Orazem EIS Spring 2008

Electrochemical Impedance Spectroscopy
Mark E. Orazem Department of Chemical Engineering University of Florida Gainesville, Florida 32611
meo@che.ufl.edu 352-392-6207
Mark E. Orazem, 2000-2008. All rights reserved.
Contents
Chapter 1. Introduction Chapter 2. Motivation Chapter 3. Impedance Measurement Chapter 4. Representations of Impedance Data Chapter 5. Development of Process Models Chapter 6. Regression Analysis Chapter 7. Error Structure Chapter 8. Kramers-Kronig Relations Chapter 9. Use of Measurement Models Chapter 10. Conclusions Chapter 11. Suggested Reading Chapter 12. Notation
Chapter 1. Introduction
page 1: 1
Mark E. Orazem Department of Chemical Engineering University of Florida Gainesville, Florida 32611
meo@che.ufl.edu 352-392-6207
page 1: 2

How to think about impedance spectroscopy EIS as a generalized transfer function Overview of applications of EIS Objective and outline of course
page 1: 3
1992 no logo
page 1: 4
The Blind Men and the Elephant

John Godfrey Saxe
It was six men of Indostan To learning much inclined, Who went to see the Elephant (Though all of them were blind), That each by observation Might satisfy his mind. The First approached the Elephant, And happening to fall Against his broad and sturdy side, At once began to bawl: God bless me! but the Elephant Is very like a wall! ...
page 1: 5

Electrochemical technique
steady-state transient impedance spectroscopy
Measurement in terms of macroscopic quantities

total current averaged potential
Not a chemical spectroscopy Type of generalized transfer-function measurement
page 1: 6
Impedance Spectroscopy
Current 10 Density, A/cm2 ~ I 5
V Z ( ) = = Z r + jZ j I
-0.2
-0.1 -5 ~ V
0.1
0.2
0.3
0.4
Potential, V
-10
page 1: 7
Applications
Electrochemical systems
Corrosion Electrodeposition Human Skin Batteries Fuel Cells
Fundamentals
Dielectric spectroscopy Acoustophoretic spectroscopy Viscometry Electrohydrodynamic impedance spectroscopy
Materials
page 1: 8
Physical Description
Electrode-Electrolyte Interface
Electrical Double Layer Diffusion Layer
Electrochemical Reactions Electrical Circuit Analogues
page 1: 9
Electrochemical Reactions
O2 + 2H2O + 4e- 4OHFaradaic current density
O2 F iF = iO2 = nO2 FkO2 cO2 exp V VO2 RT
Total current density = Faradaic + charging
dV i = i F + Cd dt
Cell potential = electrode potential + Ohmic potential drop
U = V + iRe
page 1: 10
Electrical Analogues
page 1: 11
Electrical Analogue
Simple electrochemical reaction
Simple electrochemical reaction with mass transfer
page 1: 12
Course Objectives
Benefits and advantages of impedance spectroscopy Methods to improve experimental design Interpretation of data
graphical representations regression error analysis equivalent circuits process models
page 1: 13
Contents
page 1: 14
Chapter 2. Motivation
page 2: 1

Comparison of measurements
steady state step transients single-sine impedance
In principle, step and single-sine perturbations yield same results Impedance measurements have better error structure
page 2: 2
Steady-State Polarization Curve

0.4
0.3
Current, mA
0.2
0.1
0 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
Potential, V
page 2: 3
Steady-State Techniques
Yield information on state after transient is completed Do not provide information on
system time constants capacitance
Influenced by
Ohmic potential drop non-stationarity film growth coupled reactions
page 2: 4
Transient Response to a Step in Potential
1.5
}
Current / mA
1.0
V=10 mV
potential input
10
C1
C2
Current / mA
V I= R0 + R1 (V ) + R2
10
-1
R0
0.5
R1(V)
R2
current response
10
-2
10
10
-5
10
-4
10
-3
10
-2
10
-1
10
(t-t0) / ms
(t-t0) / s
page 2: 5
Transient Response to a Step in Potential
1.5
Short times/high frequency
}
Current / mA
1.0
V=10 mV
potential input
C1
C2
R0
0.5
R1(V)
R2
current response
long times/low frequency

10
(t-t0) / ms
page 2: 6
Transient Techniques: potential or current steps

Decouples phenomena
characteristic time constants
mass transfer kinetics
capacitance
Limited by accuracy of measurements

current potential time
Limited by sample rate

<~1 kHz
page 2: 7
Sinusoidal Perturbation
V (t ) = V0 + V cos ( t ) i (t ) = i0 {exp(baV ) exp( bcV )}
iC = C0
dV dt
i f = f (V )
V (t )
page 2: 8
1.0
10 kHz 100 Hz 1 mHz
(i-i0) / max(i-i0)
0.5
0.0
-0.5
-1.0 -1.0 -0.5 0.0 0.5 1.0
(V-V0) / V0
page 2: 9
Lissajous Representation
B
1.0
0.5
Y(t)/Y0
V (t ) = V cos(t ) V I (t ) = cos(t + ) Z
D A
-0.5
-1.0 -1.0 -0.5 0 0.5 1.0
V OA | Z |= = I OB OD sin( ) = OA
X(t)/X0
page 2: 10
Impedance Response
-25
100 Hz
Zj / cm
-20 -15 -10 -5 0 0 10 20 30

-2
-2
40
50
Zr / cm
page 2: 11
Decouples phenomena
characteristic time constants
mass transfer kinetics
capacitance
Gives same type of information as DC transient. Improves information content and frequency range by repeated sampling. Takes advantage of relationship between real and imaginary impedance to check consistency.
page 2: 12
System with Large Ohmic Resistance
R0 =10,000 R1 =1,000 C1 = 10.5 F

= 0.0105 s (15 Hz)
M. E. Orazem, T. El Moustafid, C. Deslouis, and B. Tribollet, J. Electrochem. Soc., 143 (1996), 3880-3890.
page 2: 13
Impedance Spectrum
-600 -400
Zj,
-200 0 9800
100000 10000
10000
10200
10400
10600
10800
11000
11200
Zr,
Zr,
Impedance,
1000 100 10 1 0.1 0.1 1 10 100
-Zj,
1000
10000
100000
Frequency, Hz
page 2: 14
Experimental Data
100000 10000 1000
Impedance,
100 10 1 0.1 0.01 0.1 1 10 100 1000 10000 100000
Frequency, Hz
page 2: 15
Impedance Spectroscopy vs. Step-Change Transients

Information sought is the same Increased sensitivity
stochastic errors frequency range consistency check
Better decoupling of physical phenomena
page 2: 16
Chapter 3. Impedance Measurement
page 3: 1

Overview of techniques
A.C. bridge Lissajous analysis phase-sensitive detection (lock-in amplifier) Fourier analysis
Experimental design
page 3: 2
Measurement Techniques
A.C. Bridge Lissajous analysis Phase-sensitive detection (lock-in amplifier) Fourier analysis
digital transfer function analyzer fast Fourier transform
D. Macdonald, Transient Techniques in Electrochemistry, Plenum Press, NY, 1977. J. Ross Macdonald, editor, Impedance Spectroscopy Emphasizing Solid Materials and Analysis, John Wiley and Sons, New York, 1987. C. Gabrielli, Use and Applications of Electrochemical Impedance Techniques, Technical Report, Schlumberger, Farnborough, England, 1990.
page 3: 3
AC Bridge
Z1 Z2
Bridge is balanced when current at D is equal to zero
Z1Z 4 = Z 2 Z 3
Time consuming Accurate
Z3
f 10 Hz
Z4
Generator
page 3: 4
Lissajous Analysis
Current
B
V (t ) = V sin( t ) V I (t ) = sin( t + ) Z
D A
A'
D'
Potential
B'
V OA A'A | Z |= = = I OB B'B OD D'D sin( ) = = OA A'A
page 3: 5
Phase Sensitive Detection

General Signal
A = A0 sin( t + A )
1 S= sin ( 2n + 1) t + S n =0 2n + 1 4
Reference Signal
1 AS = sin ( t + A ) sin ( 2n + 1) t + S n =0 2n + 1
4 A0
ASdt =
0
2 A0
cos( A S )
Has maximum value when
A = S
page 3: 6
V (t ) = V0 cos(t ) I (t ) = I 0 cos(t + I )
Fourier Analysis:
single-frequency input
1 I r ( ) = I (t ) cos(t )dt T 0 1 I j ( ) = I (t ) sin(t )dt T 0 1 Vr ( ) = V (t ) cos(t )dt T 0 1 V j ( ) = V (t ) sin(t )dt T 0

T T T
Vr + jV j Z r ( ) = Re + I jI j r Vr + jV j Z j ( ) = Im I r + jI j
page 3: 7
Fourier Analysis:
multi-frequency input
Time
Signal Output
Signal Input
Time
Fast Fourier Transform
Z()
page 3: 8
Comparison
single-sine input
Good accuracy for stationary systems Frequency intervals of f/f
economical use of frequencies
multi-sine input
Good accuracy for stationary systems Frequency intervals of f
dense sampling at high frequency required to get good resolution at low frequency
Used for entire frequency domain Kramers-Kronig inconsistent frequencies can be deleted
Often paired with PhaseSensitive-Detection (f>10 Hz) Correlation coefficient used to determine whether spectrum is inconsistent with KramersKronig relations
page 3: 9
Measurement Techniques
A.C. bridge
obsolete
Lissajous analysis
obsolete useful to visualize impedance
Phase-sensitive detection (lock-in amplifier)

inexpensive accurate useful at high frequencies
Fourier analysis techniques

accurate
page 3: 10
Experimental Considerations
Frequency range
instrument artifacts non-stationary behavior capture system response
Linearity
low amplitude perturbation depends on polarization curve for system under study determine experimentally
Signal-to-noise ratio
page 3: 11
V (t ) = V0 + V cos ( t ) i (t ) = i0 exp(baV )
iC = C0
dV dt
i f = f (V )
V (t )
page 3: 12
Linearity
1.0
(I-I0)/max(I-I0)
0.5 0.0 -0.5 -1.0
(I-I0)/max(I-I0)
f = 1 mHz 1 mV 20 mV 40 mV
1.0 0.5 0.0 -0.5 -1.0
f = 10 Hz 1 mV 20 mV 40 mV
-1.0
-0.5
0.0
0.5
1.0
-1.0
-0.5
0.0
0.5
1.0
(V-V0)/V
1.0
f = 100 Hz 1 mV 20 mV 40 mV
(V-V0)/V
1.0
(I-I0)/max(I-I0)
0.5 0.0 -0.5 -1.0
(I-I0)/max(I-I0)
0.5 0.0 -0.5 -1.0
f = 10 kHz 1 mV 20 mV 40 mV
-1.0
-0.5
0.0
0.5
1.0
-1.0
-0.5
0.0
0.5
1.0
(V-V0)/V
(V-V0)/V
page 3: 13
Influence of Nonlinearity on Impedance

model 1 mV 20 mV 40 mV
Zj / cm
-20
-10
0 0 10 20 30 40
2
50
Zr / cm
page 3: 14
Influence of Nonlinearity on Impedance
1.0
10
2
1
0.8
|Zj| / cm
10 10 10 10
Zr / Rt
0.6 0.4 0.2
-1
-2
-3
0.0 10
-3
10
-2
10
-1
10
10
10
10
10
10
10
10
-4
10
-3
10
-2
10
-1
10
10
10
10
10
10
10
f / Hz
f / Hz
page 3: 15
Guideline for Linearity

bV 0.2
100(Rt-Z(0))/Rt
10
1 0.5 0.1
0.01
0.01
0.1
0.2
V b
page 3: 16
Influence of Ohmic Resistance

bV 0.2 (1 + Re / Rt )
Re
iC = C0 dV dt
i f = f (V )
i (t ) Re
s (t )
V (t )
page 3: 17
Influence of Ohmic Resistance
page 3: 18
Overpotential as a Function of Frequency

