Non-Noble Metal Fuel Cell Catalysts E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 882

Veröffentlichungsjahr: 2014

Beschreibung

Written and edited by top fuel cell catalyst scientists and engineers from both industry and academia, this is the first book to provide a complete overview of this hot topic. It covers the synthesis, characterization, activity validation and modeling of different non-noble metal electrocatalysts, as well as their integration into fuel cells and their performance validation, while also discussing those factors that will drive fuel cell commercialization. With its well-structured approach, this is a must-have for researchers working on the topic, and an equally valuable companion for newcomers to the field.

Leseprobe

Table of Contents

Cover

Related Titles

Titlepage Text

Copyright

Preface

List of Contributors

Chapter 1: Electrocatalysts for Acid Proton Exchange Membrane (PEM) Fuel Cells – an Overview

1.1 Introduction

1.2 Acid PEM Fuel Cell Background and Fundamentals

1.3 Acid PEM Fuel Cell Catalysis for Cathode O

2

Reduction Reaction

1.4 Catalyst Challenges and Perspective in Acid PEM Fuel Cells

1.5 Conclusion

Chapter 2: Heat-Treated Transition Metal-NxCy Electrocatalysts for the O2 Reduction Reaction in Acid PEM Fuel Cells

2.1 Introduction

2.2 Synthesis Approaches for Heat-Treated Me/N/C Catalysts

2.3 Important Parameters for Highly Active Me/N/C Catalysts

2.4 Nature of the Active Sites

2.5 Electrochemical Investigation by RDE/RRDE Methods

2.6 Conclusions

Acknowledgments

Chapter 3: Modified Carbon Materials for O2 Reduction Reaction Electrocatalysts in Acid PEM Fuel Cells

3.1 Introduction

3.2 Doped Carbon Materials

3.3 Doped Carbons as ORR Catalysts

3.4 Conclusions

Acknowledgment

Chapter 4: Transition Metal Chalcogenides for Oxygen Reduction Electrocatalysts in PEM Fuel Cells

4.1 Introduction

4.2 Non-noble Metal Chalcogenide Electrocatalysts for Oxygen Reduction Reaction

4.3 Synthesis Methods for Non-noble Metal Chalcogenides

4.4 Oxygen Reduction Reaction on Non-noble Metal Chalcogenides

4.5 Methanol Tolerance

4.6 Fuel Cell Measurements

4.7 Conclusions

Chapter 5: Transition Metal Oxides, Carbides, Nitrides, Oxynitrides, and Carbonitrides for O2 Reduction Reaction Electrocatalysts for Acid PEM Fuel Cells

5.1 Introduction

5.2 Transition Metal Nitrides and Carbonitrides as Cathode Catalysts

5.3 Stability of Oxides in Acid Electrolyte

5.4 Non-noble Metal Oxide-Based Cathode Catalysts

5.5 Conclusions

5.6 Acknowledgments

Chapter 6: Theoretical Modeling of Non-noble Metal Electrocatalysts for Acid and Alkaline PEM Fuel Cells

6.1 Introduction

6.2 Mechanisms of ORR

6.3 Simple Metal–N

4

Macrocycles

6.4 Heat-Treated Transition Metal Nitrogen–Carbon Precursors (M-N

x

/C)

6.5 Functionalized Graphitic Materials

6.6 Conducting Polymers

6.7 Outlook

Chapter 7: Membranes for Alkaline Polyelectrolyte Fuel Cells

7.1 Introduction

7.2 Two Main Challenges of APEs

7.3 APEs Reported in the Literature

7.4 Strategies for Improving the Ionic Conductivity of APE

7.5 Efforts of Improving the Chemical Stability of the Cationic Functional Group

7.6 Research on the Chemical Stability of APE Backbone

7.7 Conclusions and Perspective

Chapter 8: Electrocatalysts for Alkaline Polymer Exchange Membrane (PEM) Fuel Cells – Overview

8.1 Introduction

8.2 Alkaline Fuel Cell Overview – History, Status, and Advantages

8.3 Alkaline Fuel Cell and Alkaline PEM Fuel Cell – Thermodynamics and Kinetics

8.4 Silver-Based Materials for Cathode Electrocatalysts in Alkaline PEM Fuel Cells

8.5 Catalysts for Oxidation of a Broad Range of Fuels for Alkaline PEM Fuel Cells

8.6 Major Challenges of Alkaline Fuel Cells and Alkaline PEM Fuel Cells

Acknowledgments

Chapter 9: Carbon Composite Cathode Catalysts for Alkaline PEM Fuel Cells

9.1 Introduction

9.2 Metal-Free Carbon Catalysts

9.3 Heat-Treated M–N–C (M: Fe, Co) Carbon Composite Catalysts

9.4 Nanocarbon/Transition Metal Compound Hybrid Catalysts

9.5 ORR Mechanism on NPMCs in Alkaline Media

9.6 NPMC Cathode Performance in Anion Exchange Membrane Fuel Cell

9.7 Summary and Perspective

Chapter 10: Non-precious Metal Oxides and Metal Carbides for ORR in Alkaline-Based Fuel Cells

