-Ion cells unde
p olonged cycling condi ions.
Pa el Blažek1,3, Ondřej Kl ač2,5, Ma in Šedina2, Ondřej Čech2, Ma ké a Tkadleco á1, Zuzana
S a o á1, Tomáš Kazda2, Tomáš Zikmund1, Robe H. Schmi 3,4, Joze Kaise 1.
1Cen al Eu opean Ins i u e o Technology, B no Uni e si y o Technology, B no, Czech
Republic
2Depa 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, Czech Republic
3WZL | RWTH Aachen Uni e si y, Aachen, Ge many
4F aunho e Ins i u e o P oduc ion Technology IPT, Ge many
5The mo Fishe Scien i ic, Vlas imila Pecha 12, B no, 627 00, Czech Republic
Abs ac
Li-ion ba e ies a e a key echnology o a wide ange o applica ions including
elec omobili y and s a iona y ene gy s o age. These applica ions mus ope a e o se e al
yea s, and ba e ies need o mee he demands o hese applica ions o e a long pe iod o
ime. Knowledge o he exac mechanisms o Li-ion ba e y deg ada ion and hei
mani es a ions, as well as insigh s om he pe spec i e o p oduc ion quali y op imiza ion
leading o he ex ension o he cycle li e and sa e y o hese ba e ies, a e hus highly
ele an . This s udy examined he deg ada ion mechanisms in a cylind ical 18650 Li-ion
ba e y o e 800 cycles (90% S a e o Cha ge, 10% Dep h o Discha ge) o unde s and
pe o mance ade and s uc u al changes. Pe iodic mic o-CT scans e ealed signi ican
geome ic al e a ions in he elec ode s ack, including delamina ion and bending owa ds
he cell axis, which co ela ed wi h obse ed capaci y loss. Pos -mo em analysis using
b oad ion beam (BIB), scanning elec on mic oscopy (SEM), ene gy dispe si e spec oscopy
(EDS), and synch o on CT con i med he p esence o oids in he ca hode ac i e ma e ial.
Subs an ial coppe deposi ion was obse ed exclusi ely on he anode su ace and g aphi e
g ains. Ele a ed le els o phospho us and luo ine we e also de ec ed, likely om elec oly e
decomposi ion and SEI laye o ma ion. These insigh s shed ligh on he s uc u al changes
and ailu e modes in cylind ical Li-ion cells du ing p olonged cycling.
Keywo ds: Li hium-ion ba e y deg ada ion, 18650 cylind ical cell, Elec ode delamina ion,
Aging
1. In oduc ion
Li hium-ion ba e ies (LIBs) ha e become a key echnology o ene gy s o age due o hei
high ene gy densi y, e iciency, and e sa ili y, p o iding a su icien ly long li e ime. They
play a pi o al ole in a ious echnologies, om small po able elec onic de ices o ene gy
2
s o age sys ems and elec ic ehicles [1–3]. One o he mos common ypes o LIB cells is
18650- o ma , which is a cylind ical cell o 18 mm diame e and 65 mm leng h. I is used as a
s anda d choice in nume ous applica ions like powe ools, elec ic bicycles and elec ic ca s
[4].
Ba e y aging mani es s i sel h ough a mul i ude o complex symp oms, which e lec
changes in mic o and mac oscopic le el. I leads o a dec ease in capaci y, an inc ease in
in e nal esis ance, and physical changes such as swelling and delamina ion o elec ode
laye s. I can lead no only o de e io a ion o pe o mance bu also damage ba e y
s uc u e, a ec he sa e y o ba e y usage, and e en culmina e in comple e ba e y
ailu e[5–15]. The issue o ba e y aging is a e y b oad opic; u he desc ibed a e hose
p ocesses ha ha e been he subjec o esea ch in his pape .
Du ing cycling, he elec odes unde go olume ic changes mani es ed a he le el o whole
elec odes as well as indi idual g ains o elec oac i e ma e ial [16–18]. This is mainly due o
elec ochemical p ocesses in ol ing li hium-ion in e cala ion and also la ice s uc u al
changes [8]. Tempe a u e changes induced by high C- a e also play an essen ial ole [20].
