《锂电池研讨》PPT课件.ppt

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1、动力锂离子电池现状、安全性及寿命评测,2011汽车动力电池国际研讨会,INET,Tsinghua University,2011年2月23-24日，上海何向明清华大学核研院新型能源与材料化学研究室Institute of New Energy Technology,内容,动力电池现状锂离子动力电池的安全性锂离子动力电池的使用寿命Institute of New Energy Technology,INET,Tsinghua University,清华大学核研院锂离子电池实验室介绍,The Great Wall,Ming,Institute of Nuclear and New Energy T

2、echnology,Tsinghua University,Less than 50 minutes drive45 km,The Institute,TsinghuaBeijingInstitute of New Energy Technology,INET,Tsinghua University,Tombs,Lithium ion,Institute of New Energy Technology,INET,Tsinghua University,R&DbatteryFuel Cell,Institute of New Energy Technology,INET,Tsinghua Un

3、iversity,燃料电池实验室,学术带头人：姜长印、万春荣,学术骨干（博士）：何向明、蒲薇华、应皆荣、李建军、刘靖、郭建伟、,研究骨干（硕士）：武玉玲、冯丽娟、张丽春、孙文婷、陈敏,实验室技师：陈克勤、常彩霞、李智敏、康建峰、杨兆卫、史波,锂离子电池实验室,王 莉、任建国、李建刚、高 剑 博士生、硕士生：10-15名Institute of New Energy Technology,INET,Tsinghua University,锂离子电池研究概况,材料合成，机理诊断，电极/电池工程化，数学模型,电池,模型,Institute of New Energy Technology,INET,

4、Tsinghua University,从纳米尺度到微米尺度，再到毫米尺度,性能,电极结构,电池结构,结构材料合成材料修饰表面/界面化学,新工艺新材料安全性长寿命,电极制造电池制备电极模型,高性能锂电池电极模型,动力锂离子电池的现状Institute of New Energy Technology,INET,Tsinghua University,目前市场上的混合动力车,Institute of New Energy Technology,INET,Tsinghua University,Toyota HighlanderLexus RX400h,Honda InsightLexus GS4

5、50h,Toyota CamryHonda Civic,Toyota PriusHonda Accord,Saturn Vue,Chevy Silverado,Ford Escape,more and more,混合动力车,ELECTRIC ACCESSORIES,PETROLEUM ONLY76hp gasoline engine,67hp electric motor,1.5kWh batteryInstitute of New Energy Technology,INET,Tsinghua University,ADVANCED ENGINE,Fuel Flexibility,插电式混合

6、动力车ELECTRIC ACCESSORIES,ADVANCED ENGINE,PETROLEUMAND/ORELECTRICITYBATTERY RECHARGE76hp gasoline engine,67hp electric motor,9.0kWh battery(30mi)Institute of New Energy Technology,INET,Tsinghua University,Percentage of Vehicle Fleet In Use(%),Cumulative Fuel Consumed(gallons),5,10,15,20,25,00,105,15,2

7、0,25,30,Time of Day(hr)Institute of New Energy Technology,INET,Tsinghua University,030,10050,150,200,250,300,PHEV40,8647 total miles driven 共行驶8647英里,58 mpg&,140 Wh/mi,PHEVs:40%reduction inoperating costs,$500 annual savings,37 mpg,76 mpg&211 Wh/mi,Assumes$2.41/gal and 9/kWh,$1.58$1.21,$2.48,$3.45,$

8、0.48$0.72,-,-,5.45.1,6.5,9.1,PHEV20PHEV40,HEV,CV,混合动力车的实际节油效果40 400Conventional35 350,E-Transportation is the most significant technological revolutionafter the cellular and the internet.电动交通是移动电话和互联网后的最重要的技术革命。Institute of New Energy Technology,INET,Tsinghua University,电动车对动力电池的需求在持续增长,MW reserve p

9、ower plants.兆瓦级储能电站。,Institute of New Energy Technology,INET,Tsinghua University,钛酸锂电池移动储能电站,Electrovaya,International Battery,Ultralife,Valance,Saft.BYD磷酸铁锂电池固定储能电站,规模储能是动力电池的又一重要市场 Manage fluctuations in electricity demand.平抑电网波动。Manufacturers to take a part:A123,Altairnano,Enerdel,different cell

