NUNCA
`mas
`
`INTRATTA)
`
`s)he
`
`1
`
`APPLE-1015
`
`

`

`Electrical Engineering |
`An update of the definitive guide to
`all aspects of battery design and selection
`
`TAURN ALLA
`
`SECOND EDITION
`
`New York, NY 10020
`
`Here is the one and only referenceto offer you detailed data and information on
`the characteristics, properties, performance, and applications of all types of
`electric batteries.
`Written by a staff of leading experts in battery technology, this essential work-
`ing tool covers batteries for everything from small portable consumer items to
`electric vehicles and military and industrial equipment.
`The newedition of the Handbookof Batteries shows you how to:
`® Determine the performance characteristics of batteries underall conditions
`of use
`® Establish the conditions and proper operating procedures to achieve
`optimum use of each battery system
`® Select the most suitable battery for a given application
`The Second Edition now featuresthe latest data, tables, and figures covering
`the vast improvements in battery performance in recent years—and also
`explores new battery technologies,includinglithium and rechargeable batteries.
`Whether you’re an engineer, technician, or product designer, the updated
`edition of this one-of-a-kind sourcebook enables you to take advantage of the
`many new advancesin the fast-changingfield of battery technology.
`
`E S$ BN O- 0 7-0 3 75el- hh
`90000
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`9'780070379213
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`McGraw-Hill, Inc.
`Serving the Need for Knowledge
`1221 Avenueof the Americas
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`2
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`

`

`
`
`
`
`HANDBOOK OF
`BATTERIES
`
`David Linden Editorin Chief
`
`Second Edition
`
`McGRAW-HILL, INC.
`New York San Francisco Washington, D.C. Auckland Bogota
`Caracas Lisbon London Madrid Mexico City Milan
`Montreal New Delhi San Juan Singapore
`Sydney Tokyo Toronto
`
`
`
`
`
`3
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`

`

`
`
`
`
`Library of Congress Cataloging-in-Publication Data
`
`Handbook of batteries / David Linden, editor in chief. -- 2nd ed.
`p.
`cm.
`First ed. published undertitle: Handbookof batteries and fuel
`cells.
`Includes index.
`ISBN 0-07-037921-1
`1. Electric batteries--Handbooks, manuals, etc.
`David.
`If. Title: Handbook of batteries.
`TK2901.H36
`1994
`621.31'242--de20
`
`I. Linden,
`
`94-29189CIP
`
`To my grande.
`M
`
`i
`
`Copyright © 1995, 1984 by McGraw-Hill, Inc. All rights reserved. Printed
`in the United States of America. Except as permitted under the United
`States Copyright Act of
`1976, no part of
`this publication may be
`reproduced or distributed in any form or by any means, or stored in a data
`base or retrieval system, without
`the prior written permission of the
`publisher.
`The first edition was published under the title Handbook of Batteries
`and Fuel Cells.
`
`34567890 DOC/DOC 90987
`
`ISBN 0-07-037921-1
`
`
`
`
`The sponsoring editor for this book was Harold B. Crawford, ihe editing
`supervisor was Frank Kotowski, Jr., and the production supervisor was
`Suzanne W. B. Rapcavage. It was set in Times Roman by the Universities
`Press (Belfast) Ltd.
`
`Printed and bound by R. R. Donnelley & Sons Company.
`
`This bookis printed on acid-free paper.
`
`
`
`
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`
`
`
`Information contained in this work has been obtained by
`McGraw-Hill,
`Inc. from sources believed to be reliable. How-
`ever, neither McGraw-Hill nor
`its authors guarantees
`the
`accuracy or completeness of any information published herein
`and neither McGraw-Hill norits authors shall be responsible for
`any errors, omissions or damages arising out of use of this
`information. This work is published with the understanding that
`McGraw-Hill and its authors are supplying information but are
`not attempting to render engineering or other professional
`services.
`If such services are required,
`the assistance of an
`appropriate professional should be sought.
`
`
`
`4
`
`

