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NEW HORIZONS IN ELECTROCHEMICAL SCIENCE AND TECHNOLOGY Report of the Committee on Electrochemical Aspects of Energy Conservation and Production National Materials Advisory Board Commission on Engineering and Technical Systems National Research Council Publication NMAl3 438-1 National Academy Press Washington, D.C. 1986

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NATIONAL ACADEMY PRESS 2101 Constitution Avenue, N.W. Washington, DC 20418 NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The members of the committee responsible for the report were chosen for their special competences and with regard for appropriate balance. The report has been reviewed by a group other than the authors according to procedures approved by a Report Review Committee consisting of members of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The National Research Council was established by the National Academy of Sciences in 1916 to associate the broad community of science and technology with the Academy's purposes of furthering knowledge and of advising the federal government. The Council operates in accordance with general policies determined by the Academy under the authority of its congressional charter of 1863, which established the Academy as a private, nonprofit, self-governing membership corporation. The Council has become the principal operating agency of both the National Academy of Sciences and the National Academy of Engineering in the conduct of their services to the government, the public, and the scientific and engineering communities. It is administered jointly by both Academies and the Institute of Medicine. The National Academy of Engineering and the Institute of Medicine were established in 1964 and 1970, respectively, under the charter of the National Academy of Sciences. This study by the National Materials Advisory Board was conducted under Contract No. B-M4455-A-Z with the Department of Energy. This report is for sale by the National Technical Information Center, Springfield, Virginia 22161. International Standard Book Number 0-309-03735-2 Printed in the United States of America. On the Coyer: ELECTRICITY WITHOUT COMBUSTION The fuel cell electrochemically combines fuel and oxygen to produce electricity. Fuel gas flows across the cell's fuel electrode (anode), where it separates into hydrogen ions and electrons. The ions migrate through the electrolyte to the oxygen electrode (cathode), while the electrons move through an external circuit to the cathode. Oxygen, hydrogen ions, and electrons join at the cathode to form water. The flow of electrons through the external circuit produces electricity. A fuel ceil power plant may contain thousands of these individual cells stacked within its power section. A fuel processor converts such utility fuels as natural gas, light distillates, or synthetics to the hydrogen-rich fuel necessary for the cells, and a power conditioner converts the resulting direct-current electricity to alternating-current electricity. From EPRI Journal, Electric Power Research Institute, 3412 Hillview Avenue, Palo Alto, California 94303 First Printing, December 1986 Second Printing, August 1987 11

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ABSTRACT Electrochemical phenomena play a fundamental role in providing essential materials and devices for modern society. This report reviews the status of current knowledge of electrochemical science and tech- nology and makes recommendations for future research and development in this multidisciplinary field. The report identifies new technological opportunities in widely diverse applications, including batteries and fuel cells, biomedical and health care, coatings and films, corrosion, electrochemical surface processing, manufacturing and waste utilization, membranes, microelectronics, and sensors. In addition, opportunities for cross-cutting research in key areas that will provide the technology base needed in the future are delineated. These areas include electrochemical engineering, in situ characterization, interracial structure, materials, photoelectrochemistry, plasmas, and surface reactions. The socioeconomic impact of electrochemical technology is summarized and compared with current federal support levels. Concerns are noted regarding constraints on basic research arising from support along traditional disciplinary lines and inadequate attention given to exploratory development as well as to science and technology transfer. . . .

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PREFACE Electrochemical phenomena underpin a wide range of technologies. Included among these are the traditional electrochemical processes that for more than a century have provided essential materials, many of which cannot be created by any other economical method. In addition, there is a broad range of technological opportunities that depend intimately on electrochemical phenomena but lie outside the conventional electrolytic industries. During the past decade the study of electrochemical phenomena has advanced in several disciplines, including physics, chemistry, chemical engineering, and the life sciences, among others. Very recently, a renaissance has occurred in this field because of new-found abilities to create precisely characterized systems for fundamental study, to monitor behavior at previously unattainable levels of sensitivity, and to predict (i.e., design) with new theories and computational skill. These capabilities are creating extraordinary opportunities, both for advance- ment of science and for the transfer of that science into new products and processes. The Office of Conservation and Renewable Energy of the Department of Energy requested that the National Research Council, through the National Materials Advisory Board, assess electrochemical science and technology and recommend opportunities and priorities in research and development aimed at energy conservation. Three efforts were identified. The first was an overall assessment of electrochemical R&D that could lead to major gains in materials and energy conservation; this effort would include recommending technical directions for further study, evaluating benefits of such work, and identifying agencies with interests in these areas. The second and third efforts involved detailed evaluations in two areas electrochemical corrosion and in situ characterization of electrochemical processes. The Committee on Electrochemical Aspects of Energy Conservation and Production was established to conduct these activities. Two panels were formed one to study and publish a report on corrosion and the other on character- ization (NMAB reports 438-2 and 438-3, respectively). The committee recognized that the electrochemical science base relevant to energy conservation is also relevant to many other v

