ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY.

Introduction.
Electrochemical impedance spectroscopy is a recent tool in
corrosion and solid state laboratories that is slowly making its way into
the service environment as units are decreased in size and become
portable. Impedance Spectroscopy is also called AC Impedance or
just Impedance Spectroscopy.
The usefulness of impedance spectroscopy lies in the ability to
distinguish the dielectric and electric properties of individual
contributions of components under investigation.

Most of the material displayed in this lecture is taken from:

http://www.gamry.com/App_Notes/EIS_Primer/EIS_Primer.htm

ELECTROCHEMICAL IMPEDANCE
SPECTROSCOPY
For example, if the behavior of a coating on a metal when in salt water is
required, by the appropriate use of impedance spectroscopy, a value of
resistance and capacitance for the coating can be determined through
modeling of the electrochemical data. The modeling procedure uses electrical
circuits built from components such as resistors and capacitors to represent
the electrochemical behavior of the coating and the metal substrate. Changes
in the values for the individual components indicate their behavior and
performance.
Impedance spectroscopy is a non-destructive technique and so can provide
time dependent information about the properties but also about ongoing
processes such as corrosion or the discharge of batteries and e.g. the
electrochemical reactions in fuel cells, batteries or any other electrochemical
process.

ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY.

Below is a listing of the advantages and disadvantages of the technique.

Advantages.
1. Useful on high resistance materials such as paints and coatings.
2. Time dependent data is available
3. Non- destructive.
4. Quantitative data available.
5.Use service environments.
Disadvantages.
1. Expensive.
2. Complex data analysis for quantification.

Five major topics are covered in this

application note

1. AC Circuit Theory and Representation of Complex Impedance Values.

2. Physical Electrochemistry and Circuit Elements.
3. Common Equivalent Circuit Models.
4. Extracting Model Parameters from Impedance Data.
5. Case studies

AC Circuit Theory and Representation of Complex

Impedance Values
Impedance definition: concept of complex impedance
Ohm's law defines resistance in terms of the ratio between voltage E and current
I.

E (t )
I (t )

The relationship is limited to only one circuit element -- the ideal resistor.
An ideal resistor has several simplifying properties:

It follows Ohm's Law at all current and voltage levels

It's resistance value is independent of frequency.
AC current and voltage signals though a resistor are in phase with each other

Real World:

Circuit elements that exhibit much more complex behavior. These elements
force us to abandon the simple concept of resistance. In its place we use
impedance, which is a more general circuit parameter.
Like resistance, impedance is a measure of the ability of a circuit to resist
the flow of electrical current. Unlike resistance, impedance is not limited by
the simplifying properties listed above.

Electrochemical impedance is usually measured by applying an AC potential

to an electrochemical cell and measuring the current through the cell.

Suppose that we apply a sinusoidal potential excitation. The response to

this potential is an AC current signal, containing the excitation frequency
and it's harmonics. This current signal can be analyzed as a sum of
sinusoidal functions (a Fourier series).

Electrochemical Impedance is normally measured using a small excitation

signal. This is done so that the cell's response is pseudo-linear. Linearity is
described in more detail in a following section. In a linear (or pseudo-linear)
system, the current response to a sinusoidal potential will be a sinusoid at
the same frequency but shifted in phase.

Sinusoidal Current Response in a Linear

System

The excitation signal, expressed as a function of time, has the

form of:

E (t ) E0 cos(t )

E(t) is the potential at time tr Eo is the amplitude of the signal, and is the
radial frequency. The relationship between radial frequency (expressed in
radians/second) and frequency f (expressed in Hertz (1/sec).

=2 f

Impedance as a Complex Number

Z(,Vo) = V() / I()
The impedance at any frequency is a complex number because I()
contains phase information as well as magnitude
- the AC current may have a phase lag with respect to the AC voltage
If we apply V=Vo + V xcos( t)

and measure I = Io + I cos( t- )

Then:
Z(,Vo) = (V / I ) x{cos() + i sin()}
where i2 = -1
and both magnitude and phase of the impedance, Z and vary with

Response in a linear System

In a linear system, the response signal, the current I(t), is shifted in phase
() and has a different amplitude, I0:
I (t ) I 0 cos(t )

An expression analogous to Ohm's Law allows us to calculate the

admittance (=the AC resistance) of the system :
E0 cos(t )
E (t )
cos(t )
Z (t )

Z0
I (t ) I 0 cos(t )
cos(t )
The impedance is therefore expressed in terms of a magnitude, Z0, and a
phase shift, f.
This admittance may allso be written as complex function:

Measure Z(,Vbias)

The result will be Z(,Vo) = V() / I()

Response dI of dE from the Current (I)/Field

(E) relation:
Let us assume we have an electrical element to which we apply an
electric field E(t) and get the response I(t), then we can disturb this
system at a certain field E with a small perturbation dE and we will get at
the current I a small response perturbation dI. In the first approximation,
as the perturbation dE is small, the response dI will be a linear response
as well (mirror at the tangent oft the I(E) curve!