`

`
`
`
`
`23.10
`
`SECONDARY BATTERIES
`
`TABLE 23.3. Characteristics of the Major Secondary Battery Systems
`
`Lead-acid
`Nickel-cadmium
`Vented
`Vented
`pocket
`sintered
`
`Common name
`SLI
`Traction
`Stationary
`Portable
`plate
`plate
`Sealed
`Chemistry:
`Anode
`Cathode
`Electrolyte
`
`Pb
`PbO,
`1,804
`(aqueous
`solution)
`
`Pb
`Peo,
`HSO0,
`(aqueous
`solution}
`
`Pb
`PbO,
`H,SO,
`(aqueous
`solution)
`
`Pb
`PbO,
`H,SO,
`(aqueous
`solution)
`
`Cd
`NiOOH
`KOH
`(aqueous
`solution)
`
`Cd
`NiOOH
`KOH
`{aqueous
`solution)
`
`Cd
`NiOOH
`KOH
`(aqueous
`solution)
`
`| Nickehiron
`(conven-
`oe
`———
`
`fe
`Noon
`iKOH
`ipaquenes
`Aaition)
`1.2
`1,37
`125-105
`10
`
`Nickel-zine
`
`Zn
`NiOOH
`KOH
`(aqueous
`solution)
`1.6
`1.73
`1.6-1.4
`1.2
`
`2.0
`21
`2.0-1.8
`1.75
`
`2.0
`21
`2.0-1.8
`L.75
`(except when on
`float service)
`
`2.0
`24
`2.0-1.8
`1.75
`(when cycled)
`
`1.2
`1.29
`1.25-1.00
`10
`
`1.2
`1.29
`1,25-1.00
`1.0
`
`12
`1.29
`1.25~1.00
`10
`
`2.0
`21
`2,0-1.8
`1.75
`(lower operating
`and endvoltage
`during cranking
`operation)
`—40 to 55
`
`—20 to 40
`
`—10 to 40°
`
`—40 to 60
`
`—20 to 45
`
`—40 to 50
`
`—40 10 45
`
`=I0 to 45
`
`20 10 60
`
`35
`70
`Flat
`
`High
`
`25
`80
`Flat
`
`10-20
`50-70
`Flat
`
`Modcratcly
`high
`
`Moderately
`high
`
`30
`90
`Flat
`
`High
`
`20
`40
`Flat
`
`High
`
`37
`90
`Very flat
`
`High
`
`30-35
`80-105,
`Very flat
`
`Moderate
`to high
`
`27
`>
`Moderately lar
`
`Bisbisc 1
`hw
`
`60
`120
`Flat
`
`High
`2
`
`Cell voltage
`(typical), V:
`Nominal
`Opencircuit
`Operating
`End
`
`Operating
`temperature,
`°C
`Energydensity
`(at 20°C):
`Whike,
`Wh/L
`Discharge
`profile
`(relative)
`Power density
`Scll-discharge
`rate (at 20°C),
`% loss per
`month®
`
`4-6
`
`—
`
`4-8
`
`5
`
`10
`
`15-20
`
`20°40
`
`
`20-30
`(Sb-Pb)
`2-3
`(maintenance-
`frec)
`#25,
`
`2-5
`3-10
`8-25
`2-8
`18-25
`&
`3-6
`Calendarlife,
`years
`
`300-708
`500-2000
`500-2000
`250-500
`=
`1500
`200-700
`Cyelelife.
`AN~s00
`50-200
`cycles®
`
`High energy
`
`
`
`Advantages Lowest cost of|Designed forLowcost, ready Maintcnancc- Very rugged, Rugged; Sealed, rom
`
`
`
`density;
`'
`availability,
`competitive
`“float” service,
`free; long life on
`can withstand
`excellent
`maintenant
`relatively low
`‘
`
`gocd high-rate,—_systems (also lowest cost of float service; physical and storage; good good love awe)
`
`
`
`
`
`+
`cost; good low-
`|
`
`
`
`
`high- and low- low- and high-_—electrical abuse;see SLI) competitive specific energy tempera
`
`temperature
`i
`temperature
`systems (also
`temperature
`good charge
`and high-rate
`high 106
`performance
`operation (good
`see SLI)
`performance; no
`retention,
`and low-
`performs
`2
`cranking
`“memory™
`storage and
`temperature
`Jonglife inate
`service), good
`effect; operates
`cycle life lowest
`performance
`operales
`
`
`
`float service, in any position—_cost ofalkaline position
`new
`batleries
`maintenance-free
`Wl
`designs
`sea
`Relatively low
`Seale pelt r
`cycle life;
`battely ae
`limited energy
`density; poor
`charge retention
`and slorability;
`hydrogen
`evolution
`
`~
`
`‘
`‘
`1
`l
`'
`
`:
`
`!
`
`+
`
`10
`
`_
`
`Poorcycle life
`
`Limitations
`
`Hydrogen
`evolution
`
`Low energy
`density; less
`tugged than
`competitive
`systems;
`hydrogen
`evolution
`
`Low energy
`density
`
`Highcost;
`“memory”
`effect; thermal
`Tunaway
`
`Cannal be
`stored in
`discharged
`condition: lower
`cycle life than
`sealed nickel-
`cadmium:
`difficult to
`manufacture in
`very small sizes
`Sealed
`Based on
`Based on
`cylindrical celis:
`positive plate
`positive plate
`2,5-25 Ah;
`design: 5—
`design: 45—
`prismatic cells:
`400 Ah per
`200 Ah per
`0.9-35 Ah
`positive plaic
`positive plate
`(characteristics vary with batlery
`lithium-ion cell (sce Chap. 36)
`4 Based on C/LiCoO,
`2
`5S
`> Self-discharge rate usually decreases with increasing storage time.
`© Dependent on depth ofdischarge.
`4 Low-rate Zn/AgOcell.
`
`
`
`Majorcell types Prismatic cells:
`available
`30-200 Ahat
`20-h rate
`
`Prismatic cells:
`5-1300 Ah
`
`Prismatic cells:
`10-100 Ah
`
`Not
`
`commercially
`available
`
`
`system and design).
`y sy
`eg)
`
`5
`
`

