鋰離子動(dòng)力電池安全性設(shè)計(jì)及壽命評(píng)估

1、鋰離子動(dòng)力電池安全性設(shè)計(jì)及壽命評(píng)估北京鋰離子電池安全測(cè)評(píng)中心北京鋰離子電池安全測(cè)評(píng)中心主要內(nèi)容鋰離子動(dòng)力電池的現(xiàn)狀鋰離子動(dòng)力電池的現(xiàn)狀目前市場(chǎng)上的混合動(dòng)力車(chē)Toyota HighlanderLexus RX400hHonda InsightLexus GS450hToyota CamryHonda CivicToyota PriusHonda AccordSaturn VueChevy SilveradoFord Escapemore and more混合動(dòng)力車(chē)ELECTRIC ACCESSORIESPETROLEUM ONLY76hp gasoline engine, 67hp electr

2、ic motor, 1.5kWh batterycomADVANCED ENGINEFuel Flexibility插電式混合動(dòng)力車(chē)ELECTRIC ACCESSORIESADVANCED ENGINEPETROLEUMAND/ORELECTRICITYBATTERY RECHARGE76hp gasoline engine, 67hp electric motor, 9.0kWh battery (30mi)Percentage of Vehicle Fleet In Use (%)Cumulative Fuel Consumed (gallons)510152025001051520253

3、003010050150200250300PHEV40 8647 total miles driven 共行駛8647英里58 mpg &140 Wh/miPHEVs:40% reduction inoperating costs$500 annual savings37 mpg76 mpg &211 Wh/miAssumes $2.41/gal and 9/kWh$1.58$1.21$2.48$3.45$0.48$0.72-9.1PHEV20PHEV40HEVCV混合動(dòng)力車(chē)的實(shí)際節(jié)油效果 40 Conventional35 E-Transportation

4、is the most significant technological revolutionafter the cellular and the internet.電動(dòng)交通是移動(dòng)電話(huà)和互聯(lián)網(wǎng)后的最重要的技術(shù)革命 。電動(dòng)車(chē)對(duì)動(dòng)力電池的需求在持續(xù)增長(zhǎng) MW reserve power plants. 兆瓦級(jí)儲(chǔ)能電站。鈦酸鋰電池移動(dòng)儲(chǔ)能電站Electrovaya, International Battery, Ultralife, Valance, Saft. BYD磷酸鐵鋰電池固定儲(chǔ)能電站規(guī)模儲(chǔ)能是動(dòng)力電池的又一重要市場(chǎng) Manage fluctuations in electricity d

5、emand. 平抑電網(wǎng)波動(dòng)。 Manufacturers to take a part: A123, Altairnano, Enerdel,different cell models.t 120 different cell models Ultra High power 超高功率(20C)- 19 manufacturers,Market grow of 15% CAGR(復(fù)合年均增長(zhǎng)率) peryear driven by the EV growing market, Cell costsare decreasing by 8% per year (Source: IIT).Instit

6、ute of New Energy Technology, INET, Tsinghua University動(dòng)力電池的現(xiàn)狀 High power 高功率(10C)- 84 manufacturers, 1500 中日韓在動(dòng)力電池制造方面占支配 Far-East manufacturers dominate the market臺(tái)灣 Pouch cells動(dòng)力電池的包裝方式Prismatic cells 較好的傳熱安全性好使用壽命長(zhǎng)Cylindrical ells CellSizemmCapAhCyclelifeTemprangeWeightgrWeightenergydensityWh/Kg

7、VolumeenergydensityWh/LWeightconstantpowerdensityW/Kg VolumepowerdensityW/LA123-AHR18700M1ULTRAD=18L=700.71000to90%-10to10038601291085523169A123-AHR32157M1HDD=32L=157101000to80%-30to603041082611085526148Saft-VL12VD=47L=17312500to80%-30to6064067144843718000功率最高的磷酸鐵鋰電池See also Beijing ChinaPowerel北京中潤(rùn)

