Fuel cells are clean and efficient energy conversion devices expected to be the next generation power source. During more than 17 decades of research and development, various types of fuel cells have been developed with a view to meet the different energy demands and application requirements. Scientists have devoted a great deal of time and effort to the development and commercialization of fuel cells important for our daily lives. However, abundant issues, ranging from mechanistic study to system integration, still need to be figured out before massive applications can be used. Miniaturization is one of the main bottlenecks for the advancement and further development of fuel cells. Thus, research on miniaturization of fuel cells as well as understanding the micro and nano structural effect on fuel cell performance are necessary and of great interest to solve the challenges ahead. In this book, internationally acclaimed experts illustrate how micro & nano engineering technology can be applied as a way of removing the restrictions presently faced by fuel cells both technically and theoretically.Through the twelve well designed chapters, major issues related to the miniaturization of different types of fuel cells are addressed. Theory focusing on micro and nano scale mechanics are outlined to better optimize the performance of fuel cells from laboratory scale to industrial scale. This book will be a good reference to those scientists and researchers interested in developing fuel cells through micro and nano scale engineering.
About the book series vii
Editorial board ix
List of contributors xxvii
Preface xxix
About the editors xxxiii
1 Pore-scale water transport investigation for 1 (36)
polymer electrolyte membrane (PEM) fuel cells
Takemi Chikahisa
Yutaka Tabe
1.1 Introduction 1 (1)
1.2 Basics of cell performance and water 1 (3)
management
1.3 Water transport in the cell channels 4 (7)
1.3.1 Channel types 4 (1)
1.3.2 Observation of water production, 5 (4)
temperatures, and current density
distributions
1.3.3 Characteristics of porous separators 9 (2)
1.4 Water transport in gas diffusion layers 11 (5)
1.4.1 Water transport with different 12 (2)
anisotropic fiber directions of the GDL
1.4.2 Water transport simulation in GDLs 14 (2)
with different wettability gradients
1.5 Water transport through micro-porous 16 (6)
layers (MPL)
1.5.1 Effect of the MPL on the cell 16 (2)
performance
1.5.2 Observation of the water 18 (2)
distribution in the cell
1.5.3 Analysis of water transport through 20 (1)
MPL
1.5.4 Mechanism for improving cell 21 (1)
performance with an MPL
1.6 Transport phenomena and reactions in 22 (6)
the catalyst layers
1.6.1 Introduction 22 (1)
1.6.2 Analysis model and formulation 23 (2)
1.6.3 Results of analysis and major 25 (3)
parameters in CL affecting performance
1.7 Water transport in cold starts 28 (5)
1.7.1 Cold start characteristics and the 28 (2)
effect of the start-up temperature
1.7.2 Observation of ice distribution and 30 (1)
evaluation of the freezing mechanism
1.7.3 Strategies to improve cold start 31 (2)
performance
1.8 Summary 33 (4)
2 Reconstruction of PEM fuel cell electrodes 37 (32)
with micro- and nano-structures
Ulises Cano-Castillo
Romeli Barbosa-Pool
2.1 Introduction 37 (2)
2.1.1 The technology: complex operational 37 (2)
features required
2.1.1.1 Nano-technology to the rescue? 38 (1)
2.1.1.2 Challenges: technical and 39 (1)
economic goals still remain
2.2 Catalyst layers' structure: a reason to 39 (21)
reconstruct
2.2.1 Heterogeneous materials 40 (1)