`

`
`
`
`Nickel-cadmium
`Vented
`sintered
`
`plate
`
`INTRODUCTION
`
`23.11
`
`Zinc/silver
`oxide
`(silver-zinc)}
`
`Cadmium/
`silver oxide
`(silver-
`cadmium)
`
`2n
`AgoKOH
`(aqueous
`solution)
`
`Cd
`AgOKOH
`{aqueous
`solution)
`
`Slew Aad
`
`Nickel-
`hydrogen
`
`H,NiOOFL
`KOH
`(aqucous
`solution)
`
`14
`(.32
`1,3-1.15
`1.0
`
`Nickel-
`metal
`hydride
`
`Rechargeable
`“primary”
`lypes,
`Zn/MnO,
`
`MH
`NiOOH
`KOH
`{aqueous
`solution)
`
`Zn
`MnO,
`KOH
`(aqueous
`solution)
`
`ath
`1.25
`1.0
`
`0
`
`coluu
`
`Lithium
`syslems
`Cithium-
`jon)?
`
`ic
`LiCoO3
`Organic
`solvent
`
`4.0
`42
`4,0-2,5
`25
`
`Nickel-zine
`
`Zn
`NiOOH
`KOH
`(aqueous
`solution)
`
`6
`L.73
`1.6-1.4
`12
`
`—20 to 60
`
`—20 to 60
`
`—25 to 70
`
`0 Lo 50
`
`20 to 30
`
`—20 to 40
`
`—20 to 55
`
`60
`120
`Flat
`
`High
`
`90
`180
`Double plateau
`
`55
`10n
`Double plateau
`
`55
`60
`Moderately fat
`
`50
`175
`Flat
`
`High (for high
`rate-designs)
`
`Moderate to
`high
`
`Madlerate
`
`Moderate ta
`high
`
`85
`250
`Sloping
`
`Moderate
`
`90
`200
`Sloping
`
`Moderate
`
`a
`
`— Sealy
`Cd
`NiOOR
`KOH
`(aqueous
`Solution)
`
`
`
`
`
`Ha
`
`ug te 45
`
`335)
`bn-ahs
`Veryfit
`
`
`peetatel flat
`
`Cd
`NiOOH
`KOH
`(aqueous
`solution)
`
`1,2
`1.29
`1.25- 1.00
`1.0
`
`—40 to 50
`
`37
`90
`Very flat
`
`High
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Medlerate
`tohii”
`
`5-20
`
`3-10
`
`500-2000
`
`Rugged:
`excellent
`storage; good
`specific energy
`and high-rate
`and low-
`temperature
`performance
`
`00
`
`nd
`buse;
`
`pwest
`aline
`
`3-7)
`Sealed, na!
`maintenanee,
`good jaw
`temperate atl
`high-rate
`perfornnange,
`longlife ovthe
`operntes in amy
`position
`
`High cost:
`“memory”
`effect; thermal
`runaway
`
`Scala lead
`battery beltttiat
`high tempers
`and flout
`“quemaryele
`
`
`
`
`
`
`
`
`
`
`
`Maerite (0
`Dad
`
`0
`
`3-5
`
`1000
`
` caldn
`ect abuse;
`fy He
`Betis or|
`
`
`
`10
`
`60
`
`20
`
`5-10
`
`50-200
`
`High encrgy
`densily;
`relatively low
`cosl: good Jow-
`temperature
`performance
`
`Poorcycle life
`
`1-34
`
`100-1504
`
`2-3
`
`150-600
`
`Highest energy
`density; high
`discharge rate;
`lowself-
`discharge
`
`High energy
`density: low
`scl{-discharge,
`good cycle life
`
`1500-6000
`
`High energy
`density; long
`eyele life at high
`DOD:can
`tolerate
`overcharge
`
`2-5
`
`300-600
`
`15~25
`
`500-1000
`
`Highenergy
`density; sealed,
`operates
`
`Good shelf life:
`lowcost
`
`High specific
`energy, good
`shelf life
`
`High cost: low
`cycle life;
`decreased
`performances
`at low
`temperatures
`
`Highcost:
`decreased
`performance
`at low
`lemperatures
`
`Highinitial cost;
`self-discharge
`proportional to
`H, pressure
`
`High cost (may
`be limited to
`special military
`and aerospace
`applications)
`
`Limited cycle
`life; low drain
`applications:
`small size only
`
`Low rate
`(compared to
`aqueous systems)
`
`
`
`
`
`
`
`Prismatic cells:
`10-100 An
`
`Burton colle
`05 A ie
`cylindric ee
`to 10-Att
`
`Prismatic cells:
`
`Mainly for
`acrospace
`<1 to 800 Ah;
`ye= Metjon
`special lypes to
`applications (up
`6000 Ah
`to 100 Ah)
`elelr=—*L.
`
`Nol
`commercially
`available
`
`Prismatic cells:
`<1 to 500 Ah
`
`Button and
`cylindrical cells
`
`Cylindrical cells
`
`Cylindrical and
`prismatic cclls
`
`
`
`6
`
`