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technologies. The committee considered this broader range of technologies and presents its findings in this report as a program for research and development. The principal findings of the report are given in Chapter 1, "Overview: Conclusions and Recommendations." The emphasis of this report is placed on technical aspects of electrochemical phenomena, both those that have clearly defined commercial potential (Chapter 5, Opportunities in Particular Technologies") and others where new understanding and capabilities may ultimately lead to new products (Chapter 6, Opportunities for Cross-Cutting Researcher. These issues were addressed only peripherally by recent studies on chemistry (Opportunities in Chemistry, National Academy Press, 1985) and chemical engineering (Committee on Chemical Engineering Frontiers: Research Needs and Opportunities, a current National Research Council activity). The committee notes that the findings of these studies are compatible with those in this report. The intended audiences for this report are government and industry executives who are responsible for policy directions in their institu- tions; program managers in funding agencies responsible for identifying and responding to opportunities for economic growth; and laboratory scientists and engineers who develop technical concepts for improved understanding of the science and technology as well as the products resulting from research and development. V1

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ACKNOWLEDGMENTS Presentations and written materials were provided to the committee by a number of individuals to whom the committee wishes to express its sincere gratitude: John Appleby, Electric Power Research Institute; Stanley Bruckenstein, Department of Chemistry, State University of New York, Buffalo; Richard P. Buck, Kenan Laboratories of Chemistry, University of North Carolina; Ronald Chance, Allied Corporation; Anna W. Crull, Chemical Technology Consultants; Arthur Diaz, IBM Research Laboratories; Gregory C. Farrington, Department of Materials Science and Engineering, University of Pennsylvania; Robert Freeman, Department of Chemical and Biochemical Engineering, Rutgers University; Allen Hahn, Dalton Research Center, University of Missouri, Columbia; James Hoare, Research Laboratories, General Motors Technical Center; G. D. Hutcheson, VLSI Research; Adrianus J. Kalmijn, Scripps Institution of Oceanography, University of California, San Diego; Donald E. Koontz, AT&T Bell Laboratories, Uzie} Landau, Chemical Engineering Department, Case Western Reserve University; Imants Lauks, Integrated tonics; Chung-Chiun Liu, Electronics Design Center, Case Western Reserve University; Egon Matijevic, Department of Chemistry, Clarkson University; Patrick J. Moran, Materials Science and Engineering, Johns Hopkins University; Royce W. Murray, Kenan Laboratories of Chemistry, University of North Carolina; Dale M. Norris, Department of Entomology, Russell Labora- tories, University of Wisconsin; Boone Owens, Department of Chemical Engineering and Materials Science, University of Minnesota; Alfred R. Potvin, Medical Instrument Systems Research Division, Eli Lilly and Company; L. T. Romankiw, IBM Research Center; William Safranek, American Electroplating and Surface Finishing Society; Richard A. Sard, OMI International Corporation; Dexter D. Snyder, Electrochemistry Department, General Motors Research Laboratories; Isaac Trachtenberg, Department of Chemical Engineering, University of Texas, Austin; Harold Tuller, Department of Materials Science and Engineering, Massachusetts Institute of Technology; W. J. Walsh, Argonne National Laboratory; Jack Winnick, School of Chemical Engineering, Georgia Institute of Technology; Howard Yeager, Department of Chemistry, University of Calgary; and Petr Zuman, Depart,rnent of Chemistry, Clarkson University. v~

