[PDF] Design and Simulation of Lithium Rechargeable Batteries





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LBL-37650

UC-21O

ITlILawrenceBerkeleyLaboratory

Ii:!UNIVERSITYOFCALIFORNIA

ENERGY&ENVIRONMENT

DIVISION

DesignandSimulationofLithium

RechargeableBatteries

C.M.Doyle

(Ph.D.Thesis)

August1995

ENERGY

ANDENVIRONMENT

DIVISION

::0 ("')"Tl ......0", ,0::0 oIll", l:lIlz DlZ", r+0

Illr+(",)

o 0.--_ lC r rCD ......r

C"("')I

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Dl"0......

,'<01 'DISCLAIMER

UnitedStatesGovernment.Whilethisdocument

isbelievedtocontain agencythereof,norTheRegents oftheUniversityofCalifornia,norany service orfavoring of

UnitedStatesGovernment

oranyagencythereof,orTheRegentsofthe

UniversityofCalifornia.

is anequalopportunityemployer. 1 I J ,J J n .I .1 I rI . j j

LBL-37650

UC-21O

C.MarcDoyle

Department

ofChemicalEngineering

University

ofCalifornia,Berkeley and

EnergyandEnvironmentDivision

LawrenceBerkeleyNationalLaboratory

University

ofCalifornia

Berkeley,California94720

August1995

ContractNo.DE-AC03-76SFOO098..

n -1 1 - I d -1 ..j •j .'C"} -j r J J J n d I

Abstract

Design

by

ChristopherMarcDoyle

Doctor

ofPhilosophyinChemicalEngineering

University

ofCaliforniaatBerkeley

ProfessorJohnNewman,Chair

forelectric-vehicleapplicationsbecause toawiderangeoflithium-basedsys- kinetics,followedbydiffusion toexplorethephenomenathatoccurinside charge,andduringperiods ofrelaxation. Also, terns,wefocusonthemodeling 2 isbeingmarketed ischaracterizedexperimentallyintermsof detailedcomparisonsofsimulation ofthissystemforparticular applications powerprovided byvariousdesigns.

Duetoalack

subject

Themeanmolaractivity

isfoundbyusingthemethodofrestricted diffusion. method experimentalmethodbased concentrationrange. r !_J 11 n u J

TableofContents

Abstract

Tableofcontents

Acknowledgements

Chapter1.Introduction

1.1Rechargeablebatteries

1.2Lithiumbatteries

1.3Mathematicalmodeling

1.4Scope

ofthesis

Chapter2.DevelopmentofModelEquations

2.1Modelingapproach

2.2Concentratedsolutiontheory

2.3Porouselectrodetheory

2.4Boundaryconditions

2.5Solid-statediffusion

2.6Electrodekinetics

2.7Nonporousinsertionelectrodes

2.8Summary

ofmodelequations

2.9Numericalsolutionprocedure

2.10Computerprograms

fits

Appendix2-BDatafilesforFOILandDUAL

Appendix2-CComputerprogramsFOILandDUAL

3.1Introduction

3.2Descriptionofthesystem

iii 1 iii v 1 4 10 12 21
23
27
30
32
36
39
44
47
49
53
64
69
185
186

3.3Simulationresults

3.4Designandoptimizationconsiderations

3.5Conclusions

Appendix3-BSimplifiedmodel

ofcelldominatedbysolid-statediffusion

4.1Introduction

4.2Theoreticaldevelopment

4.3Analysis

ofthegalvanostaticpolarizationexperiment

4.4Experimentaldetails

4.5Resultsanddiscussion

4.6Simulation

4.7Effect

4.8Microscopicspeciationmodels

4.9Simulation

4.10Comparison

ofmethodstomeasuret+inSPE's

4.11Conclusions

IV 194
fl U F.- 244
252
253
n 254
t E_ 1'-1 269
271
275
280
282
298
315
320
325
335
340
341
=1 -1 -i "j n u I j cI i J u t1 iJ v

Acknowledgements

ofcon- supportformyabilities,Ithankhim.

Iwouldalsolike

myfirsttwoyearsasagraduatestu- dent.IlearnedatremendousamountfromTom ofbothatechnicalnatureandalsoonthemost mycollaboratorsinthelithium togiveaspecial thankstoYanpingMa inourexperimentalworkon ofthisproject.Last,Iwould vi includesthepastandpresentmembers finalyear.

IhopethatIcandothesameforher

J.CairnsandDr.LutgardC.

I t...:" 1 .I U n u n n I I (j n u ,1. 1 J 1

Chapter1

Introduction

1.1Rechargeablebatteries

andstoragecontinuestobeanimportant currentdecade.1Thismarket Much isalsoasizeablemarketforrecharge- ablebatteriesforconsumerapplications. ofrechargeablebattery sales.Withtheongoingminiaturization importantforabatterysystemtohaveinherent

Anexample

tialportion isinherentlylim- itedbythecapacity 2 perunitvolume. ofinterestinabattery-powered ofCali- fomiabytheCalifomia percentage targets ofvehi- cancompetesuc cessfullyin theautomobilemarket. 2 targetdate,therearestillmajorproblemsto intermsofitscost,performance, andlife.

Inorder

ofEnergy,andtheElectric

TheUSABChasquantifiedthedemandsfor

inTable1.1.ThedemandsontheUSABC thathavenotbeenmet -t II _J -j J -I .'r t J •j f u 3 of200Whlkg.Forcom- ofatmost40Wh/kg, siderationawiderange thenickel-metalhydridesystem. posalquotesdbs_dbs26.pdfusesText_32
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