`

` 23.12
`
`
`SECONDARY BATTERIES
`
`23.2.3 Advanced Batteries
`
`ABLE 23.4 Comparison
`————"——————--~—<‘<OaiCi;i‘(S
`
`Finally, the need for higher energy density, better charge retention, and other improved
`characteristics has created an unparalleled interest
`in the development of new, more
`advanced secondary battery systems. These fall into several general groups:
`
`temperature systems that are stable in aqueous electrolytcs, using zine,
`1. Ambient
`aluminum, or magnesium as the negative active materials.
`2. Ambient
`temperature systems using lithium or other alkali metals as the active
`materials but requiring nonaqueous, aprotic electrolytes as the aqueouselectrolytes are
`reactive with these metals.
`
`3. High-temperature systems, also using lithium or other alkali metals as the active
`materials. These systems use molten salt or ceramic electrolytes and operateai high
`temperatures ranging from 200 to 450°C.
`
`These advanced systems are covered in Part 5.
`
`23.3 COMPARISON OF PERFORIVIANCE
`CHARACTERISTICS FOR SECONDARY
`BATTERY SYSTEMS
`
`23.3.1 General
`
`The characteristics of the major secondary systems are summarized in Table 23.3. This
`lable is supplemented by Tables 1.2 and 6.2, which list several theoretical and practical
`electrical characteristics of these secondary battery systems. A graphic comparison ol
`the
`theoretical andpractical performances of various battery systems is given in Fig. 3.1. This
`shows that up to only about 20-30%of the theoretical capacity of a battery system 5
`attained underpractical conditions as a result of design and the discharge requirements.
`It should be noted, as discussed in detail in Chaps. 3 and6, that these types of data ane
`comparisons (as well
`as
`the performance characteristics shown in
`this section) ae
`necessarily approximations, with each system being presented under favorable discharge
`conditions. The specific performance of a battery system is very dependent on the ¢”
`design andall the detailed andspecific conditions of the use and discharge-charge of !M*
`battery.
`vals
`A qualitative comparison of the various secondarybattery systems is presented in Tab
`23.4. The different ratings given to the various designs of the same electrochemical syste ‘
`are an indication of the effects of the design on the performance characteristics of @
`battery.
`
`*Rating: 1
`
`to 5, best to pc
`
`Conventional system
`1.65 V for the nickel
`relatively little differ
`flven system. How
`Sifferences could be
`Most of the cony
`xcept for the silver
`the silver oxide elect
`_ The discharge cu
`dioxide system, is sh
`higher than those of
`tthium anode. The «
`lower Conductivity «
`“lectrode, The discl
`atleries are discusse
`
`23.3.3 Energy Der
`The del;elivere
`energ'
`ells ay aes
`ld batteries a
`With th
`theoretical
`nickel Silver oxide <
`shox, ;yd rogen cells
`.
`;
`:
`se
`Goh the Slgnificancr
`The discharge curves of the conventional secondary battery systems, at the C/5 rate, Fr
`ons under wh
`compared in Fig. 23.2. The lead-acid battery has the highest cell voltage of
`
`
`23.3.2 Voltage and Discharge Profiles
`
`Ene
`den
`
`;
`a
`2
`=
`
`hae
`
`5
`‘
`5
`
`5
`
`system
`ead-acid:
`Pasted
`“Tubular
`Plante
`Sealed
`Lihium-metal
`Lithium-ion
`Nickel:cadmium
`Pocket
`Sintered
`Sealed
`Nickel-iron
`Nickel-metal
`hydride
`Nickel-zinc
`Siver-zinc
`r
`Siver-cadmium
`
`:
`Niskel-hydrogen
`-
`MWer-hydroge
`Zine-manganese
`dioxide———————
`
`a L
`
`7
`
`€
`

`

`
`
`INTRODUCTION
`
`23.13
`
`93.4 Comparison of Secondary Batteries*
`
`
`
`elt
`
`
`“a
`
`
`
`a, and otherimproy,
`ed
`opment of new
`> More:
`groups:
`
`lectrolytes, using zing+
`
`metals as the active
`iqueous electrolytes are.
`
`i metals as the active
`‘es and operate at high’
`
`ized in Table 23.3. This
`theoretical and practical
`taphic comparison of the
`_is given in Fig. 3.1. This
`ty of a battery systems
`lischarge requirements.
`at these types of data and
`wn in this section) ae
`inder favorable discharge
`ty dependent on the cell
`d discharge-charge ofthe
`lems is presented in Table;
`ne electrochemical ee
`yance characteristics of
`
`Energy
`densily
`
`Power
`density
`
`Flat
`discharge
`profile
`
`Low-
`temp-
`Charge
`erature
`operation retention
`
`Charge
`accept-
`Effic-
`
`ance
`iency Life
`
`Mcch-
`anical
`prop-
`erties
`
`Cost
`
`4
`4
`5
`4
`1
`2
`
`4
`4
`4
`5
`3
`2
`1
`2
`2
`2
`2
`
`4
`5
`5
`3
`3
`3
`
`3
`1
`1
`5
`2
`3
`2
`3
`3
`3
`4
`
`3
`4
`4
`3
`3
`3
`
`2
`1
`2
`4
`2
`2
`5
`5
`3
`4
`5
`
`3
`3
`3
`2
`2
`2
`
`1
`1
`1
`5
`1
`3
`3
`4
`4
`4
`3
`
`4
`3
`3
`3
`1
`2
`
`2
`4
`4
`5
`4
`4
`i
`1
`5
`5
`1
`
`3
`3
`3
`3
`3
`2
`
`1
`1
`2
`2
`2
`3
`5
`:
`5
`3
`3
`4
`
`2
`2
`2
`2
`3
`2
`
`4
`3
`3
`5
`3
`3.
`1
`1
`5
`5
`4
`
`3
`2
`2
`3
`4
`2
`
`2
`2
`3
`1
`3
`4
`5
`4
`2
`2
`5
`
`5
`3
`4
`5
`3
`3
`
`1
`1
`2
`1
`2
`3
`3
`3
`3
`3
`4
`
`1
`2
`2
`2
`4
`3
`
`3
`3
`2
`3
`3
`3
`4
`4
`5
`5
`2
`
`
`
`
`
`
`Seated
`Beeon
`Mejcl-metal
`.
`ict!
`ese
`eo
`ier zinc
`Sead
`Mecliydrogen
`eyYrogen
`en ese
`
`+Rating:
`
`1
`
`to 5, best to poorest.
`
`conventional systems. The average voltage of the alkaline systems ranges from about
`{65 V for the nickel-zinc system to about 1.1 V. At the C/5 discharge rate at 20°C thereis
`relatively little difference in the shape of the discharge curve for the various designs of a
`given system. However, at higher discharge rates and at
`lower
`temperatures,
`these
`differences could be significant, depending mainly on the internal resistance of thecell.
`Most of the conventional rechargeable battery systems have a flat discharge profile,
`except for the silver oxide systems, which show the double plateau due to the discharge of
`the silver oxide electrode, and the rechargeable zinc/manganese dioxide battery.
`The discharge curve of one of the rechargeable lithium cells, the lithium/manganese
`thoxide system, is shown for comparison. The cell voltages of the lithium cells are usually
`higher than those of the conventional aqueouscells because of the characteristics of the
`lithium anode. The discharge profile of the lithium cells is usually not as flat due to the
`lower conductivity of the nonaqucous electrolytes that must be used with the lithium
`tlecttode. The discharge characteristics of the lithium and other advanced secondary
`tatteries are discussed in Part 5.
`
`#33 Energy Density
`
`The delivered energy densities, both gravimetric and volumetric, of the various secondary
`fells and batteries are shown graphically in Fig. 23.3. The values can also be compared
`Mith the theoretical values for these systems given in Table 1.2.
`hick he silver oxide systems deliver the highest capacities, followed by the nickel-zine and
`, ayhydrogen cells andfinally by the nickel-cadmium and lead-acid systems. These data
`a ; the significance of the cell and battery design on the energy output as well as the
`~Mitions under which the battery is discharged. Accordingly, there is a wide range and
`
`
`
`
`
`
`
`ate, ae
`tems, at the C/5¥ f
`the
`‘hest cell voltage O
`
`
`
`
`
`8
`
`

