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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
N
X
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
66
Zre;i Zre xi ; ak
Zim;i Zim xi ; ak
; Dim;i
AZxi ; ak A
AZxi ; ak A
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
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.
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
68
4. Data deconvolution
A fast and reliable data analysis procedure is the subtraction method [8]. Recognizable parts of the overall
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]
[Ssn]
[Ssn]
Y0
n
Y0
n
Y0
n
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 m2s 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
11
12
70
Vstep
x
14
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.
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].
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
4
4D
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
72
Fig. 10. Arrhenius plot of the Gerischer parameters, k and Y0, for the Tbdoped YSZ sample (after Ref. [43]).
19
RTW
p k jx1=2
4F 2 cB D
20
Z0
1 jxa b
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
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]
[26]
[27]
[28]
[29]
[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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