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Solid State Ionics 169 (2004) 65 73

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Electrochemical impedance spectroscopy in solid state ionics:


recent advances
Bernard A. Boukamp *
Laboratory of Inorganic Materials Science, Faculty of Chemical Technology and MESA Research Institute, University of Twente, P.O. Box 217,
AE Enschede 7500, The Netherlands
Received 20 March 2003; received in revised form 16 May 2003; accepted 31 July 2003

Abstract
Electrochemical Impedance Spectroscopy (EIS) has become an important research tool in Solid State Ionics. Some new developments are
highlighted: new methods of automatic parameter extraction from impedance measurements are briefly discussed. The Kramers Kronig data
validation test presents another powerful tool in the impedance data analysis. The partial-fit and subsequent subtraction procedure, in
combination with the K K test, can lead to a more appropriate equivalent circuit model for the Complex Nonlinear Least Squares (CNLS)-fit
routine.
Very low frequency measurements ( < 1 mHz) are of significant interest for characterization of intercalation electrodes (anodes and
cathodes) for novel high energy density batteries. The low frequency impedances can be obtained by simple means through a carefully
conducted Fourier transform of the time domain relaxation data. Impedance analysis of thin film LixCoO2 cathodes shows that combination
of a Finite Length Warburg (FLW) with a Finite Space Warburg (FSW) is viable model for the Li+ diffusion process.
D 2004 Elsevier B.V. All rights reserved.
PACS: 66.10.Ed; 66.30.Hs; 72.20.-I; 84.37; 72.60.+g
Keywords: Impedance spectroscopy; Data analysis; Kramers Kronig Test; Fourier transform; Mixed conductivity

1. Introduction
Electrochemical Impedance Spectroscopy (or EIS) has
been developed basically in the field of wet electrochemistry.
In particular, the names of Sluyters, Sluyters-Rehbach [1,2]
(as well as many others) are strongly linked to this research
field. In contrast, single frequency experiments were still
common practice up to the 1970s in the emerging Solid State
Ionics community. At that time the notion developed that
many parallels exist between wet and all-solid electrochemical systems. Impedance measurements extending over several decades of frequency were slowly introduced, in many
cases by means of hand balanced capacitance resistance
bridges. At first simple graphical means were employed to
analyze the impedance responses (see Fig. 1), which was a
method of sufficient accuracy considering the relative simplicity of the research objectives at that time.
* Tel.: +31-53-489-2990; fax: +31-53-489-4683.
E-mail address: b.a.boukamp@tnw.utwente.nl (B.A. Boukamp).
URL: http://www.ims.tnw.utwente.nl.
0167-2738/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2003.07.002

But as the research in the field of Solid State Ionics


progressed, systems became more complex making graphical analysis cumbersome or even rather impossible. It was
soon realized that with the use of the emerging computer
technology it could be possible to optimize a model function
(or equivalent circuit) to the data set, thus yielding more
reliable system parameters. An important software tool is
the nonlinear least squares fitting method, developed by
Marquardt [3] and Levenberg [4], which became the basic
engine of several data analysis programs [5 7]. The Complex Nonlinear Least Squares (CNLS) method centers on
minimizing the object function S with respect to the parameters ak of the model function Z(x, ak):
S

N
X

wi fZre;i  Zre xi ; ak 2 Zim;i  Zim xi ; ak 2 g

i1

1
where Zre,i + jZim,i represent the measured impedance at
frequency xi and wi is the weight factor. An important
control tool is the distribution of the residuals versus

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B.A. Boukamp / Solid State Ionics 169 (2004) 6573

Fig. 1. Early days data analysis by graphical means.

frequency. Using function weighting the residuals are defined by:


Dre;i

Zre;i  Zre xi ; ak
Zim;i  Zim xi ; ak
; Dim;i
AZxi ; ak A
AZxi ; ak A

For a good match between data and model, the residuals


should be randomly distributed around the log( f) axis, see
Fig. 2A. Although the noise in the residuals in Fig. 2B is
much less, the clear trace around the horizontal axis indicates a mismatch between data and model.

