Electrochemiad Impedance Spectroscopy and its Applications to Lithium Ion Cells

B. V. Ratnalnuonr, M.C. Smart, S. Surampudi

-
k
E 1 Tedmoibgies G m p , Jet Propulsion Laboratory, CiziYjimia Insrihre of Technology
~ o a k ~ e ~ CA
vPasadsrq ,

ABSTRACT
Electrochemical impeaanCe spectroscopy @IS) is a r ” c z i v e teclruique often used to understand the
interhcial behavior m electrochemical systems. The ability of the techaique to segregate various pceses, Le., ohmic
conduction, charge tmsfix, interfacial chargin& mass transfa etc, makes it an el- techuique for electrochemical
systems. Its applicability to lithium ion cells is furtherenhanced by the fact that d c e filmscover both the electrodes
and especlallytb carbonanode. This paper describesthe EIS resporse of individual elech-odesmthelithiumion cells
under a variety of experimantal conditions, i.e, &”me,high &”bmstorage and cycling.

1.0 Introduction
Elech.ochernical Impeaance Spectroscopy (EIS) is a
powerfill technique for “dmg electrochemical
syskms. Brieflyythis technique imrolves a dek”&on
. .
of cell hpdame, in respo~lseto a small (-5 mV
amplitude) ac signal at any constant DC potenhl
(prefmbly at the o(=v to “be the DC
over a span of SrepuenCes ranging t y p i d y firom 16
=
KHZ to 10-3 mw the tam impeaance spectrosoopy).
Fromthe measlned cell impeaance m the form ofreal and
imaginary components and phase angle, it is F i l e to
examine and qualitatively dek”e * several processes
such as the electromchomc m the electrode
and e e
lct
T o m intesfacial Charging either at the surhce
films or the double+la~,charge transfix pmceses and
the mass transfer effkcts, if any. The time constants for
these diffaent pnx;esses being differerb, their features
will show up at difkrcnt fiapcmics mthc EIS spcctm
The advardages of this techuiques include 1) its non-
destructive nature, since the polarbation applied is low
enough that linearpolarization conditions(is., where the
polarization inmzses linearly with Clnmt) are
maintailled and the rate equations are simplified
accordingly, 2) rapid and easy measuranent methods as
presently possiile with the advent of c o ~ u k r ~ l l e d
esuipment such as potentiostats and frequeq respoIlse
analyzers and appropriate &ware, which eMlILMlusiy
ww the * conection as well as d m t
adyses The deficiency of this techQique,on the other
b;m4 ismaidyrelatedto the d m z l t y inhteqemg * t h e
data, i.a, m emrisaging a suitable electrical equivaht
circuit to represent the electrockcal system and in
quantitatively detemhiug the relevant electrical
parameters that would help Mdetstand the response of
m m .
Historically, this technique bas been applied to a
variety of elech.ochermcal
. system. Specificall~~ithas
b e e n n s e d m l “ g * the adsorption of ( “ I)
molecules and passive films on electrode e c e s ,
determining the efkacy of corrosioninbibitor coatings
and m monitoring the energy c o m e o n devices, Le.,
batteries and k l cells. With respect to batteries, this
techxIiquehasbeennsed,seccessfhllymrnanysysterns,to
esthate the state of charge non-ctively. More
quantitatively, this technique has been used to determine
the e l m‘cal reaction rates, including corrosion
cmrents, and to measure the ionic umductivily of
electrolytes or thin films of poly”. In the case of
lithium primary cells, this techique has enabled probing
thc surfkc 6lms that affect thc voltagc &lay and &clf
He characteristics.
2.0 Lithium Ion Cells
Lithium ion rechargeable cells involve intercalation
reactions at both the anode and the cathode, wbich
involve minimal morphological changes m the electrode,
unlike the dissolution-pnxipitatim processes. Yet the
electde/ele.ctrolyte iuterhces sustain noticeable changes
mning charge-dkcharge cycling, mainly due to the
slafacefihnsonboththeelectrodes Thesurfacefilms,
formed on the anode in the first lithiation step to provide
the desired kinetic stability to the electrolyte towardsboth
the electrodes, continue to grow during chargedischarge
cycling. smce the charge tlausfer procsxs

02002 IEEE.
0-7803-7132-1/OU$1O.OO
273
c o r r e s p o n d i n g t o l i t b i l l m'onanddeirdercala
~ tion
OCCUT through the filmcovered electrodes, the 6lm
characteristics, especially its thiclrness and re&ance,
play a significant role m the rate capability and overall
performance of the d.
