锂硫电池的研发现状及前景预测.pptx

锂硫电池的研发现状及前景预测.pptx

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,锂硫电池技术发展现状与前景R&DstatusandperspectiveofLi-Sbattery,1,汇报内容Contents,研究背景及意义R&DBackground研究内容及成果R&Dcontentsandresults国内外发展现状GlobalR&Dstatus未来发展方向Perspective,储能技术是能源革命的关键技术,可再生能源由辅助能源逐步变为主导能源电驱动设备成为高新技术的主要发展方向,智能电网Smartgrid“信息+新能源+储能”Information+Newenergy+Energystorage,EnergystorageisessentialforenergyrevolutionElectricityfluxInformationflux,Renewableenergiesandelectricequipmentarebecomingdominateinthefuture,智能电网和新能源汽车是国家重大需求Smartgridandnewenergyvehiclesarenationalneeds,4,各种储能技术及适用规模,Energystoragetechnologiesandapplicablescale,hours,minutes,seconds,1kW10kW,Metalair,Supercapacitor,Li-ionsbatteryTraditionalleadacidbatteryNi-CdbatteryNi-MHbatteryFlyingwheel,Nabasedbattery,Advancedleadacid,Highpowercapacitor,Superconductor,Hydropump,Airpress,100kW1MW10MW100MW1GWSystempowerratings,Urgent/UninterruptedpowerImprovepowerquality,GridmanagementTransmissionanddistribution,EnergymanagementBulkpowerstorage,5,Flowbattery,Li-Sbattery,锂硫电池适合中小功率,长时间供电Li-Sissuitableforlongtime,smallpowerapplication,Dischargetimeatratedpower,高比能量电池是高性能电动设备发展的核心,Highenergydensitybatteryisthekernelofelectricequipment,陆Land,空Sky,海Ocean,天Aerospace,电动汽车E-car,分布式发电Distributegeneration,无人飞机Unmannedplane,水上浮标Buoy,水下动力Underseapower,卫星通讯Satellite,外星探索Extraterrestrial,锂硫电池的原理及特点PrinciplesandfeaturesofLi-Sbatteries,原理principleBasedonreactionsbetweenLiandS,特点FeatureshighEnergydensity2600Wh/kg3timesofLi-ionsbatteryLowcostofsulfurWithoutenvironmentalimpactEnvironmentalfriendlyLowpowerdensityShortcyclelifeSafetyproblemoflithiummetalShelflifeorselfdischarge？

Highandlowtemperature？

7,16LiDisch/Ch16Li16eS16Li16eDisch/Ch8LiS82,Cathodeindischarge,锂硫电池储能技术的复杂性,ThecomplexityofLi-Sbattery,electrolyte,membrane,LithiumdendriteLithiummoss,SolventflammableLi2SneasilydissolveDecomposition,Lowe-conductivityPolysulfidediffusionAccumulationofLi2SandSSn2-shuttlephenomenon,Li-SBattery,Lithiummetal,SeparatorPorouscarbon8,reduction,diffusion,diffusion,reduction,oxidation,Sn2-shuttlemechanism,1Cathode,2Anode,3,4,汇报内容Contents,研究背景及意义R&DBackground研究内容及成果R&Dcontentsandresults国内外发展现状GlobalR&Dstatus未来发展方向Perspective,2,GE,Commercialutilization,Qualitycostcontrol,PerformanceImprovement,Resin,Carbonmaterial,Electrolyte,Separator,Cathode,Buoyandetc,Performanceimprovement,Buttoncell,Weddingcell,Stackcell（10Ah）,R&Ddevelopment,Utilization,Batteries,Components,Materials,E-car,Unmannedflight,OrganicsolventFrom2009,研究内容Contents,Frommaterialstoequipment,硫载体材料要求：

高导电性、大孔容、高比表面。

Sulfurhostsrequirement:

conductivity,largeporevolumeandspecificarea.,Highlydisperseofsulfurone-conductinghosts;Inhabitthediffusionofsulfurfromcathodetoanode.,

（1）高性能正极硫载体的研究开发R&Dofhighperformancesulfurhostincathode,Porouscarbon,Li2Sn（n=18）,Li+,Sn2-,Li2Sn,discharge,：

S4Li4e2LiS824,2422,2LiS4Li4e4LiS,2,22,4LiS8Li8e8LiS,Researchcontent,2,1,固硫性能不断提高，但是导电性能下降、成本增加。

Sulfurcontrolperformanceincreased,bute-resistanceandcostincreased.,SulfurhostR&Droute:

SinCpores,SBlendwithC,SinCshell,non-carbonhosts,ScovalentwithSSabsorbon,AbsorbSwith,ofpores,capillaryforceStoreS,e-networkwithinCshell,AbsorbsulfurwithVanDervaalforce,FixSwithC-Scovalentbond,

