A128 Journal of The Electrochemical Society, 159 (2) A128-A136 (2012)

0013-4651/2012/159(2)/A128/9/$28.00 The Electrochemical Society

Analysis of Three-Electrode Setups for AC-Impedance
Measurements on Lithium-Ion Cells by FEM simulations
Moses Ender,
a,,z
Andr e Weber,
a,
and Ellen Ivers-Tiff ee
a,b,
a
Institut f ur Werkstoffe der Elektrotechnik (IWE) and
b
DFG Center for Functional Nanostructures (CFN),
Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe, Germany
Electrochemical impedance spectroscopy is a well-established method for investigating electrode processes in lithium-ion cells.
Commonly, a three-electrode setup is used, with a reference electrode positioned at the rim of the separator and centered between
working and counter electrode. The reliability of this setup is evaluated theoretically by using nite-element calculations and
experimentally by using LiFePO
4
and lithium-metal electrodes in symmetrical and mixed arrangements measured as half-cells and
full-cells. The results show that asymmetries between working and counter electrode arising from electrode misalignment and/or
different electrode characteristics, adulterate the reference electrode potential. In consequence, errors such as quantitative scaling
factors and cross contamination of electrode impedance response arise and inductive artifacts develop. Furthermore, we assess the
impedance distortion quantitatively for different ratios of electrolyte and electrode resistances.
2011 The Electrochemical Society. [DOI: 10.1149/2.100202jes] All rights reserved.
Manuscript submitted September 22, 2011; revised manuscript received October 31, 2011. Published December 20, 2011. This was
Paper 238 presented at the Montreal, QC, Canada, Meeting of the Society, May 16, 2011.
Three-electrode-setups consisting of a working (WE), a counter
(CE) and a reference electrode (RE) are well established in electro-
chemical investigations of experimental lithium-ion cells.
1, 2
The basic
idea is providing a point with a xed potential, which is realized by
an electrode without any current ow. Relative to this xed potential
both electrode potentials are monitored and the resulting electrode
overpotentials at a given current are determined. However, reliable
results are obtained only when the electrolyte potential at the posi-
tion of the reference electrode remains constant. This requirement is
only met at open-circuit conditions
c
or when the system exhibits a
perfect symmetry. In case of asymmetry, either geometrical or electri-
cal, the reference electrode potential will change at non-open-circuit
conditions.
These problems have been studied experimentally and theoreti-
cally for impedance measurements on solid electrolytes, common in
solid oxide fuel cells (SOFC).
35
It was demonstrated, that the variable
reference electrode potential was responsible for a biased measure-
ment. Adler
6
published a comprehensive study about the effects of
(a) geometrical asymmetry, created by misalignment between WE
and CE, and (b) electrical asymmetry, caused by different WE and
CE kinetics and/or frequency responses. Herein, Adler made quan-
titative error estimation by nite-element calculations and proposed
more suitable three-electrode setups for SOFC impedance measure-
ments. Adlers work clearly showed, that many published results on
impedance spectra of SOFC-electrodes, which were obtained by the
use of reference electrodes, are erroneous because articial electro-
chemical processes, which are related to the reference electrode, were
attributed to the investigated working electrodes.
Experimental lithium-ion cells are usually characterized in three-
electrode setups, which are often integrated inside Swagelok ttings.
In these T-type cells a lithium-metal reference electrode contacts the
electrolyte/separator at its outer rim. This is an appropriate setup for
determining the working and counter electrode potentials under open-
circuit voltage (OCV) conditions.
However, as soon as a current, either a charge or discharge current
(direct current, DC) or a current within an impedance measurement
(AC), is drawn, the potential of the reference electrode can shift, giving
rise to a change in the recorded half cell potentials. This effect will
distort the data quality of cyclic voltammograms, charge-discharge
curves and, above all, of AC impedance measurements.

Electrochemical Society Student Member.

Electrochemical Society Active Member.