`

` SECONDARY BATTERIES
`
`0.5
`
`
`4.0 -
`
`3.0 [
`—
`
`2.0 -
`
`Li/MnO,
`
`Lead-acid
`
`Wh/kg
`
`
`
`Cellvoltage,V
`
`[oi]
`
`Ni-Cd, Ni-MH
`
`
`==e
`
`SXNi-Fe,Ni-H,
`\PsAg-Ca, Ag-Fe
`Nninnd,
`
`410; AgZn
`100
`
`90 TTT
`
`80
`1
`70
`oaoO
`50k
`40+
`30+
`20+
`10
`
`Ag-Cd
`
`_—!
`
`220 Ag.zn
`
`160 |-
`
`Ag-Cc
`
`FIGURE 23.3. Energy
`density. (b) Volumetric
`
`120 -
`
`100 >
`
`
`
`2 80F
`
`x gw
`
`€ eb
`qQ®8
`
`6s
`
`e 40F
`
`20 F
`
`oO te
`OIG
`0.
`
`FIGURE 23.4 E
`20°C.
`
`|
`20
`
`1
`L
`60
`40
`%of capacity discharged
`
`|
`80
`
`I
`100
`
`FIGURE 23.2 Discharge profiles of conventional secondary batlery systems and
`rechargeable Li/MnO,cell at approximately C’/5 dischargerate.
`
`even an overlap in performance, indicating the need to consider all of the conditions of
`operation before making a choice ofbattery system and design.
`1
`Advanced rechargeable batteries, using lithium and other high-encrgy materials
`(covered in Part 5), have the potential of higher energy densities, ranging up to about
`125 Wh/kg and 275 Wh/L.
`
`23.3.4 Effect of Discharge Rate on Energy Density
`In Fig. 23.4 the effect of the discharge rate on the performance ofeach battery syste”! y
`100%):
`compared based on the watthour capacity for each system (capacity at 0.1Crate =
`d for
`With the exception of the conventional nickel-iron battery, which was not designe
`wi tlt
`high-rate performance, the capacity of the alkaline batteries decreases relatively fittle WE
`increasing discharge rate compared with the lead-acid system. This is due to the ine
`dise ball
`time available for the diffusion of the sulfuric acid electrolyte during a high-rate
`of
`the lead-acid battery. The sintered-plate nickel-cadmium system shows
`the
`performance.
`is als
`The performance of the rechargeable lithium/manganese dioxide cell
`While the energy density of this systemis higherat the relatively low discharge rales:
`capacity decreases with increasing discharge rates moresignificantly than the cony
`aqueous secondary batteries.
`The effects of the discharge ratc on the performance of these secondary battery 5)
`are compared again in Fig. 23.5. This figure is similar to a Ragone plot, except th
`
`
`
`9
`
`