Re
iC = C0 dV dt
i f = f (V )
i (t ) Re
s (t )
V (t )
page 3: 19
Cell Design
Use reference electrode to isolate influence of electrodes and membranes
2-electrode
Working Electrode
3-electrode
Working Electrode
4-electrode
Working Electrode
Ref 1 Ref 1 Ref 2
Counterelectrode
Counterelectrode
Counterelectrode
page 3: 20
Current Distribution
Counter Electrode Lead Wires
Seek uniform current/potential distribution

simplify interpretation reduce frequency dispersion
Electrolyte Out
Electrolyte Out Cover Flange
Working Electrode
Cell Body ID = 6 in. L = 6 in.
Flange Cover
Electrolyte In
Electrolyte In Working Electrode Seat
page 3: 21
Primary Current Distribution
page 3: 22
Modulation Technique
Potentiostatic
standard approach linearity controlled by potential
Galvanostatic
good for nonstationary systems
corrosion drug delivery
F in = iO exp M (V Vcorr ) 1 RT
2 2
requires variable perturbation amplitude to maintain linearity
2 Fe F 1 F Fe in = iO (V Vcorr ) + (V Vcorr ) + 2 RT RT
= V / Z ( ) I
= I Z ( ) V
page 3: 23
Experimental Strategies
Faraday cage Short leads Good wires Shielded wires Oscilloscope
I WE V Ref CE
page 3: 24
Reduce Stochastic Noise

Current measuring range Integration time/cycles
long/short integration on some FRAs
Delay time Avoid line frequency and harmonics (5 Hz)

60 Hz & 120 Hz 50 Hz & 100 Hz
Ignore first frequency measured (to avoid start-up transient)
page 3: 25
Reduce Non-Stationary Effects

Reduce time for measurement
shorter integration (fewer cycles)
accept more stochastic noise to get less bias error
fewer frequencies
more measured frequencies yields better parameter estimates fewer frequencies takes less time
avoid line frequency and harmonic (5 Hz)

takes a long time to measure on auto-integration cannot use data anyway
select appropriate modulation technique

decide what you want to hold constant (e.g., current or potential) system drift can increase measurement time on auto-integration
page 3: 26
Reduce Instrument Bias Errors

Faster potentiostat Short shielded leads Faraday cage Check results
against electrical circuit against independently obtained parameters
page 3: 27
Measurement Case Study
page 3: 28
Impedance Data from a Battery

potentiostatic modulation 2-electrode spiral-wound Alkaline AA -20
0.75 hours 9.5 hours 168 hours 169 hours 170 hours 171 hours
-3 -2 -1 0 0 1 2 3 4 5
Zj /
-10
0 0 10
Zr /
20
30
page 3: 29
Improve Experimental Design

Question
How can we isolate the role of positive electrode, negative electrode, and separator?
Answer - Develop a very sophisticated process model. - Use a four-electrode configuration.

Working Electrode
Ref 1 Ref 2
Counterelectrode
page 3: 30

Question
How can we reduce stochastic noise in the measurement?
Answer - Use more cycles during integration. - Add at least a 2-cycle delay. - Ensure use of optimal current measuring resistor. - Check wires and contacts. - Avoid line frequency and harmonics. - Use a Faraday cage.
page 3: 31

Question
How can we determine the cause of variability at long times?
Answer - Use the Kramers-Kronig relations to see if data are selfconsistent. - Change mode of modulation to variable-amplitude galvanostatic to ensure that the base-line is not changed by the experiment.
page 3: 32
Facilitate Interpretation
Question
How can we be certain that the instrument is not corrupting the data?
Answer - Use the Kramers-Kronig relations to see if data are selfconsistent. - Build a test circuit with the same impedance response and see if you get the correct result. - Compare results to independently obtained data (such as electrolyte resistance).
page 3: 33
Experimental Considerations
Frequency range
instrument artifacts non-stationary behavior
Linearity
low amplitude perturbation depends on polarization curve for system under study determine experimentally
Signal-to-noise ratio
page 3: 34
Can We Perform Impedance on Transient Systems?

Timeframes for measurement
Individual frequency Individual scan Multiple scans
page 3: 35
EHD Experiment
-0.2
Imaginary Impedance,A/rpm
-0.15
Data Set #2 Data Set #4 Data Set #1
-0.1
-0.05
0.05 -0.05
0.05
0.1
0.15
0.2
Real Impedance, A/rpm
page 3: 36
Time per Frequency for 200 rpm

0.01 0.1 1 10 100 1000
1000
Time per Measurement, s
100
100
10 Filter On Filter Off 1 0.01
10
0.1
10
100
Frequency, Hz
page 3: 37
Impedance Scans
-15
Zj / cm
-10
Time Interval 0-1183 s 1183-2366 s 2366-3581 s
-5
0 0 5 10 15 20 25
2
30
35
40
Zr / cm
page 3: 38
Impedance Scans
4000
Elapsed Time / s
3000
2000
1000
0 10
-2
10
-1
10
10
10
10
10
10
f / Hz
page 3: 39
Time per Frequency Measured
10
tf / s
5 cycles 3 cycles
10
5 seconds
10
-2
10
-1
10
10
10
10
10
10
f / Hz
page 3: 40
page 3: 41
Chapter 4. Representation of Impedance Data
page 4: 1

Electrical circuit components Methods to plot data

standard plots subtract electrolyte resistance
Constant phase elements
page 4: 2
Addition of Impedance
Z1
Z1 Z2
Z2
Z = Z1 + Z 2 Y= 1 1 1 + Y1 Y2
Z=
1 1 1 + Z1 Z 2
Y = Y1 + Y2
page 4: 3
Circuit Components
-Zj
Re
Z = Re Re
-Zj
Re
Cdl
Zr
1 1 Z = Re + = Re j jCdl Cdl j = 1
Re
Zr
page 4: 4
Simple RC Circuit
Cdl
Rt 2
-Zj
= Rt Cdl
Re Rf
Z = Re + 1 1 + jCdl Rt Rt 1 + j Rt Cdl 1 + ( Rt Cdl ) Rt
2
Re
Note:
Zr
Re + Rt
= Re + = Re +
= 2 f rad / s or s-1
f cycles / s or Hz
Rt 2Cdl j 2 1 + ( Rt Cdl )

1200
page 4: 5
Impedance
Zr or -Zj /
1000 800 600 400 200 real imaginary
Cdl
Re Rf
-600
10 Hz
Slope = 1
0 0.001 0.01 0.1 1 10 100 1000 10000
Frequency / Hz
10000
-400
Zj,
-200
Zr or -Zj /
100 Hz 1 Hz
1000
100
0 0 200 400 600 800 1000 1200
10
real imaginary
Slope = -1
1 10 100 1000 10000
Zr /
1 0.001 0.01 0.1
Frequency / Hz
page 4: 6
Bode Representation
10000 magnitude phase angle 1000 -90
|Z| /
Z = Z r + jZ j
100
Z r =| Z | cos ( ) Z j =| Z | sin ( )
-30
10
1 0.001
0.01
0.1
10
100
1000
0 10000
Frequency / Hz
/ degrees
-60
page 4: 7
Modified Phase Angle

Input & output are in phase
10000 1000 100
Zj * = tan Z R e r
1
-90
-60
10 1 0.1 0.01 0.001
The modified phase angle yields excellent insight, but we need an accurate estimate for the solution -30 resistance.
/ degrees
|Z| /
magnitude modified magnitude phase angle modified phase angle
Note:
0.01
0.1
10
100
1000
0 10000
Zj = tan Zr
1
Frequency / Hz
Input & output are out of phase
page 4: 8
Constant Phase Element

CPE
Re Rt
-0.6
Z Re 1 =+ Rt 1 + ( j ) Rt Q
=1 =0.9 =0.8 =0.7 =0.6 =0.5
-0.4
Zj / Rt
-0.2 0.0 0.0 0.2 0.4 0.6 0.8
1.0
(ZrRe) / Rt
page 4: 9
Slope = +
CPE: Log Imaginary

10 10
0 -1
Slope =
|Zj| / Rt
10 10 10 10
-2
-3
-4
=1 =0.9 =0.8 =0.7 =0.6 =0.5

-5 -4 -3 -2 -1 0 1 2 3 4 5
-5
10 10 10 10 10 10 10 10 10 10 10
/
Note: With a CPE (1), the asymptotic slopes are no longer 1.
page 4: 10
CPE: Modified Phase Angle

-90
/ degrees
-60
=1 =0.9 =0.8 =0.7 =0.6 =0.5
-30
Note: The high-frequency asymptote for the modified phase angle depends on the CPE coefficient .
-5 -4 -3 -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10 10 10
page 4: 11
Example for Synthetic Data
Z ( f ) = Re +
1 + ( j 2 f ) Qdl ( Rt + zd ( f ) )
Rt + zd ( f )
zd ( f ) = zd ( f )
tanh
j 2 f j 2 f
M. Orazem, B. Tribollet, and N. Pbre, J. Electrochem. Soc., 153 (2006), B129-B136.
page 4: 12
Traditional Representation
Zj / cm
2
400
=1 = 0.7 = 0.5
200
1 Hz 10 Hz 100 Hz
0 200 400 600
0.1 Hz 10 mHz 1 mHz

800
2
1000
1200
Zr / cm
| Z | / cm
/ degree
10
=1 = 0.7 = 0.5
-90 -75 -60 -45 -30 -15 0