z
E-mail: moses.ender@kit.edu
c
note that the AC-current during the impedance measurement interferes with the OCV
conditions.
Sometimes, artifacts such as inductive loops and others are present
in impedance spectra of experimental lithium-ion cells,
7, 8
but some-
times not.
9, 10
We speculate, that these impedance distortions result
from the same origin as in the case of SOFC, even though the geo-
metrical arrangements of WE, CE and RE are different. Moreover, the
positions of WE and CE are xed on the solid oxide electrolyte by
a thermal treatment, which allows quantifying a lateral shift between
them and a subsequent correction by an adequate theoretical model.
In contrast, a lithium-ion cell consists of a soft separator membrane
which is soaked with a liquid electrolyte. Both electrodes are casted
onto exible sheets (copper or aluminum foils). The entire cell assem-
bly is carried out in a glove box, making reproducibility and precise
control of WE and CE alignment very difcult.
Besides this aspect, which is relevant for geometrical asymmetry in
lithium-ion cells, different electrode kinetics or frequency responses
are responsible for electrical asymmetry. Both, anodes and cathodes,
are intercalation materials differing in lithium storage capacity and
their diffusion constants, among other characteristics. This generally
results in an impedance response with a capacitive behavior at the
lower frequency part of the spectrum. Anode and cathode character-
istics are separable when measured against a CE and RE made of
lithium-metal, which does not show a capacitive behavior. As a con-
sequence, electrodes evaluated in such a three-electrode setup show a
completely different impedance response at low frequencies than the
counter electrode, causing a strong electrical asymmetry between WE
and CE.
In Ref. 11 it was demonstrated that the geometric arrangement of
a three-electrode setup affected the current pulse measurements in a
planar lithium-ion cell. The resulting electrode resistances strongly
varied with the position of the reference electrode. This experimental
result was supported theoretically by numerical simulations.
This work analyzes the applicability of reference electrodes in
lithium-ion cells for AC impedance measurements. For this purpose,
experimental studies on half-cells and full-cells as well as nite-
element calculations were performed and the results compared. Our
studies comprise LiFePO
4
and lithium-metal as working electrode
and counter electrode, and, furthermore, lithium-metal as reference-
electrode. First, AC impedance measurements on three different cell
types, representing either electrical symmetry or electrical asymme-
try, are performed. The measurements are supposed to show differ-
ing impedance spectra for full-cells (WE vs. CE) compared to half-
cells (WE vs. RE and CE vs. RE). Second, a nite-element method
(FEM) simulation of the underlying three-electrode setup is presented,
calculating the consequences of electrical and geometrical asymme-
tries on the impedance response. The resulting impedance distor-
tions are quantitatively evaluated for different ratios of electrolyte and
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Journal of The Electrochemical Society, 159 (2) A128-A136 (2012) A129
RE
CE WE
separator/electrolyte
Figure 1. Schematic view of the experimental three-electrode set-up, consist-
ing of a T-shaped Swagelok tting and three stamps that contact the electrodes.
Electrical insulation is provided by a polypropylene tube inside the tting.
electrode resistances. Both effects, geometrical and electrical asym-
metry, are modeled separately, followed nally by simulations of a
combined asymmetry.
Experimental Setup and Measurements
The three different cell types were assembled in T-type cells. A
schematic view of the three-electrode set-up is shown in Figure 1,
consisting of a T-shaped Swagelok tting and three stamps that contact
the electrodes. Electrical insulation is provided by a polypropylene
tube inside the tting. Working and counter electrode have a diameter
of 12.0 mm each, whereas the T-cell housing itself is slightly larger
with a diameter of 12.7 mm. It should be pointed out, that a geometrical
asymmetry was not intended, but an axial shift z between WE and
CE of 0 < z < 0.7 mm is inevitable and non-reproducible among
our experiments. The reference electrode with a diameter of 5.0 mm
is positioned at the side between working and counter electrode, with
a distance of 0.8 mm from the edges.
Three different cell arrangements (cell type A, B and C) were cho-
sen to demonstrate the effects of geometrical and electrical asymmetry
independently, as summarized in Table I. Working- (WE) and counter-
electrode (CE) are denoted as E1 and E2 respectively. Cell types A
and B were assembled as symmetrical cells. Cell type A consisted of
similar lithium-metal sheet electrodes with a thickness of 0.38 mm
(Sigma Aldrich, purity 99.9%) for E1 and E2. In cell type B both
electrodes E1 and E2 were made of LiFePO
4
at 0% state of charge,
when the lattice is entirely lled with lithium. The porous electrode
structure was made of LiFePO
4
(S ud Chemie, 70%), carbon black
(Timcal, 24%) and PVDF binder (6%). The slurry obtained by adding
NMP was coated with a doctor blade method on an aluminum current
collector (thickness 100 m). The characteristics of this compos-
ite cathode were already characterized extensively, e.g. electrically
by electrochemical impedance spectroscopy
12, 13
and structurally by
focused ion beam/scanning electron microscopy (FIB/SEM).
14
Cell
type A and B were assembled with great care, and, as E1 and E2
are made of the same material, are supposed to provide electrical and
geometrical symmetry.
Cell type C represents electrical asymmetry, and was made of
LiFePO
4
as cathode (E1) and lithium-metal as anode (E2). Conse-
quently, a pronounced difference in the time constants of the electro-
chemical processes was introduced, as described in.
12, 13
The cells A, B and C were assembled with a standard electrolyte
consisting of LiPF
6
in a 1:1 mixture of EC/EMC (Merck) and a 250
m glass ber separator (VWR). For all experiments, a lithium-metal
reference electrode made of the material from Sigma Aldrich with a
purity of 99.9% was used.
The electrochemical impedance spectroscopy (EIS) measurement
was performed potentiostatically with a combination of a Solartron
1260 and a Solartron 1287 (potentiostat), covering a frequency range
from 0.5 Hz to 10
5
Hz. All cells were held at a constant temperature
of 23

