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OCR for page R1
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
OCR for page R2
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
OCR for page R3
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
OCR for page R6
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
OCR for page R7
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~
OCR for page R8
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
OCR for page R9
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
OCR for page R10
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
OCR for page R11
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
OCR for page R12
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
OCR for page R14
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
OCR for page R15
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