=1 = 0.7 = 0.5
10
10
-3
10
-2
10
-1
10
10
10
10
10
10
10
10
-3
10
-2
10
-1
10
10
10
10
10
10
10
f / Hz
f / Hz
page 4: 13
Re-Corrected Bode Phase Angle

adj
-90
Zj = tan Z R e ,est r
1
adj () = 90( )
adj / degree
-75 -60 -45 -30 -15 0 10

-3
=1 = 0.7 = 0.5
10
-2
10
-1
10
10
10
10
10
10
10
f / Hz
page 4: 14
Re-Corrected Bode Magnitude

Z
3
adj
2 Z R + Z ( r e,est ) j 2
Slope =
10
2
| Z |adj / cm
10 10 10 10
slope =
=1 = 0.7 = 0.5
-1
10
-3
10
-2
10
-1
10
10
10
10
10
10
f / Hz
page 4: 15
Slope =
Log(|Zj|)
3
10 10
| Zj | / cm
=1 = 0.7 = 0.5
Slope =
10 10 10 10
slope=
0
slope=
-1
-2
10
-3
10
-2
10
-1
10
10
10
10
10
10
10
f / Hz
page 4: 16
Effective Capacitance or CPE Coefficient

Z CPE = 1 QCPE ( j 2 f )
Qeff
1 = sin 2 ( 2 f ) Z j (f )
100
Qeff / Qdl
=1 = 0.7 = 0.5
10
10
-3
10
-2
10
-1
10
10
10
10
10
10
10
f / Hz
page 4: 17
Alternative Plots
Re-Corrected Bode Plots (Phase Angle)
Shows expected high-frequency behavior for surface High-Frequency limit reveals CPE behavior
Re-Corrected Bode Plots (Magnitude)

High-Frequency slope related to CPE behavior
Log|Zj|
Slopes related to CPE behavior Peaks reveal characteristic time constants
Effective Capacitance
High-Frequency limit yields capacitance or CPE coefficient
page 4: 18
Application
page 4: 19
Mg alloy (AZ91) in 0.1 M NaCl

-200
-100
65.5 Hz
Zj / cm
0
15.5 kHz 0.0076 Hz time / h 0.5 3.0 6.0
0.011 Hz
100
200 0 100 200 300 400

2
500
600
Zr / cm
page 4: 20
k1 Mg Mg +
Proposed Model
negative difference effect (NDE)
+ e ads
(Mg )
+
+
k2 2+ 1 + H O Mg + OH + 2 ads 2 H2
k3 Mg 2+ + e k 3
(Mg )
ads
k4 Mg 2+ + 2 OH Mg(OH) 2 k 4
k5 Mg(OH) 2 MgO + H 2 O k -5
G. Baril, G. Galicia, C. Deslouis, N. Pbre, B. Tribollet, and V. Vivier, J. Electrochem. Soc., 154 (2007), C108-C113
page 4: 21
Physical Interpretation Mg (Mg ) + e

k1 + ads
k3 2+ + Mg ads Mg + e k3
diffusion of Mg2+
-200
-100
65.5 Hz
Zj / cm
0
15.5 kHz 0.0076 Hz time / h 0.5 3.0 6.0
0.011 Hz
100
200 0 100 200 300 400

2
500
600
Zr / cm
relaxation of (Mg+)ads. intermediate
page 4: 22
Log(|Zj|
10
Slope =
|Zj| / cm
10
time / h 0.5 3.0 6.0
10
10
-3
10
-2
10
-1
10
10
10
10
10
10
f / Hz
page 4: 23
Effective CPE Coefficient

1 Qeff = sin 2 ( 2 f ) Z j (f )
Qeff / (M cm ) s
10 10 10 10 10
-2
time / h 0.5 3.0 6.0
-1
10
-2
10
-1
10
10
10
10
10
10
f / Hz
page 4: 24
Re-Corrected Phase Angle

adj () = 90
10
3
adj
Zj = tan Z R e ,est r
1
| Z |adj / cm
10
time / h 0.5 3.0 6.0
10
10
10
-3
10
-2
10
-1
10
10
10
10
10
10
f / Hz
page 4: 25
Physical Parameters
Zj / cm
2
-200
-100
65.5 Hz
0
15.5 kHz 0.0076 Hz time / h 0.5 3.0 6.0
0.011 Hz
100
200 0 100 200 300 400

2
500
600
Zr / cm
page 4: 26
Experimental device for LEIS
layer
Z local =
Vapplied ilocal
page 4: 27
Mg alloy (AZ91) in Na2SO4 10-3 M at the corrosion potential after 1 h of immersion. Electrode radius 5500 m. Global impedance
Global impedance analyzed with a CPE ( = 0.91). Only the HF loop of the diagram is analyzed
J.-B. Jorcin, M. E. Orazem, N. Pbre, and B. Tribollet, Electrochimica Acta, 51 (2006), 1473-1479.
page 4: 28
Local impedance
= 1 to 0.92
page 4: 29
Mg alloy (AZ91) in Na2SO4 10-3 M at the corrosion potential after 1 h of immersion. Electrode radius 5500 m
The local impedance has a pure RC behavior.
Local impedance
The CPE is explained by a 2d distribution of the resistance as shown in the figure.
page 4: 30
Comparison to Theory
page 4: 31
Graphical Representation of Impedance Data

Expanded Range of Plot Types
Facilitate model development Identify features without complete system model
Suggested Plots
Re-Corrected Bode Plots (Phase Angle)
Shows expected high-frequency behavior for surface High-Frequency limit reveals CPE behavior
Re-Corrected Bode Plots (Magnitude)

High-Frequency slope related to CPE behavior
Log|Zj|
Slopes related to CPE behavior Peaks reveal characteristic time constants
Effective Capacitance
High-Frequency limit yields capacitance or CPE coefficient
page 4: 32
Plots based on Deterministic Models
page 4: 33
Convective Diffusion to a RDE

low-frequency asymptote
Reduction of Fe(CN)63- on a Pt Disk, i/ilim = 1/2
-100
Zj /
-50
120 rpm 600 rpm 1200 rpm 2400 rpm
0 0 50 100 150 200 250
Zr /
page 4: 34
Normalized Impedance Plane

Zj / (Zr,maxRe )
0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 1.0 1.2
120 rpm 600 1200 2400
(ZrRe) / (Zr,maxRe)
Note: We again need an accurate estimate for the solution resistance.
page 4: 35
Normalized Real
(ZrRe ) / (Zr,maxRe )
10
0
p = /
10
-1
10
-2
120 rpm 600 1200 2400
10
-3
10
-4 -3 -2 -1 0 1 2 3 4 5
10
10
10
10
10
10
10
10
10
page 4: 36
Normalized Imaginary
10
0
Zj / (Zr,maxRe )
10
-1
10
-2
120 rpm 600 1200 2400
10
-3
10
-3
10
-2
10
-1
10
10
10
10
10
10
page 4: 37
Straight line at low frequency
1.0 0.8 0.6 0.4 0.2 0 0 0.1
120 rpm 600 1200 2400
pZj / (Zr,maxRe )
0.2
0.3
0.4
0.5
Tribollet, Newman, and Smyrl, JES 135 (1988), 134-138.
page 4: 38
Slope at low frequency yields Di

lim d Re {Z } = Sc1/ 3 = s p 0 dp Im {Z } = 1.2261 + 0.84Sc 1/ 3 + 0.63Sc 2 / 3 Sc = 1090.6
1.0
0.8
0.6
0.4 0 0.01 0.02 0.03 0.04
pZj / (Zr,maxRe)

6
page 4: 39
-4x10
Zj /
n-GaAs Diode:
scaling based on
320 K 340 K
-2x10
Arrhenius relationship
0 0
8 7 6 5 4 3 2 1 0
2x10
4x10
6x10
8x10
1x10
10 10 10
Zr /
10 10
6 5 4 3 2 1 0
Zr /
10 10 10 10 10 10
Zj /
10 10 10 10 10 10
320 K 340 K 360 K 380 K 400 K
320 K 340 K 360 K 380 K 400 K
-1
10
10
10
10
10
10
10
10
10
10
10
10
f / Hz
f / Hz
page 4: 40
Normalized Real
1.0 0.8
320 K 340 K 360 K 380 K 400 K
Zr / |Zmax|
0.6 0.4 0.2 0.0
f E f * = exp f0 kT
10
-4
10
-3
10
-2
10
-1
10
10
10
10
f*
Jansen, Orazem, Wojcik, and Agarwal, JES 143 (1996), 4066-4074.
page 4: 41
Normalized Imaginary
0.5
Zj / |Zmax|
0.4 0.3 0.2 0.1 0.0

-4
320 K 340 K 360 K 380 K 400 K
10
10
-3
10
-2
10
-1
10
10
10
10
f*
page 4: 42
Normalized Log Real

10 10
0
-1
Zr / |Zmax|
10 10 10 10 10
-2
-3
-4
320 K 340 K 360 K 380 K 400 K
-5
-6
10
-4
10
-3
10
-2
10
-1
10
10
10
10
f*
page 4: 43
Normalized Log Imaginary

10 10
0 -1
Zj / |Zmax|
10 10 10 10 10
-2
-3
-4
-5
320 K 340 K 360 K 380 K 400 K
-6
10
-4
10
-3
10
-2
10
-1
10
10
10
10
f*
page 4: 44
-4.0E+08 298.8 290 285 270 260
Superlattice Structure
Z j,
-2.0E+08
0.0E+00 0.0E+00 2.0E+08 4.0E+08 6.0E+08
Zr ,
-4.0E+07
260 292.5 297.2 297.7 297.8 297.8 298.8
-Z j,
-2.0E+07
0.0E+00 0.0E+00 2.0E+07 4.0E+07 6.0E+07
Zr ,
page 4: 45
Normalized Real Part

