SHORT COURSE

ELECTROCHEMICAL ENGINEERING
Presented at

Tianjin University
by
Uziel Landau
Professor and Chair, Chemical Engineering Department
Case Western Reserve University
Cleveland OH 44106 USA

Phone: (216) 368-4132

Fax: (216) 368-3016
e-mail: uxl@case.edu

WORKSHOP NOTES
May 27 – June 2, 2010

_ +

NOTICE
These notes are provided as reference material for students enrolled in the class. The
notes should be considered the property of the instructor and must not be duplicated
without written permission.
PREFACE

The short course is intended for graduate students, scientists, and engineers
from all disciplines who want to gain fundamental understanding and working
knowledge of the design and analysis of electrochemical systems. Topics
include:

 Fundamentals: Ionic transport, Electrochemical thermodynamics,

Overpotentials, Current and Potential Distributions, Design, Analysis and
Scale-up of Electrochemical Systems, Porous Electrodes. Transients and
Pulse Applications. Multiple Electrode Reactions.
 Industrial Applications: Plating, Batteries, Fuel-cells, Industrial
electrolysis, Corrosion.
 Case studies and Computer Simulations: Metallization of
semiconductors, evolving electrode morphology, electro-polishing, alloys
and semiconductor electrodeposition.

The short-course is similar in scope to a Semester course offered to graduate

students at Case School of Engineering. Homework problems (with solutions)
and quantitative examples will enhance the lectures.

The notes provided herein are the intellectual property of Prof. Uziel Landau and
are provided for the personal use of workshop participants. The notes should not
be duplicated or further distributed.without the written consent of Prof. Landau.

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PURPOSE OF THE SHORT COURSE

1. Gain understanding of the fundamental processes 
and engineering principles underlying the 
operation of electrochemical systems. 
 
2. Apply quantitative engineering approach to the 
rational design, scale‐up, analysis and control of 
electrochemical cells. 
 
3. Gain familiarity with important electrochemical 
systems and the issues associated with their 
application   
 
4. Stimulate thoughts and new ideas for novel 
applications and improvements of existing ones 

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 SHORT COURSE SYLLABUS
 
Day 1: Significance and uniqueness of electrochemical processes and cells. Ionic
transport. Electrochemical thermodynamics (including corrosion, batteries, alloy
codeposition principles). Irreversibilities and overpotentials. Electrode
polarization; catalysis.

Day 2: Electrode polarization: Concentration and Ohmic overpotentials. Current-voltage

relationships and three electrodes measurements. Current distribution (primary,
secondary), Mass transport and fluid-flow in electrochemical cells.

Day 3: Scaling analysis of electrochemical systems. Special operating modes: Multiple

simultaneous electrode reactions (including alloys plating and corrosion).
Resistive electrodes. Transient and pulse current and potential waveforms.
Periodic reverse plating. Porous and 3-D electrodes.

Day 4: Technology applications: Electroplating. Electropolishing and electrochemical

machining. Batteries. Fuel-Cells. Corrosion. Industrial Electrolysis.

Day 5: Corrosion.
Case Studies:
 Metallization of Semiconductor Wafers.
 Computer Simulations of special case studies.

About 5 hours of lectures + discussions are planned per day for the first 4 days.
About 4 hours are planned for the fifth day.

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Detailed Lecture Plan:
Day 1: Fundamental concepts: Electrochemical Reactions,
Electrodes, & Cells. Ionic Transport. Thermodynamics of
Electrochemical Cells. Overpotentials. (~ 5 hours).

Chapter 1: Introduction, overview and technological significance of

electrochemical processes (1/2 hour)
a. Electrochemical cell components and their role
b. Electrochemical vs. chemical process
c. Unique features of electrochemical processes
d. Industrial significance of electrochemical processes

Chapter 2: Fundamental concepts (3/4 hr)

a. Faraday’s law – coulombic and voltaic efficiencies

b. Electronic and ionic conduction
c. Ionic mobility
d. Non-aqueous solvents (Overview)
e. Molten salts (Overview)
f. Conductivity in heterogeneous systems, Bruggeman’s law
g. Conductivity measurements

Chapter 3: Transport in electrochemical cells: conduction, diffusion and

convection (1.5 hrs)

a. Ionic transport: Diuffusio,n migration, convection

b. Diffusivity and mobility
c. Transport numbers and concentration gradients
d. The Limiting current