If we plot the applied sinusoidal signal

on the X-axis of a graph and the
sinusoidal response signal I(t) on the
Y-axis, an oval is plotted. This oval is
known as a "Lissajous figure".
Analysis of Lissajous figures on
oscilloscope screens was the
accepted method of impedance
measurement prior to the availability
of lock-in amplifiers and frequency
response analyzers.

Complex writing
Z (t )

E0 cos(t )
E (t )
cos(t )

Z0
I (t ) I 0 cos(t )
cos(t )

Using Eulers relationship exp(i ) cos i sin

it is possible to express the impedance as a complex
function. The potential is described as,

E (t ) E0 exp( jt )

and the current response as,

I (t ) I 0 exp(it i )

The impedance is then represented as a complex number,

Z Z 0 exp(i ) Z 0 (cos i sin )

Data Presentation:
Nyquist Plot with Impedance Vector
Z

E
Z 0 exp(i ) Z 0 (cos i sin )
I

Look at the Equation above. The expression for Z() is composed of a real and an imaginary
part. If the real part is plotted on the X axis and the imaginary part on the Y axis of a chart, we
get a "Nyquist plot".
Notice that in this plot the y-axis is negative and that each point on the Nyquist plot is the
impedance Z at one frequency.

1 1
1

Z R iC

On the Nyquist plot the impedance can be

represented as a vector of length |Z|. The angle
between this vector and the x-axis is f.
Nyquist plots have one major shortcoming. When
you look at any data point on the plot, you cannot
tell what frequency was used to record that point.
Low frequency data are on the right side of the
plot and higher frequencies are on the left. This is
true for EIS data where impedance usually falls as
frequency rises (this is not true of all circuits).

The Nyquist plot the results from the RC circuit. The semicircle is
characteristic of a single "time constant". Electrochemical Impedance plots
often contain several time constants. Often only a portion of one or more
of their semicircles is seen.

The Bode Plot

1 1
1

Z R iC

Another popular presentation method is the "Bode plot". The impedance

is plotted with log frequency on the x-axis and both the absolute value
of the impedance (|Z| =Z0 ) and phase-shift on the y-axis.
The Bode plot for the RC circuit is shown below. Unlike the Nyquist plot,
the Bode plot explicitly shows frequency information.

The different views on impedance data

The impedance data are the red points.
Their projection onto the Z-Z plane is called the Nyquist plot
The projection onto the Z- plane is called the Cole Cole diagram

Z
am
r
g
ia
d
e
ol
C
le
Co

Nyqui
st plot

de
o
B

t
o
l
p

Electrochemistry - A Linear System?

Electrical circuit theory distinguishes between linear and non-linear systems
(circuits). Impedance analysis of linear circuits is much easier than analysis of
non-linear ones.
A linear system ... is one that possesses the important property of superposition:
If the input consists of the weighted sum of several signals, then the output is
simply the superposition, that is, the weighted sum, of the responses of the
system to each of the signals.
Mathematically, let y1(t) be the response of a continuous time system to x1(t)
ant let y2(t) be the output corresponding to the input x2(t).
Then the system is linear if:
1)The response to x1(t) + x2(t) is y1(t) + y2(t)
2) The response to ax1(t) is ay1(t) ...

Current versus Voltage Curve Showing

Pseudo-linearity
For a potentiostated electrochemical cell, the
input is the potential and the output is the
current.
Electrochemical cells are not linear! Doubling
the voltage will not necessarily double the
current.
However, we will show how electrochemical systems can be pseudolinear. When you look at a small enough portion of a cell's current versus
voltage curve, it seems to be linear.
In normal EIS practice, a small (1 to 10 mV) AC signal is applied to the
cell. The signal is small enough to confine you to a pseudo-linear
segment of the cell's current versus voltage curve. You do not measure
the cell's nonlinear response to the DC potential because in EIS you only
measure the cell current at the excitation frequency.

