Electrochemical Impedance Spectroscopy page 1

Electrochemical Impedance Spectroscopy

Mark E. Orazem
Department of Chemical Engineering
University of Florida
Gainesville, Florida 32611

[email protected]
http://www.che.ufl.edu/orazem/

352-392-6207

 Mark E. Orazem, 2000-2021. All rights reserved.

Electrochemical Impedance Spectroscopy page 2

Electrochemical Impedance Spectroscopy

• History
• Basic idea
• EIS in my group
• Unique applications
• Modeling concepts
• Graphical methods
Electrochemical Impedance Spectroscopy page 3

Orazem and Tribollet, Electrochemical Impedance Spectroscopy, 2nd edition,

Wiley, Hoboken, 2017

• Help readers make better impedance

measurements
• Provide systematic way to analyze data in terms
of physical phenomena
• Provide alternatives to electrical circuit analysis
• Emphasize that EIS is not a stand-alone technique
 Electrochemical Impedance Spectroscopy page 4

Engineering Village: “(impedance or admittance)+electrochemical”

10000 2nd edition published 2017

电化学阻抗谱 published 2014

Number of Articles
1st edition of our
book published 2008
1000

1989 1st EIS Symposium

1988 Orazem joins UF
1983 Orazem receives PhD from Berkeley
100 joins the University of Virginia
1981 Orazem and Tribollet meet at Berkeley

10
1980 1990 2000 2010 2020

Search conducted on July 27, 2021 Year Published

Electrochemical Impedance Spectroscopy page 5

When did Electrochemical Impedance

Spectroscopy Begin?
Electrochemical Impedance Spectroscopy page 6

10000 Back to Engineering Village search

conducted on July 27, 2021

Number of Articles
1000

100

10

1
1900 1920 1940 1960 1980 2000 2020

Year Published
In The Beginning…

Sistine Chapel ceiling, Michelangelo, 1508 - 1512

In Prehistoric Times…

Lascaux Caves, southwestern France, ~15,000 BC

−Z j

Zr

Lascaux Caves, southwestern France, ~15,000 BC

 Electrochemical Impedance Spectroscopy page 10

Oliver Heaviside (1850 – 1925)

Mathematical Foundation
• Linear Systems Theory
• Coined Terms
– conductance (1885)
– impedance (1886)
– admittance (1887)
• Developed
transmission line
model for
transatlantic cable

D. D. Macdonald, “Reflections on the History of Electrochemical Impedance Spectroscopy,” Electrochim.

Acta, 51 (2006), 1376-1388
 Electrochemical Impedance Spectroscopy page 11

Sir Charles Wheatstone (1802 – 1875)

Experimental Foundation

C. Wheatstone, “An Account of Several New Instruments and Processes for Determining the Constants of a
Voltaic Circuit,” Phil. Trans. R. Soc., 133 (1843) 303–327.
Electrochemical Impedance Spectroscopy page 12

Friedrich Kohlrausch (1840 – 1910)

Measurement of electrolyte resistivity

Polarization capacitance Cn
and phase shift ψ

C. Gabrielli, “Once upon a time there was EIS,” Electrochim. Acta, 331 (2020), 135324.
F. Kohlrausch, Ann. Phys., 148 (1873), 143.
Electrochemical Impedance Spectroscopy page 13

Max Wien (1840 – 1910)

Measurement of electrolyte resistivity

Polarization resistance

R  k   r
1
r 
A
  f ( A)

C. Gabrielli, “Once upon a time there was EIS,” Electrochim. Acta, 331 (2020), 135324.
M. Wien, Ann. Phys., 58 (1896), 206.
Electrochemical Impedance Spectroscopy page 14

Walther Hermann Nernst (1864–1941)

Applied Heaviside’s mathematical foundation and Wheatstone’s experimental apparatus to perform
electrochemical impedance spectroscopy measurements.

