1、锂硫电池技术发展现状与前景锂硫电池技术发展现状与前景R&D status and perspective of L S battery1汇报内容汇报内容Contents 研究背景及意义研究背景及意义R&D Background 研究内容及成果研究内容及成果R&D contents and results 国内外发展现状国内外发展现状Global R&D status 未来发展方向未来发展方向Perspective储能技术是能源革命的关键技术储能技术是能源革命的关键技术Energy storage is essential for energy revolutionElectricity flu
2、xInformation flux智能电网智能电网Smart grid“信息信息+新能源新能源+储能储能”Information+New energy+Energy storageRenewable energies and electricequipment are becomingdominate in the future可再生能源可再生能源由辅助能源逐步变为主导能源由辅助能源逐步变为主导能源电驱动设备电驱动设备成为高新技术的主要发展方向成为高新技术的主要发展方向智能电网和新能源汽车是国家重大需求智能电网和新能源汽车是国家重大需求Smart grid and new energy veh
3、icles are national needs发布主体与时间发布主体与时间相关政策相关政策主要相关内容主要相关内容中共中央中共中央中国国民经济和社会发展中国国民经济和社会发展第十三个五年规划纲要第十三个五年规划纲要集中支持集中支持新能源汽车新能源汽车等的产业发展壮大。等的产业发展壮大。2016年年3月月17日日国家能源局国家能源局全面推进全面推进电动汽车电动汽车充电设施建设；启动充电设施建设；启动“互联网互联网”+智智2016年能源工作指导意见年能源工作指导意见2016年年4月月12日日慧能源行动；积极发展慧能源行动；积极发展智能电网智能电网；推广实施电能替代。；推广实施电能替代。发改委、工
4、信部、环保发改委、工信部、环保部、商务部、质检总局部、商务部、质检总局2016年年1月月5日日电动汽车动力蓄电池回收电动汽车动力蓄电池回收 为保障人身安全，防治环境污染，促进资源再生，为保障人身安全，防治环境污染，促进资源再生，动力动力利用技术政策利用技术政策(2015年版年版) 蓄电池蓄电池设计应采取无毒无害化设计。设计应采取无毒无害化设计。发改委、能源局、工信发改委、能源局、工信部、住建部部、住建部进一步大力推进充电基础设施建设，是当前加快进一步大力推进充电基础设施建设，是当前加快电动汽电动汽电动汽车充电基础设施电动汽车充电基础设施车推广车推广应用的紧迫任务，也是推进能源消费革命的一项应用
5、的紧迫任务，也是推进能源消费革命的一项重要战略举措。重要战略举措。发展指南（发展指南（2015-2020年）年）2015年年10月月9日日重点开展动力电池系统安全性、可靠性研究和轻量化设重点开展动力电池系统安全性、可靠性研究和轻量化设计。计。到到2020年，动力电池模块比能量达到年，动力电池模块比能量达到300瓦时瓦时/公公斤以上，成本降至斤以上，成本降至1.5元元/瓦时以下瓦时以下。国务院办公厅国务院办公厅节能与新能源汽车产业发节能与新能源汽车产业发2012年年6月月展规划（展规划（20122020）4各种储能技术及适用规模各种储能技术及适用规模Energy storage technolo
6、gies and applicable scaleUrgent/Uninterrupted power Grid managementEnergy managementImprove power qualityTransmission and distribution Bulk power storageMetal airHydropumpFlow batterya based batteryL S batter yAir pressAdvanced lead acidLi-ions batteryTraditional lead acid batteryNi-Cd batteryNi-MH
7、batteryFlying wheelSuperconductorHigh power capacitor1 kW10 kW 100 kW1 MW10 MW100 MW 1 GWSystem power ratings锂硫电池适合中小功率锂硫电池适合中小功率, 长时间供电长时间供电Li-S is suitable for long time, small power application5高比能量电池是高性能电动设备发展的核心高比能量电池是高性能电动设备发展的核心High energy density battery is the kernel of electric equipment陆陆
8、 Land空空Sky电动汽车电动汽车 E-car 分布式发电分布式发电 Distribute generation无人飞机无人飞机 Unmanned plane天天 Aerospace海海 Ocean水上浮标水上浮标 Buoy水下动力水下动力 Undersea power卫星通讯卫星通讯 Satellite外星探索外星探索Extraterrestrial锂硫电池的原理及特点锂硫电池的原理及特点Principles and features of Li-S batteries原原 理理 principle特特 点点 FeaturesBased on reactions between Li an
9、d S high Energy density 2600Wh/kg3 times of Li-ions battery Low cost of sulfur Without environmental impact Environmental friendlyLow power density Short cycle life Safety problem of lithium metal Shelf life or self discharge？ High and low temperature ？16Li Disch/Ch16Li16eS 16Li 16e Disc h/Ch8Li2S87
10、锂硫电池储能技术的复杂性锂硫电池储能技术的复杂性The complexity of Li-S batteryCathode in discharge21 Lithium dendriteLithium mossLow e- conductivityPolysulfide diffusionAnodeCathodeAccumulation of Li2S and S Solvent flammable Li S easily dissolveelectrolyteS shuttle phenomenon2-2 nn Decompositionmembrane3Sn2- shuttle mecha
11、nism4L S BatterydiffusionoxidationdiffusionreductionreductionLithium metalSeparator Porous carbon8汇报内容汇报内容Contents 研究背景及意义研究背景及意义R&D Background 研究内容及成果研究内容及成果R&D contents and results 国内外发展现状国内外发展现状Global R&D status 未来发展方向未来发展方向Perspective2研究内容研究内容ContentsCommercialutilizationBuoy and etcButton cellc
