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Lawrence Berkeley National Laboratory Recent Work Lawrence Berkeley National Laboratory Recent Work Title The Secondary Alkaline Zinc Electrode Permalink https://escholarship.org/uc/item/5477c89r Journal Journal of the Electrochemical Society, 138(2) Authors McLarnon, F.R. Cairns, E.J. Publication Date 1990-06-01 eScholarship.org Powered by the California Digital Library University of California UC<:J/3 LBL-29170 Preprint IT'll ·Lawrence Berkeley Laboratory ·. ~ UNIVERSITY OF CALIFORNIA APPLIED SCIENCE DIVISION Submitted to Journal of the Electrochemical Society The Secondary Alkaline Zinc Electrode F.R. McLarnon and E.J. Cairns For Reference June 1990 Not to be taken from this room l APPLIED SCIENCE DIVISION IJ:I ....... 0.. •.0 1:::(_11 r r ttl ...... r crn 1 Prepared for the U.S. Department of Energy under Contract Number DE-AC03-76SF00098. -;o m !).! u l •.[i I ·-< f-lo "< -~! a: ~-*' C> DISCLAIMER This document was prepared as an account of work sponsored by the United States Government. Neither the United States Government nor any agency thereof, nor The Regents of the University of California, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial products process, or service by its trade name, trademark, manufacturer, or other­ wise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof, or The Regents of the University of Cali­ fornia. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof or The Regents of the University of California and shall not be used for advertising or product endorsement purposes. Lawrence Berkeley Laboratory is an equal opportunity employer. DISCLAIMER This document was prepared as an account of work sponsored by the United States Government. While this document is believed to contain correct information, neither the United States Government nor any agency thereof, nor the Regents of the University of California, nor any of their employees, makes any warranty, express or implied, or assumes any legal responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by its trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof, or the Regents of the University of Califomia. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof or the Regents of the University of California. LBL-29170 THE SECONDARY ALKALINE ZINC ELECTRODE by Frank R. McLarnon and Elton J. Cairns Applied Science Division Lawrence Berkeley Laboratory Berkeley, California 94720 This work was supported by the Assistant Secretary for Conservation and Renewable Energy, Office of Energy Storage and Distribution, Energy Storage Division of the U.S. Department of Energy under Contract No. DE-AC03-76SF00098. THE SECONDARY ALKALINE ZINC ELECTRODE Frank R. McLamon and Elton J. Cairns Applied Science Division Lawrence Berkeley Laboratory Berkeley, California 94720 ABSTRACT Zinc is the most commonly used battery electrode, and zinc primary batteries have found numerous applications. The zinc electrode is electrochemically reversible in alkaline electro- lytes, and there is a strong incentive to develop a practical secondary battery based on this metal. However, secondary batteries that use zinc electrodes typically exhibit short lifetimes, because of problems with zinc material redistribution and undesirable zinc morphologies that form during recharge. There has been a world-wide effort to develop a long-lived secondary alkaline zinc electrode, and marked improvements in cell lifetimes have resulted. This article reviews these efforts, paying particular attention to R&D during the period 1975-1990. Keywords: Zinc Electrode, Secondary Batteries, Alkaline Electrolytes v Table of Contents Abstract.................................................................................................................................... v Introduction .................... .......................... ....... ............... ....................................... .... ............... 1 Applications of Secondary Alkaline Zinc Electrodes .. ......................................... ................... 2 Secondary Alkaline Zinc Cells . ........... ................................... ...... ............................ ..... .......... 2 Zinc/N"ickel Oxide .. .. ....... ........... ........................................... .. ......... ......... .. .. .. ..... .......... 3 Zinc/Air.......................................................................................................................... 9 Zinc/Silver Oxide . .. .... ... ...... ....... ...... ............. ..... ........ ... .. .. .... ............. ... .... .... .. ..... .... .. .... 14 Zinc/Manganese Dioxide ............................................................................................... 15 Zinc/Ferricyanide ..... .. ....... ................. ....... ............. .................... .... .. ....... ........... .... ........ 15 Recent R&D on Secondary Cell Components .. .. ...... ................................. ........... .... ... ...... ...... 16 Zinc Electrode Fabrication............................................................................................. 16 Zinc Electrode Composition ... ....... ....... ............... ........... ........ ........... ... .... .. .... ... .. .... .. .... 19 Electrolyte Composition ................................................................................................ 25 Separators .... ......... ............... ........................ ............................... ............... .... ................. 28 Cell Charging ....... .... ........... .. ...................... ............. .. ... ............. ............. .. .... ....... ...... .... 31 Fundamental Studies . ... ...... ......... .... .. ..... .......................... ...................... .... ..... .. .... ........... ........ 33 Cell Thermodynamics ......... ..................................... ........... ......... .... ....... ........ ... .... ........ 33 Zinc Electrodeposition ................................................................................................... 33 Zinc Electrodissolution . ............. ........ ... .. .. .... ................ .. ........... ............... ........... ...... .... 35 Zinc Corrosion ....... ........... .. .... ......... ..... ........................ ............. ........... ........... ..... ...... .... 36 Electrolyte Properties ..................................................................................................... 37 Mathematical and Phenomenological Models ............................................................... 38 Zinc Species Migration to the Positive Electrode .... ......... ............. .. ........... .... ... ............ 41 Cell Cycle-Life Performance ......................................................................................... 41 Future Prospects ................................................................... ............................... ........... .... .. .... 44 Acknowledgements .................................................................................................................. 45 Bibliography ............................................................................................................................ 46 vii INTRODUCTION Zinc has been used by human cultures throughout recorded history, and it is a high-volume metal (1). World-wide production of zinc was about 7 million tons during 1989, including 345,000 tons of zinc produced in the U.S. (2). The U.S. now consumes about 1.34 million tons of zinc per year, half of which is used in galvanizing and electrogalvanizing for corrosion protec­ tion. Other uses of zinc include die casting, brass, zinc oxide (pigments) and battery electrodes. It is the use of zinc in battery electrodes, which represents only a small fraction of its current con­ sumption, that is the subject of this review. Batteries have long been recognized for their capacity to efficiently convert and store electr­ ical energy. Batteries now find use in a myriad of devices, and the world-wide market for bat­ teries is expected to grow along with our increasing use of electricity and electrical devices. Also, there are exciting new technologies that will use advanced batteries. For example, large­ scale energy storage technologies, such as electric vehicles or electric utility load leveling, can provide needed flexibility in the choice of primary fuels for energy generation. Advanced rechargeable batteries are the leading candidates for such applications (3). Other new uses for rechargeable batteries include power sources for cordless power tools, video equipment, com­ munications equipment, lap-top computers, etc. Much of the recent R&D on advanced recharge­ able batteries has
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