2. Data analysis
The Marquardt Levenberg search algorithm is a combination of an analytical search and a steepest gradient
descent. The first part, which is based on a linearisation

through a Taylor series development [9], is (generally) fast


near the minimum in the object function, but erratic far from
the optimum. The steepest gradient descent ensures that the
iterative procedure converges for a less optimized initial
guess of the adjustable parameters.
In case the model function or equivalent circuit is well
known, appropriate estimates can be made for the ranges of
the model parameters. For complex circuits, however, the
starting values should be quite close to the optimal values,
in order to avoid convergence to a secondary minimum, or
worse, a program crash. Depending on the complexity, a
deviation of less than 50% may be required for the initial
guesses. Because of this limitation, some researchers have
preferred the more robust fit routine based on the Nelder and
Mead [10] algorithm [11] (also known as the Simplex
routine [12]), which does not put restrictions on the initial
parameter values.
For M independent parameters the Simplex method
searches the M + 1 dimensional function space with a
Simplex with M + 1 vertices. The Simplex is constructed
from a global initial set of parameters, ak (k = 1. . .M),
defining the first vertex. Initially each subsequent vertex is
derived from the first vertex by modifying one parameter at
a time by, e.g. a preset factor. Through contraction, expansion and reflection operations applied to the Simplex [12], it
searches for a minimum value in S, Eq. (1), which is found
when the Simplex collapses. The main problem with the
Simplex routine is that often a local minimum is encountered; hence, frequent restarts of the procedure are needed to
find the absolute minimum value in S.
2.1. Genetic algorithm

Fig. 2. Residuals graphs. (A) For a correct CNLS-fit to noisy data (or
Kramers Kronig transform test of correct but noisy data). (B) For an
incorrect CNLS-fit for low noise data (or Kramers Kronig transform test
for corrupted data). The pseudo-v2 value was f 4.6
10 6 in both cases.

The Genetic Algorithm (GA) alleviates the secondary


minimum problem. VanderNoot and Abrahams [13] were
the first to apply this optimization method to impedance
spectroscopy. Yang et al. [14] have elaborated this method
further, combining it with a Gauss Newton optimization

B.A. Boukamp / Solid State Ionics 169 (2004) 6573

procedure. The GA is used here to automatically provide an


adequate set of starting values for the final optimization. In
the GA-method, a large number of parameter sets (comparable to the vertices in the Simplex routine) are generated
using a random number generator in combination with welldefined parameter range limits. Hence, the entire relevant
parameter space is searched.
Each set of parameters represent the genes of an individual, XQt, within the generation t. A generation can be
made up of a hundred or more individuals. Each individual
is characterized by a fitness parameter, which is derived
from the object function, Eq. (1), see Ref. [14]. The higher
the fitness, the more likely the individual is close to the
optimum parameter set. A selection of individuals with the
highest fitness are kept separate, called a niche, and are used
to create a new generation by crossover operations in which
genes are exchanged by individuals (parents):
XAt1 aXBt 1  aXAt
XBt1 1  aXBt aXAt

Furthermore, regulated random mutations on the other


individuals will ensure that each new generation will continue to search the entire parameter space. After creation of a
new generation, the parameter set of the fittest individual is
used for a G N optimization procedure. This creation cycle
is continued until the G N procedure converges to the
optimum solution.
Yang et al. [14] have shown that, for two specific
examples, the GA GN combination is highly efficient in
automatically establishing the circuit parameters. The major
drawback is that the equivalent circuit, or complete transfer
function, must be known beforehand. Using the equivalent
circuit approach this can be achieved by the subtraction/
deconvolution procedure as outlined in Refs. [8,15] and
briefly addressed in the related section further down. But for
an experienced person, this deconvolution process will yield
at the same time quite optimized initial guesses for the
parameter values that can be used directly in a subsequent
CNLS-fit procedure.