W. Nernst, “Methode zur Bestimmung von Dielektrizitätskonstanten,” Zeitschrift für Elektrochemie, 14

(1894) 622–663.
Electrochemical Impedance Spectroscopy page 15

Emil Gabriel Warburg (1846-1931)

Diffusion Impedance
E. Warburg, “Über das Verhalten sogenannter unpolarisirbarer Elektroden gegenWechselstrom,”
Annalen der Physik und Chemie, 67 (1899) 493–499.
Electrochemical Impedance Spectroscopy page 16

Discussions of the Faraday Society, 1 (1947), 11-19

M. E. Orazem and B. Tribollet, Electrochemical Impedance Spectroscopy, 2nd edition, John

Wiley & Sons, Hoboken, NJ, 2017.
Electrochemical Impedance Spectroscopy page 17

Electrochemical Impedance Spectroscopy

• Electrochemical technique
– Transient
– Step-change
– Single-sine or multi-sine
– Small-amplitude or nonlinear
• Measurement in terms of macroscopic quantities
– total current
– averaged potential
• Not a chemical spectroscopy
• Type of generalized transfer-function measurement
Electrochemical Impedance Spectroscopy page 18

Interrogate Electrochemical Cell

Electrochemical Impedance Spectroscopy page 19

Characteristic Time/Frequency
Rotating Disk Electrode Charging Faradaic Reaction
r0 = 0.25 cm 1 ρ RT
Re = = Rt =
C0 = 20 µ F / cm 2 4κ r0 4r0 nFi0
ρ 10 Ωcm
= τ C = C0 Re = 0.2 ms τ t = C0 Rt = 0.51 ms
Ω =400 rpm 1 f t = 310 Hz
ωC =
τC
i0 = 1 mA/cm 2
1
ν = 0.01 cm 2 / s =
fC = 4.1 kHz Mass Transfer
2πτ C
δ N2
τD = = 0.41 s
Di
f D = 0.4 Hz

Metrohm Autolab website

Electrochemical Impedance Spectroscopy page 20

Interrogate Electrochemical Cell

V (t ) = V + ∆V cos (ωt ) I (t ) = I + ∆I cos(ωt + ϕ )

{ }
= V + Re V exp( jωt ) = I + Re { I exp( jωt )}

Electrochemical
Cell

V
Z (ω=
) = Z r + jZ j
I
Electrochemical Impedance Spectroscopy page 21

Time to Frequency Domain

V (ω )

I (ω )

V (ω ) ∆t
Z (ω ) = ϕ (ω ) = 2π
I (ω ) T
Electrochemical Impedance Spectroscopy page 22

Low Frequencies
1
I (V ) : slope =
Rp

I (V )

∆I
V

lim Z ( f ) = Rp
f →0

∆V
Electrochemical Impedance Spectroscopy page 23

Moderate Frequencies

I (V )

∆I
V

Z ( f ) Z=
= exp ( jϕ ) Z r + jZ j
∆V
Electrochemical Impedance Spectroscopy page 24

Technical Applications of Impedance Spectroscopy

• Corrosion and Electrodeposition

• Biological Tissues, e.g., Human Skin
• Batteries and Fuel Cells
• Sensors
Electrochemical Impedance Spectroscopy page 25

Sunshine Skyway Bridge

Indirect impedance detection of corrosion in post-
tensioned tendons
 Electrochemical Impedance Spectroscopy page 26
Impedance of Lithium Batteries

Overcharged
Over-discharged
Over-heated
Over-cooled

S. Erol, M. E. Orazem, and R. P. Muller, "Influence of Overcharge and Over-Discharge on the Impedance Response of
LiCoO2/C Batteries," J. Power Sources, 270 (2014), 92-100.
S. Erol and M. E. Orazem, “The Influence of Anomalous Diffusion on the Impedance Response of LiCoO2/C Batteries," J.
Power Sources, 293 (2015), 57-64.
Electrochemical Impedance Spectroscopy page 27

Integrated Diabetes Management System

Images taken from Solara Medical Supplies website and Connected in Motion review of Medtronic Enlite Glucose Sensor
Electrochemical Impedance Spectroscopy page 28

Unique Applications of Impedance Spectroscopy

• Presence of Adsorbed Intermediates

• Quantification of small rates of corrosion
• Determination of thin film thicknesses
Electrochemical Impedance Spectroscopy page 29

Unique Applications of Impedance Spectroscopy

• Presence of Adsorbed Intermediates

– Some properties can be studied only by measurement of the electrochemical impedance.
• Quantification of small rates of corrosion
• Determination of thin film thicknesses
Electrochemical Impedance Spectroscopy page 30

Iron in 0.5 M H2SO4

S. Wu, M. E. Orazem, B. Tribollet, and V. Vivier, “Impedance of a Disk Electrode with Reactions Involving an Adsorbed Intermediate:
Experimental and Simulation Analysis,” J. Electrochem. Soc., 156 (2009), C214-C221
Electrochemical Impedance Spectroscopy page 31

