Polymer Electrolyte Fuel Cells: Science, Applications, and Challenges

608 Pages·2013·25.182 MB·English

by  Alejandro A. Franco

“This extremely well-organized book presents the state-of-the-art knowledge regarding P
the polymer electrolyte fuel cell technology, emphasizing critical aspects such as
o
electrode and membrane degradation and their impact on fuel cell performance.
l
Discussions on most modern catalyst fabrication and characterization techniques, as y
well as those on the latest advances in multiscale modeling techniques, and thorough
m
analyses presented in the text are invaluable for realistic assessments of the current
status and perspectives of this technology. The book is highly recommended as a e
reference for academic and industrial audiences.”
r
Prof. Perla Balbuena

Texas A&M University, USA E
l
e
Polymer electrolyte fuel cells (PEFC) have attracted much attention because of
their potential as a clean power source for many applications, including automotive, c
portable, and stationary devices. This has resulted in tremendous technological t
r
progress, such as the development of new membranes and electrocatalysts and the
o
improvement of electrode structures. However, to compete within the most attractive
l
markets, the PEFC technologies are yet to achieve the required characteristics, y
particularly in terms of cost and durability.
t
e
This book focuses on the recent research progress in the fundamental understanding

of material degradation in PEFC for automotive applications. On a multidisciplinary
F
basis, through contributions by internationally recognized researchers, this book
u
provides a complete and comprehensive critical review of crucial scientific topics
e
related to PEFC material degradation. It ensures a strong balance between experimental
and theoretical analyses and presents preparation techniques with several practical l

applications for both the research community and the industry. C
e
Alejandro A. Franco is a senior scientist at the Laboratoire de
l
Réactivité et Chimie des Solides (CNRS and Université de Picardie l
s
Jules Verne, Amiens, France). From 2006 to January 2013, he
headed the Modeling Group of Electrochemical Systems at CEA
(Grenoble, France). His research focuses on the understanding
of electrochemical processes through the use of multiscale
modeling approaches and numerical simulation applied to electrochemical
power generators such as Li-ion and Li-air batteries, supercaps, PEM fuel cells, F
r
and water electrolyzers. He is the inventor of several multiscale physical models, a
including the MS LIBER-T computational software, a unique model that scales up n
c
ab initio and microstructural data at the electrochemical device level. He is author o
of 32 patents in the field of fuel cells and electrochemical devices, and his work has
been published in several electrochemistry journals and conferences. Dr. Franco
has been also guest editor of Electrochimica Acta since July 2011.
V188
ISBN 978-981-4310-82-6
Polymer electrolyte
Fuel cells