`

` 36.42
`
`ADVANCED BATTERY SYSTEMS
`
`
`!
`
`The solid polymerelectrolyte technology provides flexibility in battery design as the cel]
`can be fabricated in a variety of shapes, forms, configurations, and sizes. The estimated
`specific energy and the energy density, up to 200 Wh/kg and 385 Wh/L, are very attractive,
`To date, however, cells have been fabricated only in small sizes, and none have been
`commercialized. Major interest
`is in using this battery system for applications requiring
`high voltages and capacity. This will
`require significant
`scaling up of
`the current
`technology, which presents a manufacturing challenge because of the thin components and
`the uniformity standards that will be required.”
`At present, solid-state rechargeable lithium polymer electrolyte cells using lithium
`anodes have limited cycle life and rate capability. The limited rate capability of these
`batteries is due to the Jower ionic conductivity, low lithium transport number, and poor
`electrode-electrolyte interface properties. The cause for
`the limited cycle life is not
`completely understood, but could be due to degradation of the presently used cathode
`materials, irreversible lithium intercalation into the cathode materials, high reactivity of
`the polymeric electrolytes toward the anode and cathode materials, or the formation of
`lithium dendrites.
`Solid polymer electrolytes have also been used with anodes other than metallic lithium,
`such as lithiated carbon in a lithium-ion cell (see Sec. 36.4.3). These cells may have lower
`capacity but may provide some of the advantages of the lithium-ion technology, such as
`longer eyele life and greater safety, and minimize potential problems due to the use of
`metallic lithium and the formation of dendritic lithium, which may form during repeated
`cycling of a lithium anodecell.
`
`36.4.3 Lithium-lon Cells
`
`The lithium-ion rechargeable cell refers to a cell whose negativeactive material is a carbon
`to which lithium cations are intercalated or deintercalated during the charge-discharge
`process, rather than metallic lithium or a lithium alloy. The positive active material is a
`lithiated metallic oxide intercalation compound from or into which a lithium ion can be
`extracted or
`inserted, respectively, during charge and discharge. LiCoO), LiNiO,, ane
`LiMn,O,are attractive materials, with advantages suchasstability in air, high voltage, a
`reversibility for the lithiuminsertion reaction. LiCoO, was used in most ofthe initial work
`on the lithium-ion technology and was the first system commercialized. This materialC
`easiest
`to prepare andholds its structure during cycling, LiNiO,
`is
`less expensive i ig
`LiCoO,,
`is more stable at higher temperatures, and has a lowerself-discharge fate.
`5
`anticipated that ultimately the industry will move to a manganese-based material, such a
`LiMn.O,, as these materials are more abundant, inexpensive, and nontoxic. The oe
`lithium-ion cells used liquid organic electrolytes, but both liquid organic and solid polyite
`electrolytes (SPE) are used, similar to the electrolytes in the metallic lithium anode celi~
`SO,-basedelectrolytes are also being investigated (see Sec. 36.4.4).
`described 1?
`The general characteristics and the chemistry of the lithium-ion cell are
`ces
`Sees, 36.2.3 and36.3. Some oftheirelectrical characteristics are listed in Table 36.12, high
`The lithium-ion cells, using the positive active materials identified earlier, ba cells
`voltages ranging from 3.0 to 4.0 V. A comparison of the discharge voltage profiles © wate
`using these positive electrode materials with petroleum coke and graphite nee
`electrode materials is shown in Fig. 36.31. The sloping discharge profile is characteris” ihe
`the lithium-ion cells using the disordered coke type carbon materials, compared
`es
`flatter discharge profile of the cells using graphite.
`soo Tit
`At present the graphite-anode cells usually have a higher capacity at low dischare’ rains:
`en
`than the petroleum coke cells, but
`they lose this advantage at
`the higher curt at
`to
`This is probably due to the potential drop across the space charge region of graphite
`swe
`:
`‘
`as.
`a
`
`10
`
`a oO
`
`
`
`Cellvoltage,V AS5
`
`1.0
`
`FIGURE 36.3
`parison of petr
`
`Ga
`
`Insula
`
`(1)
`
`(@) Cor
`FIGURE36.32.
`> 2 vent mechanismfor
`iting. (1) Aluminumt
`
` EEE
`POELEEELLITTEL:LEedELE
`the need to use a compatible ethylene carbonate-based electrolyte, which has
`
`
`
`10
`
`

`

`5.0
`
`3.0
`
`
`
`Petroleum -coke
`anode
`
`Graphite anode
`
`> a
`
`Ie
`°>
`
`40
`
`& 20
`
`1.0
`
`0
`
`25
`
`50
`Discharge capacity, %
`
`75
`
`100
`
`FIGURE 36.31 Discharge characteristics of a C/LiCoO,
`parison of petroleum-coke and graphite anodes.
`
`lithium-ion cell com-
`
`
`
`design as the cel]
`es. The eslimated
`we VeTY Allractiye
`| none have been
`lications requiring
`p of
`the current
`n components ang
`
`ells using lithium
`rapability ofthese
`number, and poor
`cycle life is poy
`intly used cathode
`_ high reactivity of
`r the formation of
`
`an metallic lithium,
`Ils may have lower
`echnology, such as
`due to the use of
`‘m during repeated
`
`
`
` a
`
`Positive cap
`
`Positive tab
`Safety
`
`Separator
`
`|
`|
`|
`
`| !
`
`|
`i
`il
`
`Gasket
`
`Insulator
`
`Negative
`electrode
`Negative
`
`Can
`
`;
`Center pin
`
`Positive
`electrode
`
`(a)
`
`material is a carbon
`ye charge-discharge
`active material is a
`jithium ion can be
`2002, LiNiO., and
`ir, high voltage, and
`‘tof the initial work
`ed. This material is
`Jess expensive than
`discharge rate. It is
`ed material, such as
`jontoxic. The carly
`ic and solid polymer
`lithium anode cells.
`
`cel] are described in
`in Table 36.12.
`d earlier, have high
`tage profiles of cells
`J graphite negative
`ie is characteristic of
`Is, comparedto the
`
`t low discharge rate
`ivher current drains.
`jn of graphite and to
`; which has a lower
`
`EEECLEA
`
`WEEEEEL| LeELECCLEEeeEEE
`
`{b}
`
`PEEREDEaUOTE
`
`aEy
`eerie
`
`TsEe
`
`(a@) Construction of a lithium-ion cell. (6) Detail of current breaker mechanismas well
`FIGURE 36.32.
`as a vent mechanism for an abnormalrise of internal pressure in case of overcharging with no voltage
`limiting. (1) Aluminumburst disk. (2) Aluminumlead. (From Sony Corp.}
`
`WEEELeetEaCeceeeLEELE
` ESTEFTEEEED|eeeed
`
`
`11
`
`

