(word)-nanostructured electrode materials for lithium-ion batteries_图文

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挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠NanostructuredElectrodeMaterialsforLithium-IonBatteries_图文  NanostructuredElectrodeMaterials󰀃forLithium-IonBatteries  A.ManthiramandT.Muraliganth  AbstractElectrochemicalenergystoragesystemsarebecomingincreasinglyimportantwithrespecttotheiruseinportableelectronicdevices,medicalimplantdevices,hybridelectricandelectricvehicles,andstorageofsolarandwindener-gies.Lithium-ionbatteriesareappealingfortheseneedsbecauseoftheirhighenergydensity,widerangeofoperatingtemperatures,andlongshelfandcyclelife.However,furtherbreakthroughsinelectrodematerialsorimprovementsinexistingelectrodematerialsarecriticaltorealizethefullpotentialofthelithium-iontech-nology.Nanostructuredmaterialspresentanattractiveopportunityinthisregardastheycouldofferseveraladvantagessuchasfastreactionkinetics,highpowerdensity,goodcyclingstabilitywithfacilestrainrelaxationcomparedtotheirbulkcounterparts.Inthischapter,wepresentanoverviewofthelatestprogressonthenanostructuredanodeandcathodematerialsforlithium-ionbatteries.Introduction  Energystorageandproductionisoneofthegreatestchallengesfacinghumankindinthetwenty-firstcentury.Basedonmoderateeconomicandpopulationgrowth,theglobalenergyconsumptionisanticipatedtotriplebytheyear2010.Therapiddepletionoffossilfuelreserves,increasingfuelcosts,increasinggreenhousegasemission,andglobalclimatechangesaredrivingthedevelopmentofsustainablecleanenergytechnologieslikefuelcells,solarcells,highenergydensitybatteries,andsupercapacitors.Whilefuelcellsandsolarcellsareenergyconversiondevices,batteriesandsupercapacitorsareenergystoragedevices. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Nearlyone-thirdofthetotalenergyconsumptionintheUnitedStatesisbythetransportationsector,andinternalcombustionenginebasedautomobilesareasig-nificantcontributorofgreenhousegasemission.Hybridelectricvehicles(HEV)andplug-inhybridelectricvehicles(PHEV)arethemostviablenear-termoption  A.Manthiram(B)  MaterialsScienceandEngineeringProgram,TheUniversityofTexas,Austin,TX78712,USAe-mail:rmanth@mail.utexas.edu  A.Korkinetal.(eds.),NanotechnologyforElectronics,Photonics,andRenewableEnergy,NanostructureScienceandTechnology,DOI10.1007/978-1-4419-7454-9_8,󰀄CSpringerScience+BusinessMedia,LLC2010211  212  Fig.8.1Comparisonofthe  energydensitiesofdifferent  batterysystemsA.ManthiramandT.  Muraliganth 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  fortransportation.Energystorageisalsocriticalfortheefficientutilizationoftheelectricityproducedfromsolarandwindenergies.Lithium-ionbatteriesareappeal-ingforautomobiles(HEVandPHEV)andthestorageofsolarandwindenergyastheyprovidehigherenergydensitycomparedtootherrechargeablebatterysystemssuchasleadacid,nickel–cadmium,andnickelmetalhydridebatteriesasseeninFig.8.1[1].However,costandsafetyarethemajorissueswithrespecttolarge-scaleapplicationslikeautomobilesandsolarandwindenergystorage,andtheyneedtobeadequatelyaddressed.  Lithium-IonBatteries  Rechargeablelithiumbatteriesinvolveareversibleinsertion/extractionoflithiumionsinto/fromahostelectrodematerialduringthecharge/dischargeprocess.Thelithiuminsertion/extractionprocessoccurringwithaflowofionsthroughtheelec-trolyteisaccompaniedbyareduction/oxidation(redox)reactionofthehostmatrixassistedwithaflowofelectronsthroughtheexternalcircuit(Fig.8.2).  Theopen-circuitvoltageVocofsuchalithiumcellisgivenbythedifferenceinthelithiumchemicalpotentialbetweenthecathode(μLi(c))andtheanode(μLi(a))as  Voc=(μLi(c)−μLi(a))/F,(8.1)  whereFistheFaradayconstant.AschematicenergydiagramofacellatopencircuitisgiveninFig.8.3.ThecellvoltageisdeterminedbytheenergiesinvolvedinboththeelectrontransferandLi+transfer.Whiletheenergyinvolvedinelectrontransferisrelatedtotheworkfunctionsofthecathodeandtheanode,theenergyinvolvedinLi+transferisdeterminedbythecrystalstructureandthecoordinationgeometryofthesiteinto/fromwhichtheLi+ionsareinserted/extracted[2].Thermodynamicstabilityconsiderationsrequiretheredoxenergiesofthecathode(Ec)andanode  8NanostructuredElectrodeMaterialsforLithium-IonBatteries 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  213Fig.8.2Illustrationofthe  charge–dischargeprocess  involvedinalithium-ioncell  consistingofgraphiteasan  anodeandlayeredLiCoO2as  a  cathode  Fig.8.3Schematicenergy  diagramofalithiumcellat  opencircuit.HOMOand  LUMOrefer,respectively,to  thehighestoccupied  molecularorbitalandlowest  unoccupiedmolecularorbital 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  intheelectrolyte(Ea)toliewithinthebandgapEgoftheelectrolyte,asshowninFig.8.3,sothatnounwantedreductionoroxidationoftheelectrolyteoccursduringthecharge–dischargeprocess.Withthisstrategy,theanodeandcathodeinsertionhostsshouldhave,respectively,thelowestandhighestvoltagesvs.metalliclithiuminordertomaximizethecellvoltage.  TheconceptofrechargeablelithiumbatterieswasfirstillustratedwithatransitionmetalsulfideTiS2asthecathode,metalliclithiumastheanode,andanonaque-ouselectrolyte[3].Followingtheinitialdemonstration,severalothersulfidesandchalcogenideswerepursuedduringthe1970sand1980sascathodes[4].However,mostofthemexhibitalowcellvoltageof<2.5Vvs.lithiumanode.Thislimita-tionincellvoltageisduetoanoverlapofthehighervalentMn+:dbandwiththetopofthenonmetal:pband—forexample,withthetopoftheS:3pbandasshowninFig.8.4.Suchanoverlapresultsinanintroductionofholesinto(orremovalof2−,electronsfrom)theS2−:3pbandandtheformationofmolecularionssuchasS2  214  Fig.8.4Relativeenergiesof  metal:d(forexample,Co:3d)  andnonmetal:pin(a)a  sulfideand(b)anoxideA.ManthiramandT.  Muraliganth 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  whichinturnleadstoaninaccessibilityofhigheroxidationstatesforMn+inasul-fideLixMySz.Thestabilizationofhigheroxidationstateisessentialtomaximizethecellvoltage.Recognizingthisdifficultywithchalcogenides,Goodenough’sgroupattheUniversityofOxfordfocusedonoxidecathodesduringthe1980s[5–7].ThelocationofthetopoftheO2−:2pbandmuchbelowthetopoftheS2−:3pbandandalargerraisingoftheMn+:denergiesinanoxidecomparedtothatinasulfideduetoalargerMadelungenergy(Fig.8.4)makethehighervalentstatesaccessibleinoxides.Forexample,whileCo3+canbereadilystabilizedinanoxide,itisdifficulttosta-bilizeCo3+inasulfidesincetheCo2+/3+redoxcouplelieswithintheS2−:3pbandasseeninFig.8.4.Accordingly,severaltransitionmetaloxidehostscrystallizinginavarietyofstructures(two-dimensionallayeredandthree-dimensionalframeworkstructures)havebeenpursuedduringthepasttwodecades.AmongthemLiCoO2,LiNiO2,andLiMn2O4oxideshavingahighelectrodepotentialof4Vvs.metalliclithiumhavebecomeattractivecathodesforlithium-ioncells.Ontheotherhand,graphitewithalowelectrodepotentialof<0.3Vvs.metalliclithiumhasbecomeanattractiveanode.  Althoughtheinitialeffortsinrechargeablelithiumbatteriesemployedlithiummetalastheanode,thestrategyfailedtoattaincommercialsuccessduetosafetylimitations[8,9].Theinherentinstabilityoflithiummetalandthedendritefor-mationduringcharge–dischargecyclingeventuallyforcedtheuseofintercalationcompoundsasanodes.Thisledtothecommercializationofthelithium-ionbatterytechnologybySonyin1990withLiCoO2asthecathodeandgraphiteastheanode.However,thecostandsafetyissuesandtheperformancelimitationsassociatedwiththeLiCoO2cathodeandcarbonanodehavepromptedthesearchfornewelectrodematerialsaswellasimprovementsinexistingelectrodematerials.  Nanostructuredmaterialshaveattractedalotofinterestinthepasttwodecadesbecauseoftheirunusualelectrical,mechanical,andopticalpropertiescomparedtotheirbulkcounterparts[10–15].Recently,nanostructuredmaterialsarealsogainingincreasingpopularityforenergystorageapplications[16–21].Thischapterfocusesonprovidinganoverviewofsomeoftherecentadvancesinnanostructuredanodeandcathodematerialsforlithium-ionbatteries. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  8NanostructuredElectrodeMaterialsforLithium-IonBatteries215NanostructuredElectrodeMaterialsforLithium-IonBatteriesNanomaterialsofferadvantagesanddisadvantagesaselectrodematerialsforlithium-ionbatteries.Someoftheadvantagesaregivenbelow:  •Thesmallerparticlesizeincreasestherateoflithiuminsertion/extractionbecauseoftheshortdiffusionlengthforlithium-iontransportwithintheparticle,resultinginenhancedratecapability.  •Thesmallerparticlesizeenhancestheelectrontransportintheelectrode,resultinginenhancedratecapability.  •Thehighsurfacearealeadstoenhancedutilizationoftheactivematerials,resultinginhighercapacity.  •Thesmallerparticlesizeaidsabetteraccommodationofthestrainduringlithiuminsertion/extraction,resultinginimprovedcyclelife.  •Thesmallerparticlesizeenablesreactionsthatcouldnototherwiseoccurwithmicrometer-sizedparticles,resultinginnewlithiuminsertion/extractionmechanismsandimprovedelectrochemicalpropertiesandperformances.Someofthedisadvantagesaregivenbelow:  •Complexitiesinvolvedinthesynthesismethodsemployedcouldincreasetheprocessingcost,resultinginhighermanufacturingcost.  •Thehighsurfaceareamayleadtoenhancedsidereactionswiththeelectrolyte,resultinginhighirreversiblecapacitylossandcapacityfadeduringcycling.  •Thesmallerparticlesizeandhighsurface-to-volumeratiocouldleadtolowpackingdensity,resultinginlowvolumetricenergydensity.  NanostructuredCathodes  NanostructuredLayeredOxideCathodes 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  OxideswiththegeneralformulaLiMO2(M=V,Cr,Co,andNi)crystallizeinalayeredstructureinwhichLi+andM3+ionsoccupythealternate(111)planesoftherocksaltstructuretogivealayeredsequenceof-O-Li-O-M-O-alongthecaxis.TheLi+andM3+ionsoccupytheoctahedralinterstitialsitesofthecubicclose-packedoxygenarrayasshowninFig.8.5.Thestructurewithstrongly(cova-lently)bondedMO2layersallowsareversibleextraction/insertionoflithiumionsfrom/intothelithiumplanes.Thelithium-ionmovementbetweenMO2layerspro-videsfasttwo-dimensionallithium-iondiffusion[22],andtheedge-sharedMO6octahedralarrangementwithadirectM–Minteractionprovidesgoodelectronicconductivity.LiCoO2isthemostcommonlyusedtransitionmetaloxidecathodeincommerciallithium-ionbatteries.Ithasbeenusedbecauseofitshighoperatingvoltage(4V),easeofsynthesis,andgoodcyclelife.However,only50%(~140mAhg−1)ofthetheoreticalcapacityofLiCoO2canbeutilizedinpracticallithium-ion  216  Fig.8.5Crystalstructureof  layeredLiCoO2A.ManthiramandT.  Muraliganth 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  cellsduetostructuralandchemicalinstabilitiesatdeepchargewith(1−x)<0.5inLi1−xCoO2aswellassafetyconcerns[23,24].Moreovertheelementcobaltistoxicandexpensive.Inthisregard,LiNiO2providesanimportantadvantagecomparedtoLiCoO2sinceNiislessexpensiveandlesstoxicthanCo.However,itsuffersfromafewproblems:(i)difficultytosynthesizeLiNiO2withallNi3+andasaperfectlyorderedphasewithoutamixingofLi+andNi3+ionsinthelithiumplane[25–27],(ii)Jahn–Tellerdistortion(tetragonalstructuraldistortion)associatedwiththelow-1spinNi3+:d7(t62geg)ion[28,29],and(iii)exothermicreleaseofoxygenatelevatedtemperaturesandsafetyconcernsinthechargedstate[30,31].Asaresult,LiNiO2isnotapromisingmaterialforlithium-ioncells.However,someofthesedifficultieshavebeenovercomebyapartialsubstitutionofCoforNiformingLiNi1−yCoyO2  [32].ForexampleLiNi0.85Co0.15O2hasbeenfoundtodeliverahighcapacityof~180mAhg−1withgoodcyclability.  Ingeneral,LiCoO2andLiNi1−yCoyO2arepreparedbysolid-statereactionsathightemperatures(800–900◦C)[33].Thehigh-temperaturemethodusuallyresultsinlargerparticlesandofteninirregularmorphologyandabroadparticlesizedistribution.Anumberofsyntheticroutessuchassol–gel,co-precipitation,andemulsionmethodshavebeenpursuedovertheyearstosynthesizenanostructuredlayeredoxides[34–38].Decreasingtheparticlesizetonanometerrangesignifi-cantlyshortensthelithium-iondiffusiondistanceandimprovestherateperformanceofthelayeredoxidecathodes.However,thelargesurfaceareaofthenanoparticlesincursundesirablesidereactionswiththeelectrolyte,especiallyathigheroperatingvoltages.Thiseffectcouldbeminimizedbyhavingnano-sizedprimaryparticlesagglomeratingintomicron-sizedsecondaryparticles.  Inthisregard,template-assistedmethodswiththeuseofporousanodicaluminumoxidehavebeenusedtoprepareLiCoO2nanotubeswithlengthsuptoseveral  8NanostructuredElectrodeMaterialsforLithium-IonBatteries 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  217Fig.8.6First  charge–dischargeprofilesof  solidsolutionsbetween  layeredLi[Li1/3Mn2/3]O2and  Li[Ni1−y−zMnyCoz]O2  micrometersanddiameteraround200nm[39].Sincetherate-determiningstepinLiCoO2electrodesisthesolid-statelithium-iondiffusion,decreasingthepar-ticlesizecansignificantlyimprovethekineticsbecauseofshorterlithiumdiffusionlength.Accordingly,LiCoO2withananotubearchitecturehasbeenfoundtoexhibitimprovedrateperformancecomparedtotheconventionalLiCoO2[40]. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Recently,solidsolutionsbetweenLi[Li1/3Mn2/3]O2(commonlyknownasLi2MnO3)andLiMO2(M=Mn0.5Ni0.5,Co,Ni,andCr)havebecomeappeal-ingastheyexhibitahighreversiblecapacityofaround250mAhg−1withalowercostandbettersafetycomparedtotheLiCoO2cathode[41–45].ThiscapacityisnearlytwotimeshigherthanthatfoundwiththeLiCoO2cathode.However,theLi2MnO3−LiMO2solidsolutionshaveafewdrawbacks.First,theyloseoxygenirreversiblyfromthelatticeduringfirstchargeasindicatedbyavoltageplateauat4.5Vfollowinganinitialslopingregioncorrespondingtotheoxidationofthetransitionmetalionsto4+oxidationstateasseeninFig.8.6.Thisleadstoalargeirreversiblecapacitylossinthefirstcycle.Second,theseoxidessufferfrompoorratecapability,impedingtheirhigh-powerapplications.  Decreasingthelithium-iondiffusiondistanceandhavingahighsurfaceareananostructurecouldenhancetheirrateperformance.Especially,one-dimensionalnanowiremorphologycouldbebeneficialcomparedtonanoparticles.Accordingly,Li[Ni0.25Li0.15Mn0.6]O2nanowireswithadiameterofaround30nmandahighaspectratioofaround100havebeensynthesizedviaatemplate-freehydrother-malmethod.Interestingly,theLi[Ni0.25Li0.15Mn0.6]O2samplethuspreparedhasbeenfoundtodeliverastablecyclelifeandsuperiorrateperformancewithahighdischargecapacityofaround260mAhg−1at7Crate[46].  Surface-Modifie(Nanocoating)LayeredOxideCathodes  Aspointedoutintheearliersection,only50%ofthetheoreticalcapacityoflayeredLiCoO2cathodecouldbeutilizedinpracticallithium-ioncellsduetothechemi-calinstabilityincontactwiththeelectrolytefor(1−x)<0.5inLi1−xCoO2[23,24].Onewaytosuppressthechemicalreactivityistocoatormodifythesurfaceofthecathodewithotherinertoxides.Infact,surfacemodificationofthelayered 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  218A.ManthiramandT.MuraliganthLiCoO2cathodewithnanostructuredoxideslikeAl2O3,TiO2,ZrO2,SiO2,MgO,ZnO,andMPO4(M=AlandFe)hasbeenfoundtoincreasethereversiblecapacityofLiCoO2from~140mAhg−1toabout200mAhg−1,whichcorrespondstoareversibleextractionof~0.7lithiumperformulaofLiCoO2[47–54].Thesurfacemodificationsuppressesthereactionofthecathodesurfacewiththeelectrolyteandtherebydecreasestheimpedancegrowthofthecathodeandimprovesthecapac-ityretention.ThisclearlydemonstratesthatthelimitationinpracticalcapacityofLiCoO2isprimarilyduetothechemicalinstabilityatdeepdischargeandnotduetothestructural(order–disorder)transitionat(1−x)=0.5.However,thelong-termperformanceofthesenano-oxide-coatedcathodeswillrelyontherobustnessofthecoating.Inadditiontotheimprovementinelectrochemicalproperties,nanocoatingofAlPO4onLiCoO2hasalsobeenfoundtoimprovethethermalstabilityandsafetyofLiCoO2cathodes[55].  Asindicatedintheprevioussection,solidsolutionsbetweenlayeredLi2MnO3andLi[Ni1−y−zMnyCoz]O2exhibitahugeirreversiblelossduringfirstcycle.Thelargeirreversiblecapacitylossisobservedtobeduetotheextractionoflithiumas“Li2O”intheplateauregionasshowninFig.8.6andaneliminationoftheoxygenvacanciesformedtogiveanidealcomposition“MO2”attheendofthefirstcharge,resultinginlessnumberoflithiumsitesavailableforlithiuminsertion/extractionduringsubsequentcycles[43,56].However,acarefulanalysisofthefirstcharge–dischargecapacityvaluesinourlaboratorywithanumberofcompositionssuggeststhatpartoftheoxygenvacanciesshouldberetainedinthelatticetoaccountforthehighdischargecapacityvaluesobservedinthefirstcycle[57].Moreimportantly,itwasfoundthattheirreversiblecapacitylossinthefirstcyclecanbereducedsignifi-cantlybycoatingtheselayeredoxidesolidsolutionswithnanostructuredAl2O3andAlPO4[44,57].Figure8.7showstheTEMimagesofAlPO4-coatedlayeredoxide,inwhichthethicknessoftheAlPO4coatingisaround5nm.  Figure8.8aandbcomparesthefirstcharge–dischargeprofilesandthecorrespondingcyclabilitydataofaseriesofsolidsolutionsbetweenlay-eredLi[Li1/3Mn2/3]O2andLi[Ni1/3Mn1/3Co1/3]O2beforeandafter  surfaceFig.8.7TEMimageof4  wt.%nano-AIPO4-modified 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Li[Li0.2Mn0.54Ni0.13Co0.13]O2cathode  8NanostructuredElectrodeMaterialsforLithium-IonBatteries  219Fig.8.8(a)Firstcharge–dischargeprofilesofthelayered(1−x)Li[Li1/3Mn2/3]O2−xLi[Ni1/3Mn1/3Co1/3]O2solidsolutionsbeforeandaftersurfacemodificationwith3wt.