MEMBRANES AND MEMBRANE ELECTRODE ASSEMBLIES FOR PEM FUEL CELLS

TABLE OF CONTENTS i

LIST OF TABLES viii

LIST OF FIGURES x

INTRODUCTION xi

• STUDY GOAL AND OBJECTIVES xi
• REASONS FOR DOING THE STUDY xi
• CONTRIBUTION OF THE STUDY AND FOR WHOM xii
• SCOPE AND FORMAT xii
• METHODOLOGY AND INFORMATION SOURCES xiii
• DISCLAIMER xiii
• RELATED BCC, INC. WORK CREDENTIALS xiv

SUMMARY xv

OVERVIEW 1

• BACKGROUND 1
• THE PRESENT SITUATION 1
• Competing Energy Systems 2
  • Hydrocarbon 2
    • Depletion 2
  • Hydrogen 3
• PROFITS AND PERILS OF PURSUING A BREAKTHROUGH TECHNOLOGY 4
  • VARIABLE FACTORS 5
  • INDUSTRY ISSUES 6
• GOVERNMENT AND NONGOVERNMENT INVOLVEMENT 6
  • FEDERAL HYDROGEN VISIONS AND GOALS 8
    • America' s Transition to a Hydrogen Economy to 2030 8
      • National Vision 10
    • National Hydrogen Energy Roadmap 11
      • Major Roadmap Findings 12
      • Major Applications 13
      • Looking Ahead 14
• ROLE OF THE DOE OFFICE OF SCIENCE 14
  • NATIONAL SCIENCE FOUNDATION 16
  • DOE?SPONSORED NATIONAL LABORATORIES INVOLVED IN FUEL CELL DEVELOPMENT 17
    • Argonne National Laboratory 17
    • Los Alamos National Laboratory 18
    • Brookhaven National Laboratory 18
    • Pacific Northwest National Laboratory 18
• OTHER FEDERAL AGENCY INVOLVEMENT 18
  • Department of Defense (DoD) 19
    • Defense Advanced Research Projects Agency 19
    • Army Research Laboratory 19
    • USAF Research Laboratory 19
    • Naval Research Laboratory 19
    • National Aeronaautics and Space Administration 20
    • Jet Propulsion Laboratory 20
• ACADEMIC INSTITUTIONS INVOLVED IN FUEL CELL DEVELOPMENT 20
  • University of Akron, Akron, Oh 20
  • Case Western Reserve University, Cleveland, Oh 21
  • Georgetown University, Washington, DC 21
  • Georgia Institute of Technology, Atlanta, GA 21
  • Houston Advanced Research Center, The Woodlands, TX 21
  • Humbolt State University, Arcata, Ca 21
  • Illinois Institute of Technology, Chicago, Il 22
  • Massachusetts Institute of Technology, Cambridge, Ma 22
  • Pennsylvania State University, University Park, Pa 22
  • Texas A&M University, College Station, TX 22
  • University of Connecticut, Storrs, Ct 22
  • University of North Dakota, Grand Forks, ND 23
  • University of Washington, Seattle, Wa 23
  • University of Wisconsin?Madison, Madison, WI 23
  • Vanderbilt University, Nashville,TN 23
  • Virginia Polytechnic Institute, Blacksburg, VA 23
  • Worcester Polytechnic Institute, Worcester, MA 24
• TYPES OF FUEL CELLS 24
  • Proton Exchange Membrane Fuel Cells 24
    • Legacy Technology 25
      • Direct Methanol Fuel Cells 26
  • Phosphoric Acid Fuel Cells 26
  • Solid Oxide Fuel Cells 26
  • Molten Carbonate Fuel Cells 26
  • Alkaline Fuel Cells 26
  • Regenerative or Reversible Fuel Cells 27
• FUEL CELL CHARACTERISTICS 27
  • FUEL PROCESSING 27
• LIFE?CYCLE COSTS 28
• Economy Of Scale 28
• PLATINUM?THE MAJOR CATALYTIC ELEMENT 29
  • Characteristics 29
  • availability 30
• HYBRIDS 30
  • Microturbine Cogeneration 31
  • Pressurized Hybrid System 31
• SYSTEM COMPONENTS 32
  • Direct Hydrogen Fueling 33
  • Methanol fueling 33
  • PERFORMANCE AND CONSTRUCTION 34
• BARRIERS TO FUEL CELL COMMERCIALIZATION 34
• GENERAL CONCLUSIONS 35