3. Data validation
Sometimes it will be difficult to obtain an acceptable
match between measurement and model, as indicated by a
systematic distribution of the residuals along the log( f)-axis
in the error plot. The reason can be an inadequate model
function or data that is corrupted by a systematic deviation.
For example, a slowly changing or aging system, as is often
found in corrosion research, or through the use of too large
an excitation voltage, resulting in nonlinear effects, will
result in a corrupted data file. It is important to be able to
discern between bad data and an inappropriate model
function. The Kramers Kronig relations [16 18], which
are based on the principle of causality, present a very useful

67

tool for data validation. A data set that complies with the
Kramers Kronig transformation rules must be:
(i) causal, i.e. the measured response is solely due to the
applied (perturbation) signal.
(ii) a linear response, i.e. no higher frequency response may
be generated by the system. For inherently nonlinear
systems, like electrodes, this implies a small excitation
voltage (typically < 10 mV).
(iii) stable, the system may not change with time, nor
continue to oscillate after the excitation is stopped.
(iv) finite for all frequencies, including x ! 0 and x ! l.
The latter condition can be relaxed under certain conditions, as explained in Ref. [19]. The K K relations are
especially used to advantage to test condition (iii): stability.
The Kramers Kronig rule states that the imaginary part
of a dispersion is completely determined by the form of the
real part of the dispersion over the frequency range
0 V x V l. Similarly the real part is determined by the
imaginary dispersion form x = 0 to x = l, apart from a
constant value Rl or R0. These relations are expressed for
the real part of the impedance, Zre(x), by:
Z
2 l xZim x  xZim x
dx
4
Zre x Rl
p 0
x2  x2
where Rl = Zre(l). Or with a dc resistance, R0 = Zre(0), as
constant value:
Z
2x l x=xZim x  Zim x
dx
5
Ze x R0
p 0
x2  x2
The imaginary part, Zim(x), is obtained from the total real
dispersion by:
Z
2x l Zre x  Zre x
dx
6
Zim x
p 0
x2  x 2
For the admittance, a similar set of equations can be
presented. In literature sometimes the point x = x is referred
to as a singularity. A Taylor series expansion of the
numerator will show, however, that the integral function
possesses a finite value at x = x [19].
For a corrupted data set, the measured real part and
transformed imaginary part, Eqs. (4) and (5), will not match.
The same holds for the measured imaginary dispersion and
the transformed real part of Eq. (6). The major problem with
applying these transforms is that the integration must be
carried out from zero to infinite frequency, an experimental
impossibility. When the impedance reaches almost constant
real values at the limits of the frequency range the integration may be limited to the experimental frequency range,
although errors may still occur near the boundaries of the
frequency range [19] but almost always the impedances will
be far from zero (or from a constant value for the real part)
at the boundaries of the experimental frequency window.
Hence, the extensions to zero and infinite frequency have to

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B.A. Boukamp / Solid State Ionics 169 (2004) 6573

Fig. 3. Arrangement of (RC) circuits for a Kramers Kronig transformation


test. The corresponding time constants, sk = RkCk, are logarithmically
spaced in relation to the frequency range of the data.

be modeled. Several different routes have been followed to


accomplish this. Urquidi-Macdonald et al. [20] suggested
the use of polynomial extrapolation. When an end region
can be modeled by a single time constant, i.e. by a simple
equivalent circuit obtained through a partial CNLS-fit, a
more realistic extrapolation can be obtained, see Ref. [19].
A different method was developed by Agarwal et al.
[21], who modeled the impedance data with an equivalent
circuit consisting of a series arrangement of a set of parallel
RC circuits. The circuit parameters were obtained by CNLSfitting. If the residuals were still lying outside a preset error
limit, further parallel RC circuits were added to the equivalent circuit, until no significant improvement was obtained.
The disadvantage of this method lies in the repeated fitting
procedure and the rather large preset error limit.
A seemingly similar route was adopted by the author
[22]. Here also a series connection of parallel(RC)
circuits was used to model the data set, see Fig. 3. The
time constants associated with the RC circuits: sk = RkCk,
however, are fixed. The M time constants are logarithmically spaced over the inverse x range, with:
1
s1 x1
1 ; sM xN

where the subscript 1 refers to the first frequency of the data


set and N to the last frequency, with M < N. In this case, the
simulated impedance is represented by:


M
X
1
x i sk
Rk
j
8
Zxi Rl
1 x2i s2k
1 x2i s2k
k1

Fig. 4. Impedance diagram for a PZT-Pt composite material, (o) measured


data, (-n-) Kramers Kronig transform test result. Frequency range: 10 Hz
to 65 kHz.

dispersion are modeled with simple subcircuits over a


limited frequency range. Subtracting the dispersion of a
selected subcircuit will reveal contributions of other subcircuits or transfer functions that are not observable by
visual inspection of the measured data. Along this route a
possible equivalent circuit can be constructed, while at the
same time optimized parameter estimates are obtained for
the subsequent full CNLS-fit.
As an example the dispersion of a lead zirconate titanate
(PZT) platinum composite [23] is presented in Fig. 4 (open
circles). The Kramers Kronig transform test result, using
seven s-values/decade in Eq. (8), is presented by the closed
squares and continuous line. In the insert of Fig. 4, the
residuals plot shows a deviation of less than 0.1%, indicating
very high quality data. The electronic conduction and the
dielectric bulk response were estimated by a partial CNLS-fit
and subtracted in parallel to the overall dispersion. The
resulting impedance is presented in Fig. 5. This dispersion
can tentatively be interpreted as the ionic path, with a grain
boundary resistance and blocking electrodes. The full CNLS-

Adjusting this model to the original data set, i.e. minimizing


Eq. (1), is reduced to solving a linear set of equations, i.e.
performing a single matrix inversion. The Rk values, however, are not necessarily all positive, but a negative Rk value
is connected to a negative capacitance Ck, as all s-values are
by definition positive, and hence are in compliance with the
Kramers Kronig rules. A plot of the residuals, Eq. (2), of
the fit of the linear model to the data set will show whether
the data set complies with the K K rules. A clear trace
around the frequency axis, as demonstrated in Fig. 2B,
indicates that the data is corrupted.

4. Data deconvolution
A fast and reliable data analysis procedure is the subtraction method [8]. Recognizable parts of the overall

Fig. 5. Residual dispersion (ionic path) after parallel subtraction of the


dielectric response and the electronic conductivity from the dispersion in
Fig. 4. Frequency range: 10 Hz to 65 kHz.

B.A. Boukamp / Solid State Ionics 169 (2004) 6573


Table 1
CNLS-fit results for the dispersion of a PZT-Pt composite at 394 jC in air,
see Fig. 3
Parameter

Value

Error [%]

Dimension

Q1,
Q1,
R2
R3
R4
Q5,
Q5,
Q6,
Q6,

7.4
10 9
0.9686
5.3
18.6
159
1.48
10 8
0.776
1.51
10 8
0.884

0.5
0.04
0.02
1.8
6
3.6
0.7
12
2.3

[S sn]

[kV]
[kV]
[kV]
[S sn]

[S sn]

Y0
n

Y0
n
Y0
n

Equivalent circuit code: (Q1R2[R3(R4Q5)Q6]). The pseudo-v2 for the


CNLS-fit: 9.7
10 8, for the K K test: 1.3
10 8.

fit using this model (circuit description code: (QR[R(RQ)Q])


[7,24]) gave a pseudo-v2 value of 9.7
10 8, while a value
of 1.3
10 8 was found for the K K transform test. The K
K test result proved to be crucial in this analysis, as it
indicates that the CNLS-fit is not subjected to over-parameterization. A simple approach, based on visual inspection of
the impedance curve, would have ignored the grain boundary
contribution, resulting in a (QR[RQ]) circuit model. The
CNLS-fit using this simple circuit still yields an acceptable
pseudo-v2 value of 4.6
10 6, but produces a residual plot
as presented in Fig. 2B.
The parameters and error estimates for the full circuit are
presented in Table 1. It shows that the nine-parameter fit
presents a quite viable interpretation of the measured
impedance response. It must be realized, however, that other
equivalent circuits may also give identical fit results.