Steady State Systems

Measuring an EIS spectrum takes time (often many hours). The system
being measured must be at a steady state throughout the time
required to measure the EIS spectrum.
A common cause of problems in EIS measurements and their analysis is
drift in the system being measured.
In practice a steady state can be difficult to achieve. The cell can
change through adsorption of solution impurities, growth of an oxide
layer, build up of reaction products in solution, coating degradation,
temperature changes, to list just a few factors.
Standard EIS analysis tools may give you wildly inaccurate results on a
system that is not at a steady state

Time and Frequency Domains and

Transforms
Signal processing theory refers to data domains. The same data can be
represented in different domains.
In EIS, we use two of these domains, the time domain and the
frequency domain.
In the time domain, signals are represented as signal amplitude versus
time. The Figure demonstrates this for a signal consisting of two
superimposed sine waves.
Two Sine Waves in the Time Domain

Time and frequency domain

Amplitude

The figures show the same data of the two sinus waves in the time and the frequency
domain.
Two Sine Waves in
the Time Domain

Time

Amplitude

Two Sine Waves in the

Frequency Domain

Frequency

Use the Fourier transform and inverse Fourier transform to switch between the domains. The
common term, FFT, refers to a fast, computerized implementation of the Fourier transform.
Detailed discussion of these transforms is beyond the scope of this manual. Several of the
references given at the end of this chapter contain more information on the Fourier transform
and its use in EIS.
In modern EIS systems, lower frequency data are usually measured in the time domain.
The controlling computer applies a digital approximation to a sine wave to the cell by means
of a digital to analog converter. The current response is measured using an analog to digital

Electrical Circuit Elements

EIS data is commonly analyzed by fitting it to an equivalent electrical circuit model. Most of
the circuit elements in the model are common electrical elements such as resistors,
capacitors, and inductors. To be useful, the elements in the model should have a basis in the
physical electrochemistry of the system. As an example, most models contain a resistor that
models the cell's solution resistance.
Some knowledge of the impedance of the standard circuit components is therefore quite
useful. The Table lists the common circuit elements, the equation for their current versus
voltage relationship, and their impedance:

Component

Current
Vs.Voltage

Impedance

resistor

E= IR

Z=R

inductor

E = L di/dt

Z = iL

capacitor

I = C dE/dt

Z = 1/iC

Notice that the impedance of a resistor is independent of frequency and has only a real
component. Because there is no imaginary impedance, the current through a resistor is
always in phase with the voltage.
The impedance of an inductor increases as frequency increases. Inductors have only an
imaginary impedance component. As a result, an inductor's current is phase shifted 90
degrees with respect to the voltage.
The impedance versus frequency behavior of a capacitor is opposite to that of an inductor. A
capacitor's impedance decreases as the frequency is raised. Capacitors also have only an
imaginary impedance component. The current through a capacitor is phase shifted -90

Serial and Parallel Combinations of

Circuit Elements

Very few electrochemical cells can be modeled using a single equivalent circuit element.
Instead, EIS models usually consist of a number of elements in a network. Both serial and
parallel combinations of elements occur.

Impedances in Series:
Impedances in Parallel

Z eq Z1 Z 2 Z3
1 1 1 1

Z eq Z1 Z 2 Z3

Serial and Parallel Combinations of Circuit

Elements
Suppose we have a 1 and a 4 resistor is series. The impedance of a
resistor is the same as its resistance (see Table 2-1). We thus calculate the total
impedance Zeq:

R1

R2

Z eq Z1 Z 2 R1 R 2 1 4 5

Resistance and impedance both go up when resistors are combined in series.

Now suppose that we connect two 2 F capacitors in series. The total capacitance
of the combined capacitors is 1 F

C1

C2

1
1
1
Z1 Z 2

Z eq
iC1 iC2

1
1
1

1 F
6
6
e 6
i (2e ) i (2e ) i (1 )

Impedance goes up, but capacitance goes down when capacitors are connected in
series.
This is a consequence of the inverse relationship between capacitance and

Example: The Zn Air battery

There are three reactions:
1.The reaction at the anode between
metal ions and electrons :

2Zn 2Zn 2 4e
2.The reaction at the cathode between
water and electrons

O2 4 H 4e 2 H 2O
3.The reaction of the whole cell, i.e. the
two half-cell reactions added together:

2Zn O2 4 H 2 Zn 2 2 H 2O

An electrochemical cell: The Zn Air

battery

2 Zn 2Zn 2 4e
O2 4 H 4e 2 H 2O

2 Zn O2 4 H 2Zn 2 2 H 2O

For each of these reactions it is true that:

where:

n y
a
Y
G is the free energy change of the reaction.
Y
G0 is what the free energy change would be if every component were in its standard
G G0 RT ln

nx
a
X
X

state.
ax is the activity of reaction product X and ay is the activity of reactant Y.
nx is the stoichiometric coefficient of reaction product X, and likewise for the reactants.
(The stoichiometric coefficient is the number of that molecule that are involved in the
reaction; for the whole-cell reaction written above, the stoichiometric coefficient of water is
2, and of oxygen gas is 1.)
R is the ideal gas constant and T is the temperature.
The symbol is the multiplying equivalent of : all the terms after it are multiplied
together.