These e ec s in he cylind ical cells lead o he de o ma ion o he elec odes and hei
buckling owa ds he cen e o he ba e y. This can esul in delamina ion o he
elec oac i e ma e ial and, in ex eme cases, dis up ion o he sepa a o . This phenomenon
can be pa ially coun e ac ed by he use o a cen al pin - a me al ube ha ills he space in
he cen e o he cylind ical cell, which, howe e , inc eases he weigh [16].
Volume changes a e also a cause o pa icle c acking [15,21,22]. I can lead o he ma e ial
losing con ac wi h he su ounding ma ix, making i inac i e and dec easing he capaci y.
Mo eo e , du ing c acking, he exis ing SEI laye is dis up ed and s a s o g ow on he
newly o med su aces. This consumes li hium ions, esul ing in u he capaci y loss. An
addi ional isk lies in he possibili y o li hium dend i e o ma ion mani es ing i sel mainly a
highe loads and lowe empe a u es [10,23,24].
In he applica ion o e y high cu en s and ope a ion o he cell ou side he ol age
ope a ing window, dissolu ion o he cu en collec o s may also occu . The cases o anodic
oxida ion o he coppe collec o and deposi ion o Cu ions on he ca hode su ace
inc easing i s olume ha e been desc ibed [25]. Also, coppe can o m an in e nal sho
ci cui h ough he o ma ion o Cu dend i es. Ra ely has he deposi ion o coppe on he
su ace o he anode o indi idual g ains been desc ibed. The educ ion o coppe dissol ed
in he elec oly e by eac ion wi h he SEI laye compounds is assumed [26,27].
E iden ly, he p ocesses con ibu ing o ba e y deg ada ion and aging a e complex, and
hei deepe unde s anding is c ucial o he u he de elopmen o LIBs. X- ay-based
echniques a e sui able o hei in es iga ion due o hei non-des uc i e cha ac e and
can also be used o in-si u analysis, whe e a scan is pe o med a e a ce ain numbe o
elec ochemical cycles. This includes X- ay adiog aphy [28] as well as ad anced CT me hods
[29,30]. I is possible o achie e esolu ion om mic ome e s when analyzing whole cells
down o sub-mic ome e esolu ion o small pieces o elec ode ma e ials and de ec e en
mild s uc u al changes [31,32].
3
Wi h scanning elec on mic oscopy (SEM), e en highe esolu ion can be achie ed o
obse e indi idual g ains, hei c acking, and he g ow h o he SEI laye [11,33–38]. In
combina ion wi h elec on dispe si e spec oscopy (EDS), i is also possible o de e mine he
elemen al composi ion and i s changes a e elec ochemical cycling [39,40].
Since he cell mus be disassembled be o e analysis, i is ad isable o discha ge i o sa e y
easons, o a oid sho -ci cui ing du ing u he handling, and o minimize con ac wi h ai .
A gon glo eboxes a e ypically used o his pu pose. The sepa a ed elec odes a e hen
examined om he su ace o c oss-sec ion. The ma e ials a e o en b i le and can be
damaged by mechanical s ess. Fo his eason, ocused ion beam (FIB) also allowing
FIB/SEM 3D econs uc ion [41–43] o b oad ion beam (BIB) [8,44–47] echniques a e o en
used o sample p epa a ion, which spu e he ma e ial wi hou mechanical o ce and allow
he samples o be obse ed in hei na i e s a e [7,8].
In his s udy, we de ailly examine 18650- ype LIB in he esh s a e and du ing 800 cycles o
cha ging and discha ging, obse ing a ious symp oms o deg ada ion. The analysis o he
cycled cell was ocused on he s uc u al and chemical changes, hei co ela ion wi h he
mic o-CT (X- ay compu ed omog aphy) analysis, and compa ison wi h ano he uncycled cell
using SEM/EDS analysis. We applied CT and i ual un olling echniques o quan i y
geome ical changes in he whole ba e y in he esh s a e and a e e e y 200 cycles o
cha ging and discha ging. Wi h each scan, we also analyze changes in ba e y capaci y and
hys e esis oge he wi h an impedance analysis by Elec ochemical Impedance Spec oscopy
(EIS). We also pe o med u he analysis o he cycled ba e y a e 800 cycles and ano he
ba e y o he same manu ac u ing ba ch in a esh s a e. To obse e pieces o ca hodes
wi h highe esolu ion we used sub-mic on CT and sSEM and analyzed elemen al
composi ion using EDS.