（1）高性能正极硫载体的研究开发R&Dofhighperformancesulfurhostincathode,Method:

Function:

Commercialadoptable,State-of-art,CarbonmaterialswithorderedhierarchicalporesaremostsuitableForexample:

（1）高性能正极硫载体的研究开发,R&DofhighperformancesulfurhostincathodeTable1.TherelationshipbetweenporousstructureandLi-Sbatteryperformance,UsetemplatesandcarbonsourceCarbonsource:

sugar,resinTemplate：

Silica，CaCO3。

JournalofMaterialsChemistryA,2016,4,1653-1662.,

（2）高性能碳硫复合电极粘结剂研发R&DofbindersforC/Scathode,14,Keephighe-conductivityandbinderingstrength；KeeptheC/Scathodeintactduringcharge/discharge.,通常，水系粘结剂的性能优于油系粘结剂，如PVDF；但不能用于硫化锂粘结Generally,waterbasedbindersareallsuperiortoPVDF。

ButnotforLi2S.,*,2,H2C,AMAC,PVDF,PVP,PEO,H2,H2HH2,*CCCCCC,HHm,CMC,SBRCD,Mostresearchedbindersinliterature：

Researchcontent,PVDF10wt.%，afterpeelingtest,N/P0.5wt.%，afterpeelingtest,Abinder“+”,Bbinder“-”,C/S,C/S,C/S,C/S,C/S,C/S,

（2）高性能碳硫复合电极粘结剂研发,R&DofbindersforC/ScathodeSelf-madebinder（N/P），basedon“+”and“-”chargescross-linking.,Peelingforcetest:

Peelingforcewithdifferentbinder,10wt.%PVDF,10wt.%N/P,Peelingforce,0.5wt.%N/PDisplacement/mm,800,1600150014001300120011001000900,10%,7%,Dischargecapacity/mAh/g,1%3%5%Bindercontent,0.5%,N/P,Afterwelding,Surfacemorphology,Initialdischargecapacityvs.bindercontent0.5wt.%N/Pbinder10wt.%PVDFbinder,颗粒在电极表面的排布密度与粘结强度直接相关Thebinderstrengthisrelatedwithparticlearrangement,Conclusion：

ACSApplMaterInterfaces,2015,7,25002-25006.,

（2）高性能碳硫复合电极粘结剂研发R&DofbindersforC/Scathode,（3）高性能锂硫电池电解液研发R&DofelectrolyteforLi-S,17,IncreasecyclelifeDecreasesidereactionwithLi,Increasecapacityretention：

ControlLi2Sndiffusion,Solvent：

Highboilingpoint;lowviscosityEther,ester,sulfones,Salt：

Highconductivity；lowcostLiTFSI、LiClO4、LiFSI、LiAsF6,Additives：

Flameretardant;FormstableSEILiNO3、P2O5、Cs+、toluene,Liquidelectrolytedidnotsolvealltheproblemaboveyet,Buthaveachievedgreatprogresssince21stcentury.,051015202530,35,Specificcapacity/mAhg-1S,Cyclenumbers,05101520253035404550,0,20,40,1008060,CoulombEfficiency/%,Cyclenumbers,CBA,x,Ksp,Li2,Baseontheory:

S2,Capacityretentionindifferentelectrolyte,Columbicefficiencyindifferentelectrolyte,sp,Kshouldbewellcontrolledviasolvent.,WesuccessivelydesignedelectrolyteC,（3）高性能锂硫电池电解液研发,R&DofelectrolyteforLi-Sbattery,S:

3mg/cm2,0.2C,（4）高性能锂硫电池隔膜研发R&DofadvanceLi-Sseparator,Separatorfunctions：

StopSn2-TransportLi+,reduction,diffusion,diffusion,reduction,oxidation,Copperfoil,AluminumfoilLithiummetalSeparatorPorouscarbon,+,_,Figure.1ShuttlephenomenonschemeThreetypesofseparatorsforLi-Sbattery：

1、CarbonmembraneCoatingcarbonlayeroncathode（basedonadsorption）.SuchasGO,SGO,CNT,carbonfiber,etc.2、PorouspolymermembraneControlporesizeinnanoscale（basedonporoussieving）.Suchas：