5. Low frequency measurements


The diffusion coefficient of the mobile ion in battery
electrodes is an important parameter determining the overall
electrode characteristics. For proper measurements of the
, or self-diffusion coefficient, D, generally a
chemical-, D
well-defined thin electrode film is used. Potential step or
current pulse experiments can be used to measure the
diffusion coefficients, but the analysis of the response is
often based on a simple diffusion only model. In the short
time approximation also double layer charging and charge
transfer through interface layers must be included, see e.g.
Ref. [25]. Using three-electrode impedance measurements,
direct information can be obtained on the various processes
that control the electrode properties. For one-dimensional
diffusion in a finite layer (thickness l) the diffusion impedance, or Finite Space Warburg (FSW), is given by:

  coth l p
jx=

D
VM dE
p
ZD x
9
nFS dy
jx D
where VM is the molar volume, S the surface area, [dE/dy] the
slope of the electrochemical titration curve and n is the
number of electrons transferred per ion. The finite length

69

effect (i.e. capacitive behavior) becomes noticeable for fre c 10 14 m2 s 1 and l c 1 Am,
/l2. With D
quencies: x < D
this frequency lies below 1.6 mHz, a frequency range which
is difficult to scan, as the current FRA-systems are quite
sensitive to interference from random signals and noise.
It is far simpler to measure the response in the time
domain after a steady state has been obtained, e.g. by
increasing the applied potential by a small step. The current
response can be measured over an extended period of time.
Especially for long times effective noise reduction can be
applied. Furthermore, this time domain method will also
clearly indicate the existence of self-discharge or corrosion
currents, i.e. a nonzero current for t ! l but it is not at all
necessary to perform the data analysis in the time domain. A
better method is to transform the time domain response to
the frequency domain, using simple Fourier Transforms,
thus combining the ease of time domain measurements with
the accuracy of frequency domain analysis with its generally
analytic expressions for the transfer functions (impedance/
admittance). Although several reports using this procedure
have appeared in literature [26 29] only few scientists
actually use this powerful method.
5.1. Time to frequency transfer
The Fourier transform of a data set, X(t), is given by:
Z l
Z l
X x
X t ejxt dt
X tcosxt  jsinxtdt
0

10
In case the measured quantity X(t) becomes equal to zero
within the measurement time limit, tN, the integration can be
restricted to t = tN. As the X(t) will only be available in
discrete values, the integration must be replaced by a
summation. The simplest approximation is calculating the
trapezoid area between point tk  1 and tk:
X xc

N
X
X tk cosxtk  X tk1 cosxtk1
tk  tk1
k1

j

X tk sinxtk  X tk1 sinxtk1


tk  tk1

11

This approximation works well in the low frequency


range. For the high frequency end of the transform, more
elaborated techniques are available [30]. In the case of finite
length diffusion, e.g. an intercalation electrode, it may be
assumed that for very long times the current decay follows
an exponential drop. This can be used to model the missing
data for the period tN ! l. If at the same time a (constant)
corrosion type current takes place, like slow electrolyte
decomposition, then this can be modeled as well:
X t X0 X1 et=s

12

By fitting this function to a limited set data points in the end


region, the parameters X0, X1 and s can be estimated. It is

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B.A. Boukamp / Solid State Ionics 169 (2004) 6573

potential steps. After each 10 mV step, the current response


was monitored over a period of 3 h. The voltage step was
assumed to be instantaneous; hence, its Fourier transform is
given by:
V x j

Fig. 6. Impedance dispersions obtained from Fourier transform of potential


step response data for a thin layer LixCoO2 electrode [31,32]. Open squares:
transform truncated at t = tN, closed circles: with exponential decay
extrapolation.

most convenient to remove the constant current (X0) from


the data set before the discrete Fourier transformation is
performed. In addition to the summation of Eq. (11) the
transform of X1e t/s is calculated:
Z l
X1 t ejxt dt X1 et=s
tN

s1 cosxtN  xsinxtN jxcosxtN s1 sinxtN


13
x2 s2

An example of this procedure is presented in Fig. 6. A thin


LixCoO2 electrode [31,32] was subjected to sequential

Vstep
x

14

Fig. 6 (open squares) shows the Fourier transform


using Eq. (11), but with the constant current term removed. The low frequency part shows quite a bit of
scatter, but clearly indicates capacitive behavior. The
closed circles in Fig. 6 present the full Fourier transform,
including Eq. (13). The polarization dependent leakage
current, X0, coincided nicely with a separately measured
leakage current. Fig. 7 presents the development of the
overall electrode impedance (at 50 mV intervals) obtained
from Fourier transformed potential step data measured
with 10 mV steps.