8、恒動(dòng)電池有限公司850 x560 x71200500 to80%?7000102211028213Lionik深圳市龍鋰實(shí)業(yè)有限公司255 x145 x55100500 to80%-20to 60360010518610551868單體電池容量最高的高功率動(dòng)力電池 Cell Size Cap Cycle Temp Weight Weight Volume mm Ah life range gr energy energy powerdensity density density densityWh/Kg Wh/L W/Kg W/Lt.CellVCapAhCyclelifeto80%Weight

9、grWeightenergydensityWh/KgVolumeenergydensityWh/L Weight powerdensityW/KgVolumePowerdensityW/LAdvancedbatteryfactory12010073.31.2100043922395525m14372Q-LiteIndustrialICR18650HH3.71.35004012027530066885CENSEnergyTechCo18650P3.21.12000457821228447742AmericanLithiumIncNo-P.N3.21.5200034.314029027985806

10、HenanBideliEnergyICR18650P3.71.45003813630627266129SamsungINR18650-15R3.61.55004512032620005443功率最高的18650電池High competitive market with almost 50 different cell models CellVCapAhCyclelifeto80%Highoper.Temp.cWeightenergydensityWh/KgVolumeenergydensityWh/LWeightpowerdensityW/KgVolumeent.cpoweromdensit

11、yW/LSaftVL32600-1254.2420012512325961129AdvancedBatteryFactory3.2v/60ah3.660300090801276661060操作溫度最高的動(dòng)力電池EV needs batteries with up to 80C hightemperature operating rangem CellI.DWh/KgChargeRateCycleLifeGPLbattery,GE-32AH-02,32AH939.38C500GAIAUHE-341440,7.5AH8416C500ToshibaSCiB6511.9C6000StandardCha

12、rgeQuickChargeFastCharge UltraFastChargeC/3C/3,2C10C快速充電動(dòng)力電池短問(wèn)題的最經(jīng)濟(jì)的方法。road charging stations.Current Market Ultra fast charging cellUltrafast charge Station 快速充電 (up to 5 min, 80% capacity) 是解決電動(dòng)車(chē)?yán)m(xù)駛里程Toshiba Super Charge Lithium IonBattery - SCiB Lithium Manganese oxide Spinel cathode - LMO Lithium

13、 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 D.O.D to 90% of initial capacity. Low temperature discharge from -30C. SCIB is currently available on the Schwinn Tailwind electric bike.2.4V

14、oc65 Wh/Kg131 wh/l650 W/Kg1316 W/lhttp:/ VW & Toshiba 1stWill dominate the rechargeable market for the near and midfuture. 2ndGeneration Li-Ion Chemistries Better performance- Up to 300 Wh/kg with fast recharge.- Wider operating temperature range.- Fast Charging. Improved safety. Reduced cost.鋰空

15、氣電池？ 下一代鋰離子電池動(dòng)力電池20Generation Li-Ion Chemistries動(dòng)力電池的安全性問(wèn)題將影響其市場(chǎng)命運(yùn)If it is not safe it will not survive動(dòng)力電池的安全性問(wèn)題鋰離子鋰離子動(dòng)力電池的安全性分析動(dòng)力電池的安全性分析鋰離子電池關(guān)鍵技術(shù)材料合成，機(jī)理診斷，電極/電池工程化，數(shù)學(xué)模型電池模型從納米尺度到微米尺度，再到毫米尺度性能電極結(jié)構(gòu)電池結(jié)構(gòu)結(jié)構(gòu)材料合成材料修飾表面/界面化學(xué)新工藝新材料安全性長(zhǎng)壽命電極制造電池制備電極模型高性能鋰電池正極負(fù)極 安全性問(wèn)題引起的損失Safety casesSafety cases安全性的概念濫用安全性

