锂硫电池关键材料研究进展与展望

232/320113PROGRESSINCHEMISTRYVol.23No.2/3Mar.2011201011201012*[e-mail]*361005。10。。10、、、。O646TM912.9A1005-281X201102/3-0533-07ResearchProgressandProspectsofLithiumSulfurBatteriesDongQuanfeng*WangChongZhengMingsenStateKeyLabofPhysicalChemistryofSolidSurfacesDepartmentofChemistryCollegeofChemistryandChemicalEngineeringXiamenUniversityXiamen361005ChinaAbstractLithiumsulfurbatteryisahighcapacityenergystoragesystemwithverybrightfutureanditisconsideredasthenextgenerationportableenergysupplydeviceforelectronicvehicleEVandhybridvehicleHEV.Throughdecadesofresearchanddevelopmentpeopleunderstandthissystemstepwisely.Theelectrochemistryofsulfurcathodeisverycomplexandhardtobeexaminedwhichisthekeypointtodeveloplithiumsulfurbattery.Althoughtherearemanyunknownmechanismsintheelectrochemicalprocessofcharge/dischargeofthelithiumsulfurbatterysomeachievementshavebeenmadeonthedevelopmentofcathodematerialswhichprovidevarioussourcestostudy.Sulfurisaninsulatingmolecularcrystalcarbonisaddedastheadditivereagenttoimprovetheelectricconductivityinthecathodesulfur/carboncompositeiscommonascathodeactivematerialinlithiumsulfurbattery.Ethersandpolymersareemployedasthecomponentsoftheelectrolytestocoordinatewithsulfurcathode.Thispaperreviewstheachievementsonlithiumsulfurbatteryinthepastdecadefromtherespectsoflithiumsulfurbatterysystemcathodematerialselectrolytescathodestructureandnewsystemsbasedonlithiumsulfurbattery.Theweaknessesarerevealedandthefutureisprospected.KeywordslithiumsulfurbatterycathodematerialscompositematerialselectrochemicalpropertyContents1Introduction2Lithiumsulfurbatterysystem3Cathodematerialoflithiumsulfurbattery3.1Organicsulfides3.2Sulfur/carboncomposite4Electrolytesforlithiumsulfurbattery5Cathodestructureforlithiumsulfurbattery6Newsystembasedonlithiumsulfurbattery·534·237Issuesandperspectives1。2000990mAh·g－1。、LiFePO4LiMn2O4200mAh·g－11。、。“conversionreaction”2。S21685mAh·g－1LiFePO410。20603。708045Licht1993Al/S62006SionPowerZephyr7。10、、、、、、、。89。10。、、。2-/。“”“”。-Li2SLi2S。10。1“”“”23He10411512。。。20Sxy－x=1—10y=0—2。。Levillain13。S8c+2e幑幐帯帯－S812－1S8幑幐帯帯2－S4－2S8幑幐帯帯2－S62－+18S83S4－+e幑幐帯帯－S42－4S82－+S4幑幐帯帯2－2S62－5S2－幑幐帯帯6S3－6S3－+e幑幐帯帯－S32－71、4、72、2/3·535·3、56。LevillainS8－/S82－S4－/S42－S3－/S32－。1CV。CV3。S32－562mAh·g－1。1CV0.2mV·s－11.5—3.0VFig.1ThetypicalCVcurveofsulfurcathodescanrate0.2mV·s－1scanrange1.5—3.0V2100mA·g－11.5—3.0VFig.2Thetypicaldischargeprofileofalithiumsulfurbatterycurrentdensity100mA·g－1votalgerange1.5—3.0VWhite14Li2S2Li2SLi2S2100%。Kolosnitsyn89Li2S15。