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Stanley M. Wolf of the National Materials Advisory Board provided staff assistance; Jennifer Tilles of the NMAB office and Nancy Carr of the University of Illinois facilitated committee activities by handling meeting logistics and typing reports and other communications. Their efforts were invaluable to the work of the committee, and we are grateful for their enthusiastic support. In addition, nearly 40 federal government program managers assisted the committee in its review of funding for electrochemistry. We appreciate the cooperation of the following individuals: Department of Commerce E. N. Pugh and U. Bertocci, National Bureau of Standards; Department of Defense, Air Force- W. S. Bishop, B. Cohen, and G. Turner, Wright-Patterson Air Force Base; J. S. Wilkes, Office of Scientific Research (Air Force Academy); Army- B. F. Spielvogel, Army Research Office (including work at Ft. Monmouth); I. Joebstl, Ft. Belvoir R&D Center; M. Levy, Materials Technology Laboratory; S. Wax and R. M. Williams, Defense Advanced Research Projects Agency; Navy A. G. S. Morton, David Taylor Naval Ship R&D Center; J. Deluccia, Naval Air Development Center; S. Rogers, Naval Sea Systems Command; J. Jenkins, Naval Civil Engineering Command; S. Pettadapur, Naval Air Systems Command; T. Crooker, Naval Research Laboratory; I. Dixon and C. E. Mueller, Naval Surface Weapons Center; I. Smith, Naval Weapons Center; J. Cedricks and R. Nowak, Office of Naval Research; Strategic Defense Initiative- J. I. Auborn (AT&T Bell Laboratories) and W. S. Bishop (Wright-Patterson Air Force Base); Department of Energy A. R. Landgrebe, Office of Conservation and Renewable Energy; I. L. Thomas, Office of Basic Energy Sciences; G. L. Hagey and S. I. Dapkunas, Office of Fossil Energy; Department of Health and Human Services F. D. Altieri and J. A. Vaillancourt, National Institutes of Health; Department of the Interior D. R. Flinn, Bureau of Mines; Department of Transportation- P. D. Vermani, Federal Highway Administration; National Aeronautics and Space Administration-E. E. van Landingham, Propulsion, Power, and Engineering Division; National Science Foundation H. N. Blount, Chemistry Division; K. Rogers, Kinetics, Catalysis, Separations, and Purification Processes Division; R. G. Stang, Materials Research Division; Nuclear Regulatory Commission C. Serpan, Reactor Research; and M. McNeill, Nuclear Waste. This study was sponsored by the Office of Conservation and Renewable Energy, U.S. Department of Energy. The assistance of A. R. Landgrebe of that office is gratefully acknowledged. . . vail

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COMMITTEE ON ELECTROCHEMICAL ASPECTS OF ENERGY CONSERVATION AND PRODUCTION Chairman RICHARD C. ALKIRE, Department of Chemical Engineering, Un Illinois, Urbana-Champaign Members iversity of ALLEN J. BARD, Department of Chemistry, University of Texas, Austin ELTON I. CAIRNS, Applied Science Division, Lawrence Berkeley Laboratory, Berkeley, California DANIEL D. CUBICCIOTTI, Nuclear Power Division, Electric Power Research Institute, Palo Alto, California LARRY R. FAULKNER, Department of Chemistry, University of Illinois, Urbana-Champaign ADAM HELLER, Electronic Materials Research Department, AT&T Bell Laboratories, Murray Hill, New Jersey NOEL JARRETT, Chemical Engineering Research and Development, Aluminum Company of America, Alcoa Center, Pennsylvania RONALD LATANISION, Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge DIGBY D. MACDONALD, Chemistry Laboratory, SRI International, Menlo Park, California WILLIAM H. SMYRL, Department of Chemical Engineering and Materials Science, Center for Corrosion Research, University of Minnesota, Minneapolis CHARLES W. TOBIAS, Department of Chemical Engineering, University of California, Berkeley ERNEST B. YEAGER, Department of Chemistry, Case Center for Electrochemical Sciences, Case Western Reserve University, Cleveland 1X

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PANEL ON ELECTROCHEMICAL CORROSION Chairman WILLIAM H. SMYRL, Department of Chemical Engineering and Materials Science, Center for Corrosion Research, University of Minnesota, Minneapolis Members THEODORE R. BECK, Electrochemical Technology Corporation, Seattle, Washington MILTON BLANDER, Argonne National Laboratories, Argonne, Illinois DAVID ]. DUQUETTE, Department of Materials Engineering, Rensselaer Polytechnic Institute, Troy, New York JEROME KRUGER, Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland RONALD LATANISION, Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge DIGBY D. MACDONALD, Chemistry Laboratory, SRI International, Menlo Park, California PAUL C. MILNER, Electrochemical and Contamination Research Department, AT&T Bell Laboratories, Murray Hill, New Jersey DENNIS W. READEY, Department of Ceramic Engineering, Ohio State University, Columbus NEILL WEBER, Ceramatec , Incorporated, Salt Lake City, Utah x

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PANEL ON IN SITU CHARACTERIZATION OF ELECTROCHEMICAL PROCESSES Chairman LARRY R. FAULKNER, Department of Chemistry, University of Illinois, Urbana-Champaign Members FRED C. ANSON, Division of Chemistry and Chemical Engineering, California Institute of Technology ALLEN I. BARD, Department of Chemistry, University of Texas, Austin JOSEPH G. GORDON, II, IBM Corporation, Yorktown Heights, New York FARREL W. LYTLE, Boeing Company, Seattle, Washington BARRY MILLER, AT&T Bell Laboratories, Murray Hill, New Jersey R. MARK WIGHTMAN, Department of Chemistry, Indiana University ERNEST B. YEAGER, Department of Chemistry, Case Center for Electrochemical Sciences, Case Western Reserve University, Cleveland Liaison Representatives FRANK D. ALTIERI, National Heart, Lung and Blood Institute, Division of Heart and Vascular Diseases, Bethesda, Maryland UGO BERTOCCI, Corrosion Group, National Bureau of Standards, Washington, D.C. HENRY W. BLOUNT, III, Chemistry Division, National Science Foundation, Washington, D.C. MARIA BURKA, Division of Chemical, Biochemical and Thermal Engineering, Process and Reaction Engineering Program, National Science Foundation, Washington, D.C. X1

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DAVID R. FLINN, Corrosion and Surface Science, Bureau of Mines, Department of the Interior, Avondale, Maryland GRAHAM L. HAGEY, Office of Fossil Energy, Department of Energy, Washington, D.C. ALBERT R. LANDGREBE, Division of Energy Storage Systems, Department of Energy, Washington, D.C. MILTON LEVY, U.S. Army Materials Technology Laboratory, Watertown, Massachusetts MATTHEW McMONIGLE, Advanced Extraction, Reduction, and Melting Branch, Department of Energy, Washington, D.C. CARL IMHOFF, Battelle Pacific Northwest Laboratories, Richiand, Washington ROBERT REYNIKj-Materials Science Division, National Science Foundation Washington, D.C. KENNETH A. ROGERS, Division of Chemical, Biochemical and Thermal Engineering, National Science Foundation, Washington, D.C. BERNARD F. SPIELVOGEL, Chemical and Biological Sciences Division, Army Research Office, Research Triangle Park, North Carolina JERRY I. SMITH, Naval Weapons Center, China Lake, California LARRY THALLER, Storage and Thermal Branch, Power Technology Division, NASA Lewis Research Center, Cleveland, Ohio IRAN C. THOMAS, Division of Materials Sciences, Department of Energy, Washington, D.C. JOHN S. WILKES, Office of Scientific Research, U.S. Air Force Academy, Colorado Springs, Colorado STEVEN WAX, Defense Advanced Research Projects Agency, Arlington, Virginia NMAB Staff STANLEY M. WOLF, Senior Staff Scientist ~ X11

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CONTENTS 1. Overview: Conclusions and Recommendations Conclusions and Recommendations Introduction Background New Developments References Socioeconomic Significance Summary Introduction Electrochemical Industries References 4. Federal Government Support 1 Summary Introduction Federal Funding Levels Committee Perspective on Federal Funding References 5. Opportunities in Particular Technologies Summary Batteries and Fuel Cells Biomedical Science and Health Care Coatings and Films Electrochemical Corrosion Electrochemical Surface Processing Manufacturing and Waste Utilization Membranes Microelectronics Sensors References ~ x~ 2 9 11 13 14 17 17 17 22 30 33 33 33 34 35 38 41 41 42 47 51 55 59 62 78 81 86 88

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6. Opportunities for Cross-Cutting Research Summary Electrochemical Engineering In Situ Characterization Interfacial Structures Materials Photoelectrochemistry Plasmas Surface Reactions References 7. Opportunities in Education Current Status Future Directions Reference Biographical Sketches of Committee Members x~v 95 95 96 100 106 113 121 122 127 136 141 141 142 143 145

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TABLES 3-1. Production of Major Electrochemicals in the United States in 1984 18 Estimated Current Major Domestic Electrochemical 18 Markets 3-3. Estimates of New or Increased Domestic Markets for Selected Electrochemical Products 3-4. Estimated 1982 Corrosion Costs for the United States 3-5. Domestic Market Potential for Electric Utility Fuel Cells 3-6. Market Potentials for Electrochemical Sensors 4-1. Summary of Federal Funding in Electrochemistry for Fiscal Years 1984- 1987 5-1. Performance Requirements for Batteries in Advanced Applications 5-2. Performance Requirements for Fuel Cells in Advanced Applications 5-3. Some Commercial Electro-Organic Processes 5-4. Some Electro-Organic Processes Shown to be Feasible on Bench Scale but Not Yet Commercialized xv 19 24 26 28 35 46 46 68 70

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FIGURES 3-1. Summary of electrochemical product/device market value in the United States. 5-1. Specific energy vs specific power for several batteries under development, compared to the Pb-PbO2 battery. 5-2. Schematic cross section of a hydrogen-oxygen fuel cell, the heart of fuel cell systems. 5-3. Theoretical specific energy for electro- chemical cells. 5-4. Gross average value of U.S. industrial production for the years shown. U.S. industrial employment (thousands of jobs averaged over the years shown). 6-1. Classification of plasmas in terms of electron temperature and electron density. 6-2. Variation of electron temperature and heavy particle temperature pressure in an air arc plasma. 6-3. Energy barrier diagram for charge transfer at an electrochemical interface. 6-4. Consecutive stages involved in the incorpo- ration of an adatom into the crystal lattice at a kink site. xv 20 43 44 45 63 63 123 124 129 132