Various techuiques are being used to examine the
"eofthe surface films oncarbon, including the direct,
often in-situ techaiques such as FTTR, Fbmau
spectroscopy and optid methods such as AFM, TEM
and ellipsometxy. These methods are hi& &onnative
about the chemical of the * , howex, they are
not easily adaptable to real cells. Electrochemical
i";e spectroscopy, on the other hand, is easier to
adapt even to sealed cells and will provide usefkl
infmmtion onthe iutedkialkpedame and itschanges.
We,at JPL, have been evaluating various lithium ion
prototype cells, of high capacity (4-40 A h ) d developed
for aerospace applications under NASA-DoD joint
eff-. Oor evaluation protocol umsists of
charaderizationof perfo"x at various rates of charge
and discharge at Wkxent temperatures,dek" . h'onof
cycle life at d i f f k r e n t temperatmes, and of storage
-cs. During these &dies, we have routine@
used electrochanical impedance spectroqy to
determanethecelllmp&ncecharacteristics.
The cell i";e has conhibntionsfrom mdividual
electrodes, as well h m 6cc"& such as
electrolyteand leads. A generalized equivalent circuit for
a t u m k m* n d device' is shommFig. 1.
There is a geometric capacitance arising out of the
twodisimw electrodes, wbich ate in pamllel with each
other. In addition, each of electrodes' impeaance
response includes 1) an mhctive h m leads
and 6um the electrode mate&&, 2) a double-layer
capacitance at the electrode/electrolyte interf8ce, 3) a
charge transfer resistance representing the activation
process and 4) a Warburg impeaance to represent the
mass &andm effeds interfering with the charge transfa
processes In other wofds, the well-known Randles
circuit,' which q"ts each of the electrode
'
impedances, is applicable only ifthe electrodes are h e
274
of any surface passive films. However, m the case of
lithium ion cells, we know tbat surfkce 6lms (SEI) exist,
especMy on the carbun an- and to some extent on
the metat oxide cathodes. The equivalent circuit may
therefore be modified acco4.dingly.
2.1 AC Impeaance of Lithiam Ion cells
A typical EIS plot of a g m p b anode in l i ~ 0 . u
ion
batteay electrolytes, e+, 1 M LiF'F6 in an equi-proporlion
mixture of ethylene, diethyl and dimethyl carbonates, is
showninFig.2.
The pattern in Fig. 2 is similar to a charge transfa
over f i h n c o v e r e d electrode, with mtederence frcnn mass
transfer effects This is consistent with the current
u"ding of the graphite anode in that it is covered
with an SEI,which is fonned hmthe reactions involving
the rertuctions of electrolyte species and also hiaders the
rates of these processes.
Figwe 2. ljrpical EIS plot of the w h i t e anode.
The relaxation loop evident at high fiquesies may
thus be athibuted to the charging ofthe SEI and the SEI
characteristics,i.e., its nsishce and capacitance may be
deduced fiom the high Sreguarcy relaxation. Such an
a s s i m may be fintha confinned by the cbanges m
SEI under dif€knmt experinrerdal conditions, e%.,
temperature, and ageing. The second relaxation loop may
be attriiuted to the charge transfer process on the SEI-
covered electrode and the corresponding rate parameters.
The capacitance of the SEVelectrolyte double-layer and
the char- transfer resistanoe may be deduced fkom it3
The mass iraDsfm effkcts, ifprominent inthe impedance
data, may be attributed to the slow solid-state difhsion of
lithium in the graphite lattice. Both the SEI
charackristics and the charge transfer kinetics at the
carbon anode are highly dependent on the nature of
electrolyte. Accordingly, we have routinely been using
the EIS kchuique at JPL to Mderstandthe film-forming
nature of the electrolytes with different solvents.