Chapter 4: Thermodynamics of electrochemical systems (1.5 hrs)

a. Fundamental relationships
b. Gibbs free energy, EMF
c. Chemical and electrochemical potential
d. The standard potential. EMF series. Electronegativity.
e. Cell potentials and direction of spontaneous reactions
f. The Nernst Eqn., Concentration cells
g. Pourbaix diagrams. Region of aqueous electrochemistry
h. Alloy co-deposition
i. Heat effect in cells
j. Electrodes of the second kind. Reference electrodes
k. Liquid junction potentials (Introduction)

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 Chapter 5 (beginning): Irreversible electrode processes – activation
overpotentials at polarized electrodes (3/4 hrs)

a. Dissipative processes in cells – overpotential balance.

b. Activation overpotential. Butler-Volmer eqn. Tafel and
Linear approximations.
c. Electrocatalysis

Day 2: Overpotentials, Current Distribution, and Mass

Transport in Electrochemical Cells. (~ 5 hours).
Review of day 1. Q&A (15 min)

Chapter 5 (Cont.): Concentration and ohmic overpotentials; Polarization

curves; Three electrode measurements (1hr)

a. Concentration Overpotential
b. Ohmic overpotential
c. Voltage balance in cells. i-V curves
d. 3 electrode measurements – reference electrodes and
potentiostats

Chapter 6: Current distribution in electrochemical cells ( 2 hrs)

a. Significance, (15 min)
b. Fundamental eqns. and method of solution. The Nernst-
Plank eqn.
c. Boundary conditions.
d. Approximations:
i. Primary distribution
ii. Secondary distrib. (kinetics control)

Chapter 7: Mass transport in electrochemical cells (1 hr)

a. Limiting currents and effects of convective flow
b. Dimensionless numbers
c. Laminar and turbulent flow correlations
d. Special Cases:
i. Rotating disk electrodes and rotating cylinders.
ii. Flow past planar electrodes and in Channels.
iii. Free and bubble induced convection.
e. Smooth and rough electrodes
f. Effect of transport on kinetically controlled current

Chapter 8: Current distribution under mixed control (1 hrs)

Tertiary distribution: (15 min)

Numerical simulations (mostly illustrative examples) (45 min)

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Day 3: Scaling Analysis and Special Operating Modes: Resistive
Electrodes, Transient Waveforms, and Multiple Electrode
Reactions. Porous Electrodes. (~ 6 hours).
Review of day 2, Q&A (15 min)

Chapter 9: Scaling Analysis of Electrochemical Cells (3/4 hr)

a. Micro and macro distributions. Dimensionless numbers
b. Controlling modes
c. Roughness evolution and leveling in plating and etching
Chapter 10: Resistive electrodes and the terminal effect (3/4 hr)

Chapter 11: Multiple simultaneous electrode reactions: (1 hrs)

a. Parasitic reactions – gas co-evolution
b. Alloy plating
c. Corrosion. Fundamentals: Mixed potential. Evans diagrams

Chapter 12: Transient and unsteady-state effects (1hrs)

a. General , time dependent solutions to the Nernst-Plank eq.
b. Galvanostatic and potentiostatic applications (1/2 hrs)
c. Pulse and periodic reverse plating (3/4 min)

Chapter 13: Porous electrodes and 3-D electrode structures (1-1/4 hrs)
a. Flooded high-area electrodes. Turtuosity and constriction
factor.
b. Gas–contacting electrodes
c. Transport and concentrations distribution in porous structures

Day 4: Technology Applications: Cell Configurations,

Electroplating, Batteries and Fuel-Cells. (~ 5 hours).
Review of day 3, Q&A (15 min)

Chapter 14: Electrodes and cell configurations; (3/4 hrs)

a. Monopolar and bi-polar electrodes
b. Shunt currents
c. Planar, porous, and particulate electrodes
d. Membranes and separators
e. Electrodes/separator stacks
f. Industrial cell configurations
g. Process design considerations

Chapter 15: Control of deposit morphology (3/4 hrs)

a. Roughness evolution and dendritic growth

b. Additives in plating

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 Chapter 16: Electroplating (1.5 hrs)
a. General considerations: applications
b. Deposit properties, cell components (10 min)
c. Plating chemistry (10 min)
d. Plating additives (10 min)
e. Common plating systems (10 min)
f. Anodes; replenishment, ‘bleed and feed’ (10 min)
g. Agitation and filtering; Separators (10 min)
h. Deposit properties: testing and analysis
i. Special plating applications:
1. Bi-polar electrodes (5 min)
2. Through hole and blind via plating (10 min)
3. Selective and pattern plating (10 min)
4. Rack plating (5 min)
5. Strip plating (5 min)
6. Basket plating (5 min)
7. Flip-chip plating (5 min)

Chapter 17: Plating on non-conductors, electroless plating (1/2 hr)

