文档名：共溶剂作用下锌沉积界面行为
摘要：电解液共溶剂改性方法是一种调控金属锌负极沉积的有效方式.本文以添加四乙二醇二甲醚(TEGDME)为共溶剂的硫酸锌电解液体系为研究对象,通过准原位原子力显微镜(AFM),原位石英晶体微天平(E-QCM)和原位阻抗时域分析(EIS-DRT)对共溶剂化作用对金属锌负极沉积行为的影响进行了多尺度详细研究.首次从微观角度揭示了共溶剂可以通过影响双电层结构,稳定局域电场来调控金属锌的沉积行为.该工作为后续共溶剂体系的开发和水系锌离子电池的机理解析提供了一种全新的研究思路和研究角度.
Abstract：IntroductionAqueouszinc-ionbatteryisconsideredasoneofthemostpromisingcandidatesforlarge-scaleenergystoragedeviceduetoitslowcost,highsafetyandrecyclability.Comparedwithotheralkali-basedbatteries,zinc-basedbatteriescanrealizeenergystoragethrough2-electronchargetransferdeliveringahighspecificcapacity(820mA?h/g)andlowprice.However,theexistingdevelopmentofzinc-ionbatteryisfarfromcommercialization.Mainchallengesexhibitinthreeaspects,i.e.,aseriousdendriteeffectcausedbytheunevendepositionofzincionsinthebattery;uncontrollablewater-inducedparasiticreactionssuchashydrogenevolutionreaction(HER)inacidicelectrolyte;andmetalcorrosionandirreversiblesidereactionsonsurfaceofanode.Thesechallengesresultinalowcoulombicefficiency,ashortencyclelifeofbatteryandevenserioussecurityrisks.Inordertosolvetheshortcomingsofzincanode,somemethods(i.e.,zincanodestructuremodification,electrolyteoptimizationandartificialinterfacelayer(SEI)construction)aredeveloped.Amongthem,atunningelectrolyteisadirectivemethodtoavoidnegativesidereactionsandinhibitthedendritegrowth.Electrolytemodificationcanrealizealong-cycle-lifezincanodeandahighefficientbattery.Inthispaper,tetraethyleneglycoldimethylether(TEGDME)wasaddedintoZnSO4basedelectrolyteassco-solventtoinvestigatetheplating/strippingbehaviorofZnmetal.Thereactionmechanismofco-solvationeffectfrommulti-scalewasanalyzed.MethodsAllreagentswithanalyticalpuritywereusedwithoutanytreatment.Forthepreparationofbareelectrolyte,2.87gofZnSO4·7H2Owasdissolvedinto10mLdistilledwatertoprepare1mol/LZnSO4electrolyte.Forthepreparationofco-solventelectrolyte,2.87gofdriedlithiumbistrifluoromethylsulfonate(LITFSI)wasdissolvedinto10mLdehydratedtetraethyleneglycoldimethylether(TEGDME)inanargongloveboxunderstirringforovernight.Thefinalconcentrationwascontrolledto1mol/LLITFSI/TEGDME.Amixedelectrolytewaspreparedviadissolving5mLaqueousZnSO4electrolyte,3mLofLITFSI/TEGDMEelectrolyte,and2mLofdistilledwater.Themixturewasstirredatroomtemperaturefor2h,andthenagedfor12htoobtainthefinalelectrolyte.Themonitoringduringcharge/dischargeprocesswascarriedoutonamodelEQCM-Dinstrument(AWS,A-20,Spain).Inthisexperiment,a12mmdiametertitanium-goldquartzwaferwasusedasacathode,andahighpurityzincfoilwasusedasananode.Theamountofelectrolytewas2mL.Beforethemeasurement,thecellwasactiveatalowcurrentdensity.Afterwards,thefrequencyanddissipationwererecordedduringtheelectrochemicalprocess.Thesurfaceroughnesswasdeterminedbyex-situatomicforcemicroscopy(AFM)(EIS)method,Theimpedancedetectionduringelectrochemicalprocesswascarriedoutbyin-situelectrochemicalimpedance.Thedistributionofrelaxationtimes(DRT)analysiswascarriedoutbasedonthein-situEISresults.Theelectrochemicalperformancewasmeasuredon1470Eelectrochemicalworkstation.ThesurfaceconditionsofthetwoelectrodeswereanalyzedbyX-raydiffraction.ResultanddiscussionAnelectrolyte(Co-Solv)foraqueouszincbatterywasdesignedviamixingaqueouselectrolytewithTEGDME/LITFSI.TheelectrochemicalmeasurementrevealsthattheCoulombefficiencies(CE)ofCo-Solvis97.2%,whichishigherthanthatofbareelectrolytebasedbattery(i.e.,94.4%).Themainreasonisduetotheco-solventeffectfromwaterandTEGDMEinCo-Solvelectrolyte.Thisfurtherconfirmedbyin-situE-QCMresults.Comparedtothefrequencyanddissipationevolutionduringcharge/dischargeprocess,thesurfaceelectro-depositionprocesscanberevealed.ArigidfilmwithTEGDME/LITFSIcanformonthetopofanode,whichfurtherinhibitstheoccurrenceofsidereactionsuchasHER.BasedontheresultsbyAFM,theroughnessinthebareelectrolyteincreasesafterelectrochemicalprocess.Theroughnesssurfaceiscloselyrelatedtothesidereactions.Theformationofirreversiblebasiczincsulfateaffectstheanodeperformance.IntheCo-Solvbasedbattery,theroughnessdecreasesandarigidfilmappearsonthetopofanodetoavoidthesidereactions.Thisprotectedfilmisdenseandfirmtoinhibittheformationofdendrite.AccordingtotheresultsfromDRTanalysis,theco-solvationeffectcanaffectthedoubleelectriclayerstructureofthemetalsurface,andinducetheuniformdepositionofmetalzincviamaintainingthestabilityofthelocalelectricfieldontheelectrodesurface.CombinedwiththeresultsbyE-QCMandAFM,theadditionofTEGDME/LITFSIcanimprovetheelectrochemicalperformanceviainhibitingdendritegrowth,reducingsidereactionsandblockingtheHER.ConclusionsTEGDME/LITFSIwasamixtureaddingintoZnSO4basedelectrolytetooptimizetheplating/strippingbehaviorofZnmetal.TEGDMEcouldpartlyreplacewatertocombinewithZn2+andformtheco-solventstructureofZn2+-TEGDME/H2O.Itwasindicatedthattheelectrochemicalreactioncouldrelatedtotheelectricdoublelayerstructurenearanode.Co-solventscouldregulatethedepositionofmetalliczincviaaffectingandstabilizingthelocalelectricfield.Thisworkcouldprovideaperspectivepotentialforfurtherdevelopmentandmechanismanalysisofco-solventsystems.
作者：许宏吉 高睿 胡灵龙 马静怡 冯明Author：XUHongji GAORui HULinglong MAJingyi FENGMing
作者单位：吉林师范大学,功能材料物理与化学教育部重点实验室,长春130103
刊名：硅酸盐学报 ISTICEIPKU
Journal：JournaloftheChineseCeramicSociety
年，卷(期)：2024, 52(7)
分类号：O64
关键词：金属锌负极 枝晶 共溶剂作用 原子力显微镜 电化学阻抗
Keywords：zincmetalanode dendrite co-solventcondition atomicforcemicroscope electrochemicalimpedance
机标分类号：O6S831.5TE121.3
在线出版日期：2024年7月24日
基金项目：国家自然科学基金，国家自然科学基金，吉林省重点研发计划共溶剂作用下锌沉积界面行为[
期刊论文] 硅酸盐学报--2024, 52(7)许宏吉 高睿 胡灵龙 马静怡 冯明电解液共溶剂改性方法是一种调控金属锌负极沉积的有效方式.本文以添加四乙二醇二甲醚(TEGDME)为共溶剂的硫酸锌电解液体系为研究对象,通过准原位原子力显微镜(AFM),原位石英晶体微天平(E-QCM)和原位阻抗时域分析(EIS-D...参考文献和引证文献
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