锂电池和锂离子电池的危险性研究.pdf
书书书 doi 10. 3969/ j. issn. 1001 8352. 2013. 05. 001 A Study on Hazard of Lithium and Lithium ion Batteries LI Xinrui①,KOSEKI Hiroshi② ①M ary Kay O Connor Process Safety Center,Texas A &MUniversity ( College Station,TX, 77843 3122,USA) ②National Research Institute of Fire and Disaster ( Chofu,Tokyo, 182 8508, Japan) [ ABSTRACT] With increasing application,lithium and lithium ion batteries show hazards during usage,storage, disposal and waste.To evaluate the thermal stability of lithium and lithium ion batteries,their electrolytes were assessed by Chemical Thermodynamic and Energy Release( CHETAH)and measured by a Differential Scanning Calorimeter ( DSC) , since they sometimes caused fires and accidents.M oreover,thermal reactivity of lithium,silver oxide and alkaline batteries were analyzed by using a modified closed pressure vessel test ( M CPVT) .As a result,lithium battery is more hazardous than the other batteries.The sensitiveness to mechanical stimuli,such as a fall hammer,of lithium battery was also much higher than other batteries.The explosive power,which was evaluated by a ballistic mortar,of lithium coin battery was higher than those of other batteries. [ KEY WORDS] lithium battery,lithium ion battery,thermal reactivity,M CPVT, mechanical stimuli,explosive power [ CLASSIFICATION CODE] X932 Introduction Battery is a high energy density device which delivers electrical energy by transforming chemical energy[ 1].Batteries come in different configurations, sizes and voltages. Conventional batteries contain heavy metals such as mercury,lead,cadmium and nickel. Lithium battery types,on the other hand,include lithium manganese dioxide,lithium sulfur dioxide and lithium thionyl chloride.The anode is composed of lithium and the cathode is composed of manganese dioxide ( or sulfur dioxide,or thionyl chloride) . The electrolyte of the lithium manganese dioxide battery is composed of an organic solvent( propylene carbonate and 1, 2 dimethoxyethane) solution of lithium perchlo rate.In the case of lithium sulfur dioxide,the electro lyte is also an organic solvent ( acetonitrile)solution with lithium bromide.The thermal reactivity of battery results from its containing electrolyte as combustible materials,which lead to heat generation,bursting or fire if it is improperly handled.With more and more widely application since 1990s in various portable con sumer electronic devices,such as cameras, electronic notes and electronic calculators,safety problem in lithium batteries arises when abuse,discard or with large amount of storage.One reported accident of pri mary lithium coin cell bateries was that in 1994,a fire happened in a cardboard box,in which 2, 000 cells were packed[ 2 3]. Lithium ion battery made accidents and fires[ 4], with sizes generally larger than that of li thium battery.The study of the hazard of lithium batteryisverylimited, andmorestudieswere concernedwiththeelectrolyteoflithium ion batteries[ 5 6]. This paper studied the risk of primary lithium battery and lithium ion battery compared with other types of batteries.Considering the electrolyte is a combustible material,the hazard was evaluated by the 12013 年 10 月 锂电池和锂离子电池的危险性研究 李新蕊等 收稿日期 2013 05 30 作者简介李新蕊( 1969 ~ ) , 女, 博士, 研究员, 主要从事可再生资源燃料的危险性评价和物质化学反应、 生产、 储存、 运输、 使用过程中的安全性评价方法等 方面的研究。E mailxinruili2008@gmail. com 通信作者古积博( 1950 ~ ) , 男, 博士, 主要从事危险物危险性评价和油罐火灾沸溢方面的研究。