1.2 1 0.8
Z/Z r,max
0.6 0.4 0.2 0 0.0001 0.01

f*=
1
f E exp f0 kT
100
10000
page 4: 46
Normalized Imaginary Part

-0.4 -0.3
Zj / Z r,max
-0.2 -0.1 0 0.1 0.0001 0.01

f*= f E exp f0 kT
100
10000
page 4: 47
DLTS of n-GaAs diode
e/T / s K
-1 2
0.48 eV 0.32 eV
0.83 eV
0.002 0.003 0.004 0.005
-1
0.006
0.007
1/T / K
page 4: 48
n-GaAs
1.E+11 1.E+10 1.E+09
0.45 eV 0.27 eV 0.25 eV
TR / K
1.E+08 1.E+07 1.E+06 0.0022 0.0024 0.0026 0.0028 0.003 0.0032 0.0034
-1
0.77 eV
1/T / K
page 4: 49
Mott-Schottky Plots
high-frequency asymptote
Blocking Contact GaAs
Ohmic Contact
qsc C= 0
d 2 e = ( p n + ( Nd Na )) 2 dy
Ec Ef Et Eg
Electron Energy
2 0 fb kT 1 e = F ( Nd Na ) C2
Ev Position
Dean and Stimming, J. Electroanal. Chem. 228 (1987), 135-151.
page 4: 50
C as a function of Potential
intrinsic semiconductor
10 10
-3
-4
C / F cm
-2
10 10 10 10
-5
-6
-7
-8
-0.4
-0.2
0.2
0.4
(-fb) / V
page 4: 51
1/C2 as a function of Potential

n- or p-doped semiconductor
4 (NdNa )= +10 cm
-2
16 -3
C / 10 cm F
(NdNa )= 10 cm
16
-3
n-type
2
p-type
-2
1
+10
17
cm
-3
10
17
cm
-3
0 -3 -2 -1 0 1 2 3
(-fb) / V
page 4: 52
GaAs-Schottky Diode
8
/ nF
4
C
2 0 -3 -2 -1 0 1 2
-2
-2
Potential / V
page 4: 53
Choice of Representation
Plotting approaches are useful to show governing phenomena Complement to regression of detailed models Sensitive analysis requires use of properly weighted complex nonlinear regression
page 4: 54
Chapter 5. Development of Process Models
page 5: 1

Use of Circuits to guide development Develop models from physical grounds Model case study Identify correspondence between physical models and electrical circuit analogues Account for mass transfer
page 5: 2
Use circuits to create framework
page 5: 3
Addition of Potential
page 5: 4
Addition of Current
page 5: 5
Equivalent Circuit at the Corrosion Potential
page 5: 6
Equivalent Circuit for a Partially Blocked Electrode
page 5: 7
Equivalent Circuit for an Electrode Coated by a Porous Layer
page 5: 8
Equivalent Electrical Circuit for an Electrode Coated by Two Porous Layers
C 2 =
0 ; 0 = 8.8452 1014 F/cm R 2 = 2 / 2
page 5: 9
Use kinetic models to determine expressions for the interfacial impedance
page 5: 10
Approach
identify reaction mechanism write expression for steady state current contributions write expression for sinusoidal steady state sum current contributions account for charging current account for ohmic potential drop account for mass transfer calculate impedance
page 5: 11
General Expression for Faradaic Current

i f = f (V , ci ,0 , i )
~ j t i = i + Re i e
f f + f = i V V ci ,0 , k i ci ,0
}
i ,0 c V ,c j , j i , k
f k + k k V , c j j , jk
page 5: 12
Reactions Considered
Dependent on Potential Dependent on Potential and Mass Transfer Dependent on Potential, Mass Transfer, and Surface Coverage Coupled Reactions
page 5: 13
Irreversible Reaction:
Dependent on Potential
z+
A A z+ + ne
Potential-dependent heterogeneous reaction Two-dimensional surface No effect of mass transfer
page 5: 14
Current Density
steady-state
A F iA = nA FkA exp V RT
iA = K A exp ( bAV )
oscillating component
= K b exp ( b V )V i A A A A
V A = i Rt ,A
Rt ,A
1 = K AbA exp ( bAV )
page 5: 15
Charging Current
high frequency
dV i = i f + Cdl dt =i f + j CdlV i
V = i + j CdlV Rt ,A 1 j C =V + dl R t ,A
low frequency
Rt ,A V = i 1 + j Rt ,ACdl
page 5: 16
Ohmic Contributions
U = iRe + V ~ ~ ~ U = i Re + V
U V Z A = = Re + i i Rt ,A = Re + 1+j Rt ,ACdl
page 5: 17
Steady Currents in Terms of Rt,A

iA = K A exp ( bAV )
iA = K A exp ( 2.303V A )
A = 2.303/ bA
Rt ,A
1 A = = K AbA exp ( bAV ) 2.303iA

iA =
A
2.303Rt ,A
A = 2.303Rt ,A iA
page 5: 18
Dependent on Potential and Mass Transfer
O + ne R
Irreversible potential-dependent heterogeneous reaction Reaction on two-dimensional surface Influence of transport of O to surface
page 5: 19
Current Density
steady-state
iO = K O cO,0 exp ( bOV )
oscillating component
K exp ( b V ) c = K b c exp ( b V )V O,0 i O O O O,0 O O O V O,0 = K O exp ( bOV ) c Rt ,O
Rt ,O 1 = K O cO,0 exp ( bOV )
page 5: 20
Mass Transfer
dcO iO = nO FDO dy
O e j t } iO = iO + Re {i
O dc iO = nO FDO dy
O,0 c iO = nO FDO (0)
page 5: 21
Combine Expressions
V = O,0 i K O exp ( bOV ) c O Rt ,O O O i O,0 = c ( 0 ) n FD
O O
page 5: 22
Current Density
= i O Rt ,O + V = Rt ,O + zd ,O
zd ,O =
V
O
nO FDO cO,0
1 1 bO (0)
O
nO FDO cO,0
1 1 bO (0)
Rt ,O
1 = K O cO,0 exp ( bOV )
page 5: 23
Calculate Impedance
dV dt =i O + j CdlV i i = i f + Cdl
V = i + j CdlV Rt ,O + zd ,O 1 j C =V + dl R +z t ,O d ,O
U = iRe + V ~ ~ ~ U = i Re + V
U V Z O = = Re + i i Rt ,O + zd ,O = Re + 1+j Cdl ( Rt ,O + zd ,O )
page 5: 24
Comparison to Circuit Analog

Z O = Re + 1+j Cdl ( Rt ,O + zd ,O )
Cdl
Rt ,O + zd ,O
Re
zd,O Rt,O
page 5: 25
Dependent on Potential and Adsorbed Intermediate
B P X X X X
k1 B X+ek2 X P+e-
Potential-dependent heterogeneous reactions Adsorption of intermediate on two-dimensional surface Maximum surface coverage
page 5: 26
Steady-State Current Density

reaction 1: formation of X
i1 = K1 (1 ) exp b1 (V V1 )
reaction 2: formation of P
i2 = K 2 exp b2 (V V2 )
total current density

i = i1 + i2
page 5: 27
Steady-State Surface Coverage

balance on
d i1 i2 = dt F F =0
steady-state value for
( = K exp ( b (V V ) ) + K
1 1 1
K1 exp b1 (V V1 )
2
) exp ( b (V V ) )
2 2
page 5: 28
Steady-State Current Density

i = K1 (1 ) exp b1 (V V1 ) + K 2 exp b2 (V V2 )
where
( = K exp ( b (V V ) ) + K
1 1 1
K1 exp b1 (V V1 )
2
) exp ( b (V V ) )
2 2
page 5: 29
Oscillating Current Density

i = K1 (1 ) exp b1 (V V1 ) + K 2 exp b2 (V V2 )
)
))
1 1 + i = V + K 2 exp b2 (V V2 ) K1 exp b1 (V V1 ) R t ,1 Rt ,2
Rt ,1 = K1b1 (1 ) exp b1 (V V1 ) Rt ,2 = K 2 b2 exp b2 (V V2 )
page 5: 30
Need Additional Equation

balance on
1 1 1 V K1 exp b1 (V V1 ) + K 2 exp b2 (V V2 ) j = F Rt ,1 Rt ,2
))
=
F j + K1 exp b1 (V V1 ) + K 2 exp b2 (V V2 )
1 1 Rt,1 Rt,2
))
V
page 5: 31
Impedance
1 1 K exp b V V K exp b V V R R ( ) ( ) t t 2 2 1 1 1 ,1 ,2 1 1 2 = + Z Rt F j + F K1 exp b1 (V V1 ) + K 2 exp b2 (V V2 )
( )
) (
))
1 A = + Rt j + B
where
1 1 1 = + Rt Rt , M Rt , X
page 5: 32
page 5: 33
page 5: 34
Potential, V (Cu/CuSO4)
Corrosion of Steel
i f = iFe + iH 2 + iO 2
-0.4
Fe Fe2+ + 2e-
-0.6
O2+2H2O + 4e- 4OH-
-0.8 -1.0
2H2O + 2e- H2+2OH-
-1.2 0.01
0.1 1 10 Current Density, mA/ft2
100
page 5: 35
Corrosion: Fe Fe2+ + 2eiFe = K Fe exp ( bFeV )
= K b exp ( b V )V i Fe Fe Fe Fe
~ V ~ iFe = Rt ,Fe
Rt ,Fe 1 = K FebFe exp ( bFeV )
page 5: 36
Steady Currents in Terms of Rt

iFe = K Fe exp ( bFeV )
iFe = K Fe exp ( 2.303V Fe )
Fe = 2.303/ bFe
Rt ,Fe
1 Fe = = K FebFe exp ( bFeV ) 2.303iFe
iFe =
Fe
2.303Rt ,Fe
Important: Note the relationship among steady-state current density, Tafel slope, and charge transfer resistance.
page 5: 37
H2 Evolution: 2H2O + 2e- H2+2OHiH 2 = K H 2 exp bH 2V
) )
= K b exp b V V i H2 H2 H2 H2
~ V ~ iH 2 = Rt ,H 2
Rt,H 2
1 = K H 2 bH 2 exp bH 2V
page 5: 38
O2 Reduction: O2+2H2O + 4e- 4OHiO2 = K O2 cO2 ,0 exp bO2V
= K b c exp b V V i O2 O2 O2 O2 ,0 O2 K O2 exp bO2
( V )c
O2 ,0
page 5: 39
O2 Evolution: O2+2H2O + 4e- 4OHmass transfer: in terms of dimensionless gradient at electrode surface
O = nO FDO i 2 2 2 O2 dc dy
0
O2 ,0 c = nO2 FDO2 ( 0 )
page 5: 40
O2 Evolution: O2+2H2O + 4e- 4OHcoupled expression

= i O2 V Rt ,O2 +
nO2 FDO2 cO2 ,0
1 bO2
1 (0)
V = Rt ,O2 + zd ,O2
zd ,O2 =
nO2 FDO2 cO2 ,0
1 bO2
1 (0)
Rt,O2
1 = K O2 bO2 cO2 ,0 exp bO2V
page 5: 41
Capacitance and Ohmic Contributions