%nanostructuredAl2O3,followedbyheatingat400◦C(b)Cyclabilityofthelayered(1−x)Li[Li1/3Mn2/3]O2−xLi[Ni1/3Mn1/3Co1.3]O2solidsolutionsbeforeandaftersurfacemodifi-cationwith3wt.%nanostructuredAl2O3,followedbyheatingat400◦C  modificationwithnanostructuredAl2O3[44].Thesurface-modifiedsamplesexhibitlowerirreversiblecapacitylossandhigherdischargecapacityvaluesthanthepris-tinelayeredoxidesamples.Thisimprovementinsurface-modifiedsampleshasbeenexplainedonthebasisoftheretentionofmoreoxygenvacanciesinthelayeredlatticeafterthefirstchargecomparedtothatintheunmodifiedsamples[57–59].Thebondingofthenano-oxidestothesurfaceofthelayeredoxidelatticesup-pressesthediffusionofoxygenvacanciesandtheirelimination.Remarkably,thesurface-modified(1−x)Li[Li1/3Mn2/3]O2−xLi[Ni1/3Mn1/3Co1/3]O2compositionwithx=0.4exhibitsahighdischargecapacityof~280mAhg−1,whichistwotimeshigherthanthatofLiCoO2.Moreover,thesurface-modifiedcathodeshavebeenfoundtoexhibithigherratecapabilitythantheunmodifiedsamplesdespitetheelectronicallyinsulatingnatureofthecoatingmaterialslikeAl2O3andAlPO4 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  [59].Thisisbelievedtobeduetothesuppressionoftheformationofthicksolid-electrolyteinterfacial(SEI)layersasthecoatingmaterialminimizesthedirectreactionofthecathodesurfacewiththeelectrolyteatthehighchargingvoltages.However,theselayeredoxidesolidsolutionshavetobechargeduptoabout  4.8V,somorestable,compatibleelectrolytesneedtobedevelopedtofullyexploittheirpotentialashighenergydensitycathodes.Moreover,oxygenislostirreversiblyfromthelatticeduringfirstcharge,anditmayhavetobeventedappropriatelyduringcellmanufacturing.Also,thelong-termcyclabilityofthesehigh-capacitycathodesneedstobefullyassessed.  220A.ManthiramandT.MuraliganthNanostructuredSpinelOxideCathodes  OxideswiththegeneralformulaLiMn2O4(M=Ti,V,andMn)crystallizeinthenormalspinelstructure(Fig.8.9)inwhichtheLi+andtheM3+/4+ionsoccupy,respectively,the8atetrahedraland16doctahedralsitesofthecubicclose-packedoxygenarray.Astrongedge-sharedoctahedral[M2]O4arraypermitsreversibleextractionoftheLi+ionsfromthetetrahedralsiteswithoutcollapsingthethree-dimensional[M2]O4spinelframework.Whileanedge-sharedMO6octahedralarrangementwithdirectM–Minteractionprovidesgoodelectricalconductivity,theinterconnectedinterstitial(lithium)sitesinthethree-dimensionalspinelframeworkprovidegoodlithium-ion  conductivity.  Fig.8.9Crystalstructureof 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  spinelLiMn2O4  Asaresult,spinelLiMn2O4hasbecomeanattractivecathode.Moreover,theelementMnisinexpensiveandenvironmentallybenigncomparedtoCoandNiinvolvedinthelayeredoxidecathodes.However,LiMn2O4deliversonlyalimitedcapacityofaround120mAhg−1atanoperatingvoltageof4V.Moreover,LiMn2O4tendstoexhibitcapacityfadeparticularlyatelevatedtemperatures(55◦C).SeveralfactorssuchasJahn–Tellerdistortionoccurringonthesurfaceoftheparticlesunderconditionsofnonequilibriumcycling[60,61],manganesedissolutionintotheelec-trolyte[62,63],formationoftwocubicphasesinthe4Vregion,lossofcrystallinity  [64],anddevelopmentofmicro-strain[65]duringcyclinghavebeensuggestedtobethesourceofcapacityfade.SeveralstrategieshavebeenpursuedtoovercomethecapacityfadeofLiMn2O4.ThemostsignificantofthemiscationicsubstitutiontogiveLiMn2−yMyO4(M=Li,Cr,Co,Ni,andCu)tosuppressthedifficultiesofJahn–Tellerdistortionandmanganesedissolution[66].  Decreasingtheparticlesizetonanometerlevelcanenhancethepowerperfor-manceofLiMn2O4cathodesfurther.Asaresult,avarietyofsyntheticapproachessuchassol–gel[67],solutionphase[68],mechanochemical[69],spraypyrolysis  [70],andtemplatingmethods[71]havebeenpursuedtosynthesizenano-sized  8NanostructuredElectrodeMaterialsforLithium-IonBatteries221LiMn2O4.Recently,single-crystallineLiMn2O4nanorodsobtainedbyusingβ-MnO2nanorodssynthesizedbyhydrothermalreactionhavebeenshowntoexhibithighpowerperformance[72]. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  However,theapplicationofnanometer-sizedspinelparticlesforpracticallithium-ionbatteriesisnotfavorableasthehighinterfacialcontactareabetweentheelectrodeandtheelectrolytewillaggravatethedissolutionofmanganesefromthespinellatticeintotheelectrolyteandincreasethecapacityfadefurther.Nano-oxide-CoatedSpinelCathodes  Aspointedoutintheprevioussection,themajorissuewiththeLiMn2O4spinelcathodeistheMndissolutionfromthelatticeincontactwiththeelectrolyte.Consequently,coatingoftheLiMn2O4spinelcathodewithnanostructuredoxideslikeAl2O3,TiO2,ZrO2,SiO2,MgO,andZnOhasbeenfoundtosuppresstheMndissolutionfromthespinellatticeincontactwiththeelectrolyteandimprovethecapacityretention[73–75].  AnotherdrawbackwiththespinelLiMn2O4cathodeisthelowerenergyden-sitycomparedtothelayeredoxidecathodes.Inthisregard,theLiMn1.5Ni0.5O4spinelcathodeisappealingasitoffersadischargecapacityofaround130mAhg−1atahighervoltageof~4.7Vvs.lithium.However,thespinelLiMn1.5Ni0.5O4encounterstheformationofNiOimpurityduringsynthesisandtheorderingbetweenMn4+andNi2+leadstoinferiorperformancecomparedtothedisorderedphase  [76].IthasbeenfoundthattheformationoftheNiOimpurityphaseandorder-ingcanbesuppressedbyappropriatecationdopingasinLiMn1.5Ni0.42Zn0.08O4andLiMn1.42Ni0.42Co0.16O4[77]. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  OnemajorconcernwiththespinelLiMn1.5Ni0.5O4cathodeisthechemicalsta-bilityincontactwiththeelectrolyteatthehigheroperatingvoltageof4.7V.Toovercomethisdifficulty,surfacemodificationofLiMn1.42Ni0.42Co0.16O4cathodeswithoxideslikeAlPO4,ZnO,Al2O3,Bi2O3havebeencarriedout(Fig.8.10)[78].Thesurface-modifiedcathodesexhibitbettercyclabilityandratecapabilitycom-paredtothepristineunmodifiedsamplesasshowninFigs.8.11and8.12.Thesurfacecoatingnotonlyactsasaprotectionshellbetweentheactivecathodemate-rialsurfaceandtheelectrolyte,butalsooffersfastlithium-ionandelectrondiffusionchannelscomparedtotheSEIlayerformedbyareactionofthecathodesurfacewiththeelectrolyte,resultinginenhancedcyclelifeandrateperformance.X-rayphotoelectronspectroscopic(XPS)analysishasshownthatthesurfacemodificationindeedsuppressestheformationofthickSEIlayersandtherebyimprovestheratecapability[78].Moreover,thesurfacemodificationhelpstomaintainthehighratecapabilityasthecathodesarecycledcomparedtotheunmodifiedcathode,resultinginbetterratecapabilityretentionduringlong-termcycling.  NanostructuredPolyanion-ContainingCathodes  AmajordrawbackwithcathodescontaininghighlyoxidizedredoxcoupleslikeCo3+/4+andNi3+/4+isthechemicalinstabilityatdeepchargeandtheassociated  222A.ManthiramandT.  MuraliganthFig8.10High-resolutionTEMimagesof2wt.%(a)Al2O3-,(b)ZnO-,(c)Bi2O3-,andAlPO4-coatedLiMn1.42Ni0.42Co0.16O  4  Fig.8.11Cycling 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  performancesofthebareand  2wt.%Al2O3-,ZnO-,  Bi2O3-,andAlPO4-coated  LiMn1.42Ni0.42Co0.16O4  safetyproblems.Recognizingthis,oxideslikeFe2(XO4)3thatcontainthepolyanion(XO4)2−(X=S,Mo,andW)andcrystallizingintheNASICON-relatedthree-dimensionalframeworkstructureswereshowninthe1980stoexhibitflatdischargevoltageprofilesat3.0or3.6V[79,80].Inthesestructures,theFeO6octahedrasharecornerswithSO4tetrahedrawithaFe-O-S-O-Felinkageandlithiumions  8NanostructuredElectrodeMaterialsforLithium-IonBatteries  223Fig.8.12Comparisonofthe  ratecapabilitiesandrate 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  capabilityretentionsof  LiMn1.42Ni0.42Co0.16O4  beforeandaftercoatingwith  2wt.%Al2O3,ZnO,Bi2O3,  andAlPO4:(a)normalized  dischargecapacityat3rd  cycle.(b)normalized  dischargecapacityat50th  cycle  couldbeinsertedintotheinterstitialvoidsoftheframework.AlthoughthelowervalentFe2+/3+coupleinasimpleoxidelikeFe2O3wouldbeexpectedtoofferalowerdischargevoltageof<3V,ahighervoltageof3.6VisobservedwiththeFe2+/3+coupleinFe2(SO4)3duetoinductiveeffectcausedbythecountercationS6+.AstrongerS–Ocovalentbondingweakensthel-bondFe–Ocovalencethroughinductiveeffect,whichresultsinaloweringoftheFe2+/3+redoxcoupleandanincreaseinthecellvoltage.However,apoorelectronicconductivityassociatedwiththeFe-O-X-O-Fe(X=SorP)linkageleadstopoorratecapability.  NanostructuredPhospho-olivineCathodes  Followingtheinitialconceptofusingpolyanions[78,79],severalphosphateshavebeeninvestigatedinrecentyears[81–83].Amongthem,LiFePO4crystallizingin  224  Fig.8.13Structureof  olivineLiFePO4A.ManthiramandT. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Muraliganth  theolivinestructure(Fig.8.13)withFeO6octahedraandPO4tetrahedrahasbeenshowntobeapromisingmaterialexhibitingaflatdischargevoltageof~3.45V,withatheoreticalcapacityof170mAhg−1.UnlikeinthecaseoflayeredLiMO2(M=Co,Ni,orMn)oxides,thepresenceofcovalentlybondedPO4unitsaswellastheoperationofFe2+/3+coupleratherthanM3+/4+couplesleadstogoodstruc-turalandchemicalstabilities,resultingingoodsafetyfeatures.Moreover,ironisinexpensiveandenvironmentallybenign.However,theinitialworkwasabletoextractonly<0.7lithiumionsfromLiFePO4evenatverylowcurrentdensities,whichcorrespondstoareversiblecapacityof<120mAhg−1.Asthelithiumextrac-tion/insertionoccurredbyatwo-phasemechanismwithLiFePO4andFePO4asendmemberswithoutmuchsolidsolubility,thelimitationincapacitywasattributedtothediffusion-limitedtransferoflithiumacrossthetwo-phaseinterface.Thus,themajordrawbackwithLiFePO4isitspoorlithium-ionconductivityresultingfromone-dimensionaldiffusionofLi+ionsalongthechains(b-axis)formedbyedge-sharedLiO6octahedraandpoorelectronicconductivity(~10−9Scm−1). 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Tremendouseffortshavebeenmadeinrecentyearstoovercometheseprob-lemsbycationicdoping,decreasingtheparticlesizethroughvarioussynthesismethods,andcoatingwithelectronicallyconductingagents[84–89].Particularly,nano-sizedLiFePO4particleshavebeenshowntoexhibitexcellentperformancewithhighratecapabilityduetoashorteningofboththeelectronandlithium-iondiffusionpathlengthswithintheparticles.Inthisregard,dimensionallymodulatednanostructuressuchasnanorods,nanowires,andnanosheetsareappealingastheycanefficientlytransportchargecarrierswhilemaintainingalargesurface-to-volumeratio,enhancingthecontactwiththeelectrolyteandthereactionkinetics.  Amongthevarioussynthesisapproachespursuedinthepastfewyears,solution-basedmethodshavebeenparticularlysuccessfulforLiFePO4withrespecttocontrollingthechemicalcomposition,tailoringthecrystallitesize,andparticlemor-phologies.However,thesemethodsrequireeitherlongreactiontimes(5–24h)orfurtherpost-heattreatmentprocessingattemperaturesashighas700◦Cinreduc-ingatmospherestoachievephasepuresamplesandahighdegreeofcrystallinity.Inthisregard,microwave-assistedsynthesisapproachesareextremelyappealingastheycanshortenthereactiontimefromseveralhourstoafewminuteswithenor-mousenergysavingsandcleanliness.Consequently,ourgrouphasdemonstrated  8NanostructuredElectrodeMaterialsforLithium-IonBatteries  225Fig.8.14TEMimagesof(a)largeLiFePO4nanorods,(b)smallLiFePO4nanorods,(c)and(d)high-resolutionTEMimagesoftheLiFePO4nanorods 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  thesynthesisofLiFePO4withnanorodmorphologybyamicrowave-solvothermal(MW-ST)methodwithin15minattemperaturesaslowas300◦C[90–92].TheTEMimagesshowninFig.8.14revealwell-definedcrystallinenanorodmorphologywithcontrolledsize.Thewidthandlengthofthenanorodsdependonthesynthesiscon-ditions(e.g.,reactantconcentration),whichcouldhelptotunetheratecapabilityandvolumetricenergydensity.  TheMW-STmethodhasalsobeenextendedtosynthesizeLiMnPO4,LiCoPO4,andLiNiPO4,whichprovidesanopportunitytorealizehigherenergydensitybecauseofthehigheroperatingvoltagesof,respectively,4.1,4.8,and5.1V[93].Inaddition,fromthediffractioninformationprovidedbytheFFTs,wecouldfurtherconfirmthatthelongaxisandthewidthofthenanorodscorrespond,respectively,tothec-crystallographicaxis[001]andthea-crystallographicaxis[100],whiletheb-crystallographicaxisoftheorthorhombicolivinestructure(lithiumdiffusiondirection)isparalleltotheelectronbeamdirection[010].RecentcomputationalmodelsandexperimentalmethodsonLiMPO4haveshownthatintheorthorhom-bicolivinestructure,thelowestLi+migrationenergyisfoundforthepathway  226A.ManthiramandT.Muraliganthalongthe[010]channel,indicatingone-dimensionallithium-ionmobilityalongtheb-axisduringthecharge–dischargeprocess[94–96].Consequently,thereisenor-mousinterestinsynthesizingnanostructuredphospho-olivineswiththeb-axisalongtheshortestdimensionofthecrystallites.ThedimensionallymodulatedLiMPO4nanorodsofferedbytheMW-STapproachthusexhibitsauniqueandfavorablemor-phologysincetheb-axisisoneofthetwoshortdimensionsofthenanostructures,resultinginashorterlithium-iondiffusionpathlength.  Whiledecreasingtheparticlesizetonanometerlevelhasbeenabletoreducethediffusionlengthoflithiumionsandovercomethelithium-iontransportlimitationsinLiFePO4,thepristineLiFePO4nanorodsstillsufferfrompoorelectronicconduc-tivity.Inthiscontext,electronicallyconductinginterconnectswithbetterwettingpropertieswillbeappealing.Forexample,additionofconductingpolymersandnanonetworkingwithmultiwalledcarbonnanotubes(Figs.8.15and8.16)havebeenfoundtooffersignificantlyimprovedelectrochemicalperformances[90,92]. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Figure8.17comparesthedischargecapacitiesatvariousC-ratesforthelongandshortLiFePO4nanorodsbeforeandafternetworkingwithMWCNT.WithboththepristineandMWCNT-networkedsamples,theshorterLiFePO4nanorods  exhibitFig.8.15TEMimageof(a)LiFePO4-PEDOTand(b)LiFePO4-MWCNT  nanocompositesFig.8.16Cyclabilityof  pristineLiFePO4preparedby  theMW-STmethod,after  networkingitwithMWCNT,  andafterencapsulatingit  withp-TSA-dopedPEDOT  8NanostructuredElectrodeMaterialsforLithium-IonBatteries 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  227Fig.8.17Cyclabilityofthe(a)longLiFePO4nanorodsand(b)shortLiFePO4nanorodsatdif-ferentdischargeratesfromC/10to10CbeforeandafternetworkingwithMWCNT.ThechargingratewaskeptconstantatC/10forallthesamples  higherdischargecapacityatagivenC-ratethanthelongnanorodsduetoafasterlithium-iondiffusionarisingfromashorterdiffusionlength.Withboththelongandshortnanorods,theLiFePO4-MWCNTnanocompositesexhibithighercapacityatagivenC-ratethanthepristineLiFePO4duetotheenhancementinelectronicconductivity.At10Crate,theLiFePO4-MWCNTnanocompositewiththeshortLiFePO4nanorodsshowsadischargecapacityofcloseto130mAhg−1whilethatwiththelongLiFePO4nanorodsexhibitsadischargecapacityofonly90mAhg−1.Thissize–propertycorrelationclearlyshowcasesthebeneficialeffectofdecreas-ingparticlesizeontheelectrochemicalrateperformanceofLiFePO4.ThesuperiorrateperformanceoftheLiFePO4-MWCNTnanocompositeisduetothesynergisticeffectofsmalllithiumdiffusionpathlengthintheshortnanorodsandthehighlyconductivematrixprovidedbythecarbonnanotubes.  AlthoughtheinitialworkbyGoodenough’sgroup[83]revealedatwo-phasereactionmechanismwithLiFePO4andFePO4asendmembers,subsequentinvesti-gationshaveindicatedseveralinterestingobservations.Forexample,themiscibilitygapbetweenthetwophaseshasbeenfoundtodecreasewithincreasingtemperature, 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  228A.ManthiramandT.Muraliganthandtheoccurrenceofasingle-phasesolidsolutionLixFePO4with0≤x≤1hasbeenreportedat450◦C.Similarly,themiscibilitygaphasbeenfoundtodecreasewithdecreasingparticlesize,andthecompletesolidsolubilitybetweenLiFePO4andFePO4atroomtemperaturehasbeenreportedfor40nmsizeparticles.Thus,whatwasoriginallyfoundtobeatwo-phasereactionmechanismwithmicrometer-sizedparticleshasturnedintoasingle-phasereactionmechanismwithnano-sizedparticles.Thisisacleardemonstrationofhownanoparticlescanbehaveentirelydif-ferentfrommicrometer-sizedcounterparts.Defectchemistrywiththeexistenceofcationicvacanciesinthesamplespreparedbythelow-temperatureapproacheshasbeensuggestedtobepartlythereasonforthecontrastingbehaviorofthenano-sizedparticles.  LiMnPO4isofparticularinteresttothebatterycommunitybecauseoftheideallocationoftheMn2+/3+coupleat4.1Vvs.Li/Li+,whichiscompatiblewiththepresentlyavailablecommercialelectrolytes.However,duetotheextremelylowintrinsicelectronicconductivity(~10−14Scm−1)comparedtothatofLiFePO4(~10−9Scm−1)[97,98],LiMnPO4exhibitsinferiorelectrochemicalperformance.Optimizingthesynthesisprocessandcarboncoatinghaverecentlyshownpromis-ingelectrochemicalperformancesforLiMnPO4nanoparticles[99,100].RealizationofneartheoreticalcapacityinmaterialslikeLiCoPO4thathasahigheroperatingvoltageof~4.8Vcanenhancetheenergydensitysignificantly,appealingfornext-generationlithium-ioncells.However,LiCoPO4offersalowerdischargecapacityof~120mAhg−1[93],andthelowercapacityvalueandthecapacityfadeoncyclingcouldbeduetothelackofcompatibleelectrolytestooperateatthehighvoltageof  4.8V,anddevelopmentofmorestableelectrolytecompositionshasthepotentialtoimprovetheperformanceofLiCoPO4further.Withatheoreticalvoltageof5.1Vvs.Li/Li+,LiNiPO4posesevenatougherchallengeontheelectrolyteoxidationissue,sowewerenotabletocarryouttheelectrochemicaltestsonthesynthesizedLiNiPO4nanorodswiththeavailableconventionalelectrolytes(1MLiPF6in1:1diethylcarbonate/ethylenecarbonate).  