E mail koseki@fri. go. jp ChemicalThermodynamicandEnergyRelease ( CHETAH) program[ 7]and a Differential Scanning Calorimeter( DSC) .Then,a modified closed pressure vessel tester( M CPVT) [ 8] was used to measure their thermal reactivity in terms of pressure and temperature histories during heating.The measurements were also performed on an alkaline and a silver oxide batery. Their sensitiveness to mechanical stimuli,such as a fall hammer,was also examined by a drop hammer test[ 9].The explosive power of battery was evaluated by a ballistic mortar[ 9]. 1 Evaluationofhazardofelectrolytesby CHETAH The thermal reactivity of battery results from its con taining electrolyte as combustible materials.The pro gram CHETAH 7. 2,the ASTM computer program for chemical thermodynamic and energy release evalua tion,was used for classifying the electrolyte of lithium battery for their ability to decompose with violence and for estimating heat of reaction or combustion by terms of the maximum heat of decomposition,the fuel value heat of decomposition,the oxygen balance and the CHETAH ERE Criterion,y,defined as y = 10( M 2W/ n) where Mis the maximum heat of decomposition,W is the weight of the composition in gram and n is the number of moles of atoms in the composition. Two electrolytes for lithium primary and one for lithium ion battery were calculated 1)Lithium perchlorate 10% +propylene carbonate ( in lithium primary battery) ; 2)Lithium perchlorate 10% +γ Butyrolactone ( in lithium primary battery) ; 3)Ethylene carbonate ( in lithium ion battery) . The results are given in Table 1,and both electro lytes for primary rated as medium energy hazard poten tial and the electrolyte for ion battery is lower. 2 Experimental 2. 1 Thermal analysis The Differential Scanning Calorimeter ( DSC)test was conducted for two electrolytes with 5% and 10% ( wt)of lithium perchlorate ( LiClO4)in propylene carbonate,and 13% ( wt)of lithium hexafluorophos phate ( LiPF6)in ethylene carbonate ( C3H4O3) .In the measurements,sample of 1. 8 1. 9 mg in a sealed SUS cell was heated at 5 K/ min from room temperature to 400℃ and heat flux was measured during the entire process. A modified closed pressure vessel tester[ 8]( M CPVT, heating rate, 2 K/ min)was used to examine the ther mal reactivity of primary lithium coin cell batteries. Lithium ion battery is too large to be measured by M CPVT.Samples were a small coin battery ( cell) , CR1220 ( 12. 4 2. 0 mm,weight0. 88 g)or CR1226 ( made in Germany, 12. 4 1. 6 mm, weight 0. 98 g) ,alkaline LR44 ( 11. 5 5. 1 mm, weight1. 96 g)and silver oxide SR44 ( 11. 5 5. 2 mm,weight 2. 19 g)batteries. Comparison of summary of DSC and M CPVT is shown in Table 2. Tab. 2 Summary of DSC and M CPVT nameDSCM CPVT Sample Electrolyte, 1. 8 1. 9 mg Entire coin battery, ca.1 2 g Heating rate/ ( Kmin -1) 52 Temperature Room temp. 400℃ Room temp. ca. 400℃ M easurementHeat of reaction Temperature and pressure 2. 2 Drop hammer test The drop hammer test,based on JIS K4810,was used to measure the sensitiveness of batteries to drop weight impact.A 5. 0 kg steel anvil was used at fall heights from 0. 5 m to 1. 0 m,in steps until the limi ting impact energy was determined.M ost samples were Tab. 1 Results of hazards evaluation by CHETAH 7. 2 Electrolyte M aximum heat of decomposition / ( kJg -1) Fuel value Heat of decomposition/ ( kJg -1) Oxygen balance/ % y 1- 1. 834( M edium)- 13. 394 ( M edium)- 106. 810 ( High)15. 949 ( Low) 2- 1. 955 ( M edium)- 18. 083 ( M edium)- 144. 510( M edium)16. 624 ( Low) 3- 1. 725 ( M edium)- 1. 118 ( M edium)- 90. 841 ( High)14. 984 ( Low) 2 爆 破 器 材 Explosive M aterials 第 42 卷第 5 期 new one.However discharged and sheared lithium bat teries were also tested.Lithium ion battery,Casio NP 20 which was used for digital camera,was added to the test samples.Sample was about 70 % charged. 2. 