Chapter 18: Batteries and fuel-cells (1.5 hrs)
a. Electrochemical energy and Power
b. Primary Batteries
c. Secondary (Rechargeable) batteries
d. Flow Batteries
e. Fuel Cells

Day 5: Corrosion and Case Studies. (~ 3 hours)

Review of day 4, Q&A (15 min)
Chapter 19: Corrosion (3/4 hrs)
a. Active dissolution, Passivation, Flade potential
b. Mixed potential, Evans diagram
c. Anodizing and galvanizing
d. Cathodic and anodic protection
e. Chemical passivation
f. Stress corrosion
g. Materials selection considerations

Chapter 21: Case Study: Metallization of Semiconductor Interconnects (1-1/4 hr)

a. Wafer-scale current distribution
b. Dual Damascene Interconnects (Bottom-up fill)
c. Through Silicon Vias (TSV’s)

Chapter 22: Computer Simulations - Case Studies of industrial significance

(1 hrs).

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Contents

Chapter 1 : Significance and Overview

Chapter 2 : Fundamental Relationships
Chapter 3 : Transport in Electrochemical Cells
Chapter 4 : Thermodynamics of Electrochemical Systems
Chapter 5 : Irreversibility in Electrochemical Systems
Chapter 6 : Current Distribution: primary and secondary
Chapter 7 : Mass Transport in Electrochemical Cells
Chapter 8 : Current Distribution - Mixed Control (Tertiary)
Chapter 9: Scaling analysis of electrochemical cells
Chapter 10 : Resistive Electrodes
Chapter 11: Multiple electrode reactions – Alloy plating
Chapter 12: Transients & Periodic Current/Voltage waveforms
Chapter 13: Porous and 3-D Electrodes
Chapter 14: Electrodes and Cell Configurations
Chapter 15: Deposit morphology; additives effects
Chapter 16 Electroplating and Electroforming
Chapter 17: Plating on non-conductors: Electroless Plating
Chapter 18: Batteries and Fuel-Cells
Chapter 19: Corrosion and Passivation
Chapter 20: Anodic Processes for Metal Finishing
Chapter 21: Case Studies
Chapter 22: Computer simulations

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 LIST OF SYMBOLS

a constant (eq. [37]), V

a activity, dimensionless
A local electrode area, cm2
b Tafel polarization slope, (=RT/F), V
b’ linear polarization slope, V cm2/A
c concentration, g mol/cm3
d deposit thickness, cm
D diffusion coefficient, cm2/s
E standard electrode potential, V
F Faraday's constant, 96,487 coul./equiv
h grid size, cm
i current density, A/cm2
io exchange current density, A/cm2
iL limiting current density ,A/cm2
iave average current density, A/cm2
icrit critical current density for smooth deposition, A/cm2
l, L length, cm
L Leveling parameter, dimensionless
M Molecular weight of deposited metal, g/mol
n number of electrons transferred in the electrode reaction, equiv/mol
N Ionic flux, mol/s cm2
R universal gas constant, 8.314 J/mol K
Rj Rate of generation of species j, M/s cm3
R*S specific surface (activation) resistance,  cm2
R*C specific concentration resistance,  cm2
R* specific ohmic resistance,  cm2
R ohmic resistance, 
t time, s

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T Absolute temperature, K
To Tobias number, dimensionless
u ionic mobility, cm2mol/J s
v velocity, cm/s
V voltage of an electrode, V
Wa Wagner number, dimensionless
zj charge number of the ionic species j, equiv./mol
Greek
 transfer coefficient
 parameter adjusting the exchange current density, (eq. [18]),
dimensionless
 parameter adjusting the exchange current density, (eq. [18]),
dimensionless
 mass transfer boundary layer thickness, cm
x spacing between grid points in the x direction, cm
y spacing between grid points in the y direction, cm
z spacing between grid points in the axial direction, cm
F Faradaic efficiency
  total overpotential, V
 S  surface (activation) overpotential, V
 C  concentration overpotential, V
  Ohmic overpotential, V
  Solution conductivity, S/cm
 constant, eq. [80], dimensionless
 viscosity, poise = g/cm s
 kinematic viscosity, cm2/s
T eddy (turbulent) viscosity, cm2/s
 ADI iteration parameter, dimensionless
 density, g/cm3
 potential in the electrolyte, V
Superscripts
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* specific, per unit area
O oxidized species
R reduced species
Subscripts
A anode
a activation (surface kinetics)
avg average value
b bulk
b backward
C cathode
c mass transport
crit. critical value
e at the electrode
elec electrode
f forward
ins insulator
j ionic species j
L linear polarization
n normal to surface
N Nernst
R reactant
s surface overpotential or resistance
T Tafel region (high field)
 Ohmic

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