A BRIEF LOOK AT THE MEMBRANE INDUSTRY 37

• MEMBRANE TECHNOLOGY 37
  • END USE MARKETS 38
• STRUCTURE 38
• RESISTANCE 39
  • Membrane Thickness 40
  • Transmembrane Pressure 40
  • Crossflow Filtration 40
• MEMBRANE PROCESSES 40
  • PRICE 43
• DIALYSIS 43
• ELECTROCHEMICAL 44
  • ELECTRODIALYSIS 44
  • PROTON EXCHANGE MEMBRANE (PEM) FUEL CELL 46
• MICROFILTRATION 48
• ULTRAFILTRATION 48
• REVERSE OSMOSIS 49
  • NANOFILTRATION 50
• PERVAPORATION 51
• GAS SEPARATION 51
• MEMBRANE FABRICATION 52
• SUMMARY VALUE MEMBRANE TECHNOLOGIES 54

PROTON EXCHANGE MEMBRANES FOR FUEL CELLS 56

• CHALLENGE TO MATERIALS 56
• CHOOSING NEW ELECTROLYTE MEMBRANES 57
  • OTHER OPTIONS 58
    • Alternative Organic Fuels 58
    • Pretreatment of Membrane 59
• WATER TRANSPORT PROCESSES 60
  • PROTONATED WATER CLUSTERS 62
  • IMPORTANCE OF MEMBRANE THICKNESS 62
• POLYMERS FOR PROTON EXCHANGE MEMBRANES 63
  • PERFLUOROCARBONSULFONIC ACID IONOMERS 63
    • Nafion 64
      • Cost 66
    • Ion Exchange/Nonfunctional Polymer Blends 68
    • Gore Select 68
    • Composites 69
    • Other Sulfonated Perfluorinated Polymers 70
      • Dow's XUS 13204.1 70
  • SULFONATED TRIFLUOROSTYRENES AND BAM 71
    • BAM2G 72
    • BAM3G Basics 72
      • Comparisons With Nafion 117 74
  • 3M's Sulfonated Perfluorocyclobutane 75
  • OTHER SULFONATED POLYSTYRENES AND HYDROCARBONS 75
    • Triblock Polymers 76
    • Ethylene Styrene Interpolymers 77
    • Polystyrene Sulfonic Acid/Polyvinyl Alcohol Blend 78
  • POLYPHOSPHAZENE?BASED / POLYBENIMIDIZOLE (PBI) 78
    • Celanese and Celtec 78
    • Sulfonate Polyphosphazenes 80
  • POLYPHOSPHAZENES 81
  • POLY(BISBENZOXAZOLE) [PBO] 82
    • Other Modifications of PBI 82
  • SULFONATED POLYIMIDES 85
    • Tailored Imides 85
  • POLYETHERETHER KETONE (PEEK) 86
  • SULFONATED POLY(ARYLENE ETHER) SULFONES 87
    • Direct Synthesis 89
      • Reduced Electro?Osmotic Drag 90
      • Conductivity 90
  • NOVEL ION SELECTIVE MEMBRANE RESEARCH 91
    • Glass Membrane 91
    • Glass Layer Improves Humidity 91
    • Metallized Bio?cellulosics 92
    • Ionic Gel Fill 92
    • Other Concepts 93
• MEMBRANES FOR DIRECT OXIDATION FUEL CELLS 93
  • ANODE PROBLEMS 94
  • MEDIS' CONDUCTIVE POLYMER 94
  • GENERICS' TACTIC 96
• MEA?TOTAL 98
  • ENERGY VENTURES RESEARCH 98
  • ADDITIONAL PROPOSED INNOVATIONS 99
    • Catalyst Preparation 100
    • Binder Layer Prevents Crossover 100
    • Toshiba Approach 100
  • COMPOSITES 101
    • Aniline As Barrier 101
    • Johnson Matthey Approach 102
  • FURTHER PROGRESS 102
    • Smart Fuel Cell 103
    • Direct Methanol Fuel Cell Corp. 103
    • Maxdem Technologies 103
    • Others 104
• STRUCTURE OF THE MEMBRANES FOR PEM FUEL CELL INDUSTRY 104
  • COMPANY PROFILES 106
    • Asahi Kasei 106
    • Ballard Power Systems 107
    • Celanese Ventures/ Ticona 108
    • DuPont Fuel Cell Enterprise 110
    • Energy Ventures, Inc. 110
    • Medis El 111
    • W. L. Gore & Associates, Inc. 112
    • Others 112
• VALUE OF PROTON EXCHANGE MEMBRANES FOR FUEL CELLS 113
• Total 114

