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T. R. Crom Re i Thirc Boo1 m Battery Reference Book Battery Reference Book Third Edition T R Crompton MSC, BSic Newnes OXFORD AlJCKLAND BOSTON JOHANNESBURG MELBOURNE NEW DELHI Newnes An imprint of Butterworth-Heinemann Linacre House, Jordan Hill, Oxford OX2 8DP 225 Wildwood Avenue, Woburn, MA 01801-2041 A division of Reed Educational and Professional Publishing Ltd -&A member of the Reed Elsevier plc group First published 1990 Second edition 1995 Thrd edition 2000 0 Reed Educational and Professional Publishing Ltd 1990, 1995, 2000 All rights reserved. No part of this publication may be reproduced in any material form (including photocopying or storing in any medium by electronic means and whether or not transiently or incidentally to some other use of this publication) without the written permission of the copyright holder except in accordance with the provisions of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency Ltd, 90 Tottenham Court Road, London, England W1P 9HE. Applications for the copyright holder's written permission to reproduce any part of this publication should be addressed to the publishers British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 07506 4625 X Library of Congress Cataloguing in Publication Data A catalogue record for this book is available from the Library of Congress Typeset by Laser Words, Madras, India Printed in Great Britain Contents Preface Acknowledgements 1 1ntroduc:tion to battery technology Electromotive force . Reversible cells . Reversible electrodes . Relationship between electrical energy and energy content of a cell . Free energy changes and elec- tromotive forces in cells . Relationship between the energy changes accompanying a cell reaction and con- centration of the reactants . Single electrode potentials . Activities of electrolyte solutions . Influence of ionic concentration1 in the electrolyte on electrode poten- tial . Effect of sulphuric acid concentration on e.m.f. in the lead-acid battery . End-of-charge and end-of- discharge e.m.f. values . Effect of cell temperature on e.m.f. in the lead-acid battery . Effect of tempera- ture and temperature coefficient of voltage dEldT on heat content change of cell reaction . Derivation of the number of electrons involved in a cell reaction . Thermodynamic calculation of the capacity of a bat- tery . Calculation of initial volume of sulphuric acid . Calculation of operating parameters for a lead-acid battery from calorimetric measurements . Calculation of optimum acid volume for a cell Effect of cell lay- out in batteries on battery characteristics . Calculation of energy density of cells . Effect of discharge rate on performance characteristics . Heating effects in batter- ies . Spontaneous reaction in electrochemical cells . Pressure development in sealed batteries 4 Nickel batteries Nickel-cadmium secondary batteries . Nickel-iron secondary batteries . Nickel-zinc secondary batteries . Nickel-hydrogen secondary batteries . Nickel-metal hydride secondary batteries . Sodium-nickel chloride secondary batteries 2 Guidelines to battery selection Primary batteries . Secondary batteries . Conclusion Pat3 1 Battery Characteristics 3 Lead-acid secondary batteries Open-type lead-acid batteries . Non-spill lead-acid batteries . Recombining sealed lead-acid batteries 5 Silver batteries Silver oxide-zinc primary batteries . Silver-zinc sec- ondary batteries . Silver-cadmium secondary batteries . Silver-hydrogen secondary batteries 6 Alkaline manganese batteries Alkaline manganese primary batteries . Alkaline man- ganese secondary batteries 7 Carbon-zinc and carbon-zinc chloride primary batteries Carbon-zinc batteries . Carbon-zinc chloride batteries 8 Mercury batteries Mercury-zinc primary batteries . Mercury-indium- bismuth and mercury -cadmium primary batteries 9 Lithium batteries Introduction . Lithium- sulphur dioxide primary batteries . Lithium-thionyl chloride primary batteries . Lithium-vanadium pentoxide primary batteries . Lithium-manganese dioxide primary batteries . Lithium-copper oxide primary batteries . Lithium- silver chromate primary batteries . Lithium-lead bismuthate primary cells . Lithium-polycarbon monofluoride primary batteries . Lithium solid electrolyte primary batteries . Lithium-iodine primary batteries . Lithium-molybdenum disulphide secondary batteries . Lithium (aluminium) iron monosulphide v vi Contents secondary batteries . Lithium-iron disulphide primary cells . Lithium- silver-vanadium pentoxide batteries 10 Manganese dioxide-magnesium perchlorate primary batteries Reserve type 11 Magnesium-organic