10、model,120 different cell models,Ultra High power 超高功率(20C)-19 manufacturers,Market grow of 15%CAGR(复合年均增长率)peryear driven by the EV growing market,Cell costsare decreasing by 8%per year(Source:IIT).Institute of New Energy Technology,INET,Tsinghua University,动力电池的现状 High power 高功率(10C)-84 manufacture

11、rs,1500,中日韩在动力电池制造方面占支配,Far-East manufacturers dominate the market,台湾Institute of New Energy Technology,INET,Tsinghua University,Pouch,Institute of New Energy Technology,INET,Tsinghua University,动力电池的包装方式,Prismaticcells,较好的传热,安全性好使用寿命长,cellsCylindricalcells,功率最高的磷酸铁锂电池,SeealsoInstitute of New Energy

12、 Technology,INET,Tsinghua University,Institute of New Energy Technology,INET,Tsinghua University,Beijing ChinaPowerel北京中润恒动电,池有限公司,850 x560 x71,200,500 to80%,?,7000,102,21,1028,213,Lionik深圳市龙锂实业有限公司,255 x145 x55,100,500 to80%,-20to 60,3600,105,186,1055,1868,单体电池容量最高的高功率动力电池Cell Size Cap Cycle Temp W

13、eight Weight Volume mm Ah life range gr energy energy density density density densityWh/Kg Wh/L W/Kg W/L,.,功率最高的18650电池,Highcompetitivemarketwithalmost50differentcellmodelsInstitute of New Energy Technology,INET,Tsinghua University,操作温度最高的动力电池,EV needs batteries with up to 80C hightemperature operat

14、ing rangemInstitute of New Energy Technology,INET,Tsinghua University,快速充电动力电池,短问题的最经济的方法。road charging stations.,Current Market Ultra fast charging cellUltrafastchargeStationInstitute of New Energy Technology,INET,Tsinghua University,快速充电(up to 5 min,80%capacity)是解决电动车续驶里程,Toshiba Super Charge Lith

15、ium Ion,Battery-SCiB Lithium Manganese oxide Spinel cathode-LMO Lithium Titanate Oxide anode LTO Recharge to 90%of full capacity in less than 5 minutes.Excellent safety because of high level anode stability.,6000 cycles of full to 90%of initial capacity.,Low temperature discharge from-30C.,SCIB is c

16、urrently available on the Schwinn Tailwind electric bike.,2.4Voc,65 Wh/Kg,131 wh/l,650 W/Kg,1316 W/l,Institute of New Energy Technology,INET,Tsinghua University,VW&Toshiba,1st,Will dominate the rechargeable market for the near and mid,future.,2nd,Generation Li-Ion Chemistries,Better performance-Up t

17、o 300 Wh/kg with fast recharge.-Wider operating temperature range.-Fast Charging.Improved safety.Reduced cost.锂空气电池？Institute of New Energy Technology,INET,Tsinghua University,下一代锂离子电池动力电池20,Generation Li-Ion Chemistries,动力电池的安全性问题将影响其市场命运,If it is not safe it will not surviveInstitute of New Energy

18、 Technology,INET,Tsinghua University,动力电池的安全性问题,锂离子电池的安全性Institute of New Energy Technology,INET,Tsinghua University,Institute of New Energy Technology,INET,Tsinghua University,Institute of New Energy Technology,INET,Tsinghua University,安全性问题引起的损失,Institute of New Energy Technology,INET,Tsinghua Uni

19、versity,Safety cases,Institute of New Energy Technology,INET,Tsinghua University,Safety cases,安全性的概念滥用安全性 abuse thermal runaway Mechanical 机械的 crush,nail penetration 挤压、针刺,Electrical 电的 short circuit,overcharge 短路、过充 Thermal 热的 thermal ramp,simulated fire 热箱、火烧,现场安全性 field failure thermal runaway Ma

20、nufacturing defects 由制造瑕疵引起 Loose connection,separator damage,foreign debris 连接问题、隔膜损坏、粉尘 Can develop into an internal short circuit 随机发生，引起内短路 Can lead to overheating and thermal runaway 引起过热与热失控Institute of New Energy Technology,INET,Tsinghua University,Institute of New Energy Technology,INET,Tsin