The EIS pa- of the cathodes is much like the
anode, as shown in Fig. 3.
 amt
lbade I
Also in the case of cathode thae are two relaxation
loops, as may be expected fromthe presa~ceofa surface
layer similar to the SEI on the anode, on the cathode as
well. Again, assigoins the high Gequency loop to the
surface film and the low fieqmcy loop to the charge
transfer kinetics with possible interference (not siguificant
m this case) firommass transfer, it is possiile to infer
osefill infarmttion an the surhce film d”kh‘cs as
well as the neaction rates h t h e impeaancespectra
Since the hpedame pattems of both the anode and
the cathode m coll[lplicatBdby the presence ofthe surfkce
fihaf~ovaallimpedanceofthecenis~ci~
complex that it should be decomposed into indivicfual
electrode contriiutio~ In order to anderstand the
hipdame behavior of individual we have
fabricatedtbe-electrode cells Here,we have adopted a
strategy that heips us llr&mhd the rmpedance
characteri.stics of several sealed prototype lithium ion
cells. We have fihkakd cells with the same electrodes
(buk d e r ) being used by ourmdn&ial partner. The
. the anode to cathode capacities are also
rati.o of
“tmxdthesameasmthesealedprototypecells. The
laboratory cells (-400 mAh) are, thlq similar to the
prototype cells, but with a relatively higher electrolyte
content. In additim, we have incorporated a lithium
ref- electrode to the impeaance
charactesistics of the mdividual electrodes as well as the
cell. Figure 4 show the EIS pattans of the anode and the
cathode agaiust the lithium reference electrock and the
cell impedance, which is campared with the snm of the
anode andthe cathofkcontnbntiolos.
275
om 0.50 1.00
2-
Figure 4. EIS patterns of a Li ion cell compared with
the s”ofindividual electrode impedances
As may be seen h m Figure 4, the sum ofthe
cathode and =de impedaocesmkk the observed mn
impedance well. F~nthermore,the cathode impedance
seems to contribute a significant portion of the cell
impedance. The anode contribution, on the other haud, is
d e r and seems to dkppear at low fkqmciw. This
is quite contrary to wbat was observed by the research
~ inturn implies that the method of
group at ~ o n y ,which
electrode coating, loa- particle size and porosity
dictate the relative kinetics of lithiaton at anode and
cathode.
The above observation of cathode contributing
more towards the cell mpedame is also supported by our
DC polarization studies. Fig. 5 shows the Tdel
polarizatiom c l w e ~of both LiNil,C%Q cathode and
graph& anode in om labomtory cell. As may be seen
fiom Figure 5, the graphite anode Sustainshighercurrents,
almost an order of magmitude higher, than the nickel
cobalt oxide cathode. The polarization of the anode is
relatively d compared to tbat of ttae cathode over a
sigdkant range of current.
A- 1p
Figure 5. DC polarizations of cathode and anode.
3.0 EIS ofLi ion Cek under Different Conditions
Based on the above interpretation of the EIS
pattems of lithium ion cells, we have been using this
teclmique to monitor the cell and electrode impedance
characteristics under various expenmental conditions.
several of these e-,tal cases are described below
3.1 EIS at Low Temperatares
Low temperatme perfonnanoe is a critical far
several of s“ planetary missions The research
effints at JPL over the last decade have foc3used mainly on
this aspect of cell performance. considerable
impm-ts have been made in this category by
opthizing the solverits that would provide good ionic
conductivity at low temperatures,and yet have good
filming properties.~ As mentioned b e f q the EIS
technique is being routinely used toundfxstmdthe SET
characteristics as a fi”of solvent compositiiolls and
temperatnre. Figs. 6a and 6b illustrate the changes m the
cell and the mdividual electrode impedances at both 0°C
A. A * A
Rpo
0’
0 m l a a m a D w D
r o
Figure 6b. EIS patterns of Li ion cells at 40°C.
As may be seen h m the figures, the anode
contriiution is greater at 0°C relative to room
&”, but is still less than that of the cathode. At a
lower kqmature of 40°C, however, the impedance
arising -the amde SEI is CompaIable to that of the
cah& surface layer. In other words, here is a change-
..
over in the rate detarmmng process as we approach low
temperatures, i.e. below -20°C. The DC polaxization
stadies perfomd under these conditions confirm that the
anode kinetics are sigruficrntly hindered at low
kmpem” such that they could be rate limiting. This
cha”hcs
. .the agnificance of suitable electrolyte
ondealines
for good low temperaane cell
perf-.
32. EIS During High Temperature Storage
The ability of Li ion cells to witbstand high
te”es(over 40°C)is another requitementfor some
aerospace applications. Similar to the low temperature
perfonnaece, the high tt” t0leram;e is also
strongly aependent an the SEI c- ‘ ‘cs, which m
tmn 82e dictated by the electrdyte composition. Again,
rising EIS techmque, ve examined the intafacial
conditionson both anode and cathode during exposure to
hightemperatures? Figures 7a and 7b showthe variation
of EIS behavior of the anode and the cathode before and
after one-week storage at 60°C. These naeasuranents
were made at the same SOC, i-e., the cells were charged
fdly prior to self-discharge.
