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Most of The Material Displayed in This Lecture Is Taken From
Most of The Material Displayed in This Lecture Is Taken From
Introduction.
Disadvantages.
1. Expensive.
2. Complex data analysis for quantification.
Five major topics are covered in this
application note
5. Case studies
AC Circuit Theory and Representation of Complex Impedance Values
Ohm's law defines resistance in terms of the ratio between voltage E and current I.
E (t )
R
I (t )
The relationship is limited to only one circuit element -- the ideal resistor.
An ideal resistor has several simplifying properties:
• 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 AC current may have a phase lag with respect to the AC voltage
Then:
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 )
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”
r am Nyqui
g st plot
dia
Cole
le
Co
Z´
plot
d e
Bo
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 x 1(t) ant let y2(t) be the
output corresponding to the input x2(t).
However, we will show how electrochemical systems can be pseudo-linear. 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.
Amplitude
Two Sine Waves in the
Time Domain
Time
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 computer. An FFT is used to convert the current signal into the
frequency domain.
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:
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 degrees with respect to the voltage.
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: Z eq Z1 Z 2 Z3
Impedances in Parallel 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 Z eq:
R1 R2
Z eq Z1 Z 2 R1 R 2 1 4 5
Now suppose that we connect two 2 µF capacitors in series. The total capacitance of the combined
capacitors is 1 µF
1 1 1
C1 C2 Z1 Z 2
Z eq iC1 iC2
1 1 1
1 µF
i (2e ) i (2e ) i (1 )
6 6 e6
Impedance goes up, but capacitance goes down when capacitors are connected in series.
This is a consequence of the inverse relationship between capacitance and impedance.
Example: The Zn Air battery
There are three reactions:
O2 4 H 4e 2 H 2O
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
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 Xnx
X
a ny k
Y
Y
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
E0 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. E 0 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.
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
R
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
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 µF of capacitance for every cm 2 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, etc.
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).
which introduces a new parameter, Rp, 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:
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 i 0 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/cm 3)
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:
Material r
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.
Y (i)1/2
1/Y0(i)1/2
W (infinite 0
Warburg)
O (finite Warburg) Y0 i coth( B i ) tanh( B i ) / Y0 i
Q (CPE) Y (i)
0
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:
R C
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 µm 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 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 µM 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 µF.
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
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 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:
• A very narrow distribution of relaxation times shows that only one polarization
mechanism exists.
• 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 Zürich, CH-8092 Zürich, Switzerlandournal of the European Ceramic Society 12
(1993) 87-96
Effect of intergranular glass films on the electrical conductivity
of 3Y-TZP
The electrical conductivity of 3Y-TZP ceramics containing Si0 2 and Al20 3 has been investigated by complex
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 1500°C 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