Iron in 0.5 M H2SO4

Fe  Fe 2+ +2e -
__________
Fe  Feads

+e - (1)
Feads

 Fe 2+ +e - (2)

1 1 A
 
Z F Rt j  B
A0  iF 
A
 V
i i
  1 2
F

J. O. Bockris, D. Drazic, and A. R. Despic, “The Electrode Kinetics of the Deposition and Dissolution of Iron,” Electrochim. Acta, 4 (1961), 325
R. D. Armstrong, R. E. Firman, and H. R. Thirsk, “AC Impedance of Complex Electrochemical Reactions,” Faraday Discuss., 56 (1973) 244.
I. Epelboin, M. Keddam, and J. C. Lestrade, “Faradaic Impedances and Intermediates in Electrochemical Reactions,” Faraday Discuss., 56
(1973) 264.
Electrochemical Impedance Spectroscopy page 32

Unique Applications of Impedance Spectroscopy

• Presence of Adsorbed Intermediates

• Quantification of small rates of corrosion
– A corrosion rate this small cannot be assessed by weight loss measurements.
• Determination of thin film thicknesses
Electrochemical Impedance Spectroscopy page 33

French Drinking Water Network

• 6 billion m3 of water / year

• 850,000 km of pipelines
• Cast iron pipes
• Issue: Consumption of Free Chlorine in
Municipal Water Supplies
Electrochemical Impedance Spectroscopy page 34

No Free Chlorine Experiments using

bottles of Evian water
Cast Iron Electrodes

2 mg/l Free Chlorine

Fe  Fe2+ +2e -
2Fe2+ +HOCl+H+  2Fe3+ +Cl - +H2O
1
O2 +2H+ +2e -  H2O
2

I. Frateur, C. Deslouis, M.E. Orazem and B. Tribollet, “Modeling of the Cast Iron/Drinking Water System by Electrochemical Impedance
Spectroscopy,” Electrochimica Acta, 44 (1999), 4345.
 Electrochemical Impedance Spectroscopy page 35

Issues Evianâ Water

• Coupled electrochemical reactions
• Surface films Red Rust (α-FeOOH, α-Fe2O3)
• Convective diffusion
• History and time-dependent parameters Green Rust & Carbonates
(Fe2+ and Fe3+)

Goals Black Rust

• Analysis of Errors (Fe3O4)
• Interpretation Model
• Identification of corrosion rate

Cast Iron
Electrochemical Impedance Spectroscopy page 36

Regression Analysis: 2 mg Cl / L
3 days

After 28 days :
Corrosion Rate = 11 µm / year

“The corrosion of pipes is not a 7 days

problem itself, but it induces a

consumption of Free Chlorine,
which is the real concern.”
28 days
Electrochemical Impedance Spectroscopy page 37

Unique Applications of Impedance Spectroscopy

• Presence of Adsorbed Intermediates

• Quantification of small rates of corrosion
• Determination of thin film thicknesses
– Inexpensive assessment of in-situ properties
Electrochemical Impedance Spectroscopy page 38

Tailoring Stainless Steel Surface Chemistry

Application: Floating heads for hard drives

Douglas Riemer
Technical Fellow http://www.htch.com
TDK (Hutchinson Technology)
Hutchinson, MN 55350-9784 303 free machining steel
Electrochemical Impedance Spectroscopy page 39

Impedance Data: Free-Machining Steel

-500 Method Sample 1 Sample 2 Sample 3

0.025 Hz
XPS 2 nm 6.3 2.5

Zj / kΩ cm2 -400 EIS 1.7 nm 5.9 nm 2.7 nm

-300

-200
0.1 Hz
“the ability to make accurate and rapid
-100 measurements of oxide film thickness
by EIS … is invaluable from a
0 manufacturing perspective.”
0 100 200
Zr / kΩ cm2
M. E. Orazem, B. Tribollet, V. Vivier, S. Marcelin, N. Pébère, A. L. Bunge, E. A. White, D. P. Riemer, I. Frateur, and M. Musiani,
“Dielectric Properties of Materials Showing Constant-Phase-Element ({CPE}) Impedance Response,” J. Electrochem. Soc., 160
(2013) C215-C225
Electrochemical Impedance Spectroscopy page 40