2. Ma e ials and me hods
2.1. Samples
We in es iga ed LIB Samsung INR18650-29E (manu ac u e s a ed capaci y 2860 mAh)
based LiNixMnyCo1-x-yO2 (NMC), he mos used ca hode ma e ials in LIBs. We used wo pieces
o accumula o s om he same manu ac u ing ba ch. The i s one, esh cell, was used o
des uc i e analysis be o e cycling, and he o he one was used o long- e m cycling and
deg ada ion s udy. A e he cycling was inished, we used i o des uc i e analysis o he
e ec s o aging.
2.2. Aging and elec ical analysis
The es cell was cha ac e ized by a baseline es using wo cycles in he ull manu ac u e -
de ined ol age ange o 2.5 - 4.2 V a 0.1C/0.1C, 0.2C/0.2C, 0.2C/0.5C and 0.2C/1C
(cha ge/discha ge). EIS was pe o med a 100% SoC du ing 0.1/0.1 C cycle in a equency
ange om 1 MHz o 30 mHz, wi h an ampli ude o 10 mV, ollowed by CT scanning. The
CCCV me hod was used wi h he limi ing cu en se o 0.02 C. The ini ial es was ollowed
by long- e m cycling a 1 C using he CCCV me hod wi h a limi cu en o 0.02 C in he ange
o 90% SoC and 10% DoD o 200 cycles, ollowed by a baseline es and subsequen ly by CT
scanning. This p ocess was epea ed un il 800 cycles we e eached. A e he las baseline
4
es and CT analysis, he cell was disassembled and analyzed by SEM. The elec ochemical
measu emen s we e pe o med wi h a Bio-Logic ba e y cycle BCS-815 wi h an EIS module.
2.3. Mic o CT analysis
The whole LIB was analyzed by mic o CT in he esh s a e, a e 200, 400, 600, and 800
cycles. Fo hese measu emen s, we used a The mo Scien i ic HeliScan mic oCT sys em
equipped wi h a la panel de ec o wi h a esolu ion o 3072x3072 px2 and pixel size 139
um and 160 kV mic o ocus ube. The whole ba e y was analyzed by one scan wi h a space-
illing helical ajec o y, which allowed he use o highe geome ical magni ica ion and
inc eased he signal- o-noise a io while a oiding cone-beam a i ac s. The X- ay ube was
se o 150 kV, and he beam was il e ed wi h 0.2 mm o s ainless s eel and 0.5 mm hick Sn
oils o educe beam-ha dening. To ob ain su icien signal, he exposu e ime was se o
0.65 s, and i e adiog aphs we e a e aged in each o he 5400 p ojec ions pe scan.
The da a we e econs uc ed wi h he i e a i e algo i hm in so wa e p o ided by
he manu ac u e . An algo i hm o sample d i co ec ion and he sel -calib a ion
algo i hm [48] we e used o co ec o geome ical e o s. The econs uc ed olume size
was app oxima ely 22 ×22 ×73 mm3 wi h (8 μm)3 oxel size.
The i ual un olling echnique was applied o all he whole-cell da ase s in The mo
Scien i ic A izo. We used he p ocedu e desc ibed in [49]. The ca hode was segmen ed using
he mul i h esholding me hod, and mo phological ope a ions such as opening/closing we e
applied. We analyzed he dis ance om he co e on he segmen ed ca hode and compa ed
esul s be ween da ase s. An un olled dis ance map hen allows o he assessmen o
ca hode posi ion and de o mi ies in he en i e cell olume.
2.4. Sample p epa a ion o SEM, EDS, and submic on CT
Be o e disassembly, ba e ies we e deeply discha ged o 1 V wi h a cu en o 0.05 C. Inside
he A - illed glo ebox, he me al case was cu abou 1 mm below he edge o he posi i e
pin using a manual ube cu e . The CT inspec ion e ealed ha he e is a ee space inside
wi h minimal isk o elec ode damage. The posi i e pin was hen emo ed using plie s, and
he me al case was un olled o app oxima ely hal he cell's heigh . The elec oly e was
d ied by lea ing he cell unde a acuum in he glo ebox an echambe o abou one hou .