An electrochemical cell: The Zn Air

battery
Equilibrium
If a reaction is at equilibrium, G=0 , and the free energy G of the system is at a
minimum with respect to how much of the reactants have been converted to products.
When this is the case, we obtain:

a
a

nx
X

k
n y
Y

where K is the equilibrium constant.

Thus we can deduce that G0 =RTlnk ; this is true of a reaction whether it is at
equilibrium or not. (G0 for a reaction is determined by the energies of the bonds within
the molecules of the reactants and products, and this is independent of how many such
molecules there are per unit volume.)

The Zn Air battery: An electrochemical

cell
The cathode reaction is at equilibrium if there is no power supply connected to the circuit. It
can do this because each atom or ion has enough energy to undergo the reaction in either
direction; there is nothing stopping it being at equilibrium. The anode reaction is also at its
own equilibrium.
The reaction for the whole cell is not at equilibrium. There is too much of an energy barrier for
it to be able to get there the ions have to diffuse through the electrolyte and the electrons
have to go around through the wires. (Or through a high impedance voltmeter, which they
almost certainly cannot do.)
Thus for the example given:

aZn2 aH2 pO1/22

G G0 RT ln

aZn aH O
2

G 0 and the quotient is not the equilibrium constant but equal to the electric
potential. We can convert this into an expression for the electrical potentials using
the general rule:

G zFE

where z is the stoichiometric number of electrons in the reaction. (This is due to

Faradays law)

An electrochemical cell: The Zn Air

battery
In this form we have the Nernst equation for the cell and :
2
1/ 2

a
a
p
2

O
Ee E 0 RT ln Zn H 2
aZn aH O
2

The activities of Zn and water are one, because Zn is in its standard state and the water is so
much more abundant than its solutes that it may as well be in its standard state. Thus:

Ee E 0 RT ln aZn2 aH2 pO1/22

E0 is the equilibrium potential it is the potential of the whole cell when the electrodes are at
equilibrium within themselves.
It can be worked out (easily, using algebra with a pen and pencil) that:

RT
ln k
zF
where K is the equilibrium constant i.e. if we were at equilibrium over the whole
electrochemical cell, then E would be zero. E0 is a property of the system like that G0 , and is
still equal to the same number even when the whole cell is not at equilibrium. If for some reason
it was required to find the value of E0 , we could use this expression. E0 is called the standard
electrode potential.
E0

Physical Electrochemistry and Equivalent Circuit

Elements
Electrolyte Resistance:

Electrolyte resistance is often a significant factor in the impedance of an

electrochemical cell. A modern 3 electrode potentiostat compensates for the
solution resistance between the counter and reference electrodes. However, any
solution resistance between the reference electrode and the working electrode
must be considered when you model your cell.
The resistance of an ionic solution depends on the ionic concentration, type of ions,
temperature and the geometry of the area in which current is carried. In a bounded
area with area A and length l carrying a uniform current the resistance is defined
as:
l

A
where r is the solution resistivity.
The conductivity of the solution, , is more commonly used in solution resistance calculations.
Its relationship with solution resistance is:
1 l
l
R=

A
RA

The electrolyte resisatnce

Standard chemical handbooks list values for specific solutions. For
other solutions and solid materials, you can calculate from specific ion
conductances. The units for are Siemens per meter (S/m). The
Siemens is the reciprocal of the ohm, so 1 S = 1/ohm
Unfortunately, most electrochemical cells do not have uniform current
distribution through a definite electrolyte area. The major problem in
calculating solution resistance therefore concerns determination of the
current flow path and the geometry of the electrolyte that carries the
current. A comprehensive discussion of the approaches used to
calculate practical resistances from ionic conductances is well beyond
the scope of this manual.
Fortunately, you don't usually calculate solution resistance from ionic
conductances. Instead, it is found when you fit a model to experimental
EIS data.