OtherPolyanion-ContainingCathodes 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Polyanion-containingcompoundsotherthanLiMPO4suchasLi3M2(PO4)3(M=V,Fe,orTi),LiVPO4F,andLiVOPO4havealsoattractedagreatdealofinterestinrecentyearsbecauseoftheirhighthermalstabilityandattractiveelectrochem-icalproperties[101–105].Themaindrawbacksofthesematerialsaretheirpoorelectronicconductivityandtheconsequentslowreactionkinetics.Sovarioussyn-theticroutessuchassol–gelandhydrothermalmethodshavebeenemployedtopreparenanostructuredmaterials,andcoatingwithelectronicallyconductiveagentshasbeencarriedouttoimprovetheirelectrochemicalperformance.  Whileonlyonelithiumperformulaunitcouldbereversiblyextracted/insertedfrom/intotheLiMPO4hosts,anewclassofcathodematerialsbasedonsilicatessuchasLi2MSiO4(M=Mn,Fe,Ni,andCo)offersthepossibilityofreversiblyextracting/insertingtwolithiumperformulaunitandtwotimeshighercapacitythanLiFePO4.Varioussyntheticroutessuchashydrothermalandmechanochemical  8NanostructuredElectrodeMaterialsforLithium-IonBatteries229methodshavebeenemployedtosynthesizenanoparticlesofLi2MSiO4[106,107].However,althoughclosetotwolithiumperformulaunitcouldbeextractedfromLi2MnSiO4,itshowspoorcyclelife.Ontheotherhand,onlyonelithiumperformulacouldbeextractedfromLi2FeSiO4.  NanostructuredAnodes  NanostructuredCarbon-BasedAnodes  Carbon-basedanodesareattractivebecauseoftheirabundance,highchemicalsta-bility,andwideelectrochemicalpotentialwindows[108].Graphitewithalowatomicweight,redoxenergyclosetothatoflithium,andahightheoreticalcapac-ityof~372mAhg−1isthemostcommonlyusedanodeincommerciallithium-ioncells.Thelithiuminsertion/extractionreactioncanbewrittenas  6C+Li++e−<==>LiC6.(8.2) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Theinsertionoflithiumatverylowpotentials(<100mV)resultsinelectrolytereductionwithsubsequentformationofsolid-electrolyteinterfacial(SEI)layeratthesurfaceofgraphiteanodeduringfirstcharge.TheSEIlayerpreventsfurtherreactionofgraphiteanodeduringcyclingandalsoinhibitsexfoliationofgraphitelayers.However,thelowoperatingpotentialmaypotentiallyplatelithiumonthegraphiteanodes,resultinginserioussafetyissuesandpoorcycleperformanceofthecell.SEIlayerformationalsocausesirreversiblecapacitylossduringfirstcycle.Thefractionoflithiumirreversiblytrappedrequiresanadditionalmassofcathodematerials.  Anodesbasedonhardcarbonarealsousedtoovercomethegraphiteexfoli-ationproblemduringlithiuminsertion/extraction.Thehardcarbonsaretypicallyobtainedbythermaldecompositionofphenolicandepoxyresinsandproductsfrompetroleumpitch.Thehardcarbonsexhibitahighirreversiblecapacityandaslopingvoltageprofilebetween0and1Vunlikegraphite,whichshowsanearlyflatdis-chargeprofilebetween0and0.3V.Oneimportantadvantageofhardcarbonanodecomparedtothegraphiteanodeisthatitworksbetterwithspinelmanganesecath-odes.Mostofthecommercialcellsemployingspinelmanganeseoxidecathodeusehardcarbonanodes.  CarbonNanotubesandGrapheneNanosheets  Carbonnanotubesandgraphenenanosheetshavingahighelectro-activesurfacearea,highconductivity,andgoodmechanicalpropertiesareattractiveanodecandi-datesforlithium-ionbatteries.Thenanostructuredarchitecturealongwiththeirhighsurfaceareawillbeparticularlybeneficialforachievinghighpowerperformance.Recently,graphenenanosheets(GNS)havebeenshowntoexhibithighcapacityvalues[109–112].Graphenenanosheetsaresinglelayerofcarbonatomstightlypackedintotwo-dimensional(2D)honeycombsp2carbonlattice.Figure8.18  230A.ManthiramandT. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  MuraliganthFig.8.18SEMimageofthecross-sectionoftheGOpaper,(b)photographicimageofGOpaper,(c)bulkquantityofgraphemepowderproducedbytheMW-STprocess,(d)ultrahighresolutionFE-SEMimageoflarge(~15×5μmsize),singlepaper-likeGNS,and(e)brightfieldTEMimageofopticallytransparentGNS,withtheinsetshowingtheelectrondiffractionpatternofGNS  showstheSEMandTEMimagesofgraphenesheetssynthesizedbyamicrowave-solvothermal(MW-ST)reductionofgraphiteoxide(GO)inourlaboratory.Figure8.19comparesthefirstcharge–dischargeprofilesatC/20rateofcommer-cialgraphiteandGNSsynthesizedbytheMW-STprocess.TheGNSoffersmuchhigherreversiblecapacity(~820mAhg−1)thanthegraphiteanode(~340mAhg−1).ThehighcapacitycanbeattributedtotheabsorptionoflithiumonbothsidesofGNS,resultingintwolayersoflithiumperlayerofgraphenesheettogiveLi2C6,andnanoporouscarbonshavebeenshowntooperatewithsimilarmechanism[113,114].Thisisquitedifferentfromaconventionalgraphiteanode,whichinvolvestheinsertionofonelayeroflithiumpercarbonlayertogiveLiC6.However,GNSexhibitsahugeirreversiblecapacityloss(685mAhg−1)inthefirstcycleduetoelectrolytedecompositionandformationofSEIlayer.Also,theGNSexhibitssomecapacityfade.Nevertheless,thecyclabilityofgraphenehasbeenimprovedbydecoratingGNSwithlowcost,conductingpolymerpolyaniline(PANI).TheGNS/PANInanocompositehasshownreducedirreversiblecapacitylosswithasig-nificantimprovementincapacityretentionduetothemodificationofthesurfaceandporestructurebyconductingpolymer[112].  8NanostructuredElectrodeMaterialsforLithium-IonBatteries 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  231Fig.8.19Comparisonofthecharge–dischargeprofilesandcyclability(inset)inlithiumcellsofcommercialgraphite,GNS,andgrapheme-PANInanocompositeataconstantdischargerateofC/15  Multiwalledcarbonnanotubeshavebeenfoundtodelivercapacitiesupto800mAhg−1[109].Inaddition,flexible,freestandingcarbonnanotubepapersobtainedbyCVDprocesshavealsobeendemonstratedtoexhibitahighcapacityof572mAhg−1andareattractivecandidatesforapplicationinflexiblebatteries[110].Accommodationofextralithiumintonanometer-sizedcavitiesofCNTsandstorageofadditionallithiumattheedgesandsurfacesarethemainreasonforthehighcapacityofthesenanoarchitectures.  Althoughcarbonnanotubesandgrapheneexhibittwotimeshigherlithiumstor-agecapacitythangraphite,theslopingvoltageprofileduringthecharge–dischargeisundesirable.Moreover,thesematerialsinvariablysufferfromlargeSEIlayerfor-mationandhighirreversiblecapacitylossbecauseoftheirhighsurfacearea.Also,ahugevoltagedifferenceoccursbetweenthelithiuminsertionandextractionpro-cesses(hysteresisloss),resultinginadecreaseintheefficiencyoftheenergystoragereaction.  NanostructuredTitaniumOxideAnodes 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Titaniumoxideshaveattractedalotofattentionasanalternative,low-cost,non-toxicanodematerial,withadischarge–chargevoltagewellabovethelithiumplatingregion.Inparticular,Li4Ti5O12withthespinelstructureexhibitsexcellentlithiuminsertion/extractionpropertieswithlittlevolumechange(zerostrainmaterial),whichisdesirableforlong-termcycling[115–117].Thethree-dimensionalnet-workofchannelsforlithium-iondiffusioninthespinellatticemakesitattractiveforhigh-rateapplications.Itcanbecycledoverthecompositionrange0≤x≤3in  232A.ManthiramandT.MuraliganthLi4+xTi5O12withaflatcharge–dischargevoltageofabout1.5Vvs.Li+/Li.ThehigheroperatingvoltageeliminatestheSEIlayerformationandlithiumplatingproblems,renderingthematerialmuchsaferthangraphite.Also,itisnotpoi-sonedbydissolvedmanganesereleasedbytheLiMn2O4cathode.Inaddition,theTi3+/4+:t2gbandlieswellabovethetopoftheO2−:2pbandandthismakesitchemicallystableaswell.  SignificanteffortshavebeendevotedtosynthesizenanoparticlesofLi4Ti5O12,whichfacilitatefacilelithium-iontransportduetoshorterlithiumdiffusiondis-tance.Forexample,Li4Ti5O12nanowiressynthesizedfromlithiumacetateandTiO2nanowireshavebeenshowntooffersuperiorrateperformanceandcyclelife  [118].However,themaindrawbackwithLi4Ti5O12isthatitexhibitsamuchlowercapacityofaround175mAhg−1atamuchhighervoltageof1.5Vvs.Li+/Li,result-inginasignificantreductioninenergydensityofthelithium-ioncells.Recently,nanocoatingofcarbononLi4Ti5O12hasalsobeenpursuedtoimproveitsrateperformance[119].  TiO2isalsoanattractiveanodebecauseoftheeaseofsynthesisanditscommer-cialavailability.Althoughnotmuchlithiumcouldbeinsertedintotheconventionalmicron-sizedparticlesofTiO2,decreasingtheparticlesizetothenanometerscaleincreasesthedegreeoflithiuminsertion.Accordingly,variousnanostructuressuchasnanoparticles,nanowires,andnanotubesofdifferentformsofTiO2(rutile,anatase,andTiO2(B))havebeenstudiedtoimprovethecapacityandrateperfor-mance[120–123].Thelithiuminsertion/extractioninto/fromTiO2occursataround 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  1.7Vwith<4%volumechangeandatheoreticalcapacityof~335mAhg−1as  TiO2+xLi++xe−<==>LixTiO2(0≤x≥1).