Pieces o he indi idual elec odes we e cu om he un olled sec ion using scisso s. Fu he
manipula ion ook place ou side he glo ebox. The cell was cu ac oss on he nega i e pin
side wi h a hacksaw abou 1 cm abo e he pin edge. The me al case in his a ea se es as a
mechanical ixa ion and p e en s s uc u e shi ing du ing c oss-sec ion p epa a ion h ough
he en i e s uc u e. This specimen was hen mechanically g ound by 30, 15, 8, and 5 μm
g ain size SiC g inde pape s wi h isop opanol. The B oad Ion Beam (BIB) polishe model
1061 SEM Mill (Fischione Ins umen s) was used o u he sample p epa a ion. The
indi idual elec odes we e p epa ed in c oss-sec ion mode, and he whole s uc u e in
plana mode using C yo cooling. SEM imaging and EDS analysis we e pe o med on a Scios 2
scanning elec on mic oscope (The mo Fische Scien i ic).
Fo nanoCT, pieces o app oxima ely 0.5 x 2 mm we e cu om indi idual elec odes wi h a
azo blade. The samples we e inse ed in o a Kap on ube and ixed wi h mol en e hylene
5
ca bona e. Fo SEM/CT co ela i e analysis, he sample was i s polished using BIB, hen
SEM analysis was pe o med, and inally placed in he Kap on ube.
2.5. Submic on CT
We used he unpolished pa o he cell and un olled he elec odes. A piece o i was cu o
dimensions app oxima ely 0.5x2 mm. This piece was hen ixed on a special holde . I was
inse ed in a Kap on ube and pou ed wi h e hylene ca bona e o educe oxida ion. The
sample was hen imaged using nanoCT Rigaku nano3DX wi h Mo a ge , 50 kV ube ol age,
35 s exposu e ime, 800 p ojec ions, and oxel size o 0.54 μm.
3. Resul s and discussion
Con inuous measu emen s e ealed capaci y dec ease du ing cell cycling (Figu e 1 a). We
also obse ed ha a e in e up ing he cycling o analysis wi h CT, egene a ion occu ed,
and capaci y was inc eased. This e ec was mos signi ican a e 200 and 400 cycles. The
mos conside able capaci y educ ion o 20.8 % occu ed a e he i s 200 cycles. A e
ha , he capaci y egene a ed o 90.8 % o he o iginal alue and, du ing ano he 200
cycles, dec eased by a simila alue as in he i s 200 cycles. This e ec epea ed also
be ween 400 and 600 cycles. A no able capaci y educ ion o 11.3 % occu ed be ween 600
and 800 cycles as well. In o al, capaci y d opped by 30.5 % a e 800 cycles (see Table 1).
Table 1. Capaci y and capaci y e en ion in di e en s ages o cycling.
Cycle numbe
Capaci y/mAh
Capaci y e en ion/%
1
2165
-
200
1714
20.8%
400
1668
23.0%
600
1717
20.7%
800
1505
30.5%
The discha ge cha ac e is ics a di e en C- a es be o e and a e cycling a e shown in
Figu e 1 b.. A all C- a es a e 800 cycles o cycling, he e was a dec ease in he achie ed
capaci y and, a he same ime, a dec ease in he discha ge pla eau. The capaci y a 0.1 C
load has been educed om 2865 mAh, which is equi alen o he capaci y decla ed by he
manu ac u e , o 2442 mAh (14.8 % capaci y d op). A 0.2C load, he capaci y d opped om
2807 o 2344 mAh (16.5% capaci y d op). A loads o 0.5C and 1C, he capaci y d opped by
19.2 % and 22.1 %, espec i ely. I is e iden ha cycling did no only lead o a dec ease in
capaci y bu also o a dec ease in load abili y a highe C- a es.