2.2.2 First steps for the reconstruction 40 (3)
of catalyst layers
2.2.2.1 Structural features matter 41 (1)
2.2.2.2 Scaling - a matter of 42 (1)
perspectives
2.2.3 Stochastic reconstruction - scaling 43 (2)
method
2.2.3.1 Statistical signatures 44 (1)
2.2.4 Let's reconstruct 45 (8)
2.2.4.1 Features of reconstructed 47 (2)
structures
2.2.4.2 Effective ohmic conductivity 49 (1)
2.2.4.3 CL voltage distribution, 50 (3)
electric and ionic transport
coefficients
2.2.5 Structural reconstruction: 53 (7)
annealing route
2.2.5.1 Image processing for 54 (1)
statistical realistic information
2.2.5.2 Structural reconstruction - 55 (2)
annealing method
2.2.5.3 Statistical functions - two 57 (2)
scales
2.2.5.4 Effective electric resistivity 59 (1)
simulation from a reconstructed
structure
2.3 New material support and new catalyst 60 (4)
approaches
2.3.1 Carbon nanotubes "decorated" with 60 (4)
platinum
2.3.1.1 Substantial differences for CNT 60 (3)
structures
2.3.1.2 CNT considerations when 63 (1)
inputting component properties
2.3.2 Core-shell-based catalyzers 64 (5)
2.3.2.1 General considerations for 64 (1)
reconstruction
2.4 Concluding remarks 64 (5)
3 Multi-scale model techniques for PEMFC 69 (26)
catalyst layers
Yu Xiao
Jinliang Yuan
Ming Hou
3.1 Introduction 69 (1)
3.1.1 Physical and chemical processes at 69 (1)
different length and time scales
3.1.2 Needs for multi-scale study in 69 (1)
PEMFCs
3.2 Models and simulation methods at 70 (6)
different scales
3.2.1 Atomistic scale models at the 70 (2)
catalyst surface
3.2.1.1 Dissociation and adsorption 71 (1)
processes on the Pt surface
3.2.1.2 Reaction thermodynamics 71 (1)
3.2.2 Modeling methods at 72 (2)
nano-/micro-scales
3.2.2.1 Molecular dynamics modeling 73 (1)
method
3.2.2.2 Monte Carlo methods 74 (1)
3.2.3 Models at meso-scales 74 (2)
3.2.3.1 Dissipative particle dynamics 74 (1)
(DPD)
3.2.3.2 Lattice Boltzmann method (LBM) 75 (1)
3.2.3.3 Smoothed particle hydrodynamics 75 (1)
(SPH) method
3.2.4 Simulation methods at macro-scales 76 (1)
3.3 Multi-scale model integration technique 76 (12)
3.3.1 Integration methods on atomistical 76 (3)
scale to nano-scale
3.3.2 Microscopic CL structure simulation 79 (1)
3.3.3 Analyses of predicted CLs 79 (3)
microscopic structures
3.3.3.1 Microscopic parameters 79 (2)
evaluation
3.3.3.2 Primary pore structure analysis 81 (1)
3.3.4 Model validation 82 (5)
3.3.4.1 Pore size distribution 82 (1)
3.3.4.2 Pt particle size distribution 83 (1)
3.3.4.3 The average active Pt surface 84 (3)
areas
3.3.5 Coupling electrochemical reactions 87 (1)
in CLs
3.4 Challenges in multi-scale modeling for 88 (1)
PEMFC CLs
3.4.1 The length scales 88 (1)
3.4.2 The time scales 88 (1)
3.4.3 The integration algorithms 88 (1)
3.5 Conclusions 89 (6)
4 Fabrication of electro-catalytic 95 (36)
nano-particles and applications to proton
exchange membrane fuel cells
Maria Victoria Martinez Huerta
Gonzalo Garcia
4.1 Introduction 95 (1)
4.2 Overview of the electro-catalytic 96 (4)
reactions
4.2.1 Hydrogen oxidation reaction 96 (1)
4.2.2 H2/CO oxidation reaction 96 (2)
4.2.3 Methanol oxidation reaction 98 (1)
4.2.4 Oxygen reduction reaction 99 (1)
4.3 Novel nano-structures of platinum 100 (5)
4.3.1 State-of-the-art supported Pt 100 (1)
catalysts
4.3.2 Surface structure of Pt catalysts 101 (1)
4.3.3 Synthesis and performance of Pt 101 (4)
catalysts
4.4 Binary and ternary platinum-based 105 (7)
catalysts
4.4.1 Electro-catalysts for CO and 105 (3)
methanol oxidation reactions
4.4.2 Electro-catalysts for the oxygen 108 (1)
reduction reaction