Faradaic
if = if ~ ~ if = if
Faradaic and Charging
dV i = i f + Cd dt ~ ~ ~ i = i f + jCdV
U = iRe + V ~ ~ ~ U = i Re + V
Ohmic
page 5: 42
~ U Z = ~ = Z r + jZ j i = 1 1 + Rt,Fe Rt,H 2 1 + Reff Rt ,O 2
Process Model
1
1 + + j C d Rt ,O + z d ,O 2 2 1 1 + jCd + z d ,O 2
Zd,O2 Rt,Fe Cdl Rt,O2 Rt,H2
1 1 1 = + Reff Rt,Fe Rt,H2
page 5: 43
Development of Impedance Models

identify reaction mechanism write expression for steady state current contributions write expression for sinusoidal steady state sum current contributions account for charging current account for ohmic potential drop account for mass transfer calculate impedance
page 5: 44
Mass Transfer
page 5: 45
Film Diffusion
2 ci ci = Di 2 t z
steady state
ci ci , ci = ci ,0
ci = ci ,0 +
as at
z
z f z=0
ci ,0 )
(c
i ,
page 5: 46
Film Diffusion
2 ci ci = Di 2 t z
~ e jt } ci = ci + Re{c i
j ce
jt
i jt d 2 ci d 2c = Di + Di e 2 2 dz dz i jt d 2c = Di e 2 dz
2
jt j ce
i
f2
i d c = Di j c d z2
Di c i = i i (0) c
Ki =
d 2 i =0 jK i i 2 d
page 5: 47
Warburg Impedance
i = A exp jK i + B exp jK i
d 2 i =0 jK i i d2
i = 0 at = 1 i = 1 at = 0
tanh jK i 1 = i(0) jK i 1 = i(0) tanh j Di j 2 Di
2
i = 0 at = i = 1 at = 0
1 = i(0) 1 = i(0) 1 jK i 1 j 2 Di
page 5: 48
1.2
c()/c()
Concentration
-40
Diffusion Impedance Only (infinite) Diffusion Impedance Only (finite) Complete Impedance
1 t=0, 2n/K 0.8 0.6 0.4 t=n/K 0.2 0 0 0.5
t=0.5n/K
t=1.5n/K
K=1
-30
1.5
/
1.2 1 t=0, 2n/K t=0.5n/K
Zj, Zj,D,
-20
-10
0 0 10 20 30 40 50 60
c()/c()
0.8 0.6
t=1.5n/K 0.4 0.2 0 0 0.5 1 1.5 2 t=n/K
Zr, Zr,D,
K=100
page 5: 49
Rotating Disk
page 5: 50
Convective Diffusion
1 rci 2ci ci ci ci + vr + vz = Di + 2 r r r z t r z
3/ 2 2 a 2 1 3 b 4 v z = z + z + z + ... 3 6
1/ 2 3/ 2 2 b z vr = r a z z 3 + ... 2 3
1/ 2 3/ 2 a 3 v = r 1 b z + z + ... 3
page 5: 51
Convective Diffusion in one-Dimension

2 ci ci ci + vz = Di 2 t z z
zi s M = ne i i i
ci ci ,
as
ci sii f Di = z nF
i f = f ( , ci )
at
z=0
page 5: 52
Sinusoidal Steady State

~ e jt } ci = ci + Re{c i
j t j ce
i j t i j t d ci dc d 2ci d 2c + vz + vz e Di D e =0 i 2 2 dz dz dz dz
~ ~ d 2c dc ~ =0 i v z i jKi c i 2 d d
Ki =
9
2 a Di
9
1
1/3 2 Sci a
3D i = i a
3 3 1 = a Sc1/3 i
page 5: 53
Finite Length Warburg Impedance

ci vz =0 z = 2.598 1/ 3 Di2/ 3
tanh j j
z d = z d ( 0)
1 = i(0)
tanh
j 2 Di j 2 Di
2 2.598 Sc1/ 3 = = Di
page 5: 54
Impedance
d i di ~ v jK z i i =0 2 d d
2
~ ~ c ~ i ( ) = c i i ,0
i 0 as i = 1 at = 0
~
f i si Z D = Rt ~ c nFD i i , 0 ,c i i (0 ) j , j i
Z D ( 0) ZD = ~ i (0)
page 5: 55
Numerical Solutions
Infinite Sc
One Term
v z = ( a =z
2
; a = 0.51203
1 z d = z d ( 0) ( pSc1/3 ) 0 p =
Finite Sc
Two Terms
1 v z = a 2 + 3 3
Z1 ( pSc1/3 ) 1 z d = z d ( 0) ( pSc1/3 ) + Sc1/3 0
Three Terms
b = 0.616
1 b v z = a 2 + 3 + 4 3 6
Z1 ( pSc1/3 ) Z2 ( pSc1/3 ) 1 z d = z d ( 0) ( pSc1/3 ) + Sc1/3 + Sc 2/3 0
page 5: 56
Coupled Diffusion Impedance
zd ,outer zd =
Di ,outer i ,inner zd ,inner + Di ,inner i ,outer Di ,outer i ,inner + D i ,inner i , outer
2 inner zd ,inner zd ,outer j D i ,inner
page 5: 57
Interpretation Models for Impedance Spectroscopy

Models can account rigorously for proposed kinetic and mass transfer mechanisms. There are significant differences between models for mass transfer. Stochastic errors in impedance spectroscopy are sufficiently small to justify use of accurate models for mass transfer.
page 5: 58
Chapter 6. Regression Analysis
page 6: 1

Regression response surfaces
noise incomplete frequency range
Adequacy of fit
quantitative qualitative
page 6: 2
Test Circuit 1: 1 Time Constant
C1
R0 = 0 R1 = 1 cm2 1 = RC = 1 s
R0
(1)
R1
page 6: 3
Linear optimization surface roughly parabolic

f (p) =
i =1 N dat
(Z
r ,dat
Z r ,mod )
2 r
+
k =1
1.5
N dat
(Z
j ,dat
Z j ,mod )
2 j
0 0.02000 0.04000
0.05 0.04
Sum of Squares
0.06000
0.03 0.02 0.01 0.00 0.6 1.4 1.2 1.0 / 0.8 1.0
2
/s
1.0
0.08000 0.1000
0.8
0.5 0.5
1.0
1.5
2
R / cm
1.2
0.6 1.4
R / cm
page 6: 4
Nonlinear Regression
f f ( p) = f ( p0 ) + j =1 p j
Np
p0
1 p p 2 f p j + 2 j =1 k =1 p j pk
N N
p j pk +
p0
For our purposes:
f =y=Z xi = i
=
2 i =1
N dat
( yi y ( xi | p))2
i2
= p
k =
i =1
N dat
yi y ( xi | p) y ( xi | p) pk i2
j ,k
Variance of data
1 y ( xi | p) y ( xi | p) 2 p p i =1 i j k
N dat
Derivative of function with respect to parameter
page 6: 5
Methods for Regression

Evaluation of derivatives
method of steepest descent Gauss-Newton method Levenberg-Marquardt method
Evaluation of function
simplex
page 6: 6
Effect of Noisy Data

Add noise: 1% of modulus
1.5
1.000 75.75 150.5
/s
225.2
Sum of Squares
300 200 100 0 1.4 1.2 1.0 1.0 1.2 0.8 0.6 1.4 0.6 0.8
1.0
300.0
/s
0.5 0.5
1.0
1.5
2
R / cm
R / cm
response surface remains parabolic value at minimum increases
page 6: 7
Test Circuit 2: 3 Time Constants

R0 = 1 cm2 R1 = 100 cm2 1 = 0.001 s R2 = 200 cm2 2 = 0.01 s R3 = 5 cm2 3 = 0.05 s
C1
C2
C3
R0
(1)
R1
(2)
R2
(3)
R3
Note: 3rd Voigt element contributes only 1.66% to DC cell impedance.
page 6: 8
Effect of Noisy Data

no noise
10
3
noise: 1% of modulus
10
3
Sum of Squares
Sum of Squares
10
10
10
10
10
10
10
-1
10
-3 3 -2 2 1
2
-1
10 4
-2
-4
10 4
-2
-1 0 -1 -2 2 0 1
2
2
-1 0 -1 -2 2 0 1
-2
-3
-4
log10(R/ cm )
log10( / s)
log10(R/ cm )
log10( / s)
Note: use of log scale for parameters
All parameters fixed except R3 and 3
page 6: 9
Resulting Spectrum
-150
Zj / cm
-100 -50 0 0 50 100 150 200

2
250
300
350
Zr / cm
Model with 1% noise added Model with no noise
page 6: 10
Test Circuit 3: 3 Time Constants

R0 = 1 cm2 R1 = 100 cm2 1 = 0.01 s R2 = 200 cm2 2 = 0.1 s R3 = 100 cm2 3 = 10 s
C1
C2
C3
R0
(1)
R1
(2)
R2
(3)
R3
Note: 3rd Voigt element contributes 25% to DC cell impedance. The time constant corresponds to a characteristic frequency 3=0.1 s-1 or f3=0.016 Hz.
page 6: 11
Resulting Test Spectra

2
Zj / cm
-100
0 0 100 200 300

2
400
Zr / cm
0.01 Hz to 100 kHz 1 Hz to 100 kHz
page 6: 12
Effect of Truncated Data

0.01 Hz to 100 kHz
10
3
1 Hz to 100 kHz
10
3
Sum of Squares
10
Sum of Squares
10
10
10
10
-2 -1 10 5
0
-2 -1 10 5
-1
0 4 1 3 2
2
0 4 1 3 2 2
2
2 1 3 0 -1 4
log10( / s)
3 0 -1 4
log10( / s)
log10(R / cm )
log10(R / cm )
All parameters fixed except R3 and 3
page 6: 13
Conclusions from Test Spectra

The presence of noise in data can have a direct impact on model identification and on the confidence interval for the regressed parameters. The correctness of the model does not determine the number of parameters that can be obtained. The frequency range of the data can have a direct impact on model identification. The model identification problem is intricately linked to the error identification problem. In other words, analysis of data requires analysis of the error structure of the measurement.
page 6: 14
When Is the Fit Adequate?

