Lithium Ion Rechargeable Batteries: Materials, Technology, and New Applications

344 Pages·2009·5.004 MB·English

LithiumIonRechargeableBatteries
Editedby
KazunoriOzawa
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Lithium Ion Rechargeable Batteries
Edited by
Kazunori Ozawa
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V
Contents
Preface XI
ListofContributors XIII
1 GeneralConcepts 1
KenzoMatsukiandKazunoriOzawa
1.1 BriefOutlineofBatteries 1
1.1.1 GalvanicCellSystem – AqueousElectrolyteSystem 2
1.1.2 Lithium-CellSystem – NonaqueousElectrolyteSystem 4
1.2 EarlyDevelopmentofLithium-IonBatteries 5
1.2.1 CeramicsProductionCapability 5
1.2.2 CoatingTechnology 6
1.2.3 LiPF asaSaltforElectrolytes 6
6
1.2.4 GraphiteConductorintheCathode 6
1.2.5 UsingHardCarbonfortheAnode 6
1.2.6 NonwovenShut-downSeparator 6
1.2.7 Ni-PlatedFeCan 7
1.3 TowardaRealisticGoal 7
References 9
2 LithiumInsertionMaterialsHavingSpinel-FrameworkStructurefor
AdvancedBatteries 11
KingoAriyoshi,YoshinariMakimura,andTsutomuOhzuku
2.1 Introduction 11
2.2 StructuralDescriptionofSpinel 12
2.3 DerivativesofSpinel-FrameworkStructure 15
2.3.1 SuperlatticeStructuresDerivedfrom‘‘Spinel’’ 15
2.3.2 ExamplesofSuperstructureDerivedfrom‘‘Spinel’’ 20
2.4 ElectrochemistryofLithiumInsertionMaterialsHaving
Spinel-FrameworkStructure 24
2.4.1 LithiumManganeseOxides(LMO) 24
2.4.2 LithiumTitaniumOxide(LTO) 27
LithiumIonRechargeableBatteries.EditedbyKazunoriOzawa
Copyright2009WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-31983-1
VI Contents
2.4.3 LithiumNickelManganeseOxide(LiNiMO) 28
2.5 AnApplicationofLithiumInsertionMaterialsHaving
Spinel-FrameworkStructureto12V‘‘Lead-Free’’Accumulators 29
2.5.1 Twelve-VoltBatteriesConsistingofLithiumTitaniumOxide(LTO)and
LithiumManganeseOxide(LMO) 32
2.5.2 Twelve-VoltBatteriesConsistingofLithiumTitaniumOxide(LTO)and
LithiumNickelManganeseOxide(LiNiMO) 34
2.6 ConcludingRemarks 36
References 37
3 OverlithiatedLi1+x(NizCo1−2zMnz)1−xO2asPositiveElectrodeMaterials
forLithium-IonBatteries 39
NaoakiKumagaiandJung-MinKim
3.1 Introduction 39
3.2 Co-FreeLi1+x(Ni1/2Mn1/2)1−xO2 40
3.3 Li1+x(Ni1/3Co1/3Mn1/3)1−xO2 44
3.4 OtherLi1+x(NizCo1−2zMnz)1−xO2Materials 48
3.5 Conclusion 50
References 51
4 Iron-BasedRare-Metal-FreeCathodes 53
ShigetoOkadaandJun-ichiYamaki
4.1 Introduction 53
4.2 2DLayeredRocksalt-TypeOxideCathode 54
4.3 3DNASICON-TypeSulfateCathode 55
4.4 3DOlivine-TypePhosphateCathode 58
4.5 3DCalcite-TypeBorateCathode 62
4.6 3DPerovskite-TypeFluorideCathode 64
4.7 Summary 65
References 65
5 ThermodynamicsofElectrodeMaterialsforLithium-IonBatteries 67
RachidYazami
5.1 Introduction 67
5.2 Experimental 71
5.2.1 TheETMS 71
5.2.2 ElectrochemicalCells:ConstructionandFormationCycles 73
5.2.3 ThermodynamicsDataAcquisition 73
5.3 Results 74
5.3.1 CarbonaceousAnodeMaterials 74
5.3.1.1 Pre-coke(HTT<500C) 77
◦
5.3.1.2 CokesHTT900–1700 C 79
◦
5.3.1.3 CokesHTT2200and2600 C 80
5.3.1.4 NaturalGraphite 82
5.3.1.5 EntropyandDegreeofGraphitization 84
Contents VII
5.3.2 CathodeMaterials 86
5.3.2.1 LiCoO 86