4.4.3 Synthetic methods of binary/ternary 109 (3)
catalysts
4.5 New electro-catalyst supports 112 (3)
4.6 Conclusions 115 (16)
5 Ordered mesoporous carbon-supported 131 (28)
nano-platinum catalysts: application in direct
methanol fuel cells
Parasuraman Selvam
Balaiah Kuppan
5.1 Introduction 131 (1)
5.2 Ordered mesoporous silicas 132 (3)
5.3 Ordered mesoporous carbons 135 (5)
5.3.1 Hard-template approach 137 (2)
5.3.2 Soft-template approach 139 (1)
5.4 Direct methanol fuel cell 140 (4)
5.5 Electrocatalysts for DMFC 144 (1)
5.5.1 Bulk platinum catalyst 144 (1)
5.5.2 Platinum alloy catalyst 145 (1)
5.5.3 Nano-platinum catalyst 145 (1)
5.5.4 Catalyst promoters 145 (1)
5.6 OMC-supported platinum catalyst 145 (8)
5.6.1 Pt/NCCR-41 147 (3)
5.6.2 Pt/CMK-3 150 (3)
5.7 Summary and conclusion 153 (6)
6 Modeling the coupled transport and reaction 159 (22)
processes in a micro-solid-oxide fuel cell
Meng Ni
6.1 Introduction 159 (1)
6.2 Model development 160 (5)
6.2.1 Computational fluid dynamic (CFD) 161 (2)
model
6.2.2 Electrochemical model 163 (1)
6.2.3 Chemical model 164 (1)
6.3 Numerical methodologies 165 (2)
6.4 Results and discussion 167 (9)
6.4.1 Base case 167 (4)
6.4.2 Temperature effect 171 (1)
6.4.3 Operating potential effect 172 (4)
6.4.4 Effect of electrochemical oxidation 176 (1)
rate of CO
6.5 Conclusions 176 (5)
7 Nano-structural effect on SOFC durability 181 (30)
Yao Wang
Changrong Xia
7.1 Introduction 181 (1)
7.2 Aging mechanism of SOFC electrodes 181 (7)
7.2.1 Aging mechanism of the anodes 181 (5)
7.2.1.1 Grain coarsening 182 (3)
7.2.1.2 Redox cycling 185 (1)
7.2.1.3 Coking and sulfur poison 185 (1)
7.2.2 Aging mechanism of cathodes 186 (2)
7.3 Stability of nano-structured electrodes 188 (4)
7.3.1 Fabrication and electrochemical 188 (1)
properties of nano-structured electrodes
7.3.2 Models about nano-structured 188 (4)
effects on stability
7.3.2.1 Nano-size effects on isothermal 190 (1)
grain growth
7.3.2.2 Nano-structured effects on 190 (2)
durability against thermal cycle
7.4 Long-term performance of 192 (12)
nano-structured electrodes
7.4.1 Anodes 192 (7)
7.4.1.1 Enhanced interfacial 192 (3)
stabilities of nano-structured anodes
7.4.1.2 Durability of nano-structured 195 (1)
anodes against redox cycle
7.4.1.3 Durability of nano-structured 196 (3)
anodes against coking and sulfur
poisoning
7.4.2 Cathodes 199 (13)
7.4.2.1 LSM 199 (1)
7.4.2.2 LSC 200 (2)
7.4.2.3 LSCF 202 (1)
7.4.2.4 SSC 203 (1)
7.5 Summary 204 (7)
8 Micro- and nano-technologies for microbial 211 (16)
fuel cells
Hao Ren
Junseok Chae
8.1 Introduction 211 (1)
8.2 Electricity generation fundamental 212 (5)
8.2.1 Electron transfer of exoelectrogens 212 (1)
8.2.2 Voltage generation 213 (1)
8.2.3 Parameter for MFC characterization 214 (6)
8.2.3.1 Open circuit voltage (Eocv) 214 (1)
8.2.3.2 Areal/volumetric current 214 (1)
density (i.-max,areal, imax,volumetric)
and areal/volumetric power density
(.Pmax,areal, Pmax,volumetnc)
8.2.3.3 Internal resistance (Ri) and 214 (1)
areal resistivity (r;)
8.2.3.4 Efficiency - Coulombic 215 (1)
efficiency (CE) and energy conversion
efficiency (EE)
8.2.3.4.1 Coulombic efficiency (CE) 215 (1)
8.2.3.4.2 Energy conversion efficiency 216 (1)
(EE)
8.2.3.5 Biofilm morphology 216 (1)
8.3 Prior art of miniaturized MFCs 217 (3)
8.4 Promises and future work of 220 (4)
miniaturized MFCs
8.4.1 Promises 220 (2)
8.4.2 Future work 222 (6)
8.4.2.1 Further enhancing current and 222 (1)
power density
8.4.2.2 Applying air-cathodes to 223 (1)
replace potassium ferricyanide
8.4.2.3 Reducing the cost of MFCs 224 (1)
8.5 Conclusion 224 (3)