PVDFbasedporousmembrane,etc.3、SolidstatemembraneInorganicLi+conductor（basedoncrystalstructure）.SuchasLISICON,LIPON,etc.,Self-madePVDFporousmembrane,Celgard2325,ThecyclestabilitycouldbeobviouslyimprovedbyseparatorsRSCAdvances,2015,5,26273,（4）高性能锂硫电池隔膜研发R&DofadvanceLi-Sseparator,2.Lithiumdendrite,Lithiumbreakdown,WithgasventAfter100cycles,TotallysealedAfter100cycles,After10cycles0.2C,Cycle100times0.2C,（5）高性能锂硫电池锂负极研发,R&Dofadvancedlithiumanode1.LithiumreactwithelectrolyteBatteryswellinganddrying,LithiumprotectionisthelargestproblemofLi-Sbattery,Whichshouldbepaidmoreattention.,（5）高性能锂硫电池锂负极研发R&Dofadvancedlithiumanode,Withoutprotection,Withprotection,Cross-section,Cross-section,Adv.Mater.,2015,28,1853-1858.,（5）高性能锂硫电池锂负极研发,R&DofadvancedlithiumanodeEg:

FormLi3PO4protectlayeronanode,Withoutprotection,Withprotection,能否用石墨或硅碳负极替代金属锂？

CouldLibereplacedwithgrapheneorSi/C?

EnergydensityofSbased20Ahbatterywithdifferentanodes,大连化物所储能技术研究部研发规划R&Dstrategyinourgroup,PrimarySecondary,Primaryuse,Secondaryuse,Researchtasks,SuperhighEnergydensity,SuperLongShelflife,ModeratePowerdensity,Moderate,Energydensity,High,Powerdensity,ExcellentCycleStability,DNL17,Buttonbattery,KeyMaterial2010.12,Batterypackage20112012,ImproveEnergydensity2013,20142015,ImproveCyclestability,Rollingbattery2.5Ah,0.01Ah,12Ah,3Ah,Z-typeStack60Ah,400500Wh/kg,BatterycapacityEnergydensity,250350Wh/kg,30,Secondarybattery:

550Wh/kg,750Wh/L,Stackbattery10Ah,900Wh/kg1cycle,300Wh/kg100cycles,大连化物所储能技术研究部研发进展R&Dprogressinourgroup,大连化物所储能技术研究部研发进展,R&Dprogressinourgroup,Li-Sbatteryispromisingastheprimarybattery,PrimarybatterywithsuperhighenergydensityEnergydensity:

900Wh/kg，1200Wh/L,Capacity:

30Ah,43.532.521.510.50,Voltage/v,0En300600900ergydensity/Wh/kgFig.1thedischargecurveofLi-SprimarybatteryFig.2thestacksofLi-Sprimarybattery,倡导锂硫一次电池研发,AppealingforR&DofLi-SprimarybatteryTable:

MajorLi-basedPrimarybatteryparameters:

Li-Svs.othersystems,TheLi-Sbatterywithsuperhighenergydensityandlowcostispromisingastheprimarybattery,倡导锂硫一次电池研发,AppealingforR&DofLi-Sprimarybattery,0.00,1.00.5,1.5,2.0,3.02.5,Opencircuitvoltage/V,OCVofLi-Sprimarybattery,Over2.35V,After2monthatroomtemperature,theOCVisstableover2.35V.ItmeansthatastableSEIwasformedonthelithiumanode.,2004006008001000120014001600shelftime/hourFig.1theOCVvs.timeoflithiumprimarybatteries,汇报内容Contents,研究背景及意义R&DBackground研究内容及成果R&Dcontentsandresults国内外发展现状GlobalR&Dstatus未来发展方向Perspective,2,美国SionPower公司锂硫电池现状,2016：

300Wh/kg,400times;400Wh/kg,150times;Safetyimproved。

张洪章，深圳,美国Polyplus公司锂硫电池现状PolyplusintheUSA,Unchangedduringthepastseveralyears,英国Oxisenergy公司锂硫电池现状R&DstatusofLi-SbatteryinOxisenergy,国际锂硫电池技术发展规划InternationalR&DstrategyofLi-Sbattery,汇报内容Contents,研究背景及意义R&DBackground研究内容及成果R&Dcontentsandresults国内外发展现状GlobalR&Dstatus未来发展方向Perspective,2,未来发展方向FutureR&D,Deeplyclarifythemechanismofsulfurconfining；Illustratetheelectrolytedecomposeprinciple；Clarifythelithiumdendriteformationmechanism；,SecondaryLi-Sbattery：

basedon350Wh/kg，improvecyclelifeover500times;?

PrimaryLi-Sbattery：

basedon900Wh/kg,promoteforpracticalapplication.?

Fundamentalresearch,Technologydevelopment,Acknowledgement,Prof.HuaminZhang，Prof.XianfengLi,FundingsupportsNationalNaturalScienceFoundationofChina（NSF）DalianInstituteofChemicalPhysics（DICP）,Recentpublications,Thanks！