Double
Layer
Capacitance
A electrical double layer exists at the interface between an electrode and its
surrounding electrolyte.
This double layer is formed as ions from the solution "stick on" the electrode surface.
Charges in the electrode are separated from the charges of these ions. The separation
is very small, on the order of angstroms.
Charges separated by an insulator form a capacitor. On a bare metal immersed in an
electrolyte, you can estimate that there will be approximately 30 F of capacitance for
every cm2 of electrode area.
The value of the double layer capacitance depends on many variables including
electrode potential, temperature, ionic concentrations, types of ions, oxide layers,
electrode roughness,
impurity
adsorption,
Principle
of the
Electricetc.
Double-Layer: Here C electrodes

Polarization Resistance
Whenever the potential of an electrode is forced away from it's value at open circuit,
that is referred to as polarizing the electrode.
When an electrode is polarized, it can cause current to flow via electrochemical
reactions that occur at the electrode surface. The amount of current is controlled by
the kinetics of the reactions and the diffusion of reactants both towards and away
from the electrode.
In cells where an electrode undergoes uniform corrosion at open circuit, the open
circuit potential is controlled by the equilibrium between two different
electrochemical reactions.
One of the reactions generates cathodic current and the other anodic current. The
open circuit potential ends up at the potential where the cathodic and anodic
currents are equal. It is referred to as a mixed potential. The value of the current for
either of the reactions is known as the corrosion current.

The Butler Volmer equation: For the

polarization resistance of simple
reactions at electrodes
When there are two simple, kinetically controlled reactions occurring, the potential of the cell is
related to the current by the following (known as the Butler-Volmer equation).

I is the measured cell current in amps,

Icorr is the corrosion current in amps,
Eoc is the open circuit potential in volts,
a is the anodic Beta coefficient in volts/decade,
c is the cathodic Beta coefficient in volts/decade
If we apply a small signal approximation (E-Eoc is small) to the buler Volmer equation, we get the
following:

which introduces a new parameter, R p, the polarization resistance. As you might guess from its name, the
polarization resistance behaves like a resistor.
If the Tafel constants i are known, you can calculate the I corr from Rp. The Icorr in turn can be used to calculate
a corrosion rate.
We will further discuss the R parameter when we discuss cell models.

Charge Transfer Resistance

A similar resistance is formed by a single kinetically controlled electrochemical reaction. In
this case we do not have a mixed potential, but rather a single reaction at equilibrium.
Consider a metal substrate in contact with an electrolyte. The metal molecules can
electrolytically dissolve into the electrolyte, according to:
or more generally:
In the forward reaction in the first equation, electrons enter the metal and metal ions diffuse
into the electrolyte. Charge is being transferred.
This charge transfer reaction has a certain speed. The speed depends on the kind of
reaction, the temperature, the concentration of the reaction products and the potential.
The general relation between the potential and the current holds:

io = exchange current density

Co = concentration of oxidant at the electrode
surface
Co* = concentration of oxidant in the bulk
CR = concentration of reductant at the electrode

F = Faradays constant
T = temperature
R = gas constant
a = reaction order
n = number of electrons involved
h = overpotential ( E - E0 )

Overvoltage potential

The overpotential, h, measures the degree of polarization. It is the electrode

potential minus the equilibrium potential for the reaction.
When the concentration in the bulk is the same as at the electrode surface, Co=Co*
and CR=CR*. This simplifies the last equation into:

This equation is called the Butler-Volmer equation. It is applicable when the

polarization depends only on the charge transfer kinetics.
Stirring will minimize diffusion effects and keep the assumptions of C o=Co* and
CR=CR* valid.
When the overpotential, h, is very small and the electrochemical system is at
equilibrium, the expression for the charge transfer resistance changes into:

From this equation the exchange current i0 density can be calculated when Rct is
known.

Diffusion: Warburg impedance with infinite

thickness
Diffusion can create an impedance
known as the Warburg impedance. This

impedance depends on the frequency of the potential perturbation. At high

frequencies the Warburg impedance is small since diffusing reactants don't have
to move very far. At low frequencies the reactants have to diffuse farther, thereby
increasing the Warburg impedance.
The equation for the "infinite" Warburg impedance

On a Nyquist plot the infinite Warburg impedance appears as a diagonal line with a
slope of 0.5. On a Bode plot, the Warburg impedance exhibits a phase shift of 45.
In the above equation, s is the Warburg coefficient defined as:

= radial frequency
DO = diffusion coefficient of the oxidant
DR = diffusion coefficient of the reductant
A = surface area of the electrode
n = number of electrons transferred
C* = bulk concentration of the diffusing species (moles/cm3)