6. New approach to modeling mixed conductivity


The low frequency electrode impedance of Fig. 6 does
not fit the basic FSW dispersion, Eq. (9). Jamnik et al.
[33,35] have recently developed a modeling procedure for
mixed conducting materials. This method is based on a
discretization of the charge transport and charge storage
mechanisms using a network model with separate rails for
ionic and electronic transport, see Fig. 8. They have
shown that for electrodes where ionic and electronic
conductivities become comparable, both must be included
in the impedance model. Model analysis then yields the

Fig. 7. Development of the low frequency impedance for a thin layer LixCoO2 electrode as function of the applied polarization [32]. Impedances at 50 mV
intervals are shown, potential step is 10 mV.

B.A. Boukamp / Solid State Ionics 169 (2004) 6573

71

Fig. 8. (A) Schematic representation of the discretization of the diffusion and redox processes in an intercalation electrode (after Jamnik [35]). Cd represents the
chemical (redox) capacitance, Cq the dielectric capacitance. (B) Schematic representation of the equivalent circuit for (A), see Eq. (15). For further details, see
Refs. [33 35].

complete finite length diffusion impedance for one-dimensional transport:


Zx

R?
Ri Re
1 Ri  Re 2
Li

?
4 Ri Re
Ri Re 1 jxR?
Li C
p
p
tanh jxs 1
coth jxs

p Ri Re p
jxs
4
jxs

15

with the time constant, s:


L2
1
s
Ri Re Cchem:

4
4D

type electrode reaction [38]. The impedance expression was


presented by Sluyters-Rehbach [39,40] in 1960s, but apparently an actual Gerischer type response was not observed
until the late 1980s [41]. Recently quite a few reports have
emerged that describe a Gerischer type frequency response
[42 44]. An example for Tb-doped yttria stabilized zirconia
(Tb-YSZ) is presented in Fig. 9. In its most simple form, the
Gerischer element can be expressed by:
Z0
ZG x p
k jx

16

Eq. (15) requires that the arguments for the coth() (Finite
Space Warburg) and tanh() (Finite Length Warburg, or FLW)
functions are exactly the same. Although the analysis
showed that in quite a number of data sets, presented in
Fig. 7, a good fit could be obtained using this FSW FLW
combination, the arguments were significantly different. Yet
it provides a more physical base for the interpretation than
the generally used Frumkin and Melik-Gaykazyan model
[36], which combines a FLW diffusion element in series with
the electrochemical capacitance, Cchem..
Diard et al. [37] have presented a different explanation for
the nonideal diffusion response. They assumed a distribution
in the diffusion length, l. Simulations based on these separate
parallel diffusion paths also presented a more physical
interpretation of the observed electrode impedances.

17

where k is the reaction rate for the chemical reaction in the


CE process. Eq. (17) can simply be derived from Ficks
second law by incorporating a sink term:
2
dDc
d Dc  k Dc
D
18
dt
dx2
where Dc represents the excess concentration, or the acperturbation of the concentration. For the terbium doped

7. New transfer functions, the Gerischer


The number of available elements (or transfer functions)
seems to be rather limited. Most of these have been known
since a long time. A special case is the Gerischer impedance, which was derived in 1950s by Gerischer for a CE-

Fig. 9. Impedance of a Tb-doped YSZ mixed conducting oxide, after


Ref. [43]. The low frequency dispersion is modeled with a Gerischer
type expression (continuous line). Frequency range 10 mHz 65 kHz,
pO2 = 0.2 atm.