edited by
Alejandro A. Franco
Polymer electrolyte
Fuel cells
science, Applications, and challenges
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742
© 2013 by Taylor & Francis Group, LLC
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Version Date: 20130624
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Contents
Preface
xvii
1. PEMFC Technologies for Automotive Applications 1
Nicolas Fouquet
1.1 A Brief History of PEMFC for the Automotive Industry 2
1.1.1 Early Prototypes: 1960–2000 2
1.1.2 Coming of Age: 2000–2005 4
1.1.3 Production-Ready Passenger
Vehicles: 2005–2010 5
1.1.4 Fuel Cell Development at PSA Peugeot
Citroën 6
1.2 Automotive Requirements for PEM Fuel Cell
Power Plants 7
1.2.1 Performance Target 7
1.2.1.1 The fuel cell electric vehicle 7
1.2.1.2 The range extender 8
1.2.2 Cost Target 8
1.2.3 Conclusion 9
1.3 The Importance of Reliable Modeling Tools 10
1.3.1 3D Computational Fluid Dynamics
Modeling 10
1.3.1.1 Motivation and background 10
1.3.1.2 Reactants’ flow inside bipolar
plate channels 11
1.3.1.3 Transport phenomena in the
gas diffusion layers 12
1.3.1.4 Reaction kinetics in the
active layers 13
vi Contents
1.3.1.5 Transport phenomena through
the membrane 14
1.3.1.6 Application example:
performance scale-up 14
1.3.1.7 Application example: bipolar
plate design 16
1.3.1.8 Conclusion and further
development 17
1.3.2 Zero-Dimensional Dynamic Modeling 17
1.3.2.1 Motivation and background 17
1.3.2.2 Fuel cell’s impedance model 22
1.3.2.3 Time-resolved EIS
measurements 24
1.3.2.4 Experimental validation 25
1.3.2.5 Limitation and further
development 26
2. Advanced Technologies for Efficient and Low Catalyst
1.4 Conclusion 27
Loading Electrodes 29
Pascal Fugier, Etienne Quesnel, and Sebastien Donet
2.1 Introduction 29
2.2 CVD and Precursors Approach 30
2.2.1 Introduction 30
2.2.2 Precursors Chemistry 33
2.2.3 Precursor Characterization 35
2.2.3.1 Physicochemical characterization
of the precursors 36
2.3 Principles of CVD Process: MOCVD 39
2.3.1 Definition 39
2.3.2 Direct Liquid Injection MOCVD Method 40
2.3.2.1 Introduction 40
2.3.2.2 Typical DLI-MOCVD catalyst 41
2.3.2.3 The precursors 43
Contents vii
2.3.2.4 The carrier gas 44
2.3.2.5 The substrate 45
2.3.2.6 The solvent 45
2.3.2.7 Nucleation and growth 47
2.3.2.8 Precursor oversaturation 47
2.3.3 Fluidized Bed — MOCVD 48
2.3.3.1 Introduction 48
2.3.3.2 Injection system 50
2.3.4 Experimental Results 51
2.3.4.1 Platinum deposition 51
2.3.4.2 Bimetallic electrodes 57
2.3.4.3 Durability tests 59
2.3.5 MOCVD Evolution: Solvent Substitution 65
2.3.6 MOCVD Technico-Economical Survey 66
2.3.6.1 MOCVD industrial prototype 67
2.3.6.2 Details on the
evaporation–injection system 68
2.3.6.3 Details on the FB-system
(deposition chamber + pumping
group + panel control) 68
2.4 Physical Vapor Deposition 69
2.4.1 Preliminary Considerations on PVD 70
2.4.2 Conventional PVD for PEMFC:
State of the Art 72
2.4.2.1 Standard sputtering process
for Pt deposition 72
2.4.2.2 Optimized sputtering process
for Pt deposition 76
2.4.2.3 Sputtering process for Pt
alloys 79
2.4.2.4 Conclusion 82
2.4.3 Advanced PVD Techniques 82
2.4.3.1 Catalyst synthesis in a
nanocluster source 83
viii Contents
2.4.3.2 PEMFC electrodes catalyzed
3. Electrocatalysis on Shape-Controlled Pt Nanoparticles 93
with a nanocluster source 84
J. Solla-Gullón, F. J. Vidal-Iglesias, E. Herrero, J. M. Feliu, and A. Aldaz
3.1 Introduction 93
3.2 Synthesis of Shape-Controlled Pt
Nanoparticles 96
3.3 Correlation between Surface Structure
and Nanoparticle Shape 98
3.4 Electrocatalysis on Shape-Controlled
Pt Nanoparticles 103
3.4.1 So-Called Hydrogen
Adsorption–Desorption Process 105
3.4.2 CO Electrooxidation 124
3.4.3 O2 Reduction 128
3.5 Additional Remarks 133
4. Ex situ Electrochemical Methods for the Characterization
3.6 Conclusions and Outlook 133
of PEFC Nanomaterial Degradation 153
Deborah J. Myers and Xiaoping Wang
ex situ
4.1 Introduction 153
4.1.1 Benefits of Techniques 153
4.1.2 Aqueous Acidic Electrolyte: Applicability
to the Fuel Cell Environment 154
4.1.2.1 Electrocatalytic activity 154
4.1.2.2 Performance degradation 156
4.2 Electrochemical Techniques 159
4.2.1 Voltammetry 159
4.2.1.1 Catalyst electrochemically active
surface area determination 161
4.2.1.2 Pt and Pt alloy oxide formation 165
4.2.1.3 Carbon support voltammetry 167
4.2.2 Chronoamperometry 171
Contents ix
4.2.3 Electrochemical Impedance
Ex situ
Spectroscopy 172
4.3 Techniques/Configurations 174
4.3.1 Non-Hydrodynamic Methods 175
4.3.2 Hydrodynamic Methods 176
4.3.2.1 Rotating ring and ring-disk

electrodes 178
4.3.2.2 Channel flow double

electrode cell 184
4.3.2.3 Requirements for thin-film
electrodes for hydrodynamic
techniques 185
4.3.3 Hybrid Techniques 186
4.3.3.1 Electrochemical quartz

crystal micro and nanobalance 186
4.3.3.2 Differential electrochemical
mass spectrometry 188
4.3.3.3 X-ray spectroscopy

and scattering 190
4.3.3.4 Spectroelectrochemical
Fourier transform

infrared spectroscopy 197

4.3.3.5 Other hybrid techniques 200
4.4 Accelerated Electrochemical Stress Tests for
PEFC Nanomaterial Durability 200
4.5 Examples of Electrochemical Characterization
5. Microstructural Characterization Methods of PEMFC
of PEFC Nanomaterial Degradation 203
Electrode Materials 233
Zhong Xie
5.1 Introduction 233
5.2 Catalyst/Support and Electrode Characterization

for PEMFC 235

5.2.1 2D Electron Microscopy Techniques 236
5.2.2 3D Electron Tomography Technique 238