21、ghua University,滥用安全性,Institute of New Energy Technology,INET,Tsinghua University,现场（随机）安全性,两种安全性概念的差异,现场安全性,滥用安全性,Institute of New Energy Technology,INET,Tsinghua University,Predictable 可预测的 Common to all cells 对每一个电池 Can/should be evaluatedat the cell level 可以通过测试进行评估 Time constants relativelylong

22、 发生过程较长 Can be augmented byprotection devices 可以通过保护措施进行改善,Not predictable 不可预测的 One-in-a-million(or less)随机小概率发生 Difficult to evaluate at thecell level,or through QC 无法通过测试进行评估，也不能通过质量管理来完全消除 can occur quickly 发生很突然 PTC,CID,shutdownseparators,electroniccontrols not are effective 目前所有的安全性措施，均不能完全消除锂

23、离子电池安全隐患,发生安全事故的锂离子电池，之前均通过UL安全认证。,发生原因基本上是不可预测的内短路所造成。而这种内短路似乎是不能完全消除。引起安全事故的电池在制造时，均是合格品。目前滥用安全性标准的测试结果，与发或者不发生安全性事故，之间没有任何联系。Institute of New Energy Technology,INET,Tsinghua University,锂离子电池安全性 对于笔记本电脑电池，发生概率在几百万分之一。,Major effort has been payed to improve the ways we,address safety in lithium-ion

24、 batteries,however,在人们如此重视锂离子电池安全性的今天，严重的安全性问题还时有发生。The battery community does not have adequate teststo evaluate safety as it relates to the safety incidentsthat have taken place or could take place.人们还没有找到合适的方法来预测和评测这类安全隐患问题 我们在做工作，希望“十二五”结束时，这个问题得到一定程度的解决。Institute of New Energy Technology,INET,T

25、singhua University,锂离子电池的安全性serious safety incidents can always occur.,Energy Released(J),热失控的机,Institute of New Energy Technology,INET,Tsinghua University,249.9,378,292.5,73.71,640,0.90,300200100,700600500400,Anode/Binder Anode/Solvent SEIDecompn,Cathode,Breakdown,Separator,Oxidn,Cathode,Solvent Ox

26、dn JouleHeating,Cathode,锂离子电池安全性9008000.8 Ah 钴酸锂手机电池,826.2,Institute of New Energy Technology,INET,Tsinghua University,负极材料的安全性改进,Institute of New Energy Technology,INET,Tsinghua University,正极材料,Institute of New Energy Technology,INET,Tsinghua University,Heat release,Safety of cathode Materials,Inst

27、itute of New Energy Technology,INET,Tsinghua University,隔膜,隔膜关闭的温度范围 Strength and physical integrity抗压机械强度 Shrinkage allowance热收缩率Institute of New Energy Technology,INET,Tsinghua University,影响电池安全性的重要指标 Shutdown performance,电解质Solvent，non-flamableSalts，high decomposition temperature,Additives，Flame-

28、RetardantGel electrolyteInstitute of New Energy Technology,INET,Tsinghua University,P(VdF-HFP)凝胶电解质在,Institute of New Energy Technology,INET,Tsinghua University,凝胶电解质 凝胶电解质的放热量与放热速率,黄倩，厦门大学博士论文,燃烧过程中的放热总量非常接近于纯液态电解液体系。并且随着P(VdF-HFP)在凝胶电解质中浓度的增加，其相应的热释放速率逐渐降低。采用P(VdF-HFP)凝胶电解质比液态电解液更为安全 PMMA凝胶电解质体系中，

29、情况却是相反:其燃烧反应的放热总量和热释放速率都随,PMMA的加入而显著增大。,锂离子电池的安全性是一个复杂的系统问题,动力电池安全性是一个系统问题。从单纯的电池材料改性（正极、负极、电解质、隔膜）是不能完全解决安全性问题，但可以大幅度地提高。Institute of New Energy Technology,INET,Tsinghua University,Institute of New Energy Technology,INET,Tsinghua University,正极材料包覆,钴酸锂包覆磷酸铝,5-10nm AlPO4,过充电前,过充电后,自制安全性手机电池,过充电试验未燃烧、

