壳结构锰酸锂正极材料制备及电化学性能分析-preparation and electrochemical performance analysis of lithium manganate cathode material with shell structure.docxVIP

AbstractSpinelLiMn2O4iscurrentlyoneofthemostpromisingcathodematerialsforLIBsbecauseofitslowcost,abundantMnresourcesandenvironmentalfriendliness.Unfortunately,thewidepracticaluseofthespinelelectrodehasbeenhinderedbyatleasttwoissues:oneismanganesedissolution,especiallywhenoperatingattemperaturesaboveambient,e.g.,above40°C,causedbythepresenceofacidsolutionandtheJahn–Tellereffect,leadingtorapiddecreaseofstoragecapacity;theothercomesfromthelowpowerdensityduetoalargepolarizationathighcurrentdensities,resultingfromsluggishLi+iondiffusioninthebulkmaterials.Inthisthesis,ahollowmicro-/nano-hybridstructuresandcoated-modifiedstrategieshavebeenconsideredtoovercomethesedrawbacksinLiMn2O4.Fourdifferentstructurespinel-phaseLiMn2O4materialswerepreparedbyone-stepsolidstatemethod.ThenthestructuralandphysicalchemistrypropertiesofthesespinelLiMn2O4cathodematerialswerediscussed.Resultsshowedthatthehollowstructuremicrospheres,whichused2hpre-calcinationMnO2asprecursor,exhibitabestratecapabilityandstability,duehollowmicro-/nano-hybridstructurescouldincreasethesurfacearea,lessenthecompoundedinternalstresses,andpreventnanoparticlesfromagglomerating.Tosolvetheproblemofmanganesedissolution,anovelcore-shellLiMn2O4@Li4Ti5O12hollowmicrosphereshavebeendesignedandsynthesizedusing2hpre-calcinationMnO2asprecursor.TheoutershellLi4Ti5O12wasasuccessfulshieldforinnershellLiMn2O4,avoidingthedirectlycontactofLiMn2O4withtheelectrolyte,theneffectivelydepressingthedissolutionofMn-ionandsuppressingthechangeofcrystalstructureofinnershellLiMn2O4.Hence,theuniquecore-shellhollowmicrospheresstructurecouldprovidesuperiorratecapacityandgoodcyclingstability.WhenvaluedascathodematerialsforLIBs,theproductexhibitahighcapacityretention(90%)after55cyclesat0.5rateandsuperiorratecapacity,90mAhg-1at2Crate.However,theLi4Ti5O12surfacemodificationsdecreasedthequalityoftheactivesubstance.Toachieveahigh-energy-densitycapabilityLiMn2O4,aactivematerialLiNi0.5Mn1.5O4hasbeenconsideredastheshieldlayer.Andanefficientroutetopreparedouble-