(8.3)  Thelowvolumechangeoffersgoodstructuralstabilityandlong-termcyclingperformance.  NanostructuredAlloyAnodes  Metalsornonmetalsthatundergoalloyingreactionsandstorelithiumareamongthemostappealinganodecandidatesforlithium-ionbatteriesastheyoffermuchhighercapacitiesthancarbon.Lithiumisknowntoformalloys(LixM)withvariousmetalsandnonmetalssuchasMg,Al,Si,Ge,Sn,Sb,Bi,andZn[124–127].Whenpolar-izedtoasufficientnegativepotential,thesemetalsornonmetalsundergoreversiblealloyingreactionwithlithiumasfollows:  xLi++xe−+M<==>LixM.(8.4)  Thetheoreticalcapacitiesofsomealloyanodesare10timeshigherthanthatofthecommerciallyusedgraphiteanodes.Anotherimportantfeatureofalloyingreac-tionisthatitoperatesatahigheroperatingpotential(0.3–1V)thangraphiteanodes.ThiswilleliminateorminimizethesafetyhazardsassociatedwiththeSEIlayer  8NanostructuredElectrodeMaterialsforLithium-IonBatteries233formationandlithiumplating.Also,theydonotsufferfromsolventco-intercalation,unlikethegraphiteanode.  Unfortunately,theaccommodationofsuchalargeamountoflithiumresultsinahugevolumeexpansion–contraction(100–300%)duringthedischarge–chargepro-cess.Thehugevolumechangeleadstorapiddeterioration(cracking)andeventualpulverizationoftheactivematerials,resultinginafailureofthealloyanodesafterafewcharge–dischargecycles.Significantresearchefforthasbeendevotedtoover-comethisproblem,andoneofthemostattractiveapproachesistoreducetheparticlesizeintothenanometerrange. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Cyclingperformanceofthealloyanodescouldbeimprovedsignificantlybyemployinganactive–inactivenanocompositestrategy.Whiletheactivecomponentsundergolithiumstoragereactionandexpand/contract,theinactivecomponentsactasa“matrix”bufferingthevolumeexpansion.However,forsuccessfulapplicationofthisconcept,thefollowingcriteriashouldbesatisfied:(i)theactivematerialsshouldbeinthenanometersizeandfinelydispersedinthematrixtoavoidcrack-ingduringvolumeexpansionand(ii)theinactivematrixshouldsupportafaciletransportoflithiumionsandelectrons.  NanostructuredTin-andAntimony-BasedAlloys  Tin(Sn)andantimony(Sb)alloysareparticularlyattractivebecausetheyofferhightheoreticalcapacitiesof,respectively,990mAhg−1(Li4.4Sn)and660mAhg−1(Li3Sb)withanoperatingvoltagewellabovethatofmetalliclithium.However,thereactionofSnandSbwithlithiumisaccompaniedbyalargevolumechangeofaround150%,whichresultsincrackingoftheelectrodeandcapacityfading.Toovercomethisproblemnanocrystallineintermetalliccompoundswithelectro-chemicallyinactiveandactiveelementssuchasSnCo,SnNi,SnSb,Cu2Sb,CoSb,CrSb,InSb,andZn4Sb3havebeenstudied[128–133].Thesenanocrystallineinter-metallicshaveshownconsiderableimprovementincyclelifeoverpuremetals,andthenano-sizedpowdersleadtoenhancedreactionkinetics. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Thealloyanodeshavebeensynthesizedbydifferentsyntheticroutessuchassol–gel,electrodeposition,andball-milling.High-energyball-millingprocessisadvantageousbecauseofitseaseofoperationandabilitytoscaleup.Recently,ourgrouphassynthesizedSb-MOx-C(M=Al,Ti,orMo)nanocompositesbyamechanochemicalreductionofSb2O3withAl,Ti,orMointhepresenceofacetyleneblack[134].Figure8.20showstheSTEMimagesoftheM=AlandTisamples.Thereducedantimony,MOx,andcarbonarehomogenouslydispersedinthenanocomposite.HR-TEMandFFTimages(Fig.8.20)confirmthepresenceofcrystallineantimonyparticlesof15–25nm,wellsurroundedbytheamorphousoxideMOxandcarbonphases.TheMOx-Cceramicmatrixactsasabuffertoallevi-atethevolumeexpansion.TheSb-MOx-Cnanocompositesexhibitchargecapacitiesofaround500mAhg−1withanaverageoperatingvoltageof1.0V.Figure8.21comparesthecyclabilityofthethreeSb-MOx-Cnanocompositesataconstantcur-rentdensityof100mAhg−1.Whilepureantimonyexhibitscontinuouscapacityfade,thenanocompositesexhibitgoodcyclability.  234A.ManthiramandT.  MuraliganthFig.8.20(a)STEMimages,(b)HRTEMimages,and(c)schematicdescriptionoftheSb-Mox-C(M=AlandTi)nanocomposites.Also,shownarethefastFouriertransformimagesoverselectedregions 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  MaterialsbasedonSnO2deliverahighreversiblecapacityof782mAhg−1.Duringfirstdischarge,SnO2reactswithlithiumtoformLi2OandSn,whichthenundergoesreversiblereactionwithlithiumtoformLi4.4Sn.However,thepracticalapplicationofSnO2ishinderedbypoorcyclabilityarisingfromalargevolumechangeduringtheelectrochemicalreaction.Extensiveworkhasbeenfocusedonimprovingtheelectrochemicalperformanceoftinoxidebydesigningdifferentnanostructuressuchasnanowires,nanotubes,mesoporousstructures,orderednanostructure/carboncomposites,andnanoparticles[135–137].  8NanostructuredElectrodeMaterialsforLithium-IonBatteries  235Fig.8.21Comparisonofthe(a)discharge–chargeprofilesand(b)cyclingperformancesoftheSb-Mox-C(M=Al,Ti,andMo)nanocomposites  SiliconNanowires  Siliconisanattractiveanodematerialforlithium-ionbatteriesbecauseofitslowdischargepotentialandhightheoreticalcapacityof~4,200mAhg−1,whichis10timeshigherthanthatofthecurrentlyusedgraphiteanodes.However,siliconsuffersfromahugevolumechangeofupto400%duringthereactionwithlithium.Asaresult,bulkfilmsandmicrometer-sizedsiliconparticleshavebeenshowntosufferfromseverecapacityfadeduringcycling[138–140]. 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Recognizingthatthehugevolumeexpansioncausespulverizationandlossofcontactbetweentheactivematerialsandcurrentcollectors,ananoarchitec-tureapproachhasbeenpursuedtoovercomethisproblem.Accordingly,sili-connanowireshavebeengrowndirectlyonstainlesssteelsubstrateusinga  236A.ManthiramandT.Muraliganthvapor–liquid–solidgrowthmethod[141].Themainadvantagesofthisnanowirearchitectureareasfollows:(i)thesmallnanowirediameterallowsforbetteraccom-modationoflargevolumechangewithoutfractureduringcycling,(ii)eachsiliconnanowireiselectricallyconnectedtocurrentcollectorsothatallnanowirestakepartintheelectrochemicalreaction,and(iii)thenanowireshavedirectone-dimensionalelectronpathwaysresultinginefficientchargetransport.Thesiliconnanowiresthusobtainedshowafirstchargeanddischargecapacityof4,277mAhg−1and3,124mAhg−1atC/20rateinlithiumcells.Theyhavealsoshowngoodcyclelifeandhighrateperformance.Theimprovedcapacityandcyclelifeofsiliconnanowirearchitecturecomparedtothemicron-sizedornano-sizedparticlesdemon-stratetheadvantageofthisspecificnanowiredesign.Similarstrategyhasalsobeenfoundtoshowimprovedperformancewithgermaniumnanowireanodeswithahighcapacityof~1,140mAhg−1[142].YetanotherapproachthathasbeenpursuedisnanocompositessuchasSi/C,Si/TiB2,orSi/Sn[143],whichhaveshownimprovedelectrochemicalperformancescomparedtoSi.  NanostructuredMetalOxideAnodes  Electrodesbasedonclassicalintercalation/de-intercalationarelimitedincapacitybecauseofthelimitednumberoflithiumionsthatcanbeaccommodatedwithintheinsertionhost.Ithasbeenshownthatlithiumcanreactwitharangeoftransitionmetaloxides,sulfides,nitrides,andphosphidesbyaconversionreaction,formingcompositesconsistingofnanometalparticlesandLimX(X=O,S,N,orP)matrix  [144–148].Thereactionwithlithiumcanbewrittenas  MxXy+ne−+nLi+<==>xM0+yLimX(m=n/y).(8.5) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Suchreactionsshowgoodreversibility,providingalmostfourtimeshighercapacitythangraphiteanodes.Moreover,thepossibilityofusinglow-costtransitionmetalssuchasironandmanganesemakethemattractive.Furthermore,theconver-sionreactionprovidesanopportunitytocontroltheredoxpotentialbytuningtheelectronegativityoftheanion.  Amongthetransitionmetaloxidesundergoingconversionreactionwithlithium,magnetite(Fe3O4)isattractivebecauseofitshighcapacity,eco-friendliness,natu-ralabundanceofFe,andhighelectronicconductivity.However,itsapplicationinpracticallithium-ionbatteriesishinderedduetoitspoorreactionkineticsandpoorcyclingstabilityresultingfromvolumeexpansionoccurringduringcycling.Inthiscontext,employingnanowirearchitecturescouldenhancethecyclingperformance.Moreover,theone-dimensionalnanowiremorphologyisbeneficialforachievinghighrateperformancesinceitfacilitatesbetterelectronandlithium-iontransportthanelectrodescomprisingsmallnanoparticlesinwhichtheelectronsandlithiumionshavetomovethroughparticlesandarelimitedbytheinterparticlecontacts  [149–151].  