The change in capaci y du ing he baseline es s is shown in Tab.2. When compa ing he
capaci ies o he cha ac e iza ion cycles, a signi ican change can be seen a e 200 and 800
cycles, whe e a e 200 cycles, he e was a signi ican change in capaci y bu s abili y a
highe loads was main ained. Thus, a a load o 1C, he e was a 4.2 % dec ease be o e
cycling and a 4.5 % dec ease a e cycling compa ed o a cu en o 0.1C. Ano he signi ican
change in his pa ame e occu ed a e 800 cycles.
The hys e esis changes a di e en C- a es du ing cycling, as shown in Figu e 1 c. I is
e iden ha he hys e esis inc eases wi h inc easing C- a e and is highes a 1 C. A e 200
cycles, he e was an inc ease in hys e esis a all C- a es. I s alue hen emained s able
6
du ing he ollowing cycling un il he las 200 cycles, when he alue inc eased again
signi ican ly o all C- a es. This inc ease o hys e esis is in co ela ion wi h he signi ican
capaci y d op du ing he las 200 cycles o cycling and co esponds o he la ge capaci y
d op a a cu en load o 1 C ha was obse ed a he end o cycling.
The EIS analysis e ealed ha he cha ge ans e esis ance (Rc ) a he beginning o cycling
was double ha a e 200 cycles, which is isible in Nyquis plo s in Figu e 1 d. This is due o
he changes in he s uc u e a he beginning o cycling, which lead o imp o ed con ac
wi h he elec oly e. Liu e al. gi e a simila desc ip ion o his change [50]. Subsequen ly, Rc
inc eases wi h cycling, and a e 800 cycles, i s alue app oaches he o iginal alues be o e
cycling.
The dV/dQ analysis be o e cycling and a e a di e en numbe o cycles (200, 400, 600, and
800) is isualized in Figu e 2. The igu e shows he ac i i y o he con ained ma e ials a he
anode and a he ca hode and hei g adual deg ada ion. An anodic peak a 3.42 V and
ca hodic a 3.38 V is ela ed o li hia ion o g aphi e anode [51]. A e 200 cycles, boo h
peaks shi ed o a highe ol age, and peaks we e less e iden . Du ing he cycling, peaks
become mo e e iden and, a he same ime, change posi ion close o 3.5 V. The magni ude
o he anode- ela ed peak a e 200, 400, and 600 cycles was simila ; howe e , a e 800
cycles, he peak magni ude dec eased, indica ing a dec ease in he ac i i y o he anode
ma e ial. This d op migh be associa ed wi h a highe d op in capaci y a a high C- a e a e
800 cycles. Ano he e y signi ican anodic peak can be obse ed a a po en ial o abou
3.65 V. This peak is ela ed o he ansi ion om a hexagonal o a monoclinic la ice o he
NMC532 ca hode [52]. I s ac i i y g adually dec eases, wi h he mos signi ican change can
be obse ed a e he i s 200 cycles and hen a e he las 200 cycles o cycling. The
anodic peak a ound 4.1 V is hen associa ed wi h high Ni ca hode ma e ials such as NMC811
o NCA (10.1149/2.0021707jes) and ep esen s he H2 o H3 phase ansi ion. The small
anodic peak loca ed a ound 3.8 V ep esen s he ansi ion om he M o he H2 phase. The
peak a ound 4.1 V was ela i ely s able o he i s 400 cycles, bu i d opped signi ican ly
a e 600 and 800 cycles. This dec ease may hen be ela ed o he capaci y d op du ing he
subsequen cycling, when he pa ial egene a ion o he ba e y capaci y no longe
occu ed when cycling s a ed again.
Table 2. Deg ada ion unde di e en loads du ing long- e m cycling.
Capaci y/mAh
Capaci y d op/%
Cycle numbe
0.1C
0.2C
0.5C
1C
0.2C s 0.1C
0.5C s 0.1C
1C s 0.1C
0
2865
2807
2742
2744
98.0%
95.7%
95.8%
200
2660
2591
2591
2541
97.4%
97.4%
95.5%
400
2583
2555
2503
2490
98.9%
96.9%
96.4%
600
2478
2459
2400
2363
99.2%
96.9%
95.4%
800
2442
2344
2215
2139
96.0%
90.7%
87.6%
7
Figu e 1. a) Capaci y dec eases due o cycling, b) Discha ging p o iles a di e en C- a e be o e and a e cycling, c) Changes
o hys e esis a di e en c- a es du ing cycling, d) EIS analysis in di e en s ages o long- e m cycling.