MEA AND BIPOLAR PLATES FOR PEM FUEL CELLS 116

• FOREWORD 116
• WORKINGS OF THE MEMBRANE ELECTRODE ASSEMBLY (MEA) 117
  • OPERATION 118
  • INTERFACES 119
  • MODIFICATIONS 121
    • JPL Research 121
    • Virginia Tech Research 122
• DOE PERFORMANCE GOALS FOR MEAs 123
• BETTER STACK ASSEMBLY 123
• BIPOLAR PLATES/FIELD FLOW PLATES/COLLECTORS 124
  • DESIRABLE CONSIDERATIONS 124
    • Graphites 126
  • IMPROVED BIPOLAR PLATES/ COLLECTORS 127
    • Avista Approach 127
    • Crystal Graphite Approach 128
    • DuPont Approach 128
    • Entegris Approach 128
    • GM Approach 129
    • Nisshinbo Approach 129
    • PEM Plate Approach 130
    • Porvair Approach 130
    • Sumitomo Metal Approach 130
    • SGL Technologies Approach 131
    • Improved Gasket Approach 132
    • Generics Porous Plates Approach 132
    • Graftech Innovations 134
  • OTHER INNOVATIONS 135
    • Ancillary Factors 136
  • INDEX TO BIPOLAR PLATE/COLLECTOR COMPANIES 136
  • VALUE OF BIPOLAR PLATE/COLLECTORS 138
• GAS DIFFUSION LAYER (GDL) 138
  • DESIRED ATTRIBUTES FOR GDLs 139
  • TECHNIQUES FOR GDL MANUFACTURE 140
    • Developments at Ballard 141
    • Developments at AET/GrafTech/UCAR 142
    • Developments at General Motors 142
    • Developments at Johnson Matthey 143
    • Developments at Mitsubishi Rayon 143
    • Developments at SGL Carbon/SGL Technik 144
    • Developments at Siemens 145
    • Developments at Toray/Mitsui 145
    • Developments at Zoltek 146
    • Other Developments 147
  • INDEX OF SPECIALTY CARBON SUPPLIERS 147
  • VALUE GDL FOR PEM FUEL CELLS 148
• CATALYST INK /ELECTRODES 149
  • ANODE LAYER 150
    • Improved Carbon Monoxide Tolerance 150
    • Changing Electrode Morphology 151
    • Graphite Nanofibers 151
  • CATHODE LAYER 151
  • FABRICATION TECHNIQUES 152
    • Sputter Deposition 152
    • GM's Vapor Deposition 154
  • INFLUENCE OF BINDER 155
    • Needs for Direct Methanol Fuel Cell (DMFC) 156
  • LOWER CATALYST LOADINGS 156
    • Developments at Naval Research Laboratory 156
    • Developments at Southwest Research Institute (SwRI) 157
    • Developments at GM 157
  • DETAILS OF INK COMPOSITION 158
  • INK MODIFICATION 159
    • Progress At SW Research and Gore 159
    • Progress At UTC Fuel Cells 159
    • Progress At Jet Propulsion Laboratory 160
    • Progress At Samsung Electronics 160
    • Progress At Aviva 161
  • VALUE OF THE CATALYST INK/ELECTRODE MARKET 161
• ASSEMBLY OF THE MEA 162
  • 3M INNOVATIVE PROPERTIES CO. APPROACH 163
• STRUCTURE OF THE MEA INDUSTRY 164
  • MEA COMPANY PROFILES 165
    • 3M 165
    • Avista Laboratory, Inc. 166
    • Ballard Power Systems 167
    • Celanese Ventures 168
    • DuPont Fuel Cell Enterprise 169
    • ElectroChem, Inc. 170
    • E?Tek Div. Of De Nora North America, Inc. 171
    • General Electric 172
    • General Motors, Corp. 173
    • Gore Fuel Cell Technologies 174
    • Johnson Matthey 175
    • Lynntech Industries, Ltd. 176
    • Materials and Electrochemical Research Corp. 177
    • NuVant Systems, Inc. 178
    • OM Group, Inc. 178
    • Palcan Fuel Cells Ltd. 179
    • Plug Power/H Power 180
    • Surfect Technologies, Inc./The Bosque Group 183
    • Superior MicroPowders,LLC 184
    • Others 185
• VALUE OF MEAs AND BIPOLAR PLATES FOR PEM FUEL CELLS 185
• Total 186