electrolyte primary batteries 12 Metal-air cells Zinc-air primary batteries . Zinc-air secondary bat- teries . Cadmium-air secondary batteries . Alu- minium-air secondary batteries . Iron-air secondary batteries 13 High-temperature thermally activated primary reserve batteries Performance characteristics of calcium anode thermal batteries . Performance characteristics of lithium anode thermal batteries 14 Zinc-halogen secondary batteries Zinc-chlorine secondary batteries . Zinc-bromine secondary batteries 15 Sodium-sulphur secondary batteries 16 Other fast-ion conducting solid systems 17 Water-activated primary batteries Magnesium-silver chloride batteries . Zinc- silver chloride batteries . Magnesium-cuprous chloride bat- teries Part 2 Battery theory and design 18 Lead-acid secondary batteries Chemical reactions during battery cycling . Mainten- ance-free lead-acid batteries . Important physical characteristics of antimonial lead battery grid alloys . Lead alloy development in standby (stationary) batteries . Separators for lead-acid automotive batteries Further reading 19 Nickel batteries Nickel-cadmium secondary batteries . Nickel-hydro- gen and silver-hydrogen secondary batteries . Nickel-zinc secondary batteries . Nickel-metal hydride secondary batteries . Nickel-iron secondary batteries . Sodium-nickel chloride secondary batteries 20 Silver batteries Silver oxide-zinc primary batteries . Silver-zinc sec- ondary batteries . Silver-cadmium secondary batteries 21 Alkaline manganese batteries Alkaline manganese primary batteries . Alkaline man- ganese secondary batteries 22 Carbon-zinc and carbon-zinc chloride batteries Carbon-zinc primary batteries . Carbon-zinc chloride primary batteries 23 Mercury-zinc batteries Mercury-zinc primary batteries . Mercury-zinc car- diac pacemaker batteries 24 Lithium batteries Lithium-sulphur dioxide primary batteries . Lithium- thionyl chloride primary batteries . Lithium-vanadium pentoxide primary batteries . Lithium solid elec- trolyte primary batteries . Lithium-iodine prim- ary batteries . Lithium-manganese dioxide primary batteries . Lithium-copper oxide primary batteries . Lithium-carbon monofluoride primary batteries . Lithium-molybdenum disulphide secondary batteries . Lithium (aluminium) iron sulphide secondary cells . Lithium-iron disulphide primary batteries 25 Manganese dioxide-magnesium perchlorate primary batteries 26 Metal-air batteries Zinc-air primary batteries . Metal-air secondary bat- teries . Aluminium-air secondary reserve batteries 27 High-temperature thermally activated primary batteries Calcium anode-based thermal batteries . Lithium anode thermal batteries . Lithium alloy thermal batteries 28 Zinc- halogen secondary batteries Zinc-chlorine batteries . Zinc-bromine batteries 29 Sodium-sulphur secondary batteries References on sodium-sulphur batteries Contents vii Pard: 3 Battery performance evaluation 30 Primary batteries Service time voltage data . Service life-ohmic load curves . Effect of operating temperature on service life Voltage-capacity curves . Shelf life-percentage capacity retained . Other characteristic curves 31 Secondary batteries Discharge curves . Terminal voltage-discharge time curves . Plateau voltage-battery temperature curves I Capacity returned (discharged capacity)-discharge rate curves . Capacity returned (discharged capa- city)-discharge temperature curves and percentage withdrawable capacity returned-temperature curves . Capacity returned (discharged capacity)-terminal voltage curves . Withdrawable capacity-terminal voltage cunies . Capacity returned (discharged capacity) -discharge current curves . Discharge rate-capacity returned (discharged capacity) curves . Discharge rate-terminal voltage curves . Discharge rate-mid-point voltage curves . Discharge rate-energy density curves . Self-discharge characteristics and shelf life . Float life characteristics Part 4 Battery Applications 32 Lead-acid secondary batteries Stationary type or standby power batteries . Traction or motive power type . Starting, lighting and ignition (SLI) or automotive batteries . Partially recombining sealed lead-acid batteries . Load levelling batteries . Electric vehicle batteries 33 Nickel lbatteries Nickel-cadmium secondary batteries . Nickel-zinc secondary batteries . Nickel-hydrogen secondary batteries . Nickel-metal hydride secondary batteries . Nickel-iron secondary batteries . Sodium-nickel chloride secondary batteries 34 Silver batteries Silver-zinc primary batteries . Silver-zinc secondary batteries . Silver-cadmium batteries 35 Alkaline manganese primary batteries 36 Carbon-zinc primary batteries Comparison