10.1 Introduction

10.2 Metal Oxides

10.3 Perovskite-Type Oxides

10.4 Spinel-Type Oxides

10.5 Metal Carbides

10.6 Conclusion and Outlook

Chapter 11: Automotive Applications of Alkaline Membrane Fuel Cells

11.1 Introduction

11.2 History of Alkaline Fuel Cells in Automotive Applications

11.3 Fuel Used in Modern Alkaline PEM Fuel Cells in Automotive Applications

11.4 Components of an Alkaline PEM Fuel Cell Membrane Electrode Assembly for Automotive Applications

11.5 Major Challenges to Overcome in Alkaline PEM Fuel Cells

11.6 Conclusion

Acknowledgments

Index

End User License Agreement

Pages

Guide

Table of Contents

List of Illustrations

Figure 1.1

Figure 1.2

Figure 1.3

Figure 1.4

Figure 1.5

Figure 1.6

Figure 1.7

Figure 1.8

Figure 1.9

Figure 1.10

Figure 2.1

Figure 2.2

Figure 2.3

Figure 2.4

Figure 2.5

Figure 2.6

Figure 2.7

Figure 2.8

Figure 2.9

Figure 2.10

Figure 2.11

Figure 2.12

Figure 2.13

Figure 2.14

Figure 2.15

Figure 2.16

Figure 2.17

Figure 2.18

Figure 2.19

Figure 2.20

Figure 2.21

Figure 2.22

Figure 2.23

Figure 2.24

Figure 2.25

Figure 2.26

Figure 2.27

Figure 2.28

Figure 2.29

Figure 2.30

Figure 2.31

Figure 2.32

Figure 2.33

Figure 2.34

Figure 2.35

Figure 2.36

Figure 2.37

Figure 2.38

Figure 3.1

Figure 3.2

Figure 3.3

Figure 3.4

Figure 3.5

Figure 3.6

Figure 3.7

Figure 3.8

Figure 3.9

Figure 3.10

Figure 3.11

Figure 3.12

Figure 3.13

Figure 3.14

Figure 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Figure 4.5

Figure 4.6

Figure 4.7

Figure 4.8

Figure 4.9

Figure 4.10

Figure 4.11

Figure 4.12

Figure 4.13

Figure 4.14

Figure 5.1

Figure 5.2

Figure 5.3

Figure 5.4

Figure 5.5

Figure 5.6

Figure 5.7

Figure 5.8

Figure 5.9

Figure 5.10

Figure 5.11

Figure 5.12

Figure 6.1

Figure 6.2

Figure 6.3

Figure 6.4

Figure 6.5

Figure 6.6

Figure 6.7

Figure 6.8

Figure 6.9

Figure 6.10

Figure 6.11

Figure 6.12

Figure 6.13

Figure 6.14

Figure 6.15

Figure 6.16

Figure 6.17

Figure 6.18

Figure 6.19

Figure 6.20

Figure 6.21

Figure 6.22

Figure 7.1

Figure 7.2

Figure 7.3

Figure 7.4

Figure 7.5

Figure 7.6

Figure 7.7

Figure 7.8

Figure 7.9

Figure 7.10

Figure 7.11

Figure 7.12

Figure 7.13

Figure 7.14

Figure 7.15

Figure 7.16

Figure 7.17

Figure 7.18

Figure 7.19

Figure 7.20

Figure 7.21

Figure 7.22

Figure 7.23

Figure 7.24

Figure 7.25

Figure 8.1

Figure 8.2

Figure 8.3

Figure 8.4

Figure 8.5

Figure 8.6

Figure 8.7

Figure 8.8

Figure 8.9

Figure 8.10

Figure 8.11

Figure 8.12

Figure 8.13

Figure 8.14

Figure 8.15

Figure 8.16

Figure 9.1

Figure 9.2

Figure 9.3

Figure 9.4

Figure 9.5

Figure 9.6

Figure 9.7

Figure 9.8

Figure 9.9

Figure 9.10

Figure 9.11

Figure 9.12

Figure 9.13

Figure 9.14

Figure 9.15

Figure 9.16

Figure 9.17

Figure 9.18

Figure 9.19

Figure 9.20

Figure 9.21

Figure 10.1

Figure 10.2

Figure 10.3

Figure 10.4

Figure 10.5

Figure 10.6

Figure 10.7

Figure 10.8

Figure 10.9

Figure 10.10

Figure 10.11

Figure 10.12

Figure 10.13

Figure 10.14

Figure 10.15

Figure 11.1

Figure 11.2

Figure 11.3

Figure 11.4

Figure 11.5

Figure 11.6

Figure 11.7

Figure 11.8

Figure 11.9

Figure 11.10

Figure 11.11

Figure 11.12

Figure 11.13

Figure 11.14

Figure 11.15

Figure 11.16

Figure 11.17

Figure 11.18

Figure 11.19

List of Tables

Table 2.1

Table 2.2

Table 4.1

Table 5.1

Table 6.1

Table 8.1

Table 8.2

Table 8.3

Table 10.1

Table 10.2

Table 10.3

Table 10.4

Table 10.5

Table 10.6

Table 11.1

Table 11.2

Table 11.3

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Non-Noble Metal Fuel Cell Catalysts

Edited by

Zhongwei Chen, Jean-Pol Dodelet, and Jiujun Zhang

Editors

Prof. Zhongwei Chen

University of Waterloo

Dept. of Chem. Engineering

200 University Avenue West

N2L 3G1 NK

Canada

Prof. Jean-Pol Dodelet

INRS

Energie, Matériaux et Télécommunications

Boulevard Lionel Boulet 1650

J3X 1S2 NK