C and measured at 0 V versus open circuit voltage (OCV). For

impedance spectroscopy measurements either a current or a voltage
excitation can be applied as the stimulus. In theory, both impedance
responses are of the same kind for an excitation signal within the linear
regime over the entire frequency range. In experiments, the impedance
values and the impedance data quality usually differ, depending on
the type of excitation as well as on the selected measurement param-
eters. This difference is caused by the chosen measurement device
as well as by the electrical connection of the cell. Therefore, recom-
mendations of the device manufacturer are to be considered. In our
studies, we applied an excitation voltage of 10 mV RMS as previous
test sequences with identical cells proved best data quality as well as
linear behavior. FEM simulations will coincide in voltage and current
excitation, because our model does not consider nonlinearity.
The impedance measurements of the full-cell (E1 vs. E2) and of
the individual electrodes (E1 vs. RE, E2 vs. RE) were performed
successively by changing the wiring of the cell (see Figure 2a2c).
All cells measured were assembled in a glove box at room tem-
perature within one hour, rested for 24 hours at 23

C. Stationary state
was ensured by repeated impedance measurements. Afterwards, the
cell types A, B, Cwere measured in quick succession within one hour.
The cell voltages were 0.5 mV for the symmetrical lithium cell (type
A), 17.8 mV for the symmetrical LiFePO
4
cell (type B) and 3.03 V
for the lithium/LiFePO
4
cell (type C).
First, the impedance of the cell was acquired without using the
reference electrode (Figure 2a). In the second course, the impedance
of electrode E1 was acquired by measuring the potential of electrode
E1 versus the potential of the reference electrode (Figure 2b), and
in the third course electrode E2 was measured versus the reference
electrode (Figure 2c). Thereafter, the rst measurement was repeated
once and the resulting impedance data were compared. This procedure
was repeated for all cells and assessed that the impedance of cell type
A, B and C were constant during the entire testing period which lasted
for about 20 minutes. In all cases reported here, the rst and the fourth
measurement delivered corresponding impedance responses with a
deviation < 5% for lithium-metal and < 1% for LiFePO
4
. It is well
known from literature that a lithium-metal electrode is of insufcient
stability over longer time periods. However, the reproducibility and
stability of the lithium-metal electrode is sufcient in our case, as
the change in impedance is less than 5% for all experimental results
reported here.
Table I. Three different cell arrangements (cell type A, B and C), experimentally characterized by
AC impedance measurements.
Cell type
Working
electrode E1
Reference
electrode RE
Counter
electrode E2
Electrical
asymmetry
Geometrical
asymmetry
A Li-metal Li-metal Li-metal no yes (but not intended)
B LiFePO
4
Li-metal LiFePO
4
no yes (but not intended)
C LiFePO
4
Li-metal Li-metal yes yes (but not intended)
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A130 Journal of The Electrochemical Society, 159 (2) A128-A136 (2012)
CE WE
RE1 RE2
CE WE
RE1 RE2
CE WE
RE1 RE2
a)
b)
c)
RE
E2
E1
RE
E2
E1
RE
E2
E1
Figure 2. Schematic view of the wiring between test cells and Solartron
1260/1287. (a) For measuring the full-cell, or separately (b) counter electrode
and (c) working electrode. In all cases, the wires labeled with CE and WE are
connected to the counter (E2) and working electrode (E1) to apply the current
for the measurement. Only the wires for the voltage measurement labeled with
RE1 and RE2 are connected to the electrodes that are supposed to be measured
(E2/E1, E1/RE or E2/RE).
FEM-model
The three-electrode setup (Figure 1) with the cell dimensions given
above is modeled using the nite-element software Comsol 3.5a. As
shown in Figure 3a, both electrodes E1 and E2 are placed face to
face with the electrolyte in between. The electrolyte thickness is set
to 100 m corresponding to the separator thickness used in earlier
measurements. Changing the electrolyte thickness to 250 m, which
is the actual thickness in our experiments, does not play a role for the
qualitative comparison of FEM simulations and experimental results.
A quantitative comparison would show the inuence of the elec-
trolyte/separator thickness but is not aimed here. Geometrical asym-
metry is introduced by a vertical shift z of the working electrode
(z = 0.4 mm). The reference electrode is positioned above the
two electrodes. E1, E2 and RE electrodes are surrounded by a larger
cylinder that is virtually lled with electrolyte. This detail differs from
the experimental cell setup, but does not lead to inconsistencies be-
tween simulation and experiment, as the currents outside the volume
between E1 and E2 are practically zero. Hence it is of no relevance
where the zero ux condition is applied. The mesh used for the sim-
ulations consists of 127,813 elements. An adaptive meshing routine
leads to a coarse mesh outside and a ne mesh at the surface and in
between the electrodes, as shown in Figure 3b.
All electrochemical processes taking place at the elec-
trode/electrolyte interface are described by one single RC-element,
with a resistance R
i
accounting for the charge transfer resistance and a
capacity C
i
considering the capacitive effect of a double layer. There-
fore any simulated impedance spectrum should consist of a single
semicircle (symmetrical cells or spectra of one of the electrodes mea-
b) bbb)))
a)
Figure 3. (a) Geometry used for the nite-element model of the three-
electrode setup: electrolyte (transparent) and electrodes, counter electrode
(blue), working electrode (red), and reference electrode (green). (b) The mesh
used for the simulations consisted of 127,813 elements. An adaptive meshing
routine leads to a coarse mesh outside and a ne mesh at the surface and in
between the electrodes.
sured versus the reference electrode) or two semicircles (in case of a
full cell with two electrodes differing in their time constant). Further
on the simulated impedance spectra should not exhibit any kind of
inductive processes.
To implement the electrode behavior in the FEM-model a vir-
tual layer is assigned to the electrode/electrolyte-interface (distributed
impedance), having a thickness d
i
(which was arbitrarily set to 10
8
m), a conductivity
i
and a relative permittivity
i
. Thus the boundary
layer yields a resistance
R
i
=
d
i
A
i
[1]
and a capacitance
C
i
=
0