12、arUnmanned flightPerformanceimprovementWedding cellStack ce （10 A ）CathodeQuality costcontrolElectrolyteSeparatorResinPerformanceImprovementOrganic solventCarbon materialFrom 2009From materials to equipment（1）高性能正极硫载体的研究开发）高性能正极硫载体的研究开发R&D of high performance sulfur host in cathode Highly disperse o
13、f sulfur on e- conducting hosts;Researchcontent Inhabit the diffusion of sulfur from cathode to anode.discharge S 4Li 4e 2Li2S4： PorouscarbonLi S2 n（n=18）Li+82Li S 4Li 4e 4Li S4Li S 8Li 8e 8Li S2 42 22 22Li S2 nSn2-硫载体材料要求：高导电性、大孔容、高比表面。硫载体材料要求：高导电性、大孔容、高比表面。Sulfur hosts requirement :conductivity, l
14、arge pore volume and specific area.（1）高性能正极硫载体的研究开发）高性能正极硫载体的研究开发R&D of high performance sulfur host in cathodeSulfur host R&D route:S covalentwith SS absorb onnon-carbonhostsS in C shellState-of-artS in C poresCommercial adoptableS Blend with Ce- networkMethod:Absorb S withcapillary forceof poresAb
15、sorb sulfurwith Van Dervaal forceStore Swithin C shellFix S with C-Scovalent bondFunction:固硫性能不断提高，但是导电性能下降、成本增加。固硫性能不断提高，但是导电性能下降、成本增加。Sulfur control performance increased, but e- resistance and cost increased.2（1）高性能正极硫载体的研究开发）高性能正极硫载体的研究开发R&D of high performance sulfur host in cathodeTable 1. The
16、 relationship between porous structure and Li-S battery performancePhysical propertyBattery propertyPores sizeof carbonCapillaryforcesLi-ionsC-rateCycleSurface area Pore volumetransfercapabilitystabilityMicro-poresMeso-poresLarge-poresDisorderedHierarchicalOrderedHierarchicalCarbon materials with rd
17、ered ierarchical pores are most suitableFor example:Use templates and carbon sourceCarbon source: sugar, resinTemplate：Silica，CaCO3。Journal of Materials Chemistry A, 2016, 4, 1653-1662.（2）高性能碳硫复合电极粘结剂研发）高性能碳硫复合电极粘结剂研发R&D of binders for C/S cathodeKeep high e- conductivity and bindering strength； Kee
18、p the C/S cathode intact during charge/discharge.ResearchcontentMost researched binders in literature：C CNOPVDFPVPPEOAMACH H HH 2* C2 C C C2 C C *m nH HSBRCDCMC通常，水系粘结剂的性能优于油系粘结剂，如通常，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；但不能用于硫化锂粘结Generally, water based binders are all superior to PVDF。But not for Li2S.1
19、4（2）高性能碳硫复合电极粘结剂研发）高性能碳硫复合电极粘结剂研发R&D of binders for C/S cathodeSelf-made binder (N/P)，based on “+” and “-”charges cross-linking.A binder“+”B binder“-”C/SC/SC/SC/SC/SC/SPeeling force test:N/P 0.5 wt. %，after peeling testPVDF10 wt.%，after peeling testPeeling force with different binder10 wt. % N/P10 w
20、t.% PVDF0.5 wt. % N/PDisplacement/ mm（2）高性能碳硫复合电极粘结剂研发）高性能碳硫复合电极粘结剂研发R&D of binders for C/S cathode16001500140013001200110010009008000.5%1%3%5%7%10%Binder contentInitial discharge capacityvs. binder content0.5 wt.% N/P binder 10 wt.%PVDF binder 颗粒在电极表面的排布密度与粘结强度直接相关颗粒在电极表面的排布密度与粘结强度直接相关The binder st
21、rength is related with particle arrangementConclusion：ACS Appl Mater Interfaces, 2015, 7, 25002-25006.（3）高性能锂硫电池电解液研发）高性能锂硫电池电解液研发R&D of electrolyte for Li-SIncrease capacity retention：Control Li2Sn diffusionIncrease cycle lifeDecrease side reaction with LiAdditives：Flame retardant;Form stable SEISo
22、lvent ：High boiling point;low viscositySalt：High conductivity；low costLiNO 、P O 、Ether, ester,sulfonesLiTFSI、LiClO4、LiFSI、LiAsF6325Cs+、tolueneLiquid electrolyte did not solve all the problem above yet,But have achieved great progress since 21st centur y.（3）高性能锂硫电池电解液研发）高性能锂硫电池电解液研发R&D of electrolyte
23、 for Li-S batteryKspBase on theory: Sx2Ksp should be well controlled via solvent.Li 2We successively designed electrolyte CElectrolyteAsolventsoluteCapacity at 20thcycleColumbic efficiencyDOL:DME=1:1 Li TFSI, 1 MDOL:DME=1:1 Li TFSI, 2 M400 mAhg 170%BC550 mAhg 186%92%DIC 1Li TFSI, 2 M1180 mAhg 1S: 3m
