高比容量锂离子电池正极材料NCA的制备及性能

NCA121212121.3003872.300387LiNi0.80Co0.15Al0.05O2NCA.、SEM、XRD1∶1.05800℃10~20h180mAh/gNCA.；TM911TQ150.1O646A1671-024X201703-0044-05SynthesisandperformanceofNCAasahighspecificcapacitycathodematerialforlithium-ionbatteriesFUWei-gui12QIRan12PANJing12CHENLi121.SchoolofMaterialScienceandEngineeringTianjinPolytechnicUniversityTianjin300387China2.StatekeyLaboratoryofSeparationMembranesandMembraneProcessesTianjinPolytechnicUniversityTianjin300387ChinaAbstractInordetofindhighspecificcapacitymaterial，highspecificcapacityLiNi0.80Co0.15Al0.05O2NCAmaterialsasthecathodeforlithiumionbatteriesweresynthesizedbyutilizingdifferentmethod.ThesizedistributionSEMXRDandelectrochemicaltestsresultsshowthattheprecursorswithuniformsizedistributionaresynthesizedusingcoprecipitationmethod.Afterwashinganddryingtheprecursorsaremixedwithlithiumhydroxideataratioof1∶1.05thencalcinedat800℃for10-20handnaturalcooling.TheuniformparticlesizeofNCAmaterialwithhighspecificcapacity180mAh/gandotherexcellentperformanceisobtained.KeywordshighspecificcapacityLi-ionbatteriescathodematerialco-precipitationmethod2016-12-23513031321980—[e-mail]ECHNICUNIVERSITY36320176Vol.36No.3June2017DOI10.3969/j.issn.1671-024x.2017.03.009[1-2].1991[3-5].、、、.LiCoO2、LiMn2O4LiFePO4[6-13].LiCoO2a-NaFeO2、、、[14].Co、.LiNiO2LiCoO2274mAh/g.CoNiLiNi1-xCoxO2LiNiO2LiCoO2、.[815-21].LiNi0.8Co0.15Al0.05O2NCA278mAh/g3.、[22-23].NCA、、[24-31].NCA.11.11.1NiSO4·6H2O、CoSO4·H2O、AlSO4·6H2O、、Na2CO3、super-P、NMP、AlfaAesarpoly-viny-lidenefluoridePVDF、AldrichCelgard.SEMJEOLJSM-6701F10kVMS2000XXRDPhilipsPW3710CuKαradiationRigakuD/max2500ArbinBT2000ArbinAu－tolabPG302N.1.2NCANCA2mol/LNiSO4·6H2OCoSO4·7H2OAlSO4·6H2OANi∶Co∶Al0.80∶0.15∶0.052mol/LNa2CO3B0.2mol/LAB5L60℃pH8.10800r/min.、2~3100℃48hNi0.8Co0.15Al0.05CO30.95OH0.15.LiOH·H2O1∶1.05450℃6h800℃15hNCA.1.3NCA1.2Ni0.8Co0.15CO30.90OH0.150.05LiOH·H2O1∶1.05450℃6h800℃15hNCA[26].1.4NCA、super-PNMPPVDF8∶1∶180℃8h1.0cm1cm23~5mg.0.1×10-6NCACelgard23001mol/LLiPF6EC/DMC/DEC1∶1∶12032.3.0~4.3V0.1C1C=200mAh/g50.5C.1.5SEMJEOLJSM-6701F10kV。MS2000。XXRDPhilipsPW3710CuKαradiationRigakuD/max2500。ArbinArbinBT20003.0~4.3Vvs.Li+/Li。CVAutolabPG302N3.0~4.3VLi+/Li0.1mV/s.21NCASEM.1a1bNCANCA.1a.1b7~10μm1cD10=8.93μmD50=12.4μmD90=17.0μm10%8.93μmNCA45——36aNCASEM2520151050/%1010.10.011000/μm100cbNCASEM1NCASEMFig.1SEMimageandsizedistributionofNCA50%12.4μm90%17.0μm.1NCA.1Ni、Co、Al、ONi∶Co∶Al=0.77∶0.15∶0.08LiNi0.77Co0.15Al0.08O2.1.2NCANCAXRD.2750℃800℃NCAα-NaFeO2R3m.750℃20°~35°c/aac1.800℃NCAc/a4.951.20.NCA800℃.3NCANCA.3aLi2CO3LiOH800℃NCA.LiOH178mAh/g82%Li2CO3154mAh/g5160mAh/g3b.3b0.1C50.5C0.5C252NCA40302010702θ/°508060113018/110107015104006/012101003750℃17h800℃17h1NCATab.1ElementcompositionandratioofNCAmaterial/%AlK0.08CoK0.15NiK0.772750℃800℃NCAXRDFig.2XRDpartternsofNCApreparedat750℃and800℃respectively4.54.03.53.02.5/V150100500250/mAh·g-1200Li2CO3LiOHa0.1C1250200150100500/mAh·g-11510503020Li2CO3LiOH253NCA0.1CFig.3Charge-dischargecurvesat0.1CandcyclingperformanceofNCAmaterialsb0.1C-5-0.5C-3046——399.0%LiOH0.5C153mAh/gLi2CO3140mAh/g.Li2CO3LiOH.LiOHLiOH.LiOHNCA3CV4.2.8~4.3V0.1mV/s.4233LiOH.3NCA、.NCA.NCA.1∶1.05800℃10~20h180mAh/gNCA.NCA、NCA.[1]NITTANWUFLEEJTetal.Li-ionbatterymaterialsPresentandfuture[J].MaterialsToday2015185252-264.[2]GOODENOUGHJBPARKKS.TheLi-ionrechargeablebatteryAperspective[J].JournaloftheAmericanChemicalSociety201313541167-1176.[3]ETACHERIVMAROMRELAZARIRetal.ChallengesinthedevelopmentofadvancedLi-ionbatteriesareview[J].En－ergy&EnvironmentalScience2011493243-3262.[4]TARASCONJMARMANDM.Issuesandchallengesfacingrechargeablelithiumbatteries[J].Nature20014146861359-367.[5]DUNNBKAMATHHTARASCONJM.ElectricalenergystorageforthegridAbatteryofchoices[J].Science20113346058928-935.[6]OHZUKUTUEDAANAGAYAMAMetal.ComparativestudyofLiCoO2LiNi12Co12O2andLiNiO2for4voltsecondarylithiumcells[J].ElectrochimicaActa19933891159-1167.[7]TARASCONJMWANGESHOKOOHIFKetal.ThespinelphaseofLiMn2O4asacathodeinsecondarylithiumcells[J].JournaloftheElectrochemicalSociety1991138102859-2864.[8]BARBOUXPTARASCONJMSHOKOOHIFK.Theuseofacetatesasprecursorsforthelow-temperaturesynthesisofLiMn2O4andLiCoO2intercalationcompounds[J].JournalofSolidStateChemistry1991941185-196.[9]THACKERAYMMJOHNSONPJDEPICCIOTTOLAetal.ElectrochemicalextractionoflithiumfromLiMn2O4[J].MaterialsResearchBulletin1984192179-187.[10]HSUKFTSAYSYHWANGBJ.Synthesisandcharacteri－zationofnano-sizedLiFePO4cathodematerialspreparedbyacitricacid-basedsol-gelroute[J].JournalofMaterialsChem－istry200414172690-2695.[11].4[J].2008221045-49.LIAOWMDAIYNYAOYCetal.Theeffectof4speciesofcathodematerialtotheperformanceoflithiumionbatteriesandtheirdevelopmenttendency[J].MaterialsReview2008221045-49inChinese.[12]JANGDHSHINYJOHSM.Dissolutionofspineloxidesandcapacitylossesin4VLi/LixMn2O4coils[J].JournaloftheElectrochemicalSociety199614372204-2211.[13]YANPXIAOLZHENGJetal.ProbingthedegradationmechanismofLi2MnO3cathodeforli-ionbatteries[J].ChemistryofMaterials2015273975-982.[14]ANTOLINIE.LiCoO2Formationstructurelithiumandoxy－gennonstoichiometryelectroc