i
A
d
i
[2]
with A the active surface of the electrode.
The conductivity
i
and the relative permittivity
i
of both types of
electrodes are adjusted to obtain a polarization resistance of 10 and
relaxation frequencies f
r
between 1 Hz and 10
4
Hz.
The electrolyte is described by a conductive media with variable
conductivity, and the calculations shown are based on ohmic resis-
tances R
o
= 1 , 10.5 and 42 . This variance allows studying the
impact of different electrolyte/separator combinations on the resulting
impedance response.
The electrical potential of both electrodes is considered as nearly
constant and the electrode volume is represented by a conductive
media with a very high conductivity of 10
9
S m
1
.
A frequency spectrum of the impedance response is obtained by
a series of nite-element simulations (FEM) performed for each fre-
quency point from 10
1
Hz to 10
6
Hz with 10 points logarithmically
distributed in every decade. For each frequency point the potential dis-
tribution is calculated. With the obtained potentials of the electrodes
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Journal of The Electrochemical Society, 159 (2) A128-A136 (2012) A131
and the predetermined current, the impedances of the full cell (E1 vs.
E2), and the individual electrodes (E1 vs. RE and E2 vs. RE) are cal-
culated, corresponding to Figure 2a2c. The FEM simulation delivers
the same results for voltage and current excitation, as nonlinearities
are excluded in our model. Therefore, it makes no difference at which
voltage/current amplitude an impedance point is calculated.
Results and Discussion
As discussed in SOFC literature
35
for three-electrode setups ap-
plied for ACimpedance measurements of solid-oxide electrolyte cells,
the impedance response can be seriously distorted. This distortion is
caused either by a geometrical asymmetry, which means a misalign-
ment of working and counter electrode, or by an electrical asymmetry,
which is caused by different kinetics and frequency response of an-
ode and cathode, or by a combination of both asymmetries. In this
study, we experimentally and theoretically analyze all three cases for
experimental lithium-ion cells as well.
In the following, the experimental results for the investigated cell
types A, B, and C are presented rst. Secondly, the corresponding
nite-element simulation results are discussed emphasizing different
cases of asymmetry and, moreover, different electrolyte/separator re-
sistances affecting the impedance response.
Measurement results.
Cell type A (lithium-metal vs. lithium-metal).The measured
impedance spectrum of E1 vs. E2 made of lithium-metal, shown as
black symbols in Figure 4a, features basically one semicircle with a
polarization resistance R
pol
= 50 . One would expect that the two
individual lithium-metal electrodes, when measured against the ref-
erence electrode result both in a polarization resistance R
pol
= 25
which is half the size of the full cell. However, and despite that both
Li-metal electrodes are nominal identical, the E1 impedance (blue
symbols) comes to a value of 40 whereas the E2 impedance (red
symbols) shows a value of only 10 . This gives evidence, that an
unintended misalignment of working and counter electrode produces
a signicant scaling factor in half-cell impedances, when measured
against a reference electrode.
Cell type B (LiFePO
4
vs. LiFePO
4
).The measured impedance spec-
trum of E1 vs. E2 made of LiFePO
4
, shown as black symbols in
Figure 4b, delivers one semicircle at higher frequencies with a polar-
ization resistance R
pol
= 50 . The imaginary part of the impedance
rises at low frequencies, pointing to a capacitive behavior. This char-
acteristic discloses the limited lithiumstorage capacity of the LiFePO
4
lattice. The E1 vs. RE (blue symbols) and E2 vs. RE (red symbols)
half-cell impedances, when compared to Cell type A, show only sub-
tle differences in their polarization resistance (error < 20%). How-
ever, both impedance spectra differ considerably in the low frequency
range, expressed by varying slopes of the capacitive branch. As in the
case for lithium-metal electrodes, both half-cell measurements give
evidence that a small, yet unintended relative displacement between
working and counter electrode, results in a still signicant difference
in impedance response.
Cell type C (LiFePO
4
-cathode (E1) vs. Lithium-metal anode (E2)).
The measured impedance spectrum of E1 vs. E2, shown as black
symbols in Figure 4c, features a depressed semicircle. Obviously,
the full-cell response consists of two overlapping polarization pro-
cesses originating from the LiFePO
4
and the lithium-metal electrode.
Furthermore, the low frequency part is assigned to the capacitive be-
havior of the LiFePO
4
electrode. It is noteworthy, that the full-cell
conguration delivers expected and unexpected characteristics. The
impedance response of the LiFePO
4
cathode, measured as E1 vs. RE
(blue symbols), consists of a capacitive branch which is unambigu-
ously assigned to solid state diffusion
12, 13
and a small polarization
process R
pol
= 15 with a relaxation frequency f
r
= 2.5 kHz. Qual-
itatively, these features agree well with the impedance response of
LiFePO
4
characterized in the symmetrical cell type B. However, the
polarization process of LiFePO
4
shows a signicant scaling factor,
a)
c)
0 20 40 60 80 100 120 140
-40
-20
0
Z
'
'