24、g/cm20.2C1001400120010008006004002000806040200CBACBAS: 3mg/cm20.2C0510 15 20 25 30 35 40 45 5005101520253035Cycle numbersCycle numbersColumbic efficiency in different electrolyteCapacity retention in different electrolyte(4) 高性能锂硫电池隔膜研发高性能锂硫电池隔膜研发R&D of advance Li-S separator_+Separator functions：di
25、ffusiondiffusion1. Stop Sn2-oxidationreduction2. Transport Li+reductionCopperfoilAluminum foilPorous carbonLithium metalSeparatorFigure. 1 Shuttle phenomenon schemeThree types of separators for Li-S battery：1、Carbon membraneCoating carbon layer on cathode（based onadsorption）. Such as GO, SGO, CNT, c
26、arbon fiber, etc.2、Porous polymer membraneControl pore size in nano scale（basedon porous sieving）. Such as：PVDF based porous membrane,etc.3、Solid state membraneInorganic Li+ conductor（based on crystalstructure）. Such as LISICON, LIPON, etc.(4) 高性能锂硫电池隔膜研发高性能锂硫电池隔膜研发R&D of advance Li-S separatorCelga
27、rd 2325Self-made PVDF porous membraneThe cycle stability could be obviously improved by separatorsRSC Advances, 2015, 5, 26273(5) 高性能锂硫电池锂负极研发高性能锂硫电池锂负极研发R&D of advanced lithium anodeBWith gas ventAfter 100 cyclesTotally sealedAfter 100 cyclesLithium break downAfter 10 cycles0.2CCycle 100 times0.2CL
28、ithium protection is the largest problem of Li-S batter y,Which should be paid more attention.(5) 高性能锂硫电池锂负极研发高性能锂硫电池锂负极研发R&D of advanced lithium anode(5) 高性能锂硫电池锂负极研发高性能锂硫电池锂负极研发R&D of advanced lithium anodeEg: Form Li PO protect layer on anode34With protectionCros sectionCros sectionWith out prote
29、ctionWith protectionWith out protectionAdv. Mater., 2015, 28, 1853-1858.能否用石墨或硅碳负极替代金属锂？能否用石墨或硅碳负极替代金属锂？Could Li be replaced with graphene or Si/C?Energy density of S based 20Ah battery with different anodes大连化物所储能技术研究部研发规划大连化物所储能技术研究部研发规划R&D strategy in our groupHighPower densitySuper LongShelf lif
30、eModerateModerateEnergy densityExcellentPower densityCycle StabilitySuper highEnergy densityPrimarySecondaryResearch tasksSecondary usePrimary use大连化物所储能技术研究部研发进展大连化物所储能技术研究部研发进展R&D progress in our groupSecondary battery :550Wh/kg, 750 Wh/L900Wh / kg1 cycle30300type Stack60 AhWh / kg100 cyclesStack
31、battery10 AhBattery capacityEnergy densityRolling battery3 Ah400500Wh / kg2.5 AhButton battery250350Wh / kg12 Ah0.01AhImproveImproveCycle stabilityBattery package20112012Energy densityKey Material2010.12201320142015大连化物所储能技术研究部研发进展大连化物所储能技术研究部研发进展R&D progress in our groupPrimary battery with super h
32、igh energy densityEnergy density:900 Wh/kg，1200 Wh/LCapacity:30Ah43.532.521.510.500300600900Energy density / Wh/kgFig.1 the discharge curve of Li-S primary battery Fig.2 the stacks of Li-S primary batteryLi-S battery is promising as the primary battery倡导锂硫一次电池研发倡导锂硫一次电池研发Appealing for R&D of Li-S pr
33、imary batteryTable: Major Li-based Primary battery parameters: Li-S vs. other systemsLi/CF +Battery systemsLi/MnO2Li/SO2Li/SOCl2Li/CFxxLi-SMnO2Energy density (Whkg-1) 150330 150315 220560 260780784200900Energy density（WhL-1） 300710 230530 7001041 4411478 1039 3001200Power density (Wkg-1)Work tempera
34、ture()Shelf life(year)250400 100230 100210508016560100-2060510-557010-551501520-20130 -4090 -20701510-Cost per WhmiddlelowmiddlehighhighlowThe L S battery with super high energy density and low costis promising as the primary battery,倡导锂硫一次电池研发倡导锂硫一次电池研发Appealing for R&D of Li-S primary battery3.02.