3 Ballistic mortar Mk. IIID test The Ballistic mortar M k. IIID test was used to mea sure the explosive power of batteries.A detonator was initiated in the battery whilst the battery was confined in the bore of a mortar.The recoil of mortar was mea sured and, after allowing for the effect of the detonator, the power was calculated as a percentage equivalence of TNT and picric acid,the explosive standards. 3 Experimental results and discussion 3. 1 Thermal analysis The results of three eletrolytes in the DSC are shown in Figure 1.It is seen that with increasing the concen tration of LiClO4,the heat of reaction increased.Com paring with standard materials,such as 80% BPO ( benzoyl peroxide)and 70% DNT ( dinitrotoluene) according to the evaluation method of Japanese Service Law,they are lower than the standard line which was obtained from the results of standard materials,and less dangerous than standard materials.However,the positions of the lithium electrolytes are close to the standard line, whereas the lithium ion electrolyte ( 13% LiPF6in C3H4O3)is much lower. Fig. 1 Evaluation of the electrolytes ( TDSConset temperature, QDSCheat of reaction) Pressure vs.temperature curves of lithium battery in the M CPVT was compared with two other batteries,sil ver oxide and alkaline cells,in Figure 2.It is seen that no reaction occurred for silver oxide and alkaline cells up to 350℃.In contrast,lithium cell was quite reactive.The pressure rise started at about 100℃. The pressure of lithium cell gradually reached a maximum of 42 kgf/ cm2at about 329℃. Fig. 2 Pressure vs.temperature curves of lithium, silver oxide and alkaline cells in M CPVT 3. 2 Drop hammer test Sensitiveness of batteries to mechanical stimuli was assessed on the basis of whether an explosion occurs at particular impact energy bydroppinga 5.0kg hammer.The impact energy,characterising the impact sensitiveness,is calculated from the mass of the drop weight and the fall height.The results are shown in Table 3 and Figure 3.It implies that explosive did not occur for alkaline and silver oxide batteries even at much larger impact energy, 50 J ( Figure 3a) .In con trast,explosive occurred in lithium battery and a dis charged one at lower impact energy,30 J ( Figure 3b) . For a sheared one, impact energy at which explo sion occurred was 25 J for lithium ion battery gave no explosion,but it increased its temperature to about 120 ℃ after three minutes from the test,which was surface temperature measured with thermal paper and 0. 1 mm ( a) ( b) 32013 年 10 月 锂电池和锂离子电池的危险性研究 李新蕊等 Tab. 3 Results of drop hammer test SampleCR1220CR1220 usedCR1220 shearedLR44SR44Li ion Fall height/ m0. 6/ 1. 00. 60. 51. 01. 01. 0 Explosion+++--- impact energy/ J30,> 503025> 505050 Electrolyte and Casio NP 20; +stands for explosion, -does no explosion. Tab. 4 Results of ballistic mortar M k. IIID test SampleCR1216CR1220CR2025LR44Electrolyte 1 Li batteryElectrolyte 3 Li ion battery Weight/ g2. 6, 5. 13. 54. 63. 95. 05. 0 M ean of TNT/ %7. 83. 916. 73. 92. 31. 6 ( c) ( a) LR44,SR44,Height = 1 m; ( b) Li battery ( CR1220) , Height = 0. 6 m; ( c) Li battery ( CR1220) ,Height = 1. 0 m Fig. 3 Results of drop hammer test diameter K type thermocouples.Impact from 1. 0 m high gave much vigorous result ( Figure 3c) . 3. 3 Ballistic mortar Mk. IIID test The explosive power was calculated as a percentage of the value given by TNT in the ballistic mortar M k. IIID test.In Table 4,lithium batteries CR2025 and CR1216 presented medium explosive power.Whereas the explosive powers of CR1220,alkaline LR44 and electrolytes were low.Electrolytes were also tested, and they gave lower values than those of coin type bat teries.Among the results,electrolyte of lithium ion battery gave the smallest value. 