A CONCISE VIEW OF THE PLATINUM AND PLATINUM GROUP METALS 188

• BASICS OF THE PRECIOUS GROUP METALS (PGM) 188
  • PLATINUMPRODUCTION 189
    • Sources 191
    • Mining 192
    • Refining 193
  • RUTHENIUM 193
  • PALLADIUM 194
  • OTHER PGMs 194
• PLATINUM MARKETS AND CONSUMPTION 194
  • CATALYTIC CONVERTERS 195
• PRICES AND PRICING 195
  • Producer vs. Consumer Conflict 196
    • Market Control 197
  • Cost Is An Issue 197
  • Availability Not An Issue? 198
• STRUCTURE OF THE PLATINUM/PGM INDUSTRY 199
  • World Fuel Cell Council 200
  • PRODUCTION AND CONSUMER INTERACTION 200
  • MAJOR PGM PLAYERS 203
    • Anglo Platinum 203
    • Aquarius Platinum Pty Ltd. 203
    • Englehard?CLAL 204
    • Haraeus Holding Gmbh 205
    • Inco Limited 205
    • Impala Platinum Holding/Implats 206
    • Johnson Matthey 207
    • Lonmin Platinum 208
    • Norilsk 210
    • OMG AG & Co. 210
    • Stillwater Mining 212
    • Tanaka Kikinzoku Kogyo K.K. (TKK) 212
• PGM SCENARIO IN MEAs 213

SUMMARY TABLE ? VALUE OF STACK COMPONENTS FOR PEM FUEL CELLS IN THE U.S., THROUGH 2008 xvi

1 MAJOR FINDINGS OF THE NATIONAL HYDROGEN VISION 9

2 PROJECTED TRANSITION TO THE HYDROGEN ECONOMY 10

3 NATIONAL SCIENCE FOUNDATION FUNDING, BY ACCOUNT 16

4 COSTS VS. NUMBER OF UNITS PRODUCED ANNUALLY 28

5 VALUE U.S. ELECTROCHEMICAL MEMBRANE MARKET
BY FUNCTION, THROUGH 2008 47

6 MEMBRANE FABRICATION TECHNIQUES 52

7 SUMMARY VALUE OF U.S. MEMBRANES BY TYPE IN THE U.S., through 2008 54

8 SYNTHESIS VARIABLE FOR NEW ELECTROLYTE MEMBRANES 57

9 PEM ELECTROLYTE ISSUES 58

10 NAFION PRODUCT THICKNESSES 65

11 PROS AND CONS OF NAFION IN PEM FUEL CELLS 66

12 CONDUCTANCES COMPARISONS 69

13 ADVANTAGES OF A HIGHER TEMPERATURE MEMBRANE
FOR A PEM FUEL CELL 79

14 VIRGINIA TECH BPS MEMBRANE PROPERTIES COMPARED WITH NAFION 117 88

15 CMR COST COMPARISONS 96

16 COMPANIES PRODUCING ION SELECTIVE MEMBRANES
FOR PEM FUEL CELLS 105

17 VALUE OF PROTON EXCHANGE MEMBRANES FOR FUEL CELLS BY TYPE 114

18 FUEL CELL MEA TARGETS 123

19 DESIGN CONSIDERATIONS FOR BIPOLAR PLATES 125

20 MATERIAL TYPES FOR BIPOLAR PLATES 125

21 SGL SIGRACET BIPOLAR PLATE TYPICAL PROPERTIES 131

22 INDEX OF BIPOLAR PLATE/COLLECTOR COMPANIES 137

23 VALUE OF BIPOLAR PLATE/COLLECTORS
FOR MEAs, THROUGH 2008 138

24 ATTRIBUTES NEEDED FOR GAS DIFFUSION LAYER MATERIALS 140

25 PROS AND CONS OF GDL MANUFACTURING TECHNIQUES 140

26 TYPICAL PROPERTIES OF SIGRACET GAS DIFFUSION LAYER 144

27 INDEX OF SPECIALTY CARBON/GDL SUPPLIERS 148

28 VALUE GDL FOR PEM FUEL CELLS, THROUGH 2008 149

29 VALUE OF THE CATALYST INK/ELECTRODE MARKET FOR MEAs, THROUGH 2008 161

30 VALUE MEAs AND BIPOLAR PLATES FOR PEM FUEL CELLS IN THE U.S., THROUGH 2008 186

31 SALIENT STATISTICS FOR PLATINUM GROUP METALS ? UNITED STATES 189

32 GLOBAL MINE PRODUCTION AND PGM RESERVES IN 2001 192

33 PGM PRODUCERS' LOCATION 199