35、5Over 2.35 V2.01.51.00.50.0OCV of Li-S primary battery02004006008001000120014001600shelf time / hourFig.1 the OCV vs. time of lithium primary batteriesAfter 2 month a room temperature, the OCV is stable over 2.35V.It means that a stable SEI was formed on the lithium anode.汇报内容汇报内容Contents 研究背景及意义研究背
36、景及意义R&D Background 研究内容及成果研究内容及成果R&D contents and results 国内外发展现状国内外发展现状Global R&D status 未来发展方向未来发展方向Perspective2美国美国Sion Power 公司锂硫电池现状公司锂硫电池现状2016： 300Wh/kg, 400 times; 400Wh/kg, 150 times; Safety improved。张洪章， 深圳美国美国Polyplus公司锂硫电池现状公司锂硫电池现状Polyplus in the USAUnchanged during the past several yea
37、rs英国英国Oxis energy公司锂硫电池现状公司锂硫电池现状R&D status of Li-S battery in Oxis energy国际锂硫电池技术发展规划国际锂硫电池技术发展规划International R&D strategy of Li-S battery汇报内容汇报内容Contents 研究背景及意义研究背景及意义R&D Background 研究内容及成果研究内容及成果R&D contents and results 国内外发展现状国内外发展现状Global R&D status 未来发展方向未来发展方向Perspective2未来发展方向未来发展方向Future
38、R&DFundamental research Deeply clarify the mechanism of sulfur confining ； Illustrate the electrolyte decompose principle； Clarify the lithium dendrite formation mechanism ；Technology development Secondary Li-S battery：based on 350Wh/kg，improvecycle life over 500 times; ? Primary Li-S battery：based
39、on 900Wh/kg, promote forpractical application. ?AcknowledgementFunding supportsNational Natural Science Foundation of China (NSF)Dalian Institute of Chemical Physics (DICP)Prof. Huamin Zhang，Prof. Xianfeng LiRecent publicationsLayer-by-Layer Assembled C/S Cathode with Trace Binder ACS Applied Materi
40、als & 2015 7 45， （ ）：for Li-S Battery Application.Interfaces25002-25006Carbon-Free CoO Mesoporous Nanowire Array Cathode ACS Applied Materials & 2015 7 41， （ ）：23182-231892015 5 26273-for High-Performance Aprotic Li-O2 BatteriesFabrication of a nano-Li+-channel interlayer for highperformance Li-S ba
41、ttery applicationInterfaces， ：26280RSC AdvancesSteam-etched spherical carbon/sulfur composite withhigh sulfur capacity and long cycle life for Li/S batteryapplication.ACS Applied Materials & 2015 7 63590-， （ ）：Interfaces3599Lithium Sulfur Primary Battery with Super High EnergyDensity: Based on the C
42、auliflower-like Structured C/SCathode.2015，5：14949-14949Scientific ReportsSulfur embedded in one-dimensional French fries-likehierarchical porous carbon derived from a metalorganicframework for high performance lithiumsulfur batteriesIridium incorporated into deoxygenated hierarchicalgraphene as a h
43、igh-performance cathode forrechargeable LiO2batteriesJournal of MaterialsChemistry A， （ ）：2015 3 2915314-15323Journal of MaterialsChemistry A， （ ）：2015 3 28145556-14561Room temperature non-aqueous ferrocene/lithium semi-liquid battery with advanced C-rate capability for energystorage applicationInte
44、rnational Journal ofHydrogen Energy， （ ）：2015 40 4616429-16433Rational design of a nested pore structure sulfur host for Journal of Materials2016，4（5）：1653-1662fast Li/S batteries with a long cycle life1-D oriented cross-linking hierarchical porous carbonfibers as a sulfur immobilizer for high performancelithium-sulfur batteriesChemistry AJournal of MaterialsChemistry A2016, 4 (16), 5965-5972Thank ！