Figare 7a. EIS plots of graphite anode in 1) bigh EC
content and 2) EC:EMC:DMC solutions A) before and
B) after storage at 60°C for one week.
I
Eigam 7b. EIS plots OF L M X d N i & ~ ~C& in 1)
high EC content and 2) EC:EMCSMC solutionsA)
before and B) after storage at 60°C for one week.
276
 For the sake of clanty, data for only two
electrolytes are shown here, hosever the data h m the
third electrolyte follow similar trends. As may be seen
kam the f i
m the cell impeaarace along with the
cathode and anode impeaanca growduringthehigh
tempesdtarestcaage. Theseacimpedancedatam
analyzed ushng equivalent Circuits above
(Section 2), CoBlSisting of a electrolyteres&ame inseries
with a parallel combination of capacitance and resistance
represerding the surface film and another parallel
“bination of cqa&ame (double4ayer) and resistance
(charge transfer) to represerrt the faTadaic process.
Analyses of the above data indicate that the SEI on the
grqthte re” intact and grows linther dnnng high
temperatnre storage, contrary to some repcpts in the
lit”that it can dissohe at high 1I-
Further tests to confiormtbis are in progress. Also, much
like the SEI onthe cathode, theresistance of the SEI on
the LiNiiCol,@ cathode bxeases during the above high
tesnperahaestorage, i s , the SEI builds on both the anode
and cathode. In other wxds, the iuk&&l impeaance
inrreasesatboththe anodeandcathode,ttmscontributbg
to a build-up of cell impedance during storage, which m
tumresoltsinapen”tcapacity1ossuponstoxage
3 3 EIS During Cycling
As mentioned before, the changes in the EIS
charactaisticsof the sealed pmtotypecells have also been
“ed during cycling. a!3sigUment of specific
impedance featares in this case is, however, not as cextain
due to the absence of a lithium ref- electrode.
Nevertheless, “ a b l e extxapolations may be made,
based on the behavior of individualelectrode as described
abow.
Fig. 8 shows the typical impedance plots of lithium
ion cells m the course of cycling. There is, in general, a
gradual imxease m the cell impedance as a fimction of
cycling.
ala
am
277
There is a d increase m the series (Ohmic)
res&ame and a somewbat larger increase m the
relaxation loop, especially for the low hquency process
combining these d t s with the threeelectrode
w -
s , it is reasonable to assunr:that the cathode
contriites significantly to cell impedance growth dming
cycling. It ‘would, bwever, be IIlMe prudent to draw
conclusionsSromcycling of balfCeHs as d m for storage.
ACKNOWMENT
The work d e s c r i i here was carried out at the Jet
Propalsion Laboratory, California Insihte of
Techlogy, for the Code S NASA Battery program,
under contract wilh the National Aeromutics and Space
AdUlidhb‘on(NASA).
REFERENCES
1) U L Gophnth and S. Sathyamrayam, J. Applied
Electrochem.,9,369 (1979).
2) J. E.B. Ftandles, Discuss Faraday Soc, 1,111 (1947).
3) M. Wagner, Eleclrochun Acta, 42,1623 (1997).
4) IC “a,Solid State Ionics, 69,212 (1994).
5) M C. Smart, B. V. Ratmkumar, and S. Surampudi, 1
E k t m ~ h e n aSoc, 146, 486 (1999).
6) M C. Smart, B. V. R a t “ a r , S. Sumnpudi, Y.
Warg, X Zbang, S. G. Grccnbaum, A. Hightowcx, C.
C. A h , and B. Fultz, J . E k t “ P L SOC, 146,3963
(199%
7) M.C. Smart, B. V. m, S. Surampudi, Use of
Organic Esters as Co-solvents m Electrolytes for
Lithium-Ion Batteries with Improved Low
Tempemke Performance”, J. E&cbvchem
Soc.(acceptedfor publication)).
8) B. V. m ,
-
M. C. Smart, and S. Surampdi,
%ff& of SEI on Li irkmlab‘onkinetics, J. Power
so- 2000.
9) B. V. R&”ar, M. C. Smart, and S. Surampudi,
“storage . . s of Lithmm-IOn cells”, hoc.
Symp. Li Batteries, 196th E l e c t ” ’cal society
Meeting,Honolulu, Hawaii, od.17-22.