/

0 20 40 60 80 100 120 140

-140
-120
-100
-80
-60
-40
-20
0
Z
'
'

/

0 20 40 60 80 100 120 140

-60
-40
-20
0
Z' /
Z
'
'

/

b)
full cell counter electrode working electrode
type A
type B
type C
+ 681 Hz
+
+
+
+ 3162 Hz
+
+
+
+ 1211 Hz
+
+
+
Figure 4. Measured impedance spectra of different cells. For every cell there
are three measurements shown, corresponding to the full-cell (black circles),
the counter electrode (red diamonds) and the working electrode (blue squares).
The rst measurement (a) shows a symmetrical lithium-lithium cell (cell type
A). Both half-cell impedances differ signicantly by a scaling factor of 5.6,
even though a similar value is expected. The second measurement (b) shows a
symmetrical LiFePO
4
/LiFePO
4
-cell, where the difference in the polarization is
not that obvious. In contrast, the full-cell impedance of (c) a LiFePO
4
/lithium-
metal shows artifacts (inductive loops) in the low frequency region of the
lithium counter electrode.
when R
pol
= 15 in cell type C is compared to R
pol
= 25 in cell
type B. Moreover, the bend between this high frequency polarization
process and the capacitive branch is less pronounced than expected
from the impedance response of cell type B.
In addition, the impedance response of the lithium-metal electrode,
measured as E2 vs. RE (red symbols), differs considerably from the
symmetrical arrangement in cell type A (Figure 4a), generating a
depressed semicircle and additionally a strong inductive loop at low
frequencies.
Intuitively, one would expect that the lithium-metal counter elec-
trode measurement in cell type C (Figure 4c) has the same shape
as observed in the full-cell measurement of cell type A. However,
the measured impedances are quite different. This divergence is a
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 150.65.7.11 Downloaded on 2014-04-29 to IP
A132 Journal of The Electrochemical Society, 159 (2) A128-A136 (2012)
Table II. Different cell arrangements theoretically analyzed by nite-element simulations.
Electrolyte Working Counter Geometrical
resistance electrode E1 electrode E2 asymmetry
Electrical
Figure R
0/
R/ f
c/Hz
R/ f
c/Hz
asymmetry shift / mm
5a 42 10 10
3
10 10
3
no no 0
5b 42 10 10
3
10 10
3
no yes 0.4
5c 10.5 10 10
3
10 10
3
no no 0
5d 10.5 10 10
3
10 10
3
no yes 0.4
5e 1 10 10
3
10 10
3
no no 0
5f 1 10 10
3
10 10
3
no yes 0.4
6a 42 10 1 10 10
3
yes no 0
6b 10.5 10 1 10 10
3
yes no 0
6c 1 10 1 10 10
3
yes no 0
7a 42 10 10
4
10 10
2
yes yes 0.4
7b 42 10 10
4
10 10
2
yes yes 0.4
strong indication for electrical asymmetry, intended by the choice of
different electrodes and furthermore, for an unintended geometrical
asymmetry.
This deliberate series of experiments demonstrates, for the rst
time, that a reference electrode in a three-electrode setup generates
pronounced inconsistencies in the impedance response of electrodes
in lithium-ion cells.
Simulation results. The nite-element model is used to cal-
culate impedance spectra for various cell arrangements and elec-
trolyte/separator resistances.
First, the impedance response of an ideal geometrical arrange-
ment is simulated. Second, the two types of asymmetries, geometrical
and electrical, are simulated separately. Third, a combination of both
effects will demonstrate how electrical and geometrical asymmetries
add up. This enables a comparison between the experimentally derived
inconsistencies and the theoretically calculated impedance responses.
Moreover, three different electrolyte resistances R
0
= 1 , 10.5
and 42 are taken into account, demonstrating how impedance dis-
tortions scale with increasing ratio between electrolyte and electrode
resistances (R
0
/R
pol
). Table II gives an overview over the various sim-
ulations performed.
Ideal symmetric arrangement.Figure 5a shows the simulated
impedance spectrum of an ideal symmetric arrangement, representing
electrical symmetry with electrodes made of the same material, and
geometrical symmetry without electrode misalignment. The spectra
for the full-cell (E1 vs. E2) as well as for working (E1 vs. RE) and
counter (E2 vs. RE) electrode display the expected characteristics.
Both impedances, simulated for E1 and E2 vs. reference electrode,
are exactly half of the full cell impedance. Furthermore, Figures 5a,
a) b)
c)
e)
d)
f)
0 20 40 60
-20
-10
0
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Z
'
'

/

0 20 40 60
-20
-10
0
Z' /
Z
'
'

/

0 20 40 60
-20
-10
0
Z' /
Z
'
'

/

0 20 40 60
-20
-10
0
Z' /
Z
'
'

/

0 20 40 60
-20
-10
0
Z' /
Z
'
'

/

0 20 40 60
-20
-10
0
Z' /
Z
'
'