Canada

Dr. Jiujun Zhang

National Res. Council Canada

Inst. for Fuel Cell Innovation

Westbrook Mall 4250

V6T 1W5 NK

Canada

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Preface

In the context of economic development and improvement in human living conditions, developing advanced technologies for energy storage and conversion has become a hot topic today. Polymer electrolyte membrane (PEM) fuel cells are one kind of important clean energy-converting devices that have drawn a great deal of attention in recent years due to their high efficiency, high energy density, and low or zero emissions, as well as their several important areas of application such as transportation, stationary and portable power, and micro-power. However, two major technical challenges, namely, high cost and low reliability/durability, have been identified as the major obstacles hindering the commercialization of PEM fuel cells. Fuel cell catalysts, such as platinum (Pt)-based catalysts and their associated catalyst layers, are the major factors related to these challenges. To overcome the challenges, exploring new catalysts, improving catalyst activity and stability/durability, and reducing catalyst cost are currently the major approaches in fuel cell technology and commercialization.

Regarding the cost reduction of Pt-based catalysts, non-noble metal catalysts, the next generation PEM fuel cell catalysts slated to replace expensive Pt, have been recognized as the sustainable solution for the commercialization of PEM fuel cells. In more recent years, intensified research and development in this area has been carried out by the world fuel cell community. To facilitate this effort, a book specifically focusing on this area is definitely necessary. This book contains comprehensive and systematic information on non-noble metal electrocatalysts for oxygen reduction reactions in both acid and alkaline PEM fuel cells with emphasis on (i) the fundamentals of electrochemical oxygen reduction catalysis with non-noble metal catalysts within acid and alkaline PEM fuel cells; (ii) the synthesis, characterization, activity validation, and modeling of various kinds of non-noble metal electrocatalysts; and (iii) the integration of the non-noble metal electrocatalysts into fuel cells and validation of their performance.

This book is written by a group of top scientists in the field of fuel cell catalysts, who not only have excellent academic records but also industrial expertise in the use of fuel cells. The book contains the latest updated information on R&D achievements and understanding in electrocatalysts for oxygen reduction reactions in both acid and alkaline PEM fuel cells. Some important R&D directions toward commercialization of both types of fuel cells are also discussed. In order to help readers understand the science and technology of the fuel cell catalysis, some important and representative figures, tables, photographs, and a comprehensive list of reference papers are presented in this book.

We believe that this book should be extremely useful to researchers and engineers who are working in energy/fuel cell industries. We sincerely hope that through reading this book, the reader will easily be able to locate the latest information on the fundamentals and applications of the catalysis of the oxygen reduction reaction in the next generation of fuel cells. It is expected that this book could be used as a reference for college/university students including undergraduates and graduates, and scientists and engineers who work in the areas of energy, electrochemistry science/technology, fuel cells, and electrocatalysis.

We would like to acknowledge with deep appreciation all of the efforts of all the contributors in writing their chapters. We also wish to thank Dr. Heike Nöthe, Senior Project Editor at STMS Books for extensive help and support.