Chi-squared statistic
includes variance of data should be near the degree of freedom
Visual examination
should look good some plots show better sensitivity than others
Parameter confidence intervals

based on linearization about solution should not include zero
page 6: 15
Test Case: Mass Transfer to a RDE

Z ( ) = Re + 1 + ( j C ) ( Rt + z d ( ) ) R t + z d ( )
Single reaction coupled with mass transfer. Consider model for a Nernst stagnant diffusion layer:
z d ( ) = z d ( )
tanh
j j
page 6: 16
Evaluation of 2 Statistic
/|Z()|
2 2/ 1 0.1 0.05 0.03 0.01
0.0408
4.08
16.32
45.32
408
0.00029
0.029
0.12
0.32
2.9
page 6: 17
Comparison of Model to Data

Impedance Plane (Nyquist)
80
Zj /
60 40 20 0 0 20 40 60 80 100 120 140 160 180 200
Value of 2 has no meaning without accurate assessment of the noise level of the data
Zr /
page 6: 18
Modulus
100
|Z| /
10
10
-2
10
-1
10
10
10
10
10
f / Hz
page 6: 19
Phase Angle
-45
/ degrees
-30
-15
0 -2 10
10
-1
10
10
10
10
10
f / Hz
page 6: 20
Real
200 160 120 80 40 0 -2 10
Zr /
10
-1
10
10
10
10
10
f / Hz
page 6: 21
Imaginary
80
60
Zj /
40
20
0 -2 10
10
-1
10
10
10
10
10
f / Hz
page 6: 22
Log Imaginary
100 Slope = -1 for RC
Zj /
10
1 -2 10
10
-1
10
10
10
10
10
f / Hz
page 6: 23

-90 -75
/ degrees
-60 -45 -30 -15 0 -2 10
Zj * = tan Z R e r
1
10
-1
10
10
10
10
10
f / Hz
page 6: 24
Real Residuals
0.06 0.04 0.02
r / Zr
0 -0.02 -0.04 -0.06 -2 10
2 noise level
10
-1
10
10
10
10
10
f / Hz
page 6: 25
Imaginary Residuals
0.3 0.2 0.1
j / Zj
0 -0.1 -0.2 -0.3 -2 10
2 noise level
10
-1
10
10
10
10
10
f / Hz
page 6: 26
Plot Sensitivity to Quality of Fit

Poor Sensitivity
Modulus Real
Modest Sensitivity
Impedance-plane
only for large impedance values
Imaginary Log Imaginary

emphasizes small values slope suggests new models
Phase Angle
high-frequency behavior is counterintuitive due to role of solution resistance

high-frequency behavior can suggest new models needs an accurate value for solution resistance
Excellent Sensitivity
Residual error plots
trending provides an indicator of problems with the regression
page 6: 27
Test Case: Better Model for Mass Transfer to a RDE

Z ( ) = Re + 1 + ( j ) Q ( R t + z d ( ) )
Rt + z d ( )
Consider 3-term expansion with CPE to account for more complicated reaction kinetics:
1/3 1/3 Z p Sc Z p Sc ) ) 1 1( 2( + + zd = zd (0) 1/3 2/3 1/3 0 ( pSc ) Sc Sc
2/=4.86
page 6: 28
Comparison of Model to Data

Impedance Plane (Nyquist)
80
Zj /
60 40 20 0 0 20 40 60 80 100 120 140 160 180 200
Zr /
page 6: 29
Phase Angle
-45
-30
Zj /
-15 0 -2 10
10
-1
10
10
10
10
10
f / Hz
page 6: 30

-90 -75
/ degrees
-60 -45 -30 -15 0 -2 10
Zj * = tan Z R e r
1
10
-1
10
10
10
10
10
f / Hz
page 6: 31
Log Imaginary
100
Zj /
10
1 -2 10
10
-1
10
10
10
10
10
f / Hz
page 6: 32
Real Residuals
0.006
0.003
r / Zr
-0.003
2
-0.006 -2 10 10
-1
10
10
10
10
10
f / Hz
page 6: 33
Imaginary Residuals
0.02
0.01
j / Zj
-0.01
2
-0.02 -2 10 10
-1
10
10
10
10
10
f / Hz
page 6: 34
Confidence Intervals
Based on linearization about trial solution Assumption valid for good fits
for normally distributed fitting errors small estimated standard deviations
Can use Monte Carlo simulations to test assumptions
page 6: 35
Regression of Models to Data

Regression is strongly influenced by
stochastic errors in data incomplete frequency range incorrect or incomplete models
Some plots more sensitive to fit quality than others. Quantitative measures of fit quality require independent assessment of error structure. The model identification problem is intricately linked to the error identification problem.
page 6: 36
Chapter 7. Error Structure
page 7: 1

Contributions to error structure Weighting strategies General approach for error analysis Experimental results
page 7: 2
Error Analysis Increasingly Important

Improved Instrumentation
improved signal-to-noise more data more detailed interpretation of data possible
New experimental techniques

more ways to study a system proper weight must be assigned to each experiment error analysis used to improve experimental design
Improved computational speed

increased use of regression increased use of detailed models
page 7: 3
Contributions to Error Structure

Sampling Errors Stochastic Phenomena Bias Errors
Lack of Fit Changing baseline (non-stationary processes) Instrumental artifacts
page 7: 4
Time-domain Frequency Domain
1 mHz
10 Hz
100 Hz
10 kHz
page 7: 5
Error Structure
resid ( ) = Z obs ( ) Z model ( ) = fit ( ) + bias ( ) + stochastic ( )

fitting error
inadequate model
noise (frequency domain)
experimental errors: inconsistent with the Kramers-Kronig relations
page 7: 6
Weighting Strategies
J=
k
)2 ( Z r ,k Z r ,k r ,k
2
+
k
)2 ( Z j ,k Z j ,k j ,k 2
Implications
Strategy
No Weighting Modulus Weighting Proportional Weighting Experimental Refined Experimental
r=j = r=j = || rj r = r|r|; j = j|j| r=j = |j| + |r| + ||2/Rm r=j = |j| + |r-Rsol| + ||2/Rm+
page 7: 7
Assumed Error Structure often Wrong

100000 6 Repeated Measurements 10000
Real
Impedance,
1000
3% of |Z| 1% of |Z|
100
Imaginary
10
1 0.1 1 10 100 1000 10000 100000
Frequency, Hz
Data obtained by T. El Moustafid, CNRS, Paris, France
page 7: 8
Reduction of Fe(CN)63- on a Pt Disk, 120 rpm

-300
I/ilim 1/4 1/2 3/4
-200
Zj,
-100 0 0 100 200
Zr,
300
400
500
page 7: 9
Reduction of Fe(CN)63- on a Pt Disk,

Imaginary Replicates @ 120 rpm, 1/4 ilim
-80
-60
Zj,
-40
-20
0 0.01 0.1 1 10 100 1000 10000 100000
Frequency, Hz
page 7: 10

Real Replicates @ 120 rpm, 1/4 ilim
1000
100
Zr,
10 1 0.01 0.1 1 10 100 1000 10000 100000
Frequency, Hz
page 7: 11

Error Structure @ 120 rpm, 1/4 ilim
10
Standard Deviation,
0.1
0.01
0.001 0.01 0.1 1 10 100 1000 10000 100000
Frequency, Hz
page 7: 12

Error Structure @ 120 rpm, 1/4 ilim
100
10
/|Z|, Percent
0.1
0.01 0.01 0.1 1 10 100 1000 10000 100000
Frequency, Hz
page 7: 13
Interpretation of Impedance Spectra

Need physical insight and knowledge of error structure
stochastic component
weighting determination of model adequacy experimental design
bias component
suitable frequency range experimental design
Approach is general
electrochemical impedance spectroscopies optical spectroscopies mechanical spectroscopies
page 7: 14
Chapter 8. Kramers-Kronig Relations
page 8: 1

Mathematical form and interpretation Application to noisy data Methods to evaluate consistency
page 8: 2
Contraints
Under the assumption that the system is
Causal Linear Stable
A complex variable Z must satisfy equations of the form: 2 Z r ( x) Z r ( ) Z j ( ) = dx 2 2 x

0
2 xZ j ( x) + Z j ( ) Z r ( ) = Z r () + dx 2 2 x
0
page 8: 3
Use of Kramers-Kronig Relations

Concept
if data do not satisfy Kramers-Kronig relations, a condition of the derivation must not be satisfied
stationarity / causality linearity stability
interpret result in terms of

instrument artifact changing baseline
if data satisfy Kramers-Kronig relations, conditions of the derivation may be satisfied
page 8: 4
For real data (with noise)

Z ob ( ) = Z ( ) + ( ) = ( Z r ( ) + r ( )) + j ( Z j ( ) + j ( ))
where
( ) = r ( ) + j j ( )
If and only if
E (Z ( ) ob ) = Z ( )
E ( ( ) ) = 0
Kramers-Kronig in an expectation sense

2 Z r ( x) Z r ( ) + r ( x) r ( ) E (Z j ( ) ) = E dx x2 2 0
xZ ( x) + Z ( ) x ( x) + ( ) 2 j j j j E (Z r ( ) Z r () ) = E dx x2 2 0
page 8: 5
The Kramers-Kronig relations can be satisfied if

E ( ( ) ) = 0
and
2 ( x) =0 r E dx 2 2 x 0
This means
the process must be stationary in the sense of replication at every measurement frequency. As the impedance is sampled at a finite number of frequencies, r(x) represents the error between an interpolated function and the true impedance value at frequency x. In the limit that quadrature and interpolation errors are negligible, the residual errors r(x) should be of the same magnitude as the stochastic noise r().
Meaning of
2 r ( x) E dx 2 2 x 0
=0
page 8: 6
(Zr(x)-Zr()) / (x - )
Correct Value -100 Interpolated Value -200
(Zr(x)-Zr()) / (x - )
-200 -400 -600 -800 -1000 10

-4
-300
-400 0.2
0.5
f / Hz
10
-3
10
-2
10
-1
10
10
10
10
10
10
f / Hz
page 8: 7
Use of Kramers-Kronig Relations

Quadrature errors
require interpolation function
Missing data at low and high frequency
page 8: 8
Methods to Resolve Problems of Insufficient Frequency Range

Direct Integration
Extrapolation
single RC polynomials 1/ and asymptotic behavior
simultaneous solution for missing data
Regression
proposed process model generalized measurement model
page 8: 9
Chapter 9. Use of Measurement Models
page 9: 1

Generalized model Identification of stochastic component of error structure Identification of bias component of error structure
page 9: 2
Approach
Experimental design
quality (signal-to-noise, bias errors) information content
Process model
account for known phenomena extract information concerning other phenomena
Regression
uncorrupted frequency range weighting strategy
Error analysis - measurement model

stochastic errors bias errors
page 9: 3
Error Structure
Z obs Z model = res Z obs Z model = fit + bias + stoch
Stochastic errors Bias errors
lack of fit experimental artifact
Kramers-Kronig consistent Kramers-Kronig inconsistent
page 9: 4
Measurement Model
Superposition of lineshapes
Rk Z = R0 + k =1 1 + j Rk Ck
page 9: 5
Identification of Stochastic Component of Error Structure