of alkaline manganese and carbon-zinc cell drain rates . Drain characteristics of major con- sumer applications 37 Mercury batteries Mercury -zinc primary batteries . Mercury-cadmium primary batteries . Mercury-indium-bismuth primary batteries 38 Lithium primary batteries Lithium- sulphur dioxide . Lithium-vanadium pentox- ide . Lithium-thionyl chloride . Lithium-manganese dioxide . Lithium-copper oxide Lithium- silver chro- mate . Lithium-lead bismuthate . Lithium-polycarbon monofluoride . Lithium solid electrolyte . Lithium- iodine . Comparison of lithium-iodine and nickel- cadmium cells in CMOS-RAM applications . Lithium-iron disulphide primary cells . Lithium- molybdenum disulphide secondary cells . Lithium (aluminium) iron sulphide secondary cells 39 Manganese dioxide-magnesium perchlorate primary batteries Reserve batteries . Non-reserve batteries 40 Metal-air batteries Zinc-air Primary batteries . Zinc-air secondary bat- teries . Aluminium-air secondary batteries 41 High-temperature thermally activated primary batteries 42 Seawater-activated primary batteries 43 Electric vehicle secondary batteries Lead-acid batteries . Other power sources for vehicle propulsion Part 5 Battery charging 44 Introduction 45 Constant-potential charging Standard CP charging . Shallow cycle CP charging of lead-acid batteries . Deep cycle CP charging of lead-acid batteries . Float CP charging of lead-acid batteries . Two-step cyclic voltage-float voltage CP charging 46 Voltage-limited taper current charging of alkaline manganese dioxide batteries 47 Constant-current charging Charge control and charge monitoring of sealed nickel-cadmium batteries . The Eveready fast-charge cell (nickel-cadmium batteries) . Types of constant- current charging . Two-step constant-current charging [...]... the planners and designers These must make decisions on the performance characteristics required in the battery and other relevant factors such as operating temperatures, occurrence of vibration and spin, etc., weight, volume, pre-use shelf life; these and many other factors play a part in governing the final selection of the battery type It is a truism to say that in many cases the piece of equipment... difference can be completely reconciled with the chemical aspect Nernst’s theory of the electrode process N Figure 1.1 The Poggendorf method of determining electromotive force In the case of a metal dipping into a solution of one of its salts, the only equilibrium that is possible is that of metal ions between the two phases The solubility of Electromotive force 1/5 the metal, as neutral metal atoms,... solution Equilibrium was supposed to be reached when these opposing tendencies balanced each other, i.e when the osmotic pressure in the solution was equal to the solution pressure In the case of a metal dipping into a solution containing its ions, the tendency of the metal ions to dissolve is th'us determined by their solution pressure, which Nemst called the electrolytic solution pressure, P , of the metal... processes In an alternative approach to the calculation of electrode potentials and of potential differences in cells, based on concentrations, it is supposed that two pieces of the same metal are dipping into solutions in which the metal ion concentrations are rnl and m2 respectively (Figure 1.3) Let the equilibrium potential differences between the metal and the solutions be V1 and V2 Suppose that... copper electrode dissolves while metallic zinc is deposited on the zinc electrode A further example of a primary cell is the well known LeclanchC carbon-zinc cell This consists of a zinc rod anode dipping into ammonium chloride paste outside a linen bag inside which is a carbon rod cathode surrounded by solid powdered manganese dioxide which acts as a chemical depolarizer The equation expressing the... source passing in the opposite direction until the electrodes have been completely re-formed A well known secondary cell is the lead-acid battery, which consists of electrodes of lead and lead dioxide, dipping in dilute sulphuric acid electrolyte and separated by an inert porous material The lead dioxide electrode is at a steady potential of about 2V above that of the lead electrode The chemical processes... overcome departure from ideal behaviour It applies to solutions of electrolytes, e.g s,dts and bases, arid is equally applicable to non-electrolytes and gases The following is a simple method of developing the concept of activity when dealing with non-ideal solutions Consider a system of two large vessels, one containing a solution in equilibrium with its vapour at the pressure p', arid the other containing