/



symmetrical cell setup relative shift between electrodes (z=0.4 mm)
d
e
c
r
e
a
s
i
n
g

e
l
e
c
t
r
o
l
y
t
e

r
e
s
i
s
t
a
n
c
e

full cell working electrode (E1) counter electrode (E2)
Figure 5. Finite-element simulations of impedance spectra for six different cells. The left column (a,c,e) shows the three cells with varying electrolyte conductivity
but no asymmetry (no lateral shift of working electrode, half-cells are perfectly matching). The right column (b,d,f) shows the same cells but with the working
electrode shifted upwards by 0.4 mm. The lateral shift causes a scaling factor of the two half-cell impedances (red diamonds and blue squares).
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 150.65.7.11 Downloaded on 2014-04-29 to IP
Journal of The Electrochemical Society, 159 (2) A128-A136 (2012) A133
a)
b)
c)
0 20 40 60
-20
-10
0
Z' /
Z
'
'

/

0 20 40 60
-20
-10
0
Z' /
Z
'
'

/

0 20 40 60
-20
-10
0
Z' /
Z
'
'

/

20 25 30
-6
-4
-2
0
Z' /
Z
'
'

/

5 10 15
-6
-4
-2
0
Z' /
Z
'
'

/

0 5 10
-6
-4
-2
0
Z' /
Z
'
'

/

electrical asymmetry zoomed half cell impedances

d
e
c
r
e
a
s
i
n
g

e
l
e
c
t
r
o
l
y
t
e

r
e
s
i
s
t
a
n
c
e

full cell working electrode (E1) counter electrode (E2)
Figure 6. Simulated impedance spectra for three cells with an electrical asymmetry (factor 1000 between the characteristic frequencies of the electrodes). The
nite-element simulations are performed for the same electrolyte conductivities than in gure 5. Again, the effect is more pronounced at higher electrolyte
resistances (a,b,c), which becomes more clearly in the zoomed region of the half-cell results (right column).
5c, and 5e demonstrate that the impedance response is independent
of the electrolyte resistance. This result is expected, as the refer-
ence electrode position is at the geometrical symmetry plane of the
setup.
This behavior is expected to change by introducing either a geo-
metrical asymmetry by electrode misalignment or an electrical asym-
metry by different electrode materials. Geometrical asymmetries are
realized in our simulations by a relative vertical shift of the elec-
trodes. Accordingly, the electrical asymmetry is realized by changing
the parameter
E1
of electrode E1 and with this their characteristic
frequency f
r
.
Geometrical asymmetry.The simulated spectra for geometrical
asymmetry are shown in Figure 5b. Herein, E1 is shifted 0.4 mm
upwards (in the direction of the reference electrode), resulting in an
asymmetric eld distribution at the electrode edges. Thus, the refer-
ence electrode potential is displaced from the middle potential of the
electrolyte. In this case, both shares of electrolyte resistance are of
different size and impedance responses for E1 vs. RE (blue symbols)
become distinct from E2 vs. RE (red symbols).
However, the effect of electrode displacement on impedance distor-
tion is strongly related to the ratio of electrolyte resistance to electrode
polarization (R
0
/R
pol
). The simulation results in Figure 5b, 5d, and 5f
demonstrate that the effect of geometrical asymmetry on the ohmic
resistance and the polarization resistance decreases toward small elec-
trolyte resistances. As the voltage drop at the electrolyte is split up
between E2 and E1 overpotentials, the error in R
0
introduced by the
reference electrode becomes insignicant for low electrolyte resis-
tance. With this also the error in R
pol
is decreased.
In practice, a ratio of R
0
/R
pol
= 0.1 can lead to an error in the
polarization resistances of up to 10%. In our setups, we measure
electrolyte resistances of 20 (@ 25

C), leading to the assumption
that a ratio of R
0
/R
pol
< 0.1 is rather exceptional. Assuming that the
electrochemical processes in the electrodes exhibit a higher activation
energy than the conductivity of the electrolyte, a measurement at lower
temperatures is favorable.
Electrical asymmetry.In case of electrical asymmetry, the electrode
polarization processes have different time constants which means that
their impedances change differently with excitation frequency. Thus,
the resulting frequency dependencies of the electrode overpotentials
affect the potential of the reference electrode.
For FEM simulations, we select a factor of 1000 between the time
constants, and a characteristic frequency of 10
3
Hz for E2 and 1 Hz
for E1. The results are displayed in Figure 6a for a frequency range
between 10
1
Hz and 10
6
Hz.
As a result of the electrical asymmetry, both half-cell impedances
deviate from a perfect semi-circle in the high frequency region. Addi-
tionally, both half-cell impedances feature an inductive artifact, which
becomes visible at high frequencies for E2 and at low frequencies
for E1.
It is pointed out again, that the resulting impedance curve depends
on the ratio between electrolyte resistance and polarization resistance
R
0
/R
pol
, as displayed in Figures 6a6c. The deviation from an ideal
RC behavior becomes negligible for small electrolyte resistances and
with this for small values of R
0
/R
pol
, as already discussed above for
the case of geometrical asymmetry.
Geometrical and electrical asymmetry.As stated above, geometri-
cal plus electrical asymmetries can cause a combined effect in three-
electrode setups. Furthermore, as impedances of two different elec-
trode materials are generally expected to differ in magnitude as well,
this effect is even more pronounced in real cells.
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 150.65.7.11 Downloaded on 2014-04-29 to IP
A134 Journal of The Electrochemical Society, 159 (2) A128-A136 (2012)
a) b)
0 20 40 60
-20
-10
0
Z' /
Z
'
'