Coating Capacitance
A capacitor is formed when two conducting plates are separated by a non-conducting
media, called the dielectric. The value of the capacitance depends on the size of the
plates, the distance between the plates and the properties of the dielectric. The
relationship is:
A
C 0 r
d
With,
o = electrical permittivity
r = relative electrical permittivity
A = surface of one plate
d = distances between two plates
Whereas the electrical permittivity is a physical constant, the relative electrical permittivity
depends on the material. Some useful r values are given in the table:
Materia r
l
vacuum 1
water

80.1 ( 20 C )

organic 4 - 8
coating
Notice the large difference between
the electrical permittivity of water and that of an organic

coating. The capacitance of a coated substrate changes as it absorbs water. EIS can be used
to measure that change

Constant Phase Element (for double layer

capacity in real electrochemical cells)

Capacitors in EIS experiments often do not behave ideally. Instead, they act like a constant
phase element (CPE) as defined below.

Z A(i )
When this equation describes a capacitor, the constant A = 1/C (the inverse of the
capacitance) and the exponent = 1. For a constant phase element, the exponent a is less
than one.
The "double layer capacitor" on real cells often behaves like a CPE instead of like a capacitor.
Several theories have been proposed to account for the non-ideal behavior of the double
layer but none has been universally accepted. In most cases, you can safely treat as an
empirical constant and not worry about its physical basis.

Common Equivalent Circuit Models

In the following section we show some common equivalent circuits models.
To elements used in the following equivalent circuits are presented in the Table.
Equations for both the admittance and impedance are given for each element.
Equivalent
element
R
C
L
W (infinite
Warburg)
O (finite
Warburg)
Q (CPE)

Admittance

Impedance

1/R

iC

1/1/iC

1/iL

iL

Y0(i)1/2

1/Y0(i)1/2

Y0 i coth( B i )
Y0(i)

tanh( B i ) / Y0 i
1/Y0(i)

A Purely Capacitive Coating

A metal covered with an undamaged coating generally has a very high impedance.
The equivalent circuit for such a situation is in the Figure:

The model includes a resistor (due primarily to the electrolyte) and the coating capacitance in series.
A Nyquist plot for this model is shown in the Figure. In making this plot, the following values were assigned:
R = 500 (a bit high but realistic for a poorly conductive solution)
C = 200 pF (realistic for a 1 cm2 sample, a 25 m coating, and r = 6 )
fi = 0.1 Hz (lowest scan frequency -- a bit higher than typical)
ff = 100 kHz (highest scan frequency)

The value of the capacitance cannot be determined from the Nyquist plot. It can be
determined by a curve fit or from an examination of the data points. Notice that the
intercept of the curve with the real axis gives an estimate of the solution resistance.
The highest impedance on this graph is close to 1010 . This is close to the limit of
measurement of most EIS systems

A Purely Capacitive Coating in the

Bode Plot
The same data are shown in a Bode plot in Figure 2-13. Notice that the
capacitance can be estimated from the graph but the solution resistance value
does not appear on the chart. Even at 100 kHz, the impedance of the coating is
higher than the solution resistance

The Voigt network

An electrical layer of a device can often be described by a resistor and capacitor in parallel

Cole-Cole Plots: Impedance Plots in the

Complex Plane
When we plot the real and imaginary components of impedance in the complex
plane (Argand diagram), we obtain a semicircle or partial semicircle for each parallel
RC Voigt network:

The diameter corresponds to the resistance R.

The frequency at the 90 position corresponds to 1/t = 1/RC

Analyzing Circuits
By using the various Cole-Cole plots we can calculate values of the elements of the
equivalent circuit for any applied bias voltage

By doing this over a range of bias voltages, we can obtain:

the field distribution in the layers of the device (potential divider) and the relative
widths of the layers, since C ~ 1/d

Randles Cell
The Randles cell is one of the simplest and most common cell models. It includes a solution
resistance, a double layer capacitor and a charge transfer or polarization resistance. In addition
to being a useful model in its own right, the Randles cell model is often the starting point for other
more complex models.
The equivalent circuit for the Randles cell is shown in the Figure. The double layer capacity is in
parallel with the impedance due to the charge transfer reaction

The Nyquist plot for a Randles cell is always a semicircle. The solution resistance can found by reading the real
axis value at the high frequency intercept. This is the intercept near the origin of the plot. Remember this plot was
generated assuming that Rs = 20 and Rp= 250 .
The real axis value at the other (low frequency) intercept is the sum of the polarization resistance and the solution
resistance. The diameter of the semicircle is therefore equal to the polarization resistance (in this case 250 ).