How?
Replicate impedance scans. Fit measurement model to each scan:
use modulus or noweighting options. same number of lineshapes. parameter estimates do not include zero.
Why?
Weight regression. Identify good fit. Improve experimental design.
Calculate standard deviation of residual errors. Fit model for error structure.
page 9: 6
Replicated Measurements
100
-Zj /
50
0 0 50 100 150 200
Zr /
page 9: 7
1 Voigt Element
100
-Z j /
50
0 0 50 100 150 200
Zr /
page 9: 8
2 Voigt Elements
100
-Z j /
50
0 0 50 100 150 200
Zr /
page 9: 9
3 Voigt Elements
100
-Z j /
50
0 0 50 100 150 200
Zr /
page 9: 10
4 Voigt Elements
100
-Z j /
50
0 0 50 100 150 200
Zr /
page 9: 11
5 Voigt Elements
100
-Z j /
50
0 0 50 100 150 200
Zr /
page 9: 12
6 Voigt Elements
100
-Z j /
50
0 0 50 100 150 200
Zr /
page 9: 13
10 Voigt Elements
100
-Z j /
50
0 0 50 100 150 200
Zr /
page 9: 14
0.03
imaginary
Residual Errors
j / Zj
-0.03 0.01 0.1 1 10 100 1000 10000 100000
Frequency / Hz
0.005
real
r / Zr
0
-0.005 0.01 0.1 1 10 100 1000 10000 100000
Frequency / Hz
page 9: 15
Residual Sum of Squares

1000000 100000 10000
(2/2)
1000 100 10 1 0.1 1 3 5 7 9 11
# Voigt Elements
page 9: 16
Fit to Repeated Data Sets

100
-Z j /
50
0 0 50 100 150 200
Zr /
page 9: 17
Residual Errors
Real
0.005
r / Z r
-0.005 0.01 0.1 1 10 100 1000 10000 100000
Frequency / Hz
page 9: 18
Standard Deviation of Residual Errors

Imaginary
0.02
j / Z j
-0.02 0.01 0.1 1 10 100 1000 10000 100000
Frequency / Hz
page 9: 19
Standard Deviation
10
direct calculation of standard deviation Imaginary Real
Standard Deviation,
0.1
0.01
standard deviation obtained from measurement model analysis
0.001 0.01 0.1 1 10 100 1000 10000 100000
Frequency, Hz
page 9: 20
Comparison to Impedance
1000 100 10
Real Imaginary 3% of |Z|
Z or ,
1 0.1 0.01
0.001 0.01 0.1 1 10 100 1000 10000 100000
Frequency, Hz
page 9: 21
Identification of Bias Component of Error Structure

How?
Fit measurement model to real component:
predict imaginary component. Use Monte Carlo calculations to estimate confidence interval.
Why?
Identify suitable frequency range for regression. Improve experimental design.
Fit measurement model to imaginary component:

predict real component. Use Monte Carlo calculations to estimate confidence interval.
page 9: 22
1st of Repeated Measurements

Imaginary
-80
-60
Zj /
-40
-20
0 0.01 0.1 1 10 100 1000 10000 100000
Frequency / Hz
page 9: 23
1st of Repeated Measurements

Real
1000
100
Zr /
10 1 0.01 0.1 1 10 100 1000 10000 100000
Frequency / Hz
page 9: 24
Fit to Imaginary Part

100
-Z j /
50
0 0.01 0.1 1 10 100 1000 10000 100000
Frequency / Hz
page 9: 25
Fit to Imaginary Part

0.03
j / Z j
-0.03 0.01 0.1 1 10 100 1000 10000 100000
Frequency / Hz
page 9: 26
Predict Real Part

200
190
150
170
Zr /
100
150 0.01
50
0.1
0 0.01 0.1 1 10 100 1000 10000 100000
Frequency / Hz
page 9: 27
Predict Real Part

0.03
r / Z r
-0.03 0.01 0.1 1 10 100 1000 10000 100000
Frequency / Hz
page 9: 28
Validation of Measurement Model Approach
page 9: 29
The error structure identified should be independent of measurement model used

Voigt:
Ri Z () = R0 + i =1 1+ ( j) i
ni b ( j ) i nj a ( j ) j j =0 i =0 P M
Transfer Function:
Z () =
n = 1/ 2
b0 + b1( j)1/ 2 + b2 ( j) ++ bM ( j)M / 2 Z () = ; 1/ 2 P/ 2 a0 + a1( j) + a2 ( j) ++ ( j)
M = P; aP = 1
page 9: 30

Reduction of Fe(CN)63- on a Pt Disk: i/ilim = ; 120 rpm
-80 -60
0 0.33 0.66 1.0 1.34 1.67 1.99 2.33 8.93 9.25 9.58 9.91 0.15 Hz
Zj /
-40 -20 0 0
0.0.022 Hz
40
80
120
160
200
Zr /
page 9: 31

Reduction of Fe(CN)63- on a Pt Disk: i/ilim = ; 120 rpm
real part
-80
200 160
0 0.33 0.66 1.0 1.34 1.67 1.99 2.33 8.93 9.25 9.58 9.91
imaginary part
-70 -60 -50
0 0.33 0.66 1.0 1.34 1.67 1.99 2.33 8.93 9.25 9.58 9.91
Zr /
Zj /
103 104 105
120 80 40 0 10-2 10-1 100 101
-40 -30 -20 -10 0
102
10-2
10-1
100
101
102
103
104
105
f / Hz
f / Hz
page 9: 32
Data Sets for Analysis

-86
1 2
measurement before impedance scan after impedance scan
-87
Current / mA
-88 -89 -90 -91 -92 0 2 4 6 8 10
time / h
page 9: 33
Regression Results for Set #1: 0-1 h

Data:
74 frequencies 148 data points 10 elements + Re 21 parameters
Current / mA
-86
1 2 3
-87 -88 -89 -90 -91 -92 0 2 4 6 8 10
Voigt Model:
Transfer Function:
5 ai + 6 bi 11 parameters
time / h
page 9: 34
Stochastic Error Structure for Set #1: Voigt

100
Z , Z /
10-1
10-2
real imag direct VMM
10-3
10-2
10-1
100
101
102
103
104
105
f / Hz
page 9: 35
Stochastic Error Structure for Set #1: Voigt & Transfer Function
100
Z , Z / r j
10-1
10-2
real imag direct VMM
10-3
10-2
10-1
100
101
102
103
104
105
f / Hz
page 9: 36
Regression Results for Set #3: 8.9-9.9 h

Data:
74 frequencies 148 data points 9 elements + Re 19 parameters
Current / mA
-86
1 2 3
-87 -88 -89 -90 -91 -92 0 2 4 6 8 10
Voigt Model:
Transfer Function:
5 ai + 6 bi 11 parameters
time / h
page 9: 37
Stochastic Error Structure for Set #3: Voigt

100
Z , Z / r j
10-1
10-2
real imag VMM
10-3
10-2
10-1
100
101
102
103
104
105
f / Hz
page 9: 38
Stochastic Error Structure for Set #3: Voigt & Transfer Function
100
Z , Z / r j
10-1
10-2
real imag TMM VMM
10-3
10-2
10-1
100
101
102
103
104
105
f / Hz
page 9: 39
Identification of Stochastic Component of Error Structure

Direct evaluation of standard deviation includes significant contributions from changes in system behavior The error structure identified was independent of measurement model used Selection of measurement model
Ease of identification of initial parameters Voigt Number of parameters Transfer Function
page 9: 40
Evaluation of Consistency with the Kramers-Kronig relations

Approach
Fit measurement model to imaginary component Use experimental variance to weight regression Predict real component Compare prediction to measured data Use Monte Carlo calculations to estimate confidence interval
Assumption
Measurement model satisfies the Kramers-Kronig relations
page 9: 41
Voigt Measurement Model: Data 1

Fit to Imaginary
0.02 0.04
Prediction of Real
(Zr-Zr,mod) / Zr,mod
0.02
(Zj-Zj,mod) / Zj,mod
0.01
-0.01
-0.02
-0.02 10-2 10-1 100 101 102 103 104 105
-0.04 10-2 10-1 100 101 102 103 104 105
f / Hz
f / Hz
20 parameters, guessed value for Re Tight confidence interval at low frequency Justify deleting 5 data points at lowest frequency
page 9: 42
Voigt Measurement Model: Data 5

Fit to Imaginary
0.010 0.04
Prediction of Real
(Zr-Zr,mod) / Zr,mod
(Zj-Zj,mod) / Zj,mod
0.005
0.02
-0.005
-0.02
-0.010 10
-2
-0.04 10
-1
10
10
10
10
10
10
10-2
10-1
100
101
102
103
104
105
f / Hz
f / Hz
20 parameters, guessed value for Re Justify keeping all data points
page 9: 43
Interpretation of Impedance Spectra

Physical insight and knowledge of error structure
stochastic component
weighting determination of model adequacy experimental design
bias component
suitable frequency range experimental design
Measurement model approach is general

electrochemical impedance spectroscopies optical spectroscopies mechanical spectroscopies
page 9: 44
Chapter 10. Conclusions
page 10: 1

Overview of Course Credits
page 10: 2
Overview of Course
page 10: 3
Electrochemical measurement of macroscopic properties Example of a generalized transfer-function measurement Can be used to extract contributions of
electrode reactions mass transfer surface layers
Can be used to estimate

reaction rates transport properties
Interpretation of data
graphical representations regression process models error analysis
Integrated Approach
page 10: 4
Acknowledgements
page 10: 5
Students
University of Florida
P. Agarwal, M. Durbha, S. Carson, M. Membrino, P. Shukla, V. Huang, S. Roy, B. Hirschorn, S-L Wu
CNRS
T. El Moustafid, I. Frateur, H. G. de Melo
CIRIMAT
J-B Jorcin
Collaborators
University of South Florida
L. Garca-Rubio
University of Florida
O. Crisalle
CNRS, Paris
B. Tribollet, C. Deslouis, H. Takenouti, V. Vivier
CIRIMAT, Toulouse
N. Pbre
CNR, Italy
M. Musiani
Funding
NSF, ONR, SC Johnson, CNRS, NASA
Other
The Electrochemical Society The Fuel Cell Seminar
page 10: 6
Chapter 11. Suggested Reading
page 11: 1