/

0 20 40 60
-20
-10
0
Z' /
Z
'
'

/

20 30 40
-10
-5
0
Z' /
Z
'
'

/

20 30 40
-10
-5
0
Z' /
Z
'
'

/

electr. & geom. asymmetry (z

E1
= -0.4 mm) electr. & geom. asymmetry (z
E1
= 0.4 mm)
full cell working electrode (E1) counter electrode (E2)
Figure 7. Simulated impedance spectra for a cell with both, electrical and geometrical asymmetry. In the rst case (a) the working electrode is shifted downwards
by 0.4 mm and has a characteristic frequency of f
E1
=10
4
Hz. The counter electrode has a characteristic frequency of f
E2
=10
2
Hz. (b) Same electrical properties
than before, but with the working electrode shifted 0.4 mmupwards instead. In both cases, one half-cell impedance shows two semicircles that can be misinterpreted
as two physical processes. The lower row shows again the zoomed region of the half-cell impedances.
In our FEM simulations, we study a full-cell with one polarization
impedance of 10 at a characteristic frequency of 10
2
Hz for E2 and
another polarization process of 10 at a characteristic frequency of
10
4
Hz for E1. Furthermore, the geometrical asymmetry is realized
by an E1-misalignment of z
E1
= 0.4 mm in Figure 7a, and of
z
E1
= +0.4 mm in Figure 7b.
Interestingly, in both cases, one of the half-cell impedances fea-
tures a second, yet smaller semicircle. This distortion, involving the
risk of misinterpretation as a real second physical process, was
already identied by Adler
6
and denominated as a cross contami-
nation of the electrode impedance responses. Furthermore, the other
half-cell impedance deviates from the perfect semicircle shape of a
RC element. Obviously, an interpretation of both half-cell measure-
ments will not conclude, that counter and working electrode account
each for a single polarization process with the same magnitude of
R = 10 .
The FEM simulations prove to the experimenter that electrical
and/or geometrical asymmetries within the electrode materials and/or
inside the test setup are responsible for a distortion of the impedance
response. Whereas a geometrical asymmetry leads to a change in
magnitude of polarization, an electrical asymmetry links with induc-
tive loops and other distortions. Furthermore, a combination of both
types of asymmetry provokes a second, articial semicircle among the
physical electrode process. This distortion is denominated as a cross
contamination between the electrodes, expressing that a part of the
polarization process of one electrode infects the impedance response
of the other electrode.
This knowledge is helpful for explaining the experimental results
of cell type C, where LiFePO
4
is measured vs. lithium-metal (see
Figure 4c). First, the most prominent feature of the impedance spec-
trum is the inductive loop of the counter electrode. Now, we can
attribute this impedance distortion to the presence of an electrical
asymmetry in cell type C. Furthermore, the high frequency process of
the working electrode is smaller compared to the expectation from the
symmetrical cell type B (see Figure 4b). Obviously, this points to the
presence of a geometrical asymmetry within cell type C. Even though
a geometrical asymmetry is not intended in cell type C, a small mis-
alignment during cell assembly in a glove box is always very probable.
In addition, the cross contamination among electrode impedances is
observable in cell type C. Figure 4c demonstrates, that a part of the
lithium-metal (E2) process distorts the LiFePO
4
(E1) response, as the
minimum between the high frequency process and the capacitive
branch is masked.
In Figure 8 equivalent circuit models for the simulated impedance
spectra and the related ts are shown. The simulated impedance spec-
tra of the half cells (Figure 8a and 8b) cannot be tted with the under-
lying RC-elements and half of the electrolyte resistance as the series
resistance, which would corresponds to the elements applied in the
FEM-simulation. Due to the errors related to the reference electrode
the spectra have to be described by at least two RQ-elements, one RL-
element and a series resistance each. This rather complex equivalent
circuit gives an acceptable t result. Figure 8c shows the simulated
impedance spectra of the full cell. It is obvious, that this spectrum can
be tted by two RC-elements differing in time constant and a series
resistance. On the other hand, a series connection of the two equivalent
circuits obtained from the half cell measurements gives an excellent
agreement as well. The error introduced by the reference electrode
during the impedance measurement of electrode E1 is compensated
by the error which is introduced within the impedance measurement of
electrode E2. There is no possibility to detect the errors by comparing
the impedance spectra of the half cells and the full cell.
This is critical if somebody wants to gather information about the
polarization resistance of an electrode (anode or cathode) measured
against a reference electrode. The impedance response of the indi-
vidual electrodes is falsied by the reference electrode resulting in
a rather complex equivalent circuit. The equivalent circuit elements
required for an acceptable approximation of the measured data are not
related to physicochemical processes in the electrode. In our case, a
simple RC-element is transformed into two distributed elements dif-
fering in time constant plus an inductive artifact at high respectively
low frequencies.
As already mentioned before, the lithium-metal electrode gener-
ally shows a poor stability, which would be absolutely essential for
quantitative studies. The polarization resistance of a lithium-metal
electrode varies strongly with testing time and current density ap-
plied. However, as only a voltage measurement is performed over the
reference electrode in our experiments, a possible change in polariza-
tion resistance is insignicant for the signal given by the reference
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 150.65.7.11 Downloaded on 2014-04-29 to IP
Journal of The Electrochemical Society, 159 (2) A128-A136 (2012) A135
R=10.59
T=7.7910
-4