Figu e 2. dQ/dV analysis o INR18650-29E cell be o e cycling and a e 200, 400, 600 and 800 cycles.
P olonged cycling o he cell caused damage o he inne geome y o he cell. The
elec odes a e de o med, and he elec oac i e ma e ial is c acked and delamina ed om
he cu en collec o . These de o ma ions a e clea ly isible in omog aphic c oss-sec ions
(Figu e 3) as well as an SEM image o he c oss-sec ion h ough he whole s uc u e (Figu e
4). The de o ma ion is i s isible a e 200 cycles on he i s h ee windings o he
elec ode s ack and is ge ing mo e p onounced wi h cycling. A e 800 cycles, hey each up
o he se en h winding o elec odes. SEM image (Figu e 4) shows, in addi ion o elec ode
wa ing, c acks, and loss o con ac wi h he cu en collec o , also loss o con ac o he
anode wi h he sepa a o and, he e o e, wi h he opposi e ca hode.
8
Figu e 3. Tomog aphic c oss-sec ions, de ail o he de o ma ion’s de elopmen h ough cycling. Top ow: Axial iew, bo om
ow: axial iew. Red a ow poin o he highes de o ma ion p esen in he inne mos winding, which is he same posi ion as
show in Figu e 5.
Figu e 4. De ail o c oss-sec ion h ough he whole ba e y s uc u e. Elec odes a e bending owa ds he cen al pin, a ows
poin s o loss o con ac wi h sepa a o and cu en collec o .
The i ual un olling echnique allowed us o isualize he geome y o he ca hode ac oss
he en i e olume a di e en cycling s ages. Elec ode de o ma ions appea as e ical
s ipes in he dis ance- om-co e map. S ipes isible in he esh da ase (Figu e 5 a) ha
pe sis in da a om he cycled cell indica e ha he elec ode de ia es om an ideal spi al.
De o mi ies a ising in he inne winding due o cycling a e also e iden in he un olled da a
as addi ional s ipes in he co esponding sec ions. These de o mi ies ex end h ough he
en i e heigh o he elec ode spi al and become mo e p onounced wi h an inc easing
numbe o cycles. A limi a ion o his un olled map is he p esence o a i ac s in he o m o
sha p bo de s be ween ho izon al sec ions. These a i ac s s em om he un olling
algo i hm in A izo, which equi ed di iding he da a in o sec ions o educe compu a ional
demands and in oduced in e pola ion e o s ha likely s uggled o handle de ia ions om
he ideal spi al. Due o hese a i ac s, his da a canno be used o quan i a i e
measu emen s, such as compa ing dis ance om he co e be ween da ase s. Howe e , he
un olled da a show a ca hode leng h inc ease o 3.5 mm (0.5%) o e 800 cycles (see Figu e
9
6), likely esul ing om inc eased bending and de o ma ions. The da a shows ha he mos
p ominen change occu ed again a e he i s 200 cycles and a e he las 200 cycles,
which co ela es wi h he esul s o elec ochemical measu emen s. The change o
hys e esis occu ed a a simila ime; a he las 200 cycles, he e was a signi ican dec ease
in capaci y a high C- a es.
Figu e 5. Visualiza ion o 10 inne mos windings o he un olled ca hode as an un olled dis ance om he cell co e colo
map. Red a ows poin o he highes de o ma ion p esen in he inne mos winding, which is he same posi ion as shown in
Figu e 3.
Figu e 6. Leng h o ca hode a e un olling
C oss-sec ion images o he esh cells ob ained bo h by CT (Figu e 3) and SEM (Figu e 4)
show he manu ac u ing de ec s in he s uc u e. These a e un illed a eas wi hin he
elec oac i e laye s uc u e and bends o he cu en collec o . These a eas co espond o
he ' oids' in he CT model. The cause is p obably due o he inhomogeneous composi ion o
he ca hode pas e, whe e a bubble o ms on one side o he cu en collec o . Subsequen
p essing leads o i s den ing and damage o he ca hode ma e ial pa icles. De ails o hese
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