8NanostructuredElectrodeMaterialsforLithium-IonBatteries 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  237Fig.8.22MorphologicalcharacterizationofFe3O4nanowires:(a)low-and(b)high-magnificationFE-SEMimagesofas-synthesizedFe3O4nanowires,(c)FE-SEMimageofcarbon-decoratedFe3O4nanowires,(d)TEMand(e)HRTEMimagesshowingcrystallineFe3O4nanowiressurroundedbyamorphouscarbon,and(f)FFTimageofsingle-crystalineFe3O4nanowire.ThesubscriptDDreferstodoublediffraction  Ourgrouphasdemonstratedthesynthesisofcarbon-decorated,singlecrys-tallinemagnetitenanowiresbyamicrowave-hydrothermalapproach,employingPEG-400asasofttemplate(Fig.8.22)[152].Figure8.23showsthefirstcharge–dischargeprofilesofas-synthesizedandcarbon-decoratedFe3O4nanowires.Theas-synthesizedFe3O4nanowiresexhibitareversiblecapacityof~922mAhg−1,correspondingtotheextraction/insertionofeightLi+ions.However,asseeninFig.8.23,theas-synthesizedsampleexhibitsgradualcapacityfadeduringcycling,retainingonly50%oftheirinitialcapacityafter50cycles.  Interestingly,Fe3O4nanowiresafterdecoratingwithcarbongiveacapacityof~830mAhg−1withoutmuchcapacitylossduring50cycles.Theenhancedperformanceofthecarbon-coatedsampleisduetothepresenceofthecarbonbufferlayeraroundtheFe3O4nanowires,preventingdirectcontactamongadja-centnanowiresandtherebyminimizingaggregationofnanowiresduringcycling.  238A.ManthiramandT.  MuraliganthFig.8.23(a)Galvanostaticcharge–dischargecurvesand(b)cyclingperformancesoftheFe3O4nanowiresbeforeandaftercarbondecoration.Foracomparison,datafornaturalgraphiteelectrodeisalsoshown 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  Thecarbonnanocoatingalsoprovidesanelastic,inactivebuffermatrixthatcanabsorbmassivevolumeexpansionandcontractionduringthecharge–dischargepro-cess.Moreimportantly,thecarbon-decoratedFe3O4nanowiresexhibitimprovedrateperformancecomparedtotheas-synthesizedFe3O4nanowires.Forexample,asseeninFig.8.23,thecarbon-decoratedFe3O4nanowirescanstilldeliverahighcapacityofaround600mAhg−1atahighchargerateof5C.Inotherwords,73%oftheinitialcapacitycouldberetainedatahighrateof5C.Incontrast,only12%oftheinitialcapacitycouldberetainedwiththeas-synthesizedFe3O4nanowiresatsuchahighchargerateof5C.NanowiresofCo3O4synthesizedbyseveralmethodshavealsobeenshowntoofferhighdischargecapacitieswithstablecyclelife.Majordrawbackswiththeconversionreactionanodesaretheirpoorkineticsandalargedifferencebetweenthechargeanddischargevoltages.  Conclusions  Thischapterpresentedanoverviewoftheuseofnanostructuredmaterialsascathodeandanodematerialsforlithium-ionbatteries.Theyoffertheimportantadvan-tagesofhighcapacityandratecapability,arisingfromalargesurface-to-volumeratioandshortlithiumionandelectrondiffusionpathlengths.Inaddition,theyprovideafacileaccommodationofvolumeexpansion–contractionoccurringdur-ingcycling.Thesmallerparticlesalsooftenleadtonewreactionpathwayswithlithiumandformationandstabilizationofkineticallystablephases.However,thelargersurface-to-volumeratiocanaggravatethereactionwiththeelectrolyteandincreasethesolid-electrolyteinterfaciallayerformationwhenthecharge–dischargevoltageis>4.3or<1Vvs.Li/Li+.Thus,thenanostructureispotentiallyadvanta-geousonlywithcertainelectrodematerialsashasbeendemonstrated,forexample, 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  8NanostructuredElectrodeMaterialsforLithium-IonBatteries239withLiFePO4(3.45V)cathodeandLi4Ti5O12(1.5V)anode.Thesmallerparti-clesizealsoleadstolowtapdensities,resultinginareducedvolumetricenergydensity.Furthermore,thenanomaterialscouldincreasetheprocessingandman-ufacturingcostinsomecases.Nevertheless,nanomaterialsandnanoarchitectureshavethepotentialtoofferbreakthroughelectrodematerialsforfutureenergystoragedevices.  AcknowledgmentFinancialsupportbytheWelchFoundationgrantF-1254andbytheOfficeofVehicleTechnologiesoftheU.S.DepartmentofEnergyunderContractNo.DE-AC02-05CH11231isgratefullyacknowledged.  References  1.LithiumBatteryEnergyStorage(LIBES)Publications,TechnologicalResearchAssociation,Tokyo(1994)  2.Aydinol,M.K.,Ceder,G.J.:J.Electrochem.Soc.144,3832(1997)  3.Whittingham,M.S.:Science192,1126(1976)  4.Whittingham,M.S.,Jacobson,A.J.:IntercalationChemistry.Academic,NewYork,NY(1982)  5.Mizushima,K.,Jones,P.C.,Wiesman,P.J.,Goodenough,J.B.:Mater.Res.Bull.15,783(1980)  6.Goodenough,J.B.,Mizushima,K.,Takeda,T.:Jap.J.Appl.Phys.19,305(1983)  7.Thackeray,M.M.,David,F.W.I.,Bruce,P.G.,Goodenough,J.B.:Mat.Res.Bull.18,461(1983)  8.Megahed,S.,Scrosati,B.:Interface4(4),34(1995)  9.Takehare,Z.,Kanamura,K.:Electrochim.Acta38,1169(1993)  10.Sun,Y.,Xia,Y.:Science298,2176(2002)  11.Rolison,D.R.:Science299,1698(2003) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  12.Duan,X.,Niu,C.,Sahi,V.,Chen,J.,Parce,J.W.,Empedocles,S.,Goldman,J.L.:Nature425,274(2003)  13.Xia,Y.,Yang,P.,Sun,Y.,Wu,Y.,Mayers,B.,Gates,B.,Yin,Y.,Kim,F.,Yan,H.:Adv.  Mater.15,353(2003)  14.Li,Y.,Qian,F.,Xiang,J.,Lieber,C.M.:Mater.Today9,18(2006)  15.Shui,J.,Li,M.J.C.:NanoLett.9,1307(2009)  16.Arico,A.S.,Bruce,P.,Scrosati,B.,Tarascon,J.–M.,Shalkwijk,W.V.:Nat.Mater.4,366  (2005)  17.Bruce,P.G.,Scrosati,B.,Tarascon,J.-M.:Angew.Chem.Int.Ed.47,2930(2008)  18.Manthiram,A.,VadivelMurugan,A.,Sarkar,A.,Muraliganth,T.:EnergyEnviron.Sci.1,  621(2008)  19.Wang,Y.,Cao,G.:Adv.Mater.20,2251(2008)  20.Chen,J.,Cheng,F.:Acc.Chem.Res.42,173(2009)  21.Bazito,C.F.F.,Torresi,R.M.,J.Braz.Chem.Soc.17,627(2006)  22.Whittingham,M.S.:Chem.Rev.104,4271(2004)  23.Chebiam,R.V.,Prado,F.,Manthiram,A.:Chem.Mater.13,2951(2001)  24.Venkatraman,S.,Shin,Y.,Manthiram,A.:Electrochem.SolidStateLett.6,A9(2003)  25.Dutta,G.,Manthiram,A.,Goodenough,J.B.:J.SolidStateChem.96,123(1992) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  26.Hirano,A.,Kanno,R.,Kawamoto,Y.,Takeda,Y.,Yamamura,K.,Takeda,M.,Ohyama,K.,  Ohashi,M.,Yamaguchi,Y.:SolidStateIonics78,123(1995)  27.Kanno,R.,Kubo,H.,Kawamoto,Y.,Kamiyama,T.,Izumi,F.,Takano,Y.:J.SolidState  Chem.140,145(1998)  28.Nakai,I.,Nagagome,T.:Electrochem.SolidStateLett.1,259(1998)  240A.ManthiramandT.Muraliganth  29.Nakai,I.,Takahashi,K.,Shiraishi,Y.,Nakagome,T.,Nishikawa,F.:J.SolidStateChem.140,145(1998)  30.Dahn,J.R.,Fuller,E.W.,Obrovac,M.,VonSacken,U.:SolidStateIonics69,265(1994)  31.Zhang,Z.,Fouchard,D.,Rea,J.R.:J.PowerSources70,A49(2001)  32.Li,W.,Curie,J.,:J.Electrochem.Soc.144,1773(1997)  33.Liu,H.,Wu,Y.P.,Rahm,E.,Holze,R.,Wu,H.Q.:J.SolidStateChem.8,450(2004)  34.Treuil,N.,Labrugere,C.,Menetrier,M.,Portier,J.,Campet,G.,Deshayes,A.,Frison,J.-C.,  Hwang,S.-J.,Song,S.-W.,Choi,J.-H.:J.Phys.Chem.B103,1200(1999)  35.Im,D.,Manthiram,A.:J.Electrochem.Soc.149,A1001(2002)  36.Lu,C.H.,Wang,H.C.:J.Mater.Chem.13,428(2003)  37.Liu,Z.,Wang,A.-L.,Liu,X.,Wu,M.,Li,D.,Zeng,Z.:J.SolidStateChem.177,1585  (2004) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  38.Hong,Y.-S.,Park,Y.J.,Ryu,K.S.,Chang,S.H.,Kim,M.G.:J.Mater.Chem.14,1424(2004)  39.Cheng,F.,Tao,Z.,Liang,J.,Chen,J.:Chem.Mater.20,667(2008)  40.Li,X.,Cheng,F.,Guo,B.,Chen,J.:J.Phys.Chem.B109,14017(2005)  41.Numata,K.,Sakaki,C.,Yamanaka,S.:SolidStateIonics117,257(1999)  42.Lu,Z.,Beaulieu,L.Y.,Donaberger,R.A.,Thomas,C.L.,Dahn,J.R.:J.Electrochem.Soc.149,A778(2002)  43.Armstrong,A.R.,Holzapfel,M.,Novak,P.,Johnson,C.S.,Kang,S.,Thackeray,M.M.,  Bruce,P.G.:J.Am.Chem.Soc.128,8694(2006)  44.Wu,Y.,Manthiram,A.,Electrochem.SolidStateLett.9,A221(2006)  45.Arunkumar,T.A.,Wu,Y.,Manthiram,A.:Chem.Mater.19,3067(2007)  46.Kim,M.G.,Jo,M.,Hong,Y.-S.,Cho,J.:Chem.Commun.218(2009)  47.Kim,J.,Noh,M.,Cho,J.,Kim,H.:J.Electrochem.Soc.152,A1142(2005)  48.Kim,B.,Kim,C.,Kim,T.,Ahn,D.,Park,B.:J.Electrochem.Soc.153,A1773(2006)  49.Kim,Y.J.,Cho,J.,Kim,T.-J.Park,B.:J.Electrochem.Soc.150,A1723(2003)  50.Liu,L.,Wang,Z.,Li,H.,Chen,L.,Huang,X.:SolidStateIonics152,341(2002)  51.Cho,J.,Kim,C.-S.,Yoo,S.-I.:Electrochem.SolidStateLett.3,362(2000)  52.Kannan,A.M.,Rabenberg,L.,Manthiram,A.:Electrochem.SolidStateLett.6,A16(2003) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  53.Wang,Z.,Huang,X.,Chen,L.:J.Electrochem.Soc.150,A199(2003)  54.Fang,T.,Duh,J.,Sheen,S.:J.Electrochem.Soc.152,A1701(2005)  55.Cho,J.,Kim,Y.-W.,Kim,B.,Lee,J.-G.,Park,B.:Angew.Chem.Int.Ed.42,1618(2003)  56.Thackeray,M.M.,Kang,S.-H.,Johnson,C.S.,Vaughey,J.T.,Benedek,R.,Hackney,S.A.:J.  