If technical errors are found in this book, we and all the contributors would deeply appreciate the readers’ constructive comments for correction and further improvement.

January 2014

Dr. Zhongwei Chen,Waterloo, Ontario, Canada

Dr. Jean-Pol DodeletMontreal, Quebec, Canada

Dr. Jiujun ZhangVancouver, British Columbia,Canada

List of Contributors

Nicolas Alonso-Vante

IC2MP-CNRS 7285

University of Poitiers 4 Michel

Brunet Street

86022 Poitiers

France

Koichiro Asazawa

Daihatsu Motor Co., Ltd.

Frontier technology R&D

Department

R&D Division

3000 Yamanoue

Ryuo

Gamo

Shiga 520-2593

Japan

Michael Bron

Martin Luther University

Halle-Wittenberg

Faculty of Natural Sciences II

Department of Chemistry

von-Danckelmann-Platz 4

06120 Halle

Germany

Rui Cai

Chinese Academy of Sciences

State Key Laboratory of Catalysis

Dalian Institute of Chemical

Physics

457 Zhongshan Road

Dalian 116023

China

Chen Chen

Wuhan University

College of Chemistry and

Molecular Sciences

Luojia Hill Street

Wu Chang

Wuhan 430072

China

Zhongwei Chen

University of Waterloo

Department of Chemical

Engineering

Waterloo Institute for

Nanotechnology

Waterloo Institute for Sustainable

Energy

200 University Avenue West.

Waterloo

Ontario

N2L 3G1

Canada

Deryn Chu

U.S. Army Research Laboratory

Sensors and Electron Devices

Directorate

2800 Powder Mill Road

Adelphi

MD 20783-1197

USA

Wenling Chu

Chinese Academy of Sciences

State Key Laboratory of Catalysis

Dalian Institute of Chemical

Physics

457 Zhongshan Road

Dalian 116023

China

Eben Dy

National Research Council

Canada

Institute for Fuel Cell Innovation

4250 Wesbrook Mall

V6T 1W5

Vancouver BC

Canada

Drew Higgins

University of Waterloo

Department of Chemical

Engineering

Waterloo Institute for

Nanotechnology

Waterloo Institute for Sustainable

Energy

200 University Avenue West.

Waterloo

Ontario

N2L 3G1

Canada

Hideto Imai

NISSAN ARC Ltd.

Energy-Device Analysis

Department

1 Natsushima

Yokosuka

Japan

Akimitsu Ishihara

Yokohama National University

Green Hydrogen Research Center

79-5 Tokiwadai

Hodogaya-ku

Yokohama

Japan

Frédéric Jaouen

Université de Montpellier II

Institut Charles Gerhardt

Montpellier

Laboratory of Aggregates,

Interfaces and Materials for

Energy

CNRS-UMR 5253

2 Place Eugène Bataillon

34095 Montpellier

France

Rongzhong Jiang

U.S. Army Research Laboratory

Sensors and Electron Devices

Directorate

2800 Powder Mill Road

Adelphi

MD 20783-1197

USA

Jesaiah King

The Ohio State University

Department of Chemical and

Biomolecular Engineering

Koffolt Laboratories

140 W. 19th Ave.

Columbus

OH 43210

USA

Kunchan Lee

Showa Denko K.K.

Institute for Advanced and Core

Technology

1-1-1, Ohnodai

Midori-ku, Chiba-shi

Chiba 267-0056

Japan

Qing Li

Materials Physics and

Applications Division

Los Alamos National Laboratory

P.O. Box 1663

Mailstop D429

Los Alamos

NM 87545

USA

Ken-ichiro Ota

Yokohama National University

Green Hydrogen Research Center

79-5 Tokiwadai

Hodogaya-ku

Yokohama

Japan

Umit S. Ozkan

The Ohio State University

Department of Chemical and

Biomolecular Engineering

Koffolt Laboratories

140 W. 19th Ave.

Columbus

OH 43210

USA

Jing Pan

Wuhan University

College of Chemistry and

Molecular Sciences

Luojia Hill Street

Wu Chang

Wuhan, 430072

China

Tomokazu Sakamoto

Daihatsu Motor Co., Ltd.

Frontier technology R&D

Department

R&D Division

3000 Yamanoue

Ryuo

Gamo

Shiga 520-2593

Japan

Zheng Shi

National Research Council

Canada

Institute for Fuel Cell Innovation

4250 Wesbrook Mall

V6T 1W5

Vancouver BC

Canada

Deepika Singh

The Ohio State University

Department of Chemical and

Biomolecular Engineering

Koffolt Laboratories

140 W. 19th Ave.

Columbus

OH 43210

USA

Hirohisa Tanaka

Daihatsu Motor Co., Ltd.