n=0.96
E1
fit
10 15 20 25 30
-10
-5
0
5

25 30 35 40 45
-10
-5
0
5

E2
fit
R
E1,0
RQ
E1,1
RQ
E1,2
RL
E1
RL
E2
R
E2,0
RQ
E2,2
RQ
E2,1
R=10.97 R=0.95
Q=1.4910
-5

n=1.0
R=6.98
Q=1.4410
-5

n=0.99
R=1.33
L=1.6210
-3
H
R=28.26 R=4.49
T=1.4010
-5

n=0.79
R=1.68
L=2.410
-5
H
35 40 45 50 55 60 65 70
-10
-5
0
5

full-cell
E1
mod
+ E2
mod
R
E1,0
RQ
E1,1
RQ
E1,2
RL
E1
RL
E2
R
E2,0
RQ
E2,2
RQ
E2,1
R
0
RC
1
RC
2
a) b)
c)
+
Figure 8. Equivalent circuit models and CNLS ts of the simulated impedance spectra of the half cells shown in Figure 7b. Due to the application of the reference
electrode the simple RC-elements were transformed into (at least) two RQ-elements and one RL-element each. The series connection of the equivalent circuits
from Figure 8a) and 8b) is given in Figure 8c). It shows an excellent agreement with the simulated spectrum of the full cell.
electrode. In contrast, a possible shift of the reference electrode po-
tential, arising from impurities and undesirable side reactions, would
seriously interfere with the measurement of exact electrode potentials.
Conclusions
A three-electrode setup, commonly used for AC impedance mea-
surements of experimental lithium-ion cells, contains the risk of
signicant errors in the measured half-cell impedances. Finite-element
simulations and experimental measurements proof impedance dis-
tortions, inherently created by an electrode misalignment and/or by
different impedance responses of anode and cathode, giving rise to
geometrical and/or electrical asymmetries. Furthermore, we have an-
alyzed the combined effect of both kinds of asymmetries theoretically
by our model. The following impedance distortions, already analyzed
thoroughly for solid oxide fuel cells have to be considered in half-cell
measurements of lithium-ion cells:
r
quantitative scaling factors of the impedance response in half
cells with identical working and counter electrode shifted against each
other (geometrical misalignment)
r
inductive artifacts in perfectly aligned half cells with different
working and counter electrode (electrical asymmetry)
r
additional cross contamination of working and counter elec-
trode frequency responses in most test cells with an unavoidable elec-
trode misalignment and different electrodes (geometrical and electri-
cal asymmetry)
Therefore, we recommend taking measures against impedance distor-
tions of half-cells such as:
r
Minimize geometrical asymmetry, by using a cell design with a
minimumprobability of working electrode and counter electrode mis-
alignment. Furthermore, the reference electrode must be positioned
symmetrically to the electrode stack.
r
Use electrolyte systems with lowest possible resistance com-
bined with a thin separator sheet. Impedance distortions increase
with increasing ratio between electrolyte and electrode resistances
(R
0
/R
pol
). Therefore, errors are kept small at low electrolyte resis-
tance.
r
Record half-cell impedances always for working electrode (E1)
and counter electrode (E2). Comparing both, impedance distortions
) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 150.65.7.11 Downloaded on 2014-04-29 to IP
A136 Journal of The Electrochemical Society, 159 (2) A128-A136 (2012)
are indicated by inductive loops or by differing ohmic resistances for
E1 and E2.
To avoid errors introduced by a reference electrode we recom-
mend the application of symmetrical cells to analyze the impedance
response of the individual electrodes (anode or cathode) and full cells
exhibiting anode and cathode as shown in.
12, 13
However, location and
shape of the reference electrode will inuence the magnitude of the
observed effects. Therefore, we continue our studies with other ge-
ometries, especially a micro-reference electrode inserted between the
electrodes
15
is considered as subject of future works.
Abbreviations
AC alternating current
CPE constant phase element
DC direct current
E1, WE working electrode
E2, CE counter electrode
EIS electrochemical impedance spectroscopy
f
c
characteristic frequency of a RC element
FEM nite element method
FIB focused ion beam
OCV open circuit voltage
RC parallel circuit of a resistor and a capacitor
RE reference electrode
RMS root mean square
RQ parallel circuit of a resistor and a constant phase element
SEM scanning electron microscope
Acknowledgments
The German Federal Ministry of Education and Research (BMBF
PTJ-03SF0343H and BMBF PTJ-03KP801) is acknowledged for -
nancial support.
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