Bode Plot oft Randalls cell

This Figure is the Bode plot for the same cell. The solution resistance and the sum of the solution resistance
and the polarization resistance can be read from the magnitude plot. The phase angle does not reach 90 as it
would for a pure capacitive impedance. If the values for R s and Rp were more widely separated the phase
would approach 90.
Bode Plot for 1 mm/year Corrosion Rate

Mixed Kinetic and Diffusion Control

First consider a cell where semi-infinite diffusion is the rate determining step, with a series solution
resistance as the only other cell impedance.
A Nyquist plot for this cell is shown in Figure 2-17. R s was assumed to be 20 W. The Warburg coefficient
calculated to be about 120 sec-1/2 at room temperature for a two electron transfer, diffusion of a single
species with a bulk concentration of 100 M and a typical diffusion coefficient of 1.6 x10 -5 cm2/sec.
Notice that the Warburg Impedance appears as a straight line with a slope of 45.

Example: Half a fuel cell

Adding to the previous example a double layer with capacitance and a charge transfer impedance, we
get the equivalent circuit:
This circuit models a cell where polarization is due to a combination of
kinetic and diffusion processes. The Nyquist plot for this circuit is shown in
the Figure. As in the above example, the Warbug coefficient is assumed to
be about 150 W sec-1/2. Other assumptions: Rs = 20 , Rct = 250 , and
Cdl = 40 F.

Bode plot

The Bode plot for the same data is shown here. The lower frequency limit was moved down to 1mHz to
better illustrate the differences in the slope of the magnitude and in the phase between the capacitor and
the Warburg impedance. Note that the phase approaches 45 at low frequency.

Case studies

1. Relaxation Dispersion of O2- Ionic Conductivity in a ZrO0.85Ca0.15O1.85 Single

Crystal
2. Effect of intergranular glass films on the electrical conductivity
of 3Y-TZP

Relaxation Dispersion of O2- Ionic Conductivity in a

ZrO0.85Ca0.15O1.85 Single Crystal
The aim oft the study was:
To study the dynamic behavior of the oxygen ion conductivity of a cubic ZrO0.85Ca0.15O1.85 Single Crystal with AC impedance
spectroscopy and a dynamic pulse method as a function of both, the frequency and temperature in the range of 450 to1200 K
and 20 to 108 Hz. We had the hypothesis that the oxygen vacancies are clustered e.g. forming pairs with the Ca dopant.
Somewhen when heating up the material we expected that the conductivity slope in the Arrhenius plot would show two slopes:
One for the O2- conductivity via clustered vacancies and at higher temperature when the clusters are broken up an lower
activation energy.
The Method and Materials:
Single crytals of dimensions of . 10 x 5 x 2 m3 were contacted in four probe mode with Platinum . The electrodes were
painted on the specimen by applying a conductive platinum paste (Delnetron 308A) from Heraeus To minimize the
stray capacitance of the test leads, they were kept as short as possible. The shields of the measurement terminals were
grounded.

The relaxation dispersion regions of the ionic conductivity shift towards higher frequencies with increasing temperature.
This indicates that these dispersions are thermally activated. At low temperatures the intragrain relaxation process in the
zirconia lattice can be seen at high frequencies, but the electrode effects are too slow to be detected. In the temperature
range from 673 K to 873K both dispersions of the electrodes and the bulk material are observed in the frequency range
between 20 and 10 6 Hz. At higher temperatures the effect 0f the intragrain processes disappears and only the dispersion
of the electrodes can be seen in the middle of the frequency window.

Relaxation Dispersion of Ionic Conductivity in a

ZrO0.85Ca0.15O1.85 Single Crystal
The results:

The relaxation dispersion regions of the ionic conductivity shift towards higher frequencies with
increasing temperature. This indicates that these dispersions are thermally activated. At low
temperatures the intragrain relaxation process in the zirconia lattice can be seen at high frequencies,
but the electrode effects are too slow to be detected. In the temperature range from 673 K to 873K both
dispersions of the electrodes and the bulk material are observed in the frequency range between 20
and 106 Hz. At higher temperatures the effect 0f the intragrain processes disappears and only the
dispersion of the electrodes can be seen in the middle of the frequency window.

Relaxation Dispersion of Ionic Conductivity in a

ZrO0.85Ca0.15O1.85 Single Crystal
The temperature dependence of the intragrain bulk ionic conductivity as determined from AC impedance
spectroscopy is shown as two Arrhenius plots, log (J against l/T and log (J against l/T,) in Fig. 5. No
curvature in the Arrhenius plots can be observed which would indicate that some of the vacancy clusters
would break up.
The slope of the straight line of the plot corresponds to the activation energy of the ionic conductivity.

