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www.elsevier.com/locate/ssi

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

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

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

Dre;i

Zre;i Zre xi ; ak

Zim;i Zim xi ; ak

; Dim;i

AZxi ; ak A

AZxi ; ak A

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

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.

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

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

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

68

test. The corresponding time constants, sk = RkCk, are logarithmically

spaced in relation to the frequency range of the data.

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

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

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

to 65 kHz.

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-

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

dielectric response and the electronic conductivity from the dispersion in

Fig. 4. Frequency range: 10 Hz to 65 kHz.

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]

[Ssn]

[Ssn]

Y0

n

Y0

n

Y0

n

CNLS-fit: 9.7

10 8, for the K K test: 1.3

10 8.

[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.

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 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

tk tk1

11

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

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

70

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

step response data for a thin layer LixCoO2 electrode [31,32]. Open squares:

transform truncated at t = tN, closed circles: with exponential decay

extrapolation.

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

13

x2 s2

LixCoO2 electrode [31,32] was subjected to sequential

Vstep

x

14

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.

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.

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].

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

L2

1

s

Ri Re Cchem:

4

4D

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

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

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-

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.

72

presented here very briefly:

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

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

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

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

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

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.

References

[33]

[34]

[35]

[36]

[37]

[38]

[39]

[40]

[1] M. Sluyters-Rehbach, J.H. Sluyters, in: A.J. Bard (Ed.), Electroanalytical Chemistry, vol. 4, Marcel Dekker, New York, 1970,

pp. 1 127.

[2] M. Sluyters-Rehbach, J.H. Sluyters, in: E. Yaeger, J.OM. Bockris,

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