16、abuse thermal runaway Mechanical 機(jī)械的 crush, nail penetration 擠壓、針刺 Electrical 電的 short circuit, overcharge 短路、過(guò)充 Thermal 熱的 thermal ramp, simulated fire 熱箱、火燒現(xiàn)場(chǎng)安全性 field failure thermal runaway Manufacturing defects 由制造瑕疵引起 Loose connection, separator damage, foreign debris 連接問(wèn)題、隔膜損壞、粉塵 Can develop

17、into an internal short circuit 隨機(jī)發(fā)生，引起內(nèi)短路 Can lead to overheating and thermal runaway 引起過(guò)熱與熱失控Institute of New Energy Technology, INET, Tsinghua University濫用安全性現(xiàn)場(chǎng)（隨機(jī)）安全性?xún)煞N安全性概念的差異現(xiàn)場(chǎng)安全性濫用安全性 Predictable 可預(yù)測(cè)的 Common to all cells 對(duì)每一個(gè)電池 Can/should be evaluatedat the cell level 可以通過(guò)測(cè)試進(jìn)行評(píng)估 Time constants

18、 relativelylong 發(fā)生過(guò)程較長(zhǎng) Can be augmented byprotection devices 可以通過(guò)保護(hù)措施進(jìn)行改善 Not predictable 不可預(yù)測(cè)的 One-in-a-million (or less) 隨機(jī)小概率發(fā)生 Difficult to evaluate at thecell level, or through QC 無(wú)法通過(guò)測(cè)試進(jìn)行評(píng)估，也不能通過(guò)質(zhì)量管理來(lái)完全消除 can occur quickly 發(fā)生很突然 PTC, CID, shutdownseparators, electroniccontrols not are effectiv

19、e 目前所有的安全性措施，均不能完全消除鋰離子電池安全隱患 發(fā)生安全事故的鋰離子電池，之前均通過(guò)UL安全認(rèn)證。 發(fā)生原因基本上是不可預(yù)測(cè)的內(nèi)短路所造成。而這種內(nèi)短路似乎是不能完全消除。 引起安全事故的電池在制造時(shí)，均是合格品。 目前濫用安全性標(biāo)準(zhǔn)的測(cè)試結(jié)果，與發(fā)或者不發(fā)生安全性事故，之間沒(méi)有任何聯(lián)系。鋰離子電池安全性 對(duì)于筆記本電腦電池，發(fā)生概率在幾百萬(wàn)分之一。 Major effort has been payed to improve the ways weaddress safety in lithium-ion batteries, however 在人們?nèi)绱酥匾曚囯x子電池安全性的今天

20、，嚴(yán)重的安全性問(wèn)題還時(shí)有發(fā)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. 人們還沒(méi)有找到合適的方法來(lái)預(yù)測(cè)和評(píng)測(cè)這類(lèi)安全隱患問(wèn)題 我們?cè)谧龉ぷ鳎Ｍ笆濉苯Y(jié)束時(shí)，這個(gè)問(wèn)題得到一定程度的解決。鋰離子電池的安全性 serious safety incidents can always occur. Energy Released (J)熱失控的

21、機(jī)理249.9378292.573.710.90300200100700600500400Anode/Binder Anode/Solvent SEIDecompnCathodeBreakdownSeparatorOxidnCathodeSolvent Oxdn JouleHeatingCathode鋰離子電池安全性9008000.8 Ah 鈷酸鋰手機(jī)電池826.2負(fù)極材料的安全性改進(jìn)正極材料Heat releaseSafety of cathode Materials隔膜隔膜關(guān)閉的溫度范圍 Strength and physical integrity抗壓機(jī)械強(qiáng)度 Shrinkage all

22、owance熱收縮率 影響電池安全性的重要指標(biāo) Shutdown performance電解質(zhì)Solvent，non-flamableSalts，high decomposition temperatureAdditives，F(xiàn)lame-RetardantGel electrolyte P(VdF-HFP)凝膠電解質(zhì)在凝膠電解質(zhì) 凝膠電解質(zhì)的放熱量與放熱速率黃倩，廈門(mén)大學(xué)博士論文燃燒過(guò)程中的放熱總量非常接近于純液態(tài)電解液體系。并且隨著P(VdF-HFP)在凝膠電解質(zhì)中濃度的增加，其相應(yīng)的熱釋放速率逐漸降低。采用P(VdF-HFP)凝膠電解質(zhì)比液態(tài)電解液更為安全 PMMA凝膠電解質(zhì)體系中，情況卻