Relaxation Dispersion of Ionic Conductivity in a

ZrO0.85Ca0.15O1.85 Single Crystal
Conclusion:

The determination of the relaxation frequency, r==2fr, corresponding to a mean

jump frequency of oxygen vacancies, 1/ allows the determination of their mobility as
weIl as the diffusion coefficient.

A very narrow distribution of relaxation times shows that only one polarization
mechanism exists.

Activation energy of the ionic conductivity = act. eng. of . relaxation frequency =

mobility of charge carriers

It follows that the concentration of hopping charge carriers in calcia stabilized zirconia
is invariant with temperature and no cluster break up was observed in the
temperature range studied.
JA. Orliukas, P. Bohac,* K. Sasaki & L. Gauckler
Nichtmetallische Werkstoffe, ETH Zrich, CH-8092 Zrich, Switzerlandournal of the European Ceramic Society 12
(1993) 87-96

Effect of intergranular glass films on the electrical

conductivity
ofcontaining
3Y-TZP
The electrical conductivity of 3Y-TZP ceramics
Si0 and Al 0 has been investigated by complex
2

impedance spectroscopy between 500 and 1270 K.

At low temperatures, the total electrical conductivity is suppressed by the grain boundary glass films. The
equilibrium thickness of intergranular films is 1-2 nm, as derived using the "brick-Iayer" model and measured
by HRTEM. A change in the slope of the conductivity Arrhenius plots occurs at the characteristic temperature
Tb at which the macroscopic grain boundary resistivity has the same value as the resistivity of the grains.
The temperature dependence of the conductivity is discussed in terms of a series combination of Re
elements.

TZP 3Y

Specimens were round pellets oft ca 1.5 cm in diameter and 5 mm in height oft sintered
ceramics oft TZP with varous amounts oft SiO2 and Al2O3 additions . The coprecipitated
powders were calcined at 1050 C reground and pressed and then sintered at 1500C to full
density. The pellets were carefully lapped to have planar faces and contacted with sintered Pt
paste (without glass additive!!!)

Intergranular glass films on the electrical conductivity of

3Y-TZP

Usually it is not possible to observe all three dispersions simultaneously, due to a

limited frequency range used in this study (40 Hz-l MHz). At temperatures below 500
K only the grain dispersion can be seen at high frequencies.4o The grain boundary
and the electrode dispersion are too slow to be detected at this temperature. In the
medium temperature range (500 K-800 K), we can observe two dispersions, that of
the grains and that of the grain boundaries. Finally, above 800 K the intragrain
dispersion shifts out of the frequency window and the sluggish dispersion due to the
slower electrode processes becomes visible.

Intergranular glass films on the electrical

conductivity of 3Y-TZP

In Fig. 3 the frequency dependence of the specific imaginary impedance contribution, p fI = Z" . LIA, is
shown. From this figure the individual dispersion regions of grains, grain boundaries, and electrodes
can be seen more distinctly. The complex impedance data can be displayed in the complex
impedance plane with real part ' as the abscissa and the imaginary part as the ordinate (Cole
Cole diagram). A typical complex impedance spectrum of 3Y-TZP (sample E-10) at a medium
temperature of 596 K is shown in Fig. 4.

Intergranular glass films on the electrical

conductivity of 3Y-TZP

Since the time constants ( = RC) of individual RC-elements differ by orders of magnitude, individual
semicircles of the grains and that of the grain boundaries can clearly be distinguished in this temperature
range. The real specific impedance sections between the distinct minima in the imaginary part reveal
the macroscopic specific resistivities of the grains ( G) and the grain boundaries ('B), respectively. The
macroscopic specific resistivity of the grain boundaries is equal to the difference between the total (dc)
specific resistivity of the sampie (p T) and the macroscopic specific resistivity of the grains: GB = T - G.
Moreover, from the maximum of imaginary impedance at the top of each semicircle, the relaxation
frequency of the corresponding process can be determined from the relation = 1, where = 2rfr, is
the angular frequency [rad' s-1], fr the corresponding frequency of the applied electrical ac-field [Hz], and
= RC the time constant of the relaxation circuit.

Intergranular glass films on the electrical

conductivity of 3Y-TZP

Intergranular glass films on the electrical

conductivity of 3Y-TZP

Result:
3 mol Y TZP zirconia specimens with a ratio of 1:1 of SiO2 to Al2O3 impurities
have highest grain boundary resistances