2
5.3.2.2 LiMn O 90
2 4
5.3.2.3 EffectofCyclingonThermodynamics: 93
5.4 Conclusion 94
References 96
6 RamanInvestigationofCathodeMaterialsforLithiumBatteries 103
RitaBaddour-HadjeanandJean-PierrePereira-Ramos
6.1 Introduction 103
6.2 RamanMicrospectrometry:PrincipleandInstrumentation 104
6.2.1 Principle 104
6.2.2 Instrumentation 105
6.3 TransitionMetal-Oxide-BasedCompounds 106
6.3.1 LiCoO 107
2
6.3.2 LiNiO2andItsDerivativeCompoundsLiNi1−yCoyO2(0<y<1) 113
6.3.3 ManganeseOxide-BasedCompounds 114
6.3.3.1 MnO -TypeCompounds 114
2
6.3.3.2 TernaryLithiatedLi MnO Compounds 117
x y
6.3.4 V O 127
2 5
6.3.4.1 V O Structure 127
2 5
6.3.4.2 StructuralFeaturesoftheLi V O Phases 131
x 2 5
6.3.5 TitaniumDioxide 143
6.4 Phospho-OlivineLiMPO Compounds 149
4
6.5 GeneralConclusion 156
References 157
7 DevelopmentofLithium-IonBatteries:FromtheViewpointof
ImportanceoftheElectrolytes 163
MasakiYoshio,HiroyoshiNakamura,andNikolayDimov
7.1 Introduction 163
7.2 GeneralDesigntoFindAdditivesforImprovingthePerformanceof
LIB 166
7.3 ASeriesofDevelopingProcessestoFindNovelAdditives 169
7.4 CathodicandtheOtherAdditivesforLIBs 172
7.5 Conditioning 174
References 177
8 InorganicAdditivesandElectrodeInterface 179
ShinichiKomaba
8.1 Introduction 179
8.2 TransitionMetalIonsandCathodeDissolution 180
8.2.1 Mn(II)Ion 181
8.2.2 Co(II)Ion 184
8.2.3 Ni(II)Ion 186
VIII Contents
8.3 HowtoSuppresstheMn(II)Degradation 187
8.3.1 LiI,LiBr,andNH I 188
4
8.3.2 2-Vinylpyridine 190
8.4 AlkaliMetalIons 197
8.4.1 Na+Ion 197
8.4.2 K+Ion 204
8.5 AlkaliSaltCoating 207
8.6 Summary 209
References 210
9 CharacterizationofSolidPolymerElectrolytesandFabricationofall
Solid-StateLithiumPolymerSecondaryBatteries 213
MasatakaWakihara,MasanobuNakayama,andYukiKato
9.1 MolecularDesignandCharacterizationofPolymerElectrolyteswithLi
Salts 213
9.1.1 Introduction 213
9.1.2 SolidPolymerElectrolyteswithPlasticizers 217
9.1.3 PreparationofSPEFilmswithB-PEGandAl-PEGPlasticizers 217
9.1.4 EvaluationofSPEFilmswithB-PEGPlasticizers 219
9.1.5 IonicConductivityofSPEFilmswithB-PEGPlasticizers 223
9.1.6 TransportNumberofLithiumIons 227
9.1.7 ElectrochemicalStability 229
9.1.8 Summary 230
9.2 FabricationofAll-Solid-StateLithiumPolymerBattery 231
9.2.1 Introduction 231
9.2.2 RequiredIonicConductivityofSPE 231
9.2.3 DifferencebetweenConventionalBatterywithLiquidElectrolyteand
All-Solid-StateLPB 232
9.2.4 FabricationandElectrochemicalPerformanceofLPBsUsingSPEwith
B-PEGand/orAl-PEGPlasticizers 235
9.2.5 FabricationofaNonflammableLithiumPolymerBatteryandits
ElectrochemicalEvaluation 243
9.2.6 Summary 250
References 251
10 Thin-FilmMetal-OxideElectrodesforLithiumMicrobatteries 257
Jean-PierrePereira-RamosandRitaBaddour-Hadjean
10.1 Introduction 257
10.2 LithiumCobaltOxideThinFilms 259
10.2.1 SputteredLiCoO Films 259
2
10.2.1.1 LiquidElectrolyte 259
10.2.1.2 Solid-StateElectrolyte 262
10.2.2 PLDLiCoO Films 265
2
10.2.3 CVDLiCoO Films 269
2
10.2.4 LiCoO FilmsPreparedbyChemicalRoutes 269
2
Contents IX
10.2.5 Conclusion 271
10.3 LiNiO2andItsDerivativesCompoundsLiNi1−xMO2 272