9 Microbial fuel cells: the microbes and 227 (18)
materials
Keaton L. Lesnik
Hong Liu
9.1 Introduction 227 (1)
9.2 How microbial fuel cells work 227 (1)
9.3 Understanding exoelectrogens 228 (3)
9.3.1 Origins of microbe-electrode 228 (1)
interactions
9.3.2 Extracellular electron transfer 229 (2)
(EET) mechanisms
9.3.2.1 Redox shuttles/mediators 229 (1)
9.3.2.2 c-type cytochromes 230 (1)
9.3.2.3 Conductive pill 231 (1)
9.3.3 Interactions and implications 231 (1)
9.4 Anode materials and modifications 231 (3)
9.4.1 Carbon-based anode materials 232 (1)
9.4.2 Anode modifications 233 (1)
9.5 Cathode materials and catalysts 234 (2)
9.5.1 Cathode construction 234 (1)
9.5.2 Catalysts 235 (1)
9.5.3 Cathode modifications 235 (1)
9.5.4 Biocathodes 236 (1)
9.6 Membranes/separators 236 (2)
9.7 Summary 238 (1)
9.8 Outlook 238 (7)
10 Modeling and analysis of miniaturized 245 (12)
packed-bed reactors for mobile devices powered
by fuel cells
Srinivas Palanki
Nicholas D. Sylvester
10.1 Introduction 245 (1)
10.2 Reactor and fuel cell modeling 245 (2)
10.2.1 Design equations of the reactor 245(1)
10.2.2 Design equations for the fuel cell 246 (1)
stack
10.3 Applications 247 (8)
10.3.1 Methanol-based system 247 (5)
10.3.2 Ammonia-based system 252 (3)
10.4 Conclusions 255 (2)
11 Photocatalytic fuel cells 257 (18)
Michael K.H. Leung
Bin Wang
Li Li
Yiyi She
11.1 Introduction 257 (1)
11.2 PFC concept 257 (1)
11.2.1 Fuel cell 257 (1)
11.2.2 Photocatalysis 257 (1)
11.2.3 Photocatalytic fuel cell 258 (1)
11.3 PFC architecture and mechanisms 258 (5)
11.3.1 Cell configurations 258 (1)
11.3.2 Bifunctional photoanode 258 (4)
11.3.2.1 Photocatalyst 258 (2)
11.3.2.2 Substrate materials 260 (1)
11.3.2.3 Catalyst deposition methods 261 (1)
11.3.3 Cathode 262 (1)
11.4 Electrochemical kinetics 263 (7)
11.4.1 Current-voltage characteristics 263 (6)
11.4.1.1 Ideal thermodynamically 265 (1)
predicted voltage
11.4.1.2 Activation losses 265 (1)
11.4.1.3 Ohmic losses 266 (1)
11.4.1.4 Concentration losses 267 (2)
11.4.2 Efficiency of a photocatalytic 269 (1)
fuel cell
11.4.2.1 Pseudo-photovoltaic efficiency 269 (1)
11.4.2.2 External quantum efficiency 269 (1)
11.4.2.3 Internal quantum efficiency 269 (1)
11.4.2.4 Current doubling effect 269 (1)
11.5 PFC applications 270 (1)
11.5.1 Wastewater problems 270 (1)
11.5.2 Practical micro-fluidic 270 (1)
photocatalytic fuel cell (MPFC)
applications
11.6 Conclusion 270 (5)
12 Transport phenomena and reactions in 275 (24)
micro-fluidic aluminum-air fuel cells
Huizhi Wang
Dennis Y.C. Leung
Kwong-Yu Chan
Jin Xuan
Hao Zhang
12.1 Introduction 275 (1)
12.2 Mathematical model 276 (6)
12.2.1 Problem description 276 (1)
12.2.2 Cell hydrodynamics 277 (1)
12.2.3 Charge conservation 278 (1)
12.2.4 Ionic species transport 279 (1)
12.2.5 Electrode kinetics 280 (2)
12.2.5.1 Anode kinetics 280 (1)
12.2.5.2 Cathode kinetics 280 (2)
12.2.5.3 Expression of overpotentials 282 (1)
12.2.6 Boundary conditions 282 (1)
12.3 Numerical procedures 282 (1)
12.4 Results and discussion 283 (10)
12.4.1 Model validation 283 (1)
12.4.2 Hydrogen distribution 284 (3)
12.4.3 Velocity distribution 287 (1)
12.4.4 Species distribution 287 (3)
12.4.4.1 Single-phase flow 287 (1)
12.4.4.1.1 Ionic species concentration 287 (1)
distributions
12.4.4.1.2 Migration contribution to 288 (1)
transverse species transport
12.4.4.2 The effect of bubbles 289 (1)
12.4.5 Current density and potential 290 (3)
distributions
12.5 Conclusions 293 (6)
Subject Index 299 (4)
Book Series Page 303
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