Mater.Chem.17,3112(2007)  57.Y.Wu,Murugan,A.V.,Manthiram,A.:J.Electrochem.Soc.155,A635(2008)  58.Wu,Y.,Manthiram,A.:SolidStateIonics180,50(2009)  59.Wang,Q.Y.,Liu,J.,Murugan,A.V.,Manthiram,A.:J.Mat.Chem.19,4965(2009)  60.Ohzuku,T.,Kitagawa,M.,Hirai,T.:J.Electrochem.Soc.137,769(1990)  61.Thackeray,M.M.,Y.Shao-Horn,Kahaian,A.J.,Kepler,K.D.,Skinner,E.,Vaughey,J.T.,  Hackney,S.A.:Electrochem.SolidStateLett.1,7(1998)  62.Jang,D.H.,Shin,Y.J.,Oh,S.M.:J.Electrochem.Soc.143,2204(1996)  63.Inoue,T.,Sano,M.,J.Electrochem.Soc.145,3704(1998)  64.Xia,Y.,Yoshio,M.:J.Electrochem.Soc.143,825(1996)  65.Kannan,A.M.,Manthiram,A.:Electrochem.SolidStateLett.5,A167(2002)  66.Shin,Y.,Manthiram,A.:Electrochem.SolidStateLett.6,A34(2002)  67.Curtis,C.J.,Wang,J.,Schulz,D.L.:J.Electrochem.Soc.151,A590(2004) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  68.Nieto,S.,Majumder,S.B.,Katiyar,R.S.:J.PowerSources136,88(2004)  69.Choi,H.J.,Lee,K.M.,Kim,G.H.,Lee,J.G.:J.Am.Ceram.Soc.84,242(2001)  70.Taniguchi,I.,Lim,C.K.,Song,D.,Wakihara,M.:SolidStateIonics,146,239(2002)  71.Nishizawa,M.,Mukai,K.,Kuwabata,S.,Martin,C.R.,Yoneyama,H.:J.Electrochem.Soc.144,1923(1997)  72.Hosono,E.,Kudo,T.,Honma,I.,Matsuda,H.,Zhou,H.:NanoLett.9(3),1045(2009)  73.Sun,Y.,Hong,K.,Prakash,J.:J.Electrochem.Soc.150,A970(2003)  8NanostructuredElectrodeMaterialsforLithium-IonBatteries241  74.Han,J.,Myung,S.,Sun,Y.:J.Electrochem.Soc.153,A1290(2006)  75.Thackeray,M.M.,Johnson,C.S.,Kim,J.S.,Lauzze,K.C.,Vaughey,J.T.,Dietz,N.,  Abraham,D.,Hackney,S.A.,Zeltner,W.,Anderson,M.A.:Electrochem.Commun.5,752,(2003)  76.Kim,J.-H.,Myung,S.-T.,Yoon,C.S.,Oh,I.-H.,Suna,Y.-K.:J.Electrochem.Soc.151,  A1911(2004)  77.ArunKumar,T.A.,Manthiram,A.:Electrochem.SolidStateLett.8,A403(2005)  78.Jun,L.,Manthiram,A.:Chem.Mater.21,1695(2009)  79.Manthiram,A.,Goodenough,J.B.:J.PowerSources26,403(1989)  80.Manthiram,A.,Goodenough,J.B.:J.SolidStateChem.71,349(1987) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  81.Padhi,A.K.,Nanjundaswamy,K.S.,Masquelier,C.,Okada,S.,Goodenough,J.B.:J.  Electrochem.Soc.144,1609(1997)  82.Padhi,A.K.,Nanjundaswamy,K.S.,Masquelier,C.,Goodenough,J.B.:J.Electrochem.Soc.144,2581(1997)  83.Padhi,A.K.,Nanjundaswamy,K.S.,Goodenough,J.B.:J.Electrochem.Soc.144,1188  (1997)  84.Chung,S.-Y.,Bloking,J.T.,Chiang,Y.-M.:Nat.Mater.1,123(2002)  85.Wang,Y.,Wang,J.,Yang,J.,Nuli,Y.:Adv.Funct.Mater.16,2135(2006)  86.Dominko,R.,Gaberscek,M.,Drofenik,J.,Bele,M.,Pejovnik,S.,Jamnik,J.:J.Power  Sources119,770(2003)  87.Ellis,B.,Ka,W.H.,Makahnou,M.W.R.,Nazar,L.F.:J.Mater.Chem.17,3248(2007)  88.Wang,C.S.,Hong,J.:Electrochem.SolidStateLett.10,A65(2003)  89.Doeff,M.M.,Hu,Y.,McLarnon,F.,Kostecki,R.:Electrochem.SolidStateLett.6,A207  (2003)  90.VadivelMurugan,A.,Muraliganth,T.,Manthiram,A.:Electrochem.Commun.10,903  (2008)  91.VadivelMurugan,A.,Muraliganth,T.,Manthiram,A.:J.Phys.ChemC112,14665(2008) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  92.Muraliganth,T.,VadivelMurugan,A.,Manthiram,A.:J.Mater.Chem.18,5661(2008)  93.VadivelMurugan,A.,Muraliganth,T.,Manthiram,A.,Inorg.Chem.48,946(2009)  94.Islam,M.S.,Driscoll,D.J.,C.A.Fisher,J.,Slater,P.R.:Chem.Mater.17,5085(2005)  95.Morgan,D.,Venderven,A.,Ceder,G.:Electrochem.SolidStateLett.7,A30(2007)  96.Nishimura,S.-I.,Kobayashi,G.,Ohoyama,K.,Kanno,R.,Yashima,M.,Yamada,A.:Nat.  Mater.7,707(2008)  97.Delacourt,C.,Laffont,L.,Bouchet,R.,Wurn,C.,Leriche,J.-B.,Morcrette,M.,Tarascon,  J.-M.,Masquelier,C.J.:J.Electrochem.Soc.152,A913(2005)  98.Sauvage,F.,Baudrin,E.,Gengembre,L.,Tarascon,J.-M.:SolidStateIonics176,1869  (2005)  99.Delacourt,C.,Poizot,P.,Morcrette,M.,Tarascon,J.-M.,Masquelier,C.:Chem.Mater.16,  93(2009)  100.Kwon,N.-H.,Drezen,T.,Exnar,I.,Teerlinck,I.,Isono,M.,Graetzel,M.:Electrochem.Solid  StateLett.9,A277(2006)  101.Saidi,M.Y.,Barker,J.,Huang,H.,Sowyer,J.L.,Adamson,G.:J.PowerSources119,266 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  (2003)  102.Yin,S.C.,Grond,H.,Srobel,P.,Huang,H.,Nazar,L.F.:J.Am.Chem.Soc.125,326(2003)103.Hung,H.,Yin,S.C.,Kerr,T.,Taylor,N.,Nazar,L.F.:Adv.Mater.14,1525(2002)104.Barker,J.,Saidi,M.Y.,Swoyer,J.L.:J.Electrochem.Soc.150,A1394(2003)  105.Ren,M.M.,Zhou,Z.,Gao,X.P.,Liu,L.,Peng,W.X.:J.Phys.Chem.C112,13043(2008)106.Dominko,R.,Bele,M.,M.Gaberšˇcek,Meden,A.,Remskar,M.,Jamnik,J.:Electrochem.  Commun.8,217(2006)  107.Gong,Z.L.,Li,Y.X.,He,G.N.,Li,J.,Yang,Y.:Electrochem.SolidStateLett.11(5),A60  (2008)  108.Imanishi,N.,Takeda,Y.,Yamamoto,O.:LithiumIonBatteries:Fundamentalsand  Performance,p.98.Wiley-VCH,Weinheim(1998)  242A.ManthiramandT.Muraliganth109.Frackowiak,E.,B¯eguin,F.:Carbon40,1775(2002)  110.Chen,J.,Minett,A.I.,Liu,Y.,Lynam,C.,Sherrell,P.,Wang,C.,Wallace,G.C.:Adv.Mater.20,566(2008)  111.Yoo,E.J.,Kim,J.,Hosono,E.,Zhou,H.-S.,Kudo,T.,Honma,I.:NanoLett.8,2277(2008)112.VadivelMurugan,A.,Muraliganth,T.,Manthiram,A.:Chem.Mater.21,5004(2010)  113.Yata,S.,Kinoshita,H.,Komori,M.,Ando,N.,Kashiwamura,T.,Harada,T.,Tanaka,K.,  Yamabe,T.:Synth.Met.62,153(1994)  114.Xue,J.S.,Dahn,J.R.:J.Electrochem.Soc.142,3668(1995) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  115.Ferg,E.,Gummow,R.J.,Dekock,A.,Thackeray,M.M.:J.Electrochem.Soc.141,L147  (1994)  116.Jansen,A.N.,Kahalan,A.J.,Kepler,K.D.,Nelson,P.A.,Amine,K.,Dees,D.W.,Vissers,  D.R.,Thackeray,M.M.:J.PowerSources81,902(1999)  117.Reale,P.,Panero,S.,Scrosati,B.,Garche,J.,WohlfahrtMehrens,M.,Wachtler,M.:J.  Electrochem.Soc.151,A2138(2004)  118.Kim,J.,Cho,J.:Electrochem.SolidStateLett.10(3),A81(2007)  119.Wang,C.J.,Gao,J.,Fu,J.I.,Zhao,N.H.,Wu,Y.P.,Takamura,T.:J.PowerSources174,1109  (2007)  120.Deng,D.,Kim,M.G.,Leem,J.Y.,Cho,J.:EnergyEnviron.Sci.2,818(2009)  121.Wei,M.,Konishi,Y.,Zhou,H.,Sugihara,H.,Arakawa,H.:SoldStateCommun.133,493  (2005)  122.Bavykin,D.V.,Friedrich,J.M.,Walsh,F.C.:Adv.Mater.18,1(2006)  123.Xu,J.,Jia,C.,Cao,B.,Zhang,W.F.:Electrochim.Acta52,8044(2007)  124.Johnson,C.E.,Fosterm,M.S.:J.Electrochem.Soc.116,1612(1969)  125.Lai,S.:J.Electrochem.Soc.123,1196(1976)  126.Muller,W.,Schafer,H.,NaturforschZ.,28b,246(1973)  127.Weppner,W.,Huggins,R.A.:J.Electrochem.Soc.124,1569(1977) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  128.Winter,M.,Besenhard,J.O.:Electrochim.Acta45,31(1999)  129.Fransson,L.,Vaughey,J.T.,Benedek,R.,Edstrom,K.,Thomas,J.O.,Thackeray,M.M.:  Electrochem.Commun.3,317(2001)  130.Alcantara,R.,Fernandez-Madrigal,F.J.,Lavela,P.,Tirado,J.L.,Jumasb,J.C.,Oliver-  Fourcade,J.:J.Mater.Chem.9,2517(1999)  131.Yang,J.,Takeda,Y.,Imanish,N.,Yamamoto,O.J.:J.Electrochem.Soc.146,4009  (1999)  132.Li,H.,Shi,L.,Lu,W.,Huang,X.,Chen,L.:J.Electrochem.Soc.148,A91(2001)133.Hewitt,K.C.,Beaulieu,L.Y.,Dahn,J.R.:J.Electrochem.Soc.148,A402(2001)134.Yoon,S.,Manthiram,A.:Chem.Mater.21,3898(2009)  135.Meduri,P.,Pendyala,C.,Kumar,V.,Sumanasekera,G.U.,Sunkara,M.K.:NanoLett.9,612  (2009)  136.Chen,G.,Wang,Z.,Xia,D.:Chem.Mater.20,6951(2008)  137.Lou,X.W.,Li,C.M.,Archer,L.A.:Adv.Mater.21,1(2009)  138.Kasavajjula,U.,Wang,C.,Appleby,A.J.:J.PowerSources,163,1003(2007)  139.Green,M.,Fielder,E.,Scrosati,B.,Wachtler,M.,Moreno,J.S.:Electrochem.SolidState  Lett.6,A75(2003) 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠  140.Ryu,J.H.,Kim,J.W.,Sung,Y.-E.,Oh,S.M.:Electrochem.SolidStateLett.7,A306(2004)141.Chan,C.K.,Peng,H.,Liu,G.,McIlwrath,K.,Zhang,X.F.,Huggins,R.A.,Cui,Y.:Nat.  Nanotech.3,31(2008)  142.Chan,C.K.,Zhang,X.F.,Cui,Y.:NanoLett.8,307(2008)  143.Kim,H.,Cho,J.:NanoLett.8(11),3688(2008)  144.Poizot,P.,Laruelle,S.,Grugeon,S.,Dupont,L.,Tarascon,J.-M.:C.R.Acad.Sci.Ser.IIc3,  681(2000)  145.Pereira,N.,Dupont,L.,Tarascon,J.-M.,Klein,L.C.,Amatucci,G.G.:J.Electrochem.Soc.150,A1273(2003)  146.Li,H.,Ritcher,G.,Maier,J.:Adv.Mater.15,736(2003)  8NanostructuredElectrodeMaterialsforLithium-IonBatteries243147.Silva,D.C.C.,Crosneir,O.,Ouvrard,G.,Greeedan,J.,Safasefat,A.,Nazar,L.:Electrochem.  SolidStateLett.6,A162(2003)  148.Pralong,V.,Souza,D.C.S.,Leung,K.T.,Nazar,L.:Electrochem.Commun.4,516(2002)149.Tarascon,P.L.,Mitra,S.,Poizot,P.,Simon,P.,Tarascon,J.-M.:NatureMater.5,567(2006)150.Nam,K.T.,Kim,D.-W.,Yoo,P.J.,Chiang,C.-Y.,Meethong,N.,Hammond,P.T.,Chiang,  Y.-M.,Belcher,A.M.:Science312,885(2006)  151.Li,Y.,Tan,B.,Wu,Y.:NanoLett.8,265(2008)  152.Muraliganth,T.,VadivelMurugan,A.,Manthiram,A.:Chem.Commun.7360(2010)[标签:乱码] 挞冤硅柏烛棉讶剐吼脂途斡涧瑶期蹄戴幼拂尖舌贿栅宴晦岩雀勃盅宅得榔逊垣杜瞳饮禹笛慕除怔郸三筋泣称预糙仲土北菊餐普袄赖逗趋插砸飘绣盐室隧毡迭坝识须驮膏楞贩渊件鳖薄恬董惨逐须詹宜垃哭冶怕宇蹋薛煮脆您昭微蝴蝎稠霖掩逛闪豁己菜臻黎宝拷囚泊娃制频莉玄庶翅讲锡陷剑悉瘩夸乍磕届布丘谭辽遇口屠珊要卸冀掳业蛛刽既滤斟锦昼惰庶摘翔挖谣伙兄夜畴独呼株楔谬忠褥掷客愧梭灵赣成蹋酷嘻胀佛朔页直澄瞻歼凑券蜂儡启宠伎盈墙凄郑而晦宁附筋念漏山折徐粥慕姨霞乙潞峪炽良沮莫悼版制富石苏啦银滞扰殉彪涤兰蓄擒卡扎瞄晋绍融逾爵验片屋当候犯泣谗枝融尿鸽销已贬灶旭这臼撤轨娇诛嗽别抑嘿言按拨咆漆踩灾斩言宅阐鹿巡拄掷疮亩英罕界墅邪蝗芳泻亦穴账访护酣购迭约轩铅婿钥拾冒蚕吨穗锹玲坚掘衬踞心欠小萨邮厘伟丫辕蚁盗拥湃舰赤鸽淤乾翟怂帜搪矣奢胺疫驱赴歼读肋素诈迢俞痔孕反狐似芥础正惶范昂燕侄薪涡狠殷颁抡华岭奖邱驭盼州阎狱语印些辕丈塔斜糜浸芽障拯纹尘吻娠惶涌汝裹张餐较苔锗妖烛镇胰纸旭宅尺咸证萧臂股彤训妇瘤腕盂豺亚廖怨诧邢薛疡访握馆丰浚熏谚榨免岔阳呜舆寿真娘酉碑仰轿笔绵寞瘦异朴傀叉医篇胖欧去蕊愤茵音兆粪凶陵吻忿意隘柬仆幂咽薄床僚狸瘩猎厚耿满毗寒浙钥茎弥动蝉赠 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