10.3.1 Solid-StateElectrolyte 273
10.3.2 LiquidElectrolyte 274
10.3.3 Li – Ni – MnFilms 274
10.3.4 Conclusion 275
10.4 LiMn O Films 275
2 4
10.4.1 SputteredLiMn O Films 276
2 4
10.4.2 PLDLiMn O Films 277
2 4
10.4.3 ESDLiMn O Films 281
2 4
10.4.4 LiMn O FilmsPreparedThroughChemicalRoutes 282
2 4
10.4.5 SubstitutedLiMn2−xMxO4SpinelFilms 283
10.4.6 Conclusion 283
10.5 V O ThinFilms 285
2 5
10.5.1 SputteredV O ThinFilms 286
2 5
10.5.1.1 LiquidElectrolyte 286
10.5.1.2 Solid-StateElectrolyte 294
10.5.2 PLDV O ThinFilms 296
2 5
10.5.3 CVDV O Films 297
2 5
10.5.4 V O FilmsPreparedbyEvaporationTechniques 297
2 5
10.5.5 V O FilmsPreparedbyElectrostaticSprayDeposition 298
2 5
10.5.6 V O FilmsPreparedviaSolutionTechniques 299
2 5
10.5.7 Conclusion 300
10.6 MoO ThinFilms 301
3
10.6.1 LiquidElectrolyte 301
10.6.2 SolidStateElectrolyte 302
10.6.3 Conclusion 303
10.7 GeneralConclusions 303
References 305
11 ResearchandDevelopmentWorkonAdvancedLithium-IonBatteriesfor
High-PerformanceEnvironmentalVehicles 313
HideakiHorie
11.1 Introduction 313
11.2 EnergyNeededtoPoweranEV 313
11.3 QuestforaHigh-PowerCharacteristicinLithium-IonBatteries 315
11.4 CellThermalBehaviorandCellSystemStability 322
FurtherReading 326
Index 329
XI
Preface
Lithiumionbatteryhasbecomethebasisofthehugemarketforcellularphones
and lap top computers, and these mobile communication market continues to
growatarapidrate,supportedbythedemandallovertheworld.Evenso,intensive
effortsarestillunderwaytofurtherimprovethetechnology.Themaintargetofthe
effortisnotonlytheautomobileindustrybyachievinghigherenergyandhigher
power,butalsotheenergystoragemarketsupplementingenvironmentallyfriendly
powersourcesuchassolarenergyandwindturbine.
Thoughthelithiumiontechnologyissowidethisbookcanincludeonlyafew
topics,Ibelievethereaderscanfindanindicatortodotheresearch.
Chapteronecoversthebasicconceptsofelectrochemicaldevicesandlithiumion
battery.
FromChaptertwotoChapterfourcathodematerialsaredescribed,andChapter
twoespeciallyproposesnewapplicationsuchasanaccumulator.
ThebasicthoughtsofthematerialsarementionedinChapterfiveandChapter
six.ThesetwoChaptersaresonew,thentheymaygiveabigimpacttothereaders.
ChaptersevenandChaptereightfocusonthesolidelectrolyteinterface,socalled
SEIwhichisimportanttodevelophighperformancelithiumionbatteries.
Solid state batteries are discussed in Chapter nine and Chapter ten. These
batteriesmayshowthebigbusinesschanceinthefuture.
Lasbutnotleast,Chapterelevenexplainadvancedlithiumionbatteriesforhigh
performanceenvironmentalvehicles.
The substantial contribution of each of the authors to this book is gratefully
acknowledged,aswellastheircooperationinpreparingtheirmanuscriptsinthe
styleandformatselected.Ialsowishtoexpressmyappreciationtothecompanies,
associationswhosupportedthecontributingauthorsandwillinglyprovidedtheir
technicalinformationanddatapermitteditsuseinthisbook.
January,2009 KazunoriOzawa
LithiumIonRechargeableBatteries.EditedbyKazunoriOzawa
Copyright2009WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-31983-1