D. P. Riemer and M. E. Orazem, “Impedance Based Characterization of Raw Materials Used in Electrochemical Manufacturing,” ECS
Interface, 23:3 (2014), 63-67.
Electrochemical Impedance Spectroscopy page 41

Electrochemical Impedance Spectroscopy

• Dynamically growing field with rich tradition

• Transfer function method applied to electrochemistry
• Exciting capability to quantify important properties
Electrochemical Impedance Spectroscopy page 42

Approach
• Impedance
– Excellent sensitivity
– Allows use of the Kramers-Kronig relations
• Measurement
– First, the steady state
– Then modulate
– Let the system decide
• Modeling
– Circuits provide a framework
– Reaction stoichiometry and transport develop the model
• Interpretation
– Use graphs wisely
– Fit parameters have meaning
• Impedance data have errors
• Impedance does not stand alone
Electrochemical Impedance Spectroscopy page 43
Electrochemical Impedance Spectroscopy page 44

Development of Process Models

• 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
Electrochemical Impedance Spectroscopy page 45

Use circuits to create framework

Electrochemical Impedance Spectroscopy page 46

Addition of Potential
Electrochemical Impedance Spectroscopy page 47

Addition of Current
Electrochemical Impedance Spectroscopy page 48

Equivalent Circuit at the Corrosion Potential

Electrochemical Impedance Spectroscopy page 49

Impedance ± 10 mV OCP
Electrochemical Impedance Spectroscopy page 50

Diagnostics
Electrochemical Impedance Spectroscopy page 51

Equivalent Circuit for a Partially Blocked Electrode

ZF
= Re +
Z
1 − γ + jω ( γ C + (1 − γ )Cdl ) Z F
Electrochemical Impedance Spectroscopy page 52

Implications: Normalized Nyquist

Electrochemical Impedance Spectroscopy page 53

Implications: Normalized Impedance

Electrochemical Impedance Spectroscopy page 54

Equivalent Circuit for an Electrode Coated by a Porous Layer

Electrochemical Impedance Spectroscopy page 55

Equivalent Electrical Circuit for an Electrode Coated by Two Porous

Layers

εε 0
=
C 2 =; ε 0 8.8452 × 10−14 F/cm
δ2
R 2 = δ2 / κ2

 ZF 
 R + 
R 2  1 + j ω Cdl F 
Z
Z=
Re + +
1 + jω R 2 C 2  ZF 
1 − γ + jωγ C  R + 
 1 + jωCdl Z F 
Electrochemical Impedance Spectroscopy page 56

Scaling and Corrosion of a Steel Electrode

L Bousselmi, C. Fiaud, B. Tribollet, and E. Triki, “Impedance Spectroscopic Study of a Steel Electrode in
Condition of Scaling and Corrosion: Interphase Model,” Electrochimica Acta, 44 (1999), 4357-4363.
Electrochemical Impedance Spectroscopy page 57

Use kinetic models to determine expressions for

the interfacial impedance
Electrochemical Impedance Spectroscopy page 58

General Expression for Faradaic Current

iF = f (V , ci (0), γ i )

{
 jω t
i= i + Re ie }
 ∂f   ∂f   ∂f 
iF =
  V + ∑
  ci (0) + ∑   γk
 ∂V ci (0),γ k i  ∂ci (0) V , c ,γ k  ∂γ k V , c γ
j,j≠i k j j,j≠ k
Electrochemical Impedance Spectroscopy page 59

Irreversible Reaction:
Dependent on Potential
Az+

A A A A A A A A A
A → A +e
+ -
A A A A A A A A A A
A A A A A A A A A

• Potential-dependent heterogeneous reaction

• Two-dimensional surface
• No effect of mass transfer
Electrochemical Impedance Spectroscopy page 60

Impedance Model Development

steady-state
 αA F  iA = K A exp ( bAV )
iA = nA FkA exp  V
 RT 
phasor component

∂ iA 
V K A bA exp ( bAV )  1 
=iA = = V V
∂V Rt,A
1
Rt,A =
K A bA exp ( bAV )
β A = 2.303/ bA βA
iA =
2.303Rt,A
β A = 2.303Rt,A iA
Electrochemical Impedance Spectroscopy page 61

A. Caprani and J. P. Frayret, “Behaviour of Titanium in Concentrated Hydrochloric Acid: Dissolution-

Passivation Mechanism,” Electrochim. Acta, 24 (1979), 835-842
Electrochemical Impedance Spectroscopy page 62