30、未爆炸。,市售品牌电,过充电,池电芯Institute of New剧烈燃Technology,INET,Tsinghua University,Energy 烧,高性能高安全性动力电池,采用正极材料表面与界面控制技术、电解质添,加剂等技术，制备出高安全性动力电池。,20V过充,150热箱5小时以上标称容量12Ah，三元氧化物正极材料。电池比能量大于160wh/kg，比功率大于,1200W/kg，Institute of New Energy Technology,INET,Tsinghua University,安全,很好的倍率性能,目前市售三元动力电池的过充电,充电到5.2V时，发生剧烈燃

31、烧,Institute of New Energy Technology,INET,Tsinghua University,目前市售三元动力电池,充电到4.15V，加热到120，发生剧烈燃烧,Institute of New Energy Technology,INET,Tsinghua University,动力电池的使用寿命与成本 如何评测动力电池的使用寿命 现场检测电池的寿命状态（SOH）Institute of New Energy Technology,INET,Tsinghua University,锂离子动力电池的使用寿命,PHEV battery likely to deep-

32、cycle each day driven:15 yrs equates to 4000-5000 deep cycles,Also need to consider combination of high and low frequency cycling and calendarwlife 电池,电池循环寿命,70%50%4000Data presented by Christian Rosenkranz(Johnson Controls)at EVS 20,2006Institute of New Energy Technology,INET,Tsinghua University,52

33、%EV,Institute of New Energy Technology,INET,Tsinghua University,$4,005,$2,865,$2,919,$3,002,$1,998,$1,992,$2,004,$2,020,$2,079,$2,407,$2,454,$2,433,$5,117,$8,433,$663,$-,$2,000,$4,000,$6,000,$10,000$8,000,$14,000$12,000,$18,000$16,000,CV,HEV,PHEV20,PHEV40,transmissionengine,25%,电池占电动车成本比例Projected R

34、etail Powertrain Costs-Midsize Sedans1)including manufacturer and dealer markups2)all component costs assume projected statuscharger/plugbattery 40%motor/inverter,60%,动力电池的使用寿命,电池的成本占整个电动车成本的2560%。是一个,非常重要的零部件。,车的使用寿命：10-15年,动力电池目前的使用寿命是3-7年，LG化学声称可以有10-15年的寿命保证。因此大幅度地延长动力锂离子电池的使用寿命，使之达到与电动车的寿命相当，是目

35、前动力锂离子电池发展的关键问题。需要动力电池使用寿命评测技术做支撑。Institute of New Energy Technology,INET,Tsinghua University,Ohmic Resistance,Ohmic Resistance,Ohmic Resistance,temperature,lar,ge,1.5,1.3 Hi,gh,de,Cycles,50,100 150 200 250 300 350 400 450CyclesInstitute of New Energy Technology,INET,Tsinghua University,1.2,1.11,1.1

36、,1,Effects of charging/discharging depth2.5,21.5,10,0,50,100 150 200 250 300 350 400 450Cycles,0,50,100 150,200,250 300,350 400 450,ep,影响动力电池的使用寿命的因素 温度 电流,充放电深度,动力电池的使用寿命评测Effects of charge current Effects of 1.61.71.51.61.41.41.2 1.3,1.8 2,1.7 1.9,Internal Resistance,Voltage V,Current A,R=V/I,动力电池

37、的使用寿命评测,Degradation,3500,3.75,Remaining life,Institute of New Energy Technology,INET,Tsinghua University,Temperature of a battery,3.653.63.55,3.83.7,0,772,500-500-1500-2500,450025001500,Voltage response/VCurrent/A,Day,Present,Battery,*BMS:Battery Management System,*PLC:Programmable Logic Controller,

38、-Battery Temperature-Battery Voltage-Battery CurrentBMS*Controller(PLC*),-Internal resistancedegradation rate-Remaining batterylife(Estimated)Monitor,(ex.Based on an Internal resistance degradation rate),1623 2510 3410 4197 5022Time s,t,Drate kt x 1Degradation rateof Internal resistance Target Accuracy:10%Lifetime judgmentcriteriaDegradation rate(Present)1(Estimated),(ex.Based on the detection of an internal resistance status),Institute of New Energy Technology,INET,Tsinghua University,58,