`

`
`
`Active material:
`Binder:
`Loading (total):
`
`LiCoO,
`PVDF
`11.57 g
`
`Current collector:
`Leads:
`ae
`
`Al]foil (25 wm)
`Al
`
`0.018 cm
`Thickness (total):
`49.5cem
`Cathode length:
`52.0cm
`Substrate length:
`5.4cm
`width:
`Area (both sides):
`535m"
`
`
`
`
` p
`
`36.44
`ADVANCED BATTERY SYSTEMS
`
`
`
`
`conductivity than other clectrolytes. The diffusion coefficient of Liv into graphite is about
`
`two orders of magnitude lower than that in petroleum coke.
`
`The lithium-ion cell can be designed in any of the typical cell constructions: flat orcoin
`
`
`spirally woundcylindrical, or prismatic configurations. While most of the developments tq
`date have concentrated on the smaller cells for portable applications, larger prismaticcells
`
`are under investigation for applications ranging up to power levels required forelectric
`vehicles.
`
`
`
`Carbon[Lithium Cobalt Oxide Cells. These cells use the spirally wound cylindrical
`
`construction, as shownin Fig. 36.32. The cell is fabricated with the active material in the
`
`
`discharged state. The positive electrode is made by coating a thin aluminumfoil collector
`
`
`with the lithiated metal oxide compound (LiCoO,) for the active material.“““* Metal-
`doped(Al, In, or Sn) LiCoO, has also been used as a cathode.””? The current collectorof
`
`
`the negative electrode is a thin copper foil onto which a petroleum coke type carbon
`
`
`material is coated for the active material. Graphitic carbon, however, delivers much higher
`
`
`capacity.””"* The electrolyte consists of an organic solvent, such as propylene carbonate-
`
`
`diethyl carbonate, in which a salt such as LiPF, has been dissolved. LiBF, has also been
`
`
`used as the electrolyte.” The electrodes are rolled up in a ‘“‘jelly-roll” configuration with a
`
`
`polypropylene separator between them. The cell contains a safety vent
`to release any
`
`
`pressure that may devclop if the ccll
`is overcharged or otherwise abused. Some cells
`
`
`contain a positive temperature coefficient device to protect
`the cell against excessive
`
`
`currents that may occur during discharge, charge, or short circuits.
`
`
`The design parameters of a lithium-ioncell, using a nongraphitized carbon anode anda
`
`
`LiCoO, cathode, are listed in Table 36.17. The discharge characteristics, at various
`
`
`discharge rates and temperatures, are plotted in Fig. 36.33. The cell has a high voltage,
`
`
`ranging from about 4 to 2.7V during discharge, and a
`sloping discharge profile.
`
`
`
`SSHoHSoS!!};:SS——SoS
`
`TABLE 36.17 Typical Design Parameters for C/LiCoQ, Cylindrical Cell (Size 18650)
`
`
`AM|SYY _LS_WJNTS—2er_7Js_—S
`
`
`Cathode
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`ut
`
`ny
`
`
`
`Cellvoltage,V
`
`
`
`Cellvoltage,V
`
`FIGURI
`carbon <
`0.2C rate
`
`Continuous discha
`Up to the 5-6C ra
`Problem due to in
`collector. The inte
`drop during the di
`Other batteries in \
`Figure 36.34 sh
`(node. The discha
`Coke,
`The shelflife c
`Netallic lithium ce
`at 20°C, but it is |
`Testored with cycli
`Lithium-ion cel
`Control
`the chargii
`Vollages may caus
`
`a
`
`z
`
`Anodc
`
`Active material:
`Binder:
`Loading (total):
`
`Nongraphitized carbon
`PVDF
`4.92 g
`
`Current collector:
`
`Cu foil (25 wm)
`
`Thickness (total):
`Anode length:
`Substrate length:
`width:
`Area (bothsides):
`
`0.020 cm
`51.1em
`53.7 cn
`5.4m |
`552 cm”
`
`
`Other Components
`PC/DEC, LiPF,
`Celgard (25 um)
`PP disk
`Aluminum
`Nickel-plated steel
`Aluminumsafety vent
`Crimp
`
`Electrolyte:
`Separator:
`Insulator:
`Leads:
`Case:
`Header:
`Closure:
`
`_=
`
`—
`
`12
`
`12
`
`