2。Mikhaylik516。S62－+2S3幑幐帯帯2－3S42－8S42－+2e幑幐帯帯－S22－93。。10/。3.1S—S。、。S—CS。2005。171。3.2/S—C。。。Choi50%18。、19。·536·231Table1Thestructureandperformanceofvariousorgano-sulfides20。“”21。。22、23、24、25、、26、2728。、、。。、3。29。。、、/。。Wang300℃86%50mA·g－11300mAh·g－130。3132。。3、。3、/Fig.3Theschemeofthesulfur/carboncompositespreparedbythreedifferentmethodsballmillingthermotreatingandwetmethod85%。41000mA·g－1981mAh·g－130400mAh·g－133。“”“”2。“”。21、28、34、35。。21283435S1300mAh·g－1。。2/3·537·485%S/MWCNTs1000mA·g－11.5—3.0VFig.4Thecyclicprofileof85%sulfurcontentS/MWCNTscompositeat1000mA·g－1voltagerange1.5—3.0V/。。50.2C1107.1mAh·g－130800mAh·g－1。“”。。5/0.2C300mA·g－11.5—3.0VFig.5Thecyclicprofileofcarbonxerogel/sulfurcompositeat0.2Crate300mA·g－1voltagerange1.5—3.0V4123456、、。、“”11。。PEOPEO60℃2036。HayashiLi2S-P2S5700mAh·g－11.5V。“”。。EC、DMC、EMC37。。13-DOLCH2OCH2DGM。DOLDOL。DOLDGM。DGMTEGDME。。38—40。Kim、DME∶DGM∶DOL=4∶4∶241。Choi42。Li2S43。·538·2344。5Kim19。N-NMP。NMP。。PEO“”LA“”LA45。。。46—49。6。。。50。“”“”。Ren。ScrosatiHassounLi2S“”。/Li2SPEO0.05C0.2—4VLi2S/C600mAh·g－135400mAh·g－151。CuiLi2S“”1.1—2.6VC/8146mA·g－1482mAh·g－1630Wh·kg－152。Zhang857mAh·g－153。710。。/、、。、、。。。1ScrosatiBGarcheJ.J.PowerSources201019592419—24302ArmandM.TarasconJMNature20084517179652—6573SelisSMWondowskiJPJustusRF.JournaloftheElectrochemicalSociety196411116—132/3·539·4RauhRDAbrahamKMPearsonGFSurprenantJKBrummerSB.JournaloftheElectrochemicalSociety19791264523—5275YaminHPeledE.J.PowerSources198393/4281—2876PeramunageDLichtS.Science199326151241029—10327NothAEngelMWSiegwardR.IEEERobot.Autom.Mag.200613344—528PiHBWangCXWangJHWuXM.BatteryBimonthly2009392113—1159ZhangYWuXBZhangAQWangLZ.BatteryBimonthly2008384257—25910HeXMRenJGWangLPuWHJiangCYWanCR.JournalofPowerSources20091901154—15611MikhaylikYVAkridgeJR.JournaloftheElectrochemicalSociety200415111A1969—A197612RyuHSGuoZPAhnHJChoGBLiuHK.JournalofPowerSources200918921179—118313LevillainEDemortierALelieurJP.EncyclopediaofElectrochemistry20067a253255—27114KumaresanKMikhaylikYWhiteRE.JournaloftheElectrochemicalSociety20081558A576—A58215KolosnitsynVSKarasevaEVAminevaNABatyrshinaGA.Russ.J.Electrochem.2002383329—33116MikhaylikYVAkridgeJR.J.Electrochem.Soc.20031503A306—A31117SunWNYingJRHuangZLJiangCYWanCR.Prog.Chem.20092191963—196818ChoiYSKimSChoiSSHanJSKimJDJeonSEJungBH.ElectrochimicaActa2004502/3833—83519KimNILeeCBSeoJMLeeWJRohYB.JournalofPowerSources20041321/2209—21220ShimJStriebelKACairnsEJ.J.Electrochem.Soc.200214910A1321—A132521JiXLLeeKTNazarLF.NatureMaterials200986500—50622ZhangBChenSTGaoXP.El