LithiumIonRechargeableBatteries Editedby KazunoriOzawa Related Titles Mitsos,A./Barton,P.I.(eds.) Microfabricated PowerGeneration Devices DesignandTechnology 2009 ISBN:978-3-527-32081-3 Liu,Hansan/Zhang,Jiujun(eds.) ElectrocatalysisofDirect Methanol FuelCells FromFundamentalstoApplications 2010 ISBN:978-0-471-68958-4 Sundmacher,K.,Kienle,A.,Pesch,H.J., Berndt,J.F.,Huppmann,G.(eds.) MoltenCarbonateFuelCells Modeling,Analysis,Simulation,andControl 2007 ISBN:978-3-527-31474-4 Zu¨ttel,A./Borgschulte,A./Schlapbach,L. (eds.) HydrogenasaFutureEnergy Carrier 2008 ISBN:978-3-527-30817-0 Lithium Ion Rechargeable Batteries Edited by Kazunori Ozawa TheEditor AllbookspublishedbyWiley-VCHare carefullyproduced.Nevertheless,authors, Dr.KazunoriOzawa editors,andpublisherdonotwarrantthe Enax,Inc. informationcontainedinthesebooks,includ- President&CEO ingthisbook,tobefreeoferrors.Readers 2-11-19Otowa,Bunkyo-ku areadvisedtokeepinmindthatstatements, Tokyo112-0013 data,illustrations,proceduraldetailsorother Japan itemsmayinadvertentlybeinaccurate. LibraryofCongressCardNo.: appliedfor BritishLibraryCataloguing-in-PublicationData Acataloguerecordforthisbookisavailable fromtheBritishLibrary. Bibliographicinformationpublishedby theDeutscheNationalbibliothek TheDeutscheNationalbibliothekliststhis publicationintheDeutscheNationalbibli- ografie;detailedbibliographicdataareavail- ableontheInternetathttp://dnb.d-nb.de. 2009WILEY-VCHVerlagGmbH&Co. KGaA,Weinheim Allrightsreserved(includingthoseoftrans- lationintootherlanguages).Nopartofthis bookmaybereproducedinanyform–by photoprinting,microfilm,oranyother means–nortransmittedortranslated intoamachinelanguagewithoutwritten permissionfromthepublishers.Registered names,trademarks,etc.usedinthisbook, evenwhennotspecificallymarkedassuch, arenottobeconsideredunprotectedbylaw. PrintedintheFederalRepublicofGermany Printedonacid-freepaper Typesetting LaserwordsPrivateLimited, Chennai,India Printing StraussGmbH,Mo¨rlenbach Binding Litges&DopfGmbH,Heppenheim CoverDesign Adam-Design,Weinheim ISBN:978-3-527-31983-1 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