4 Conclusion In order to understand hazard of lithium battery and lithium ion battery,CHETAH calculation and various evaluation tests were conducted.Based on the results lithium coin battery was most hazard. 1) The reactivity of the electrolytes of lithium battery and lithium ion battery was predicted by the CHETAH program. Lithium electrolytes presented medium hazard by CHETAH,whereas the electrolyte of lithium ion battery was lower. 2) The electrolytes of these batteries were measured by the DSC.The hazard of lithium battery electrolytes was lower than those of BPO and DNT,but higher than that of lithium ion battery. 3) The entire cells were measured by the M CPVT. As a result,the reactivity of lithium coin battery was much higher than those of silver oxide and alkaline bat teries.Lithium ion battery was too large to be tested by the M CPVT. 4) The drop hammer test resulted that lithium coin battery gave high sensitiveness.And the explosive power of lithium coin battery,which was evaluated by the ballistic mortar,was higher than those of other types of batteries. Acknowledgements This work was partly supported by a research fund from the M inistry of the Environment. References [ 1] Sanyo Lithium Batteries[ OL] .http / / www. sanyo. co. jp/ energy. [ 2] Battery Association of Japan.Guideline and manual of lithium battery[ S] .Japan, 1995. [ 3] Hashimoto O,Yamadera A,Abe K.Safety problem in the process of crush unit possibility of fire and loss pre vention of lithium battery[ C] / / 15th Annual conference of JSWM E.Japan, 2004. [ 4] Wang Qingsong,Sun Jinhua, Yao Xiaolin,et al.M icro calorimeter study on the thermal stability of lithium ion battery electrolytes[ J] .Journal of Loss Prevention in the Process Industries, 2006, 19( 6) 561 569. [ 5] Yamanaka H, Tamura M, Arai M. Study on safety problem of lithium ion battery[ R] . Technical Report at Research Group of Disaster.Japan, 2000. [ 6] Wang Qingsong,Sun Jinhua,Chen Chunhua.Enhancing 4 爆 破 器 材 Explosive M aterials 第 42 卷第 5 期 the thermal stability of LiCoO2electrode by 4 isopropyl phenyl diphenyl phoshhate in lithium ion batteries[ J] . Jounal of Power Sources, 2006, 162( 2) 1363 1366. [ 7] Balaraju B.The ASTM computer program for chemical thermodynamic and energy release evaluation, chetah, version 7. 3 User s Guide[ M] . USA ASTM Internation al, 2002. [ 8] Li Xinrui,Koseki H,Liu Dabin,et al.Results of mini round robin tests of M CPVT[ J] .Fire Safety Science, 2004, 13( 1) 11 17. [ 9] The United Nations.Recommendations on the Transport of Dangerous Goods[ M] / / M anual of Tests and Criteria. 4th ed. 2003. 锂电池和锂离子电池的危险性研究 李新蕊① 古积博② ①美国德克萨斯 A& M大学玫琳凯奥康纳过程安全中心( 美国德克萨斯州大学城, 77843 3122) ②日本国立消防研究所( 日本东京调布, 182 8508) [ 摘 要] 随着锂和锂离子电池应用的不断增加, 在其使用、 储存、 处理和废弃过程中也呈现出越来越多的危险 性。锂和锂离子电池的电解质是可燃物质, 会引起火灾, 其热稳定性分别由 CHETAH 和 DSC 评估和测定。另外, 锂电池、 氧化银电池和碱性电池的热稳定性通过在一个改性的密闭压力容器中测定( M CPVT) 。结果表明锂电池比 其它电池的危险性更大。锂电池对力学冲击( 如落锤试验) 的敏感度高于其它电池。其爆炸威力( 如对弹道冲击) 也高于其它电池。 [ 关键词] 锂电池 锂离子电池 热反应性 改性密闭压力容器试验 力学冲击 檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼檼 檸檸檸檸檸檸 檸檸 檸檸檸檸檸檸 檸檸 殠 殠 殠 殠 爆炸威力 文 摘 1 适用于爆破药包和煤矿装药的工业炸药 俄罗斯专利, RU2159757, 2000 年 10 月 27 日 ( 俄文) 这种炸药为 5 级工业炸药, 适用于作为煤矿爆 破药包, 不会引爆煤矿地区空气中的甲烷和煤尘。 这种炸药含有硝酸酯、 氯化铵、 硝酸钾、 羧甲基纤维 素钠、 硬脂酸锌、 胶态棉、 苏打灰和聚氯乙烯。这种 炸药具有低的摩擦感度、 易于处理和高的贮存安定 性。 2 防水粒状炸药组成 日本专利, JP2002, 29877, 2002 年 1 月29 日, 共 5 页( 日文) 这种防水粒状炸药由多孔粒状硝酸铵和燃料油 组成。多孔粒状硝酸铵用聚合物包覆, 聚加物在热 熔后为液态或乳状液状态, 并在包覆后凝固。所用 聚合物有丙烯酸树脂、 苯乙烯丁二烯聚合物、 聚氨 酯、 苯乙烯丁二烯共聚橡胶、 丙烯腈丁二烯共聚 橡胶或它们的混合物。这种炸药在使用上, 对松密 度、 流动性和抗水性方面与铵油炸药( ANFO) 有相 同的特性。 3 2′ , 4′ 二硝基苯基 1, 2, 4 三唑酮 5 的合成 火工品 , 2001( 2) , 36 37, 44( 中文) 题称的化合物是由草酸、 氨基脲和 2, 4 二硝基 氟苯合成的, 并通过熔点、 1H 核磁共振和元素分析 对它作出鉴定。 4 防水粒状炸药组成 日本专利, JP2002, 47088, 2002 年2 月