General Process Models Orazem group work on Fuel Cells Measurement Models CPE Plotting
page 11: 2
Suggested Reading
General
J. R. Macdonald, editor, Impedance Spectroscopy Emphasizing Solid Materials and Analysis, John Wiley and Sons, New York, 1987. E. Barsoukov and J. R. Macdonald, editors, Impedance Spectroscopy: Theory, Experiment, and Applications, 2nd Edition, John Wiley and Sons, New York, 2005. C. Gabrielli, Use and Applications of Electrochemical Impedance Techniques, Technical Report, Schlumberger, Farnborough, England, 1990. D. Macdonald, Transient Techniques in Electrochemistry, Plenum Press, NY, 1977. M. E. Orazem and B. Tribollet, Electrochemical Spectroscopy, John Wiley and Sons, New York, 2008. Other Sources
See instrument vendor websites for for application notes.
Impedance
page 11: 3
Suggested Reading
Process Models
A. Lasia, Electrochemical Impedance Spectroscopy and Its Applications, Modern Aspects of Electrochemistry, 32, R. E. White, J. O'M. Bockris and B. E. Conway, editors, Plenum Press, New York, 1999, 143-248. C. Deslouis and B. Tribollet, Flow Modulation Techniques in Electrochemistry, Advances in Electrochemical Science and Engineering, 2, H. Gerischer and C. W. Tobias, editors, VCH, Weinheim, 1992, 205-264. M. E. Orazem, Tutorial: Application of Mathematical Models for Interpretation of Impedance Spectra, Tutorials in Electrochemical Engineering - Mathematical Modeling, PV 99-14, R.F. Savinell, A.C. West, J.M. Fenton and J. Weidner, editors, Electrochemical Society, Inc., Pennington, N.J., 68-99, 1999. B. Tribollet, Look-up Tables for Rotating Disk Electrode, April 28, 2000, http://www.ccr.jussieu.fr/lple/EnglishVersion.html
page 11: 4
Suggested Reading
Orazem group work on Fuel Cells
S. K. Roy and M. E. Orazem, Error Analysis of the Impedance Response of PEM Fuel Cells, Journal of the Electrochemical Society, 154 (2007), B883-B891 S. K. Roy and M. E. Orazem, Deterministic Impedance Models for Interpretation of Low-Frequency Inductive Loops in PEM Fuel Cells, in Proton Exchange Membrane Fuel Cells 6, T. Fuller, C. Bock, S. Cleghorn, H. Gasteiger, T. Jarvi, M. Mathias, M. Murthy, T. Nguyen, V. Ramani, E. Stuve, T. Zawodzinski, editors, ECS Transactions, 3:1 (2006), 1031-1040. S. K. Roy and M. E. Orazem, Stochastic Analysis of Flooding in PEM Fuel Cells by Electrochemical Impedance Spectroscopy, in Proton Exchange Membrane Fuel Cells 7, T. Fuller, H. Gasteiger, S. Cleghorn, V. Ramani, T. Zhao, T. Nguyen, A. Haug, C. Bock, C. Lamy, and K. Ota, editors, Electrochemical Society Transactions, 11:1 (2007), 485495. S. K. Roy, M. E. Orazem, and B. Tribollet Interpretation of LowFrequency Inductive Loops in PEM Fuel Cells, Journal of the Electrochemical Society, 154 (2007), B1378-B1388.
page 11: 5
Suggested Reading
CPE
G. J. Brug, A. L. G. van den Eeden, M. Sluyters-Rehbach, and J. H. Sluyters, The Analysis of Electrode Impedances Complicated by the Presence of a Constant Phase Element, Journal of Electroanalytic Chemistry, 176 (1984), 275-295. V. Huang, V. Vivier, M. Orazem, N. Pbre, and B. Tribollet, The Apparent CPE Behavior of an Ideally Polarized Blocking Electrode: A Global and Local Impedance Analysis, Journal of the Electrochemical Society, 154 (2007), C81-C88. V. Huang, V. Vivier, M. Orazem, I. Frateur, and B. Tribollet, The Global and Local Impedance Response of a Blocking Disk Electrode with Local CPE Behavior, Journal of the Electrochemical Society, 154 (2007), C89-C98. V. Huang, V. Vivier, M. Orazem, N. Pbre, and B. Tribollet, The Apparent CPE Behavior of a Disk Electrode with Faradaic Reactions: A Global and Local Impedance Analysis, Journal of the Electrochemical Society, 154 (2007), C99-C107.
page 11: 6
Suggested Reading
Measurement Models
P. Agarwal, M. E. Orazem, and L. H. Garca-Rubio, "Measurement Models for Electrochemical Impedance Spectroscopy: 1. Demonstration of Applicability," Journal of the Electrochemical Society, 139 (1992), 1917-1927. P. Agarwal, Oscar D. Crisalle, M. E. Orazem, and L. H. Garca-Rubio, "Measurement Models for Electrochemical Impedance Spectroscopy: 2. Determination of the Stochastic Contribution to the Error Structure," Journal of the Electrochemical Society, 142 (1995), 4149-4158. P. Agarwal, M. E. Orazem, and L. H. Garca-Rubio, "Measurement Models for Electrochemical Impedance Spectroscopy: 3. Evaluation of Consistency with the Kramers-Kronig Relations, Journal of the Electrochemical Society, 142 (1995), 4159-4168. M. E. Orazem A Systematic Approach toward Error Structure Identification for Impedance Spectroscopy, Journal of Electroanalytical Chemistry, 572 (2004), 317-327.
page 11: 7
Suggested Reading
Plotting
M. Orazem, B. Tribollet, and N. Pbre, Enhanced Graphical Representation of Electrochemical Impedance Data, Journal of the Electrochemical Society, 153 (2006), B129-B136.

Chapter 12. Notation
Roman Greek
page 12: 2
Roman
a
b
coefficient in the Cochran expansion for velocity, a = 0.51023 coefficient in the Cochran expansion for velocity, b = -0.61592 concentration of reacting species i , mol/cm3 steady-state value of the concentration of reacting species i , mol/cm3 Oscillating component of the concentration of reacting species i , mol/cm3 concentration of species i on the electrode surface, mol/cm3 steady-state value of the concentration of species i on the electrode surface, mol/cm3 Oscillating component of the concentration of species i on the electrode surface, mol/cm3 bulk concentration of the reacting species, mol/cm3 double layer capacitance, F/cm2 double layer capacitance, F/cm2 diffusion coefficient of species i , cm2/s arbitrary function, e.g., i f = f (V , ci ) Faradays constant, C/equiv Total current density, A/cm2 Steady-state total current density, A/cm2
ci ci i c
ci ,o ci ,o i ,o c
c
Cd C dl Di
f
F
i

i
page 12: 3
Oscillating component of total current density, A/cm2 Faradic current density, A/cm2 Steady-state Faradic current density, A/cm2 Oscillating component of Faradic current density, A/cm2 Exchange current density, A/cm2 imaginary number,
if if
i f
i0
j
kA
rate constant for reaction identified by index A (units depend on reaction stoichiometry) dimensionless frequency, Ki = notation for species i number of electrons produced when one reactant ion or molecule reacts universal gas constant, J/mol/K Ohmic resistance, cm2 Charge-transfer resistance associated with reaction A, cm2 radial coordinate, cm radius of disk, cm stoichiometric coefficient for species i , ( si > 0 for a reactant and si < 0 for a product)
9
a 2 Di
1/3 2 Sci a
Mi
n
R
Re
Rt , A
r
r0 si
Chapter 12. Notation Sci Schmidt number, Sci = / Di electrolyte temperature, K time, s radial and axial velocity components, respectively, cm/s potential, V steady-state potential, V oscillating contribution to potential, V impedance, cm2 axial position, cm diffusion impedance, cm2 charge for species i
page 12: 4
T t
vr , v z
V
V
V
Z
z
zd zi
Greek
coefficient used in the exponent for a constant-phase element. When = 0 , the element behaves as an ideal capacitor in parallel with a resistor. apparent transfer coefficient for reaction A Tafel slope for reaction A, V Fractional surface coverage by species i
A A
i
page 12: 5
Maximum surface coverage characteristic diffusion length for species i homogeneous solution to the oscillating dimensionless convective diffusion equation derivative of the solution to the oscillating dimensionless convective diffusion equation evaluated at the electrode surface surface overpotential, V solution conductivity, ( cm)-1 characteristic length for a finite-length diffusion layer, = 2.598 1/ 3 Di2 / 3 / viscosity, g/cm s kinematic viscosity, = / , cm2/s density, g/cm3 finite-length diffusion time constant, = 2 / Di normalized axial position, = z / i ohmic potential, V frequency of perturbation, rad/s rotation speed, rad/sec
i

(0)

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Electrochemical Impedance Spectroscopy

Electrochemical Impedance Spectroscopy

Electrochemical Impedance Spectroscopy

Mark E. Orazem, 2000-2007. All rights reserved.

The Blind Men and the Elephant

Electrochemical Impedance Spectroscopy

Measurement in terms of macroscopic quantities

Not a chemical spectroscopy Type of generalized transfer-function measurement

Electrochemical Reactions Electrical Circuit Analogues

O2 F iF = iO2 = nO2 FkO2 cO2 exp V VO2 RT

Total current density = Faradaic + charging

Simple electrochemical reaction with mass transfer

Electrochemical Impedance Spectroscopy

Mark E. Orazem, 2000-2007. All rights reserved.

Steady-State Polarization Curve

0 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35

Transient Response to a Step in Potential

Transient Response to a Step in Potential

Short times/high frequency

long times/low frequency

Transient Techniques: potential or current steps

Limited by accuracy of measurements

Limited by sample rate

10 kHz 100 Hz 1 mHz

-1.0 -1.0 -0.5 0.0 0.5 1.0

-1.0 -1.0 -0.5 0 0.5 1.0

-20 -15 -10 -5 0 0 10 20 30

System with Large Ohmic Resistance

R0 =10,000 R1 =1,000 C1 = 10.5 F

1000 100 10 1 0.1 0.1 1 10 100

100 10 1 0.1 0.01 0.1 1 10 100 1000 10000 100000

Impedance Spectroscopy vs. Step-Change Transients

Better decoupling of physical phenomena

Chapter 3. Impedance Measurement

Electrochemical Impedance Spectroscopy

Mark E. Orazem, 2000-2008. All rights reserved.

Chapter 3. Impedance Measurement

Chapter 3. Impedance Measurement

Chapter 3. Impedance Measurement

V OA A'A | Z |= = = I OB B'B OD D'D sin( ) = = OA A'A

Chapter 3. Impedance Measurement

Phase Sensitive Detection

Has maximum value when

Chapter 3. Impedance Measurement

1 I r ( ) = I (t ) cos(t )dt T 0 1 I j ( ) = I (t ) sin(t )dt T 0 1 Vr ( ) = V (t ) cos(t )dt T 0 1 V j ( ) = V (t ) sin(t )dt T 0

Chapter 3. Impedance Measurement

Fast Fourier Transform

Chapter 3. Impedance Measurement

Chapter 3. Impedance Measurement

Phase-sensitive detection (lock-in amplifier)

Fourier analysis techniques

Chapter 3. Impedance Measurement

Chapter 3. Impedance Measurement

Chapter 3. Impedance Measurement

0.5 0.0 -0.5 -1.0

1.0 0.5 0.0 -0.5 -1.0

0.5 0.0 -0.5 -1.0

0.5 0.0 -0.5 -1.0

Chapter 3. Impedance Measurement

Influence of Nonlinearity on Impedance

Chapter 3. Impedance Measurement

Influence of Nonlinearity on Impedance

0.6 0.4 0.2

Chapter 3. Impedance Measurement