Significance of Rt I
Electrochemical Impedance Spectroscopy page 63

Approach for Model Development

• Circuits provide framework
• Reaction mechanism provides faradaic
impedance

 ∂ iA  1 
=iA = V V
∂V Rt,A
V
Z F = = Rt,A
iA
Electrochemical Impedance Spectroscopy page 64

Use Graphical Methods to Facilitate

Interpretation

• Nyquist plots
• Phase angle
Electrochemical Impedance Spectroscopy page 65

Superposition of Nyquist Plots

Orazem and Tribollet, Electrochemical Impedance Spectroscopy, 2nd edition, John Wiley &
Sons, Hoboken, 2017
Electrochemical Impedance Spectroscopy page 66

Superposition of Nyquist Plots

Electrochemical Impedance Spectroscopy page 67

Superposition of Nyquist Plots

S. Erol, M. E. Orazem, and R. P. Muller, "Influence of Overcharge and Over-Discharge on the

Impedance Response of LiCoO2/C Batteries," J. Power Sources, 270 (2014), 92.
Electrochemical Impedance Spectroscopy page 68

Superposition of Nyquist Plots

S. Erol, M. E. Orazem, and R. P. Muller, "Influence of Overcharge and Over-Discharge on the

Impedance Response of LiCoO2/C Batteries," J. Power Sources, 270 (2014), 92.
Electrochemical Impedance Spectroscopy page 69

Superposition of Nyquist Plots

G. Baril, G. Galicia, C. Deslouis, N. Pèbére, B. Tribollet, and V. Vivier, “An Impedance Investigation
of the Mechanism of Pure Magnesium Corrosion in Sodium Sulfate Solutions,” J. Electrochem.
Soc., 154 (2007) C108–C113.
Electrochemical Impedance Spectroscopy page 70

Superposition of Nyquist Plots

G. Baril, G. Galicia, C. Deslouis, N. Pèbére, B. Tribollet, and V. Vivier, “An Impedance Investigation
of the Mechanism of Pure Magnesium Corrosion in Sodium Sulfate Solutions,” J. Electrochem.
Soc., 154 (2007) C108–C113.
Electrochemical Impedance Spectroscopy page 71

When Is a Time-Constant Distribution a CPE?

Oxide on steel Oxide on niobium

I. Frateur, L. Lartundo-Rojas, C. Méthivier, A. Galtayries, and P. Marcus, “Influence of Bovine Serum Albumin
in Sulphuric Acid Aqueous Solution on the Corrosion and the Passivation of an Iron-Chromium Alloy,”
Electrochim. Acta, 51 (2006) 1550.
S. Cattarin, M. Musiani, and B. Tribollet, “Nb Electrodissolution in Acid Fluoride Medium,” J. Electrochem.
Soc., 149 (2002) B457.
Electrochemical Impedance Spectroscopy page 72

Bode Plots

Oxide on steel

Oxide on niobium
Electrochemical Impedance Spectroscopy page 73

Ohmic-Resistance Corrected Bode Plots

 Zj 
ϕadj = tan −1  
 r
Z − Re 

Z adj = Z j2 + ( Z r − Re )
2

Oxide on niobium

Oxide on steel

Orazem and Tribollet, Electrochemical Impedance Spectroscopy, 2nd edition, John Wiley & Sons, Hoboken,
NJ, 2017
Electrochemical Impedance Spectroscopy page 74

Ohmic-Resistance Corrected Bode Plots

 Zj 
ϕadj = tan −1  
 r
Z − Re 

Z adj = Z j2 + ( Z r − Re )
2

Oxide on steel
Electrochemical Impedance Spectroscopy page 75

Influence of Disk Radius

V. Huang, V. Vivier, M. E. Orazem, N. Pébère, and B. Tribollet, “The Apparent Constant-Phase-Element Behavior of an Ideally Polarized
Blocking Electrode: A Global and Local Impedance Analysis,” J. Electrochem. Soc., 154 (2007), C81-C88.
Electrochemical Impedance Spectroscopy page 76

Interpretation Models for Impedance Spectroscopy

• Models can account rigorously for proposed kinetic and mass transfer mechanisms.
• Circuits can provide a framework for model development.
• Models can be expressed in terms of circuits.
• Graphical methods facilitate interpretation of data.