Frontier technology R&D

Department

R&D Division

3000 Yamanoue

Ryuo

Gamo

Shiga 520-2593

Japan

Gang Wu

Materials Physics and

Applications Division

Los Alamos National Laboratory

P.O. Box 1663

Mailstop D429

Los Alamos

NM 87545

USA

Jiujun Zhang

National Research Council

Canada

Institute for Fuel Cell Innovation

Westbrook Mall 4250

Vancouver

BC V6T 1W5

Canada

Lin Zhuang

Wuhan University

College of Chemistry and

Molecular Sciences

Luojia Hill Street

Wu Chang

Wuhan, 430072

China

1Electrocatalysts for Acid Proton Exchange Membrane (PEM) Fuel Cells – an Overview

Michael Bron

1.1 Introduction

Fuel cells are devices that directly convert chemical energy stored in a fuel into electricity. The main components of fuel cells are the electrodes (anode and cathode), which are separated by an electrolyte. Several of these electrode–electrolyte units may be connected in series to give a so-called fuel cell stack. In a fuel cell, the fuel (typically hydrogen, but also others like methanol) is oxidized at the anode, and the electrons released during oxidation are conducted to the cathode, where the oxidant (typically oxygen, either pure or as air) is reduced. The driving force for this process is the negative Gibbs free energy of the overall reaction (see Section 1.2.2). The first description of the fuel cell principle dates back to the year 1839/1842, when Sir William Grove described his gaseous voltaic battery based on Schönbeins findings. Since then, different types of fuel cells have been developed [1–3], which differ in the electrodes and the electrolyte used, their operation temperature, and the fuel used. The main types of fuel cells are the low-temperature fuel cells, namely, the “alkaline fuel cell” (AFC) and “proton exchange membrane fuel cell” (PEMFC), including the “direct methanol fuel cell” (DMFC); the medium-temperature fuel cell, namely, “phosphoric acid fuel cell” (PAFC); and the high-temperature types, namely, the “molten carbonate fuel cell” (MCFC) and “solid oxide fuel cell” (SOFC). These fuel cells are labeled according to the electrolyte used; however, the DMFC, which is a proton exchange membrane (PEM) type FC, is an exception. Details on the design and operation of these fuel cells can be found in the cited literature. Other types of fuel cells have also been described, for example, biofuel cells, which use enzymes or even microorganisms to catalyze reactions, and borohydride fuel cells.

The aim of this chapter is to give an overview of the PEMFC, its design and operation, and to discuss the basics of its cathode reaction, namely, electrocatalytic oxygen reduction (ORR, oxygen reduction reaction). As will become clear, the ORR is a major challenge in current fuel cell research both from the fundamental as well as from the applications point of view. This chapter is intended to provide the background for more specialized chapters that follow.

1.2 Acid PEM Fuel Cell Background and Fundamentals

1.2.1 Acid PEM Fuel Cell Overview – History, Status, and Advantages

As mentioned above, the first description of the fuel cell principle dates back to Grove's gaseous voltaic battery. It is amazing that this first system already used hydrogen and oxygen, which were converted at Pt electrodes in an acid electrolyte. However, it took a long time and significant efforts to progress from Grove's Pt sheet electrodes to today's advanced catalysts, from the acid liquid electrolyte to today's proton-conducting membranes [3]. At that time, further development of the “gaseous voltaic battery” was impeded by two main factors. The first was that larger amounts of hydrogen were not easily available at that time and hydrogen was produced by laboratory techniques, for example, by the dissolution of Zn. The second issue was the development of the dynamo by Siemens in 1866/1867, which made available electrical energy on a larger scale, thus there was no technical need to further develop the gaseous voltaic battery. It thus took more than a century until the development of fuel cells gained momentum again, albeit research and development activities have been reported on during that time [1]. The development of fuel cells was boosted in the 1950s, with focus on the AFC, which found early application in spaceflight, where sources of electrical energy with high energy density were needed and cost was not an issue. Despite having certain advantages such as high efficiency, the necessity to use high-purity gases and the highly corrosive liquid electrolyte posed a challenge at that time. The next impulse for further developing the fuel cell technology was the oil crisis in the early 1970s. During these periods of technical progress, the above types of fuel cells were developed to an advanced state. However, in all these fuel cells, issues occurred that hindered their commercialization and it was only during the last 20 years that commercialization of fuel cells for a mass market came within reach. More details on the history and the state-of-the-art of fuel cells can be found in the literature [2–4].