`

`
`
`
`
`0 graphite js about
`ictions:flat OFcoin
`ne developments
`42to
`irger Prismatic Cells
`equired for electrie
`
`wound Rie
`‘live material in the
`ninum foil|collector
`naterial."""* Metaj.
`current collector of
`a coke type carbon
`lelivers much higher
`opylene carbonate.
`LIBF, has also heen
`configuration with a
`vent
`to release any
`abused. Some cells
`oll against excessive
`
`carbon anode anda
`cleristics, al various
`has a high voltage,
`g discharge profile.
`
`¢ 18650)
`
`0.018 cm
`49.5 cm
`52.0cm
`5.4cem
`535 cm"
`
`
`
`0.020 cm
`5l..cem
`33.7cm
`5.4cm
`552cm"
`
`vent
`
`FIGURE 36.33 Discharge curves af C/LiCoO,lithium-ion cell (nongraphitized
`carbon anode). Charge limited to 4.1 V. (@) Discharge at 20°C. (b) Discharges at
`0.2€
`rate at various temperatures. (From Sony Corp.)
`
`Continuous discharge currents can be as high as the 1.5-2C rate, with pulse discharges of
`up to the 5-6C rate. Overdischarging should be avoided as it may cause a performance
`problem due to internal short-circuiting resulting from the corrosion of the anode current
`collector. The internal impedanceis relatively constant during the discharge. The voltage
`drop during the discharge results from potential changes in the negative electrode, unlike
`other balteries in which the drop in voltage is due to an increase inthe cell’s impedance.
`Figure 36.34 shows the discharge characteristics of a C/LiCoO, ccll using a graphite
`anode. The discharge profile of these cells is flatter than that of the cells using petroleum
`coke,
`The shelf life or charge retention of these lithium-ion cells is poorer than that of the
`melallic lithium cells. For the C/LiCoO,cell it can be as high as 10% per month of storage
`at 20°C, but it is lower with the other cathode matcrials. The capacity of the cell can be
`Testored with cycling.
`Lithium-ion cells are capable of being recharged quickly within 1-2 h. It is necessary to
`Control the charging voltage for the LiCoO,cell to about 4.2 V percell. Higher charge
`voltages may cause the decomposition of the electrolyte at the positive electrode with a
`
`
`
`RECHARGEABLE LITHIUM BATTERLES
`
`36.45
`
`4
`
`O.2C
`
`ec
`
`ic
`
`ee c
`
`80
`
`400
`
`20
`
`40
`
`60
`Roted capacity, %
`(a)
`
`40°C
`
`
` orc
`~20%¢ 60°C
`
`80
`
`100
`
`120
`
`oO
`
`20
`
`60
`40
`Rated capacity, %
`(b)
`
`= 3
`
`o$
`
`se
`3aoO
`
`1 °
`
`Oo
`
`
`
`Cellvaltage,V n
`
`0
`
`13
`
`

`

` ADVANCED BATYERY SYSTEMS
`5.0 4.0
`
`33
`
`
`lithium on the carbonsurface. Figure 36.9
`rise in the internal pressure and the plating of
`shows the voltage and current characteristics of a modified constant-current charge @
`several charge rates, with the maximum charge voltage limited to 4.2 V. The tenrperalll
`range during charge should be between 0 and 45°C.
`ic lithium
`Typically the cycle life of the lithium-ion cell
`is superior to that of the metall
`own ne}
`rechargeable cells. Over 500 cycles can be obtained to 75% of rated capacity, as sh
`scl
`Fig. 36.356.
`._
`Lithium-ion (C/LiCoQ,) cells are commercially available in a spirally wound cylindtie
`configuration. The physical andelectrical characteristics of some of these cells are listed :
`Table 36.18. Manufacturers’ data sheets should be consulted for more recent and detailet
`information.
`;
`a
`The C/LiCoO; system has also been examined in other configurations. The dischaTe
`
`> &Q
`
`=
`
`Voltage,V
`
`
`
`Chornedlevel%
`
`lit
`1
`
`100
`
`Retention,% nn °o
`
`FIGURE 36.35)
`current rate to 4.
`
`
`
`
`3.0
`
`6>
`3
`92.0
`
`25
`
`75
`50
`Rated capacity, %
`(a)
`
`100
`
`1.0
`
`Oo
`
`0
`
`>o
`
`soa
`=fe}S
`
`0
`
`25
`
`75
`50
`Rated capacity, %
`(b)
`
`4100
`
`FIGURE 36.34 Discharge characteristics of C/LiCoO,lithium-ion cell (graphite
`anode). (a) Discharges at 20°C. (b) Discharges al 0.2C rate at various lempera-
`tures. (From Sanyo Energy Corp.)
`
`14
`
`14
`
`

`

`RECHARGEABLE LITHIUM BATTERIES
`
`36.47
`
`4,20 V/cell >
`
`eoCc
`
`e5
`
`oO
`
`Constant voltage
`
`SI
`
`2s
`
`oO
`
`1
`
`2
`Charge time, h
`
`3
`
`4
`
`100 14.5C rate
`
`|
`100 1.0 Crate
`
`80 30
`(a)
`
`100 0.5 Crate
`
`{
`|
`508090
`
`50
`
`'
`80 90
`
`50
`
`= ©
`
`ca
`°
`aoke
`
`&z
`
`£G
`
`O
`
`a C/LICoQ,
`of
`characteristics
`FIGURE 36.35a¢@ Charging
`lithium-ion cell at 20°C. Constant current charge (at 0.5, 1.0, and
`1.5 C€ rate) to 4.2 V/cell. (From A&T Banery Corp.)
`
`32°C
`
`(graphite
`lempera-
`
`100
`
`urface. Figure 36.35
`t-current charge al
`V. The temperature
`
`the metallic lithium
`apacity, as shown lm
`
`ly wound cylindrical
`‘se cells are listed in
`recent and detailed
`
`‘ions. The discharge
`
`{00
`
`300
`
`200
`Number of cycles
`(b)
`
`400
`
`aaa
`
`[C constant
`lithium-ion cell at 25°C. C