23、是相反:其燃燒反應(yīng)的放熱總量和熱釋放速率都隨PMMA的加入而顯著增大。鋰離子電池的安全性是一個(gè)復(fù)雜的系統(tǒng)問(wèn)題 動(dòng)力電池安全性是一個(gè)系統(tǒng)問(wèn)題。 從單純的電池材料改性（正極、負(fù)極、電解質(zhì)、隔膜）是不能完全解決安全性問(wèn)題，但可以大幅度地提高。鋰離子鋰離子動(dòng)力電池的安全性設(shè)計(jì)動(dòng)力電池的安全性設(shè)計(jì)安全性能設(shè)計(jì)安全性能設(shè)計(jì)正極材料包覆鈷酸鋰包覆磷酸鋁5-10nm AlPO4過(guò)充電前過(guò)充電后自制安全性手機(jī)電池過(guò)充電試驗(yàn)未燃燒、未爆炸。市售品牌電過(guò)充電池電芯Energy 燃燒高性能高安全性動(dòng)力電池采用正極材料表面與界面控制技術(shù)、電解質(zhì)添加劑等技術(shù)，制備出高安全性動(dòng)力電池。20V過(guò)充150熱箱5小時(shí)以上標(biāo)稱(chēng)容量

24、12Ah，三元氧化物正極材料。電池比能量大于160wh/kg，比功率大于1200W/kg， 安全很好的倍率性能目前市售三元?jiǎng)恿﹄姵氐倪^(guò)充電 充電到5.2V時(shí)，發(fā)生劇烈燃燒目前市售三元?jiǎng)恿﹄姵?充電到4.15V，加熱到120，發(fā)生劇烈燃燒鋰離子動(dòng)力電池的使用壽命 動(dòng)力電池的使用壽命與成本 如何評(píng)測(cè)動(dòng)力電池的使用壽命 現(xiàn)場(chǎng)檢測(cè)電池的壽命狀態(tài)（SOH）鋰離子動(dòng)力電池的使用壽命 PHEV battery likely to deep-cycle each day driven: 15 yrs equates to 4000-5000 deep cycles Also need to consider

25、combination of high and low frequency cycling and calendarwlife 電池電池循環(huán)壽命70%50%4000Data presented by Christian Rosenkranz (Johnson Controls) at EVS 20, 200652% EV$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,

26、000$16,000CVHEVPHEV20PHEV40transmissionengine25%電池占電動(dòng)車(chē)成本比例Projected Retail Powertrain Costs - Midsize Sedans1) including manufacturer and dealer markups2) all component costs assume projected statuscharger/plugbattery 40%motor/inverter60%$663動(dòng)力電池的使用壽命 電池的成本占整個(gè)電動(dòng)車(chē)成本的2560%。是一個(gè)非常重要的零部件。 車(chē)的使用壽命：10-15年 動(dòng)力電池目前的使用壽命是3-7年，LG化學(xué)聲稱(chēng)可以有10-15年的壽命保證。 因此大幅度地延長(zhǎng)動(dòng)力鋰離子電池的使用壽命，使之達(dá)到與電動(dòng)車(chē)的壽命相當(dāng)，是目前動(dòng)力鋰離子電池發(fā)展的關(guān)鍵問(wèn)題。 需要?jiǎng)恿﹄姵厥褂脡勖u(píng)測(cè)技術(shù)做支撐。Ohmic Resistance Ohmic Resistance Ohmic Resistance large1.51.3 HighdeCycles50100 150 200 250 300 350 400 450Cycles 1Effects of charging/discharging depth2.521.51005