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B.A. Boukamp / Solid State Ionics 169 (2004) 6573

developments cannot be discussed in detail, but will be


presented here very briefly:


Fig. 10. Arrhenius plot of the Gerischer parameters, k and Y0, for the Tbdoped YSZ sample (after Ref. [43]).

yttria stabilized zirconia system (Tb-YSZ) [43], the sink


term is tentatively interpreted as oxygen vacancy immobilization through complex formation with the trivalent
cations:
VOSS MZr
V ZVO MZr S ; with M Tb; Y

19

Further combination with Ficks first law for the electrode/


electrolyte response and under the assumption that
bl2the resulting impedance for the ionic part of the
D
resistance becomes [43]:
Zx

RTW
p k jx1=2
4F 2 cB D

20

The temperature dependence of the Gerischer parameters,


G  Y0 and k, is presented in Fig. 10, which shows a quite
consistent behavior.
The important result is that this dispersion has become
independent of the sample thickness. In fact the Gerischer
represents a finite dc-resistance for a semi-infinite diffusion
situation. Data analysis clearly indicates that in practice
fractal exponents also apply to the Gerischer impedance
[45]. Hence, Eq. (17) can be presented in a more general
way by:
ZG x

Z0
1 jxa b

The finite element method is a powerful tool for


calculating or simulating impedance spectra for systems
in which complex geometries play an important role.
Examples are grain/grain-boundary conduction (Fleig et
al. [47,48]), influence of porous or badly adhering
electrodes on electrode dispersion [49], or the influence
of misalignment of the working and counter electrodes
and the placement of the reference electrodes in a three
electrode cell (Adler [50]). The importance is that with
the finite element modeling the change and shift in the
current distribution can be followed as function of
frequency.
Single grain boundary impedance spectra can be obtained
by micro-contacting impedance spectroscopy [51,52].
Especially for grain boundaries with a relatively high
conductivity, this is the only means of studying its
electrochemical behavior.
But also the preparation and study of geometrically welldefined electrodes, which can be seen as almost ideal
electrodes, represents an important advancement in
understanding the electrode properties of SOFC electrodes (Brichzin et al. [53]).
The complex electrode processes of adsorption, diffusion, dissociation and charge transfer at solid electrolyte/
gas phase electrode interface can be modeled using the
Langmuir isotherm adsorption formalism as introduced
by Epelboin [54]. Based on this concept Van Hassel et al.
[55] have presented an impedance model for the oxygen
transfer at a YSZ/Au electrode system. Bieberle and
Gauckler [56] have extended it recently to the more
complex SOFC anode processes in an H2/H2O ambient
(State-Space modeling).
The introduction of the Constant Phase Element (or CPE,
Bottelberghs and Broers [57]) at the Solid State Ionics
Conference in Schenectady (1975) has roused an intense
debate. Based on the principle of fractals, Le Mehaute
and Crepy [58] were the first to present some degree of
understanding for the electrode response CPE. With
respect to the CPE type dielectric or bulk response
recently an interesting modeling has been presented by
Funke et al. with their concept of mismatch and
relaxation [59,60].

21

which bears a striking resemblance with the phenomenological Havriliak Negami dielectric response function [46].

8. Discussion
Unfortunately it is impossible to be complete on this
subject in the allotted printing space. Several important

9. Conclusion
Several advances in EIS for solid state ionics have been
presented. Kramers Kronig data validation is of great importance in the data analysis procedure for complex systems.
New optimization techniques allow automatic parameter
estimations, but the subtraction/deconvolution system provides more insight in minor contributions to the overall
dispersion. Frequency domain analysis is in general to be

B.A. Boukamp / Solid State Ionics 169 (2004) 6573

preferred over time domain analysis. Time domain measurements, followed by Fourier transformation, present a simple
means of extending the frequency range below the mHz limit.
New modeling techniques, using discretization of the
charge transport and transfer processes result in enhanced
understanding of the complex frequency responses of mixed
conducting systems. Thorough analysis of the measured
impedance data can result in the finding of surprising
response functions, although some of these have already
been derived from theoretical considerations.
Final remark: although there are distinct differences
between solid state and wet electrochemistry, much is to
be learned from the, sometimes surprising, similarities.

[24]
[25]
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[27]
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[30]
[31]
[32]

Acknowledgements
The author is indebted to Dr. Peter Bouwman and Miss
Mai Pham for their help in providing excellent demonstration examples.

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