不同环境体系下锂离子电池热失控特性实验研究

针对锂离子电池热失控引发的航空运输安全问题,自主设计并搭建锂离子电池热失控灾害演化及危险性分析实验平台。在敞开和密封环境体系下,对电加热触发荷电量(State of Charge,SOC)为0%、50%和100%的18650型锂离子电池热失控规律进行了实验研究。观察单体锂离子电池在敞开和密封体系中的热失控现象,并记录单体锂离子电池热失控时间、温度峰值及相应的温度变化。数据结果显示,相比敞开体系,密封体系有效的延缓了锂离子电池发生热失控的时间,并降低了锂离子热失控时释放的能量,为锂离子电池的航空运输安全性研究提供了理论依据和工程技术参考。     

锂离子电池热解气体爆炸极限测定及其危险性分析

为定量研究锂离子电池热失控的危险性,利用锂离子电池在滥用条件下释放气体的种类及体积分数,计算锂离子电池热解气体爆炸极限并研究锂电池荷电状态对热解气体爆炸极限的影响。结果表明:在一定热失控条件下锂离子电池荷电状态为100%时其热解气爆炸下限为6.22%,上限为38.4%,在相同热失控条件下,锂离子电池热解气体的爆炸极限范围随着荷电状态的升高而增大,锂电池的荷电状态对热解气体的爆炸上限影响较大而对爆炸下限影响较小。在相似条件下,锂离子电池热解气体的爆炸极限范围比普通烃类气体大,一旦锂电池发生热失控会对锂离子电池运输造成潜在威胁。     

高温环境下18650型锂离子电池热失控过程的数值分析

采用ANSYS对高温条件下铜棒代替锂离子电池的空白试验进行数值模拟,获得拟合的陶瓷化纤棉毯的比热容;然后对18650型锂离子电池的热响应进行模拟,通过模拟结果与试验数据的比较分析,获得锂离子电池内部的反应放热量;最后应用得出的陶瓷化纤棉毯比热容和化学反应热对高温环境下18650型锂离子电池的热失控进行模拟,研究18650型锂离子电池热失控的变化规律.结果表明:20W加热条件下,锂离子电池的放热反应热为30 kJ;锂离子电池在加热1 287 s后发生热失控,热失控持续113 s后锂离子电池温度达最高,之后开始缓慢减小;锂离子电池热失控温度为500 K,热失控前温度几乎是线性增加,之后热失控导致温度迅速增加(呈指数倍增长);锂离子电池保温材料陶瓷化纤棉毯的温度变化是非线性的.     

低压细水雾系统扑救锂电池箱火灾的试验研究北大核心CSCD

为了提升动力锂离子电池系统的安全性,除了一些常规保护措施(电池冷却、电量监测、过热报警等)外,增加抑制锂离子电池早期热失控及火灾的防护系统也是必要的。针对某型电动客车锂离子电池箱的50 Ah三元锂离子电池,开展了锂离子电池单体火灾试验、锂离子电池箱火灾抑制试验及锂离子电池早期热失控抑制试验,验证低压细水雾灭火系统对于锂离子电池箱热失控安全防护的效果。结果表明,该类型三元锂离子在800 W功率的加热下,会瞬间发生爆燃,燃烧时间为69 s。低压细水雾系统成功实现了对动力锂离子电池箱内火灾及单颗锂离子电池早期热失控的抑制。在锂离子电池火灾及早期热失控抑制的过程中,均未观察到复燃及模组间热失控的传播。     

不同加热功率触发锂离子电池热失控特性研究

针对目前频发的锂离子电池热失控事故,自主设计并搭建了圆柱形锂离子电池热失控实验平台,对不同加热功率触发的锂离子电池热失控过程进行了实验研究。数据结果表明,外在热源功率对锂离子电池热失控行为影响很大。锂离子电池热失控过程中响应温度随加热棒功率的升高而降低,而最高温度随加热棒功率的升高而升高。通过对不同加热功率触发锂离子电池热失控特性的研究,可为锂离子电池的储存和运输安全性研究提供理论依据和工程技术参考。     

太空环境下锂离子电池热失控与火灾的研究展望

综述了锂离子电池的热失控机理,介绍了由于电池内部电解液、电池隔膜和电极材料分解的链式热反应过程而引发的热失控和火灾现象。同时,讨论了锂离子电池在微重力太空环境中可能产生的烟黑浓度倍增,加速火蔓延,火焰喷射等极端火行为。进而探讨了开展锂离子电池的低压、落塔和抛物飞行等地面实验模拟太空微重力燃烧的方法可行性,建立数值模型预测太空微重力环境下锂离子电池热失控临界条件与火灾行为的必要性,以及如何通过基础研究科学地指导空间站电池热管理和消防系统的设计。     

低压环境下新型清洁灭火剂抑灭锂离子电池火试验

为研究可替代哈龙的新型气体灭火剂2-溴-3,3,3三氟丙烯(2-BTP)抑制和扑灭航空货运锂离子电池火的有效性,基于动压变温试验舱和灭火系统开展试验。在80k Pa、60 k Pa和40 k Pa低压环境下对100%电量的21700锂离子电池用加热棒进行加热并引发其热失控,同时启动灭火系统释放灭火剂。在试验过程中实时采集记录锂离子电池的温度、热失控现象,以及舱内环境空气中CO体积分数的变化。结果表明,2-BTP灭火剂在低压环境下能有效扑灭锂离子电池火且无复燃,减少CO的生成量,同时能够抑制相邻锂离子电池间的热传播,从而阻止连锁热失控。     

不同荷电状态下三元锂离子电池针刺热失控试验研究

基于锂离子电池实际存储与应用的普遍性和危险性,利用自主设计并搭建的试验平台,分别对不同荷电状态(SOC)的锂离子电池进行了针刺热失控试验.利用直径5 mm的钨钢针触发圆柱形21700三元锂离子电池热失控,记录其试验现象,测定锂离子电池的温度、开路电压与质量等参数.结果表明:锂离子电池SOC越高,针刺时发生热失控的现象越剧烈,且当锂离子电池SOC高于60％时,电池各测温点的最高温度都在电池正极处,电池外表面的温度峰值均高于电池内部的温度峰值;随针刺的锂离子电池SOC增大,电池各测温点温度峰值升高,电池正极处到达峰值所需时间变短;不同荷电状态的锂离子电池在进行针刺试验后,两端开路电压掉落的时间点不同,电池SOC越高,开路电压掉落的时间越快,在发生针刺后三元锂离子电池安全阀能保护电池不发生明显热失控现象的最大SOC在60％左右;SOC越高的锂离子电池在发生热失控过程中电池损坏越严重,其质量损失率越大.     

模组箱体空间内磷酸铁锂电池热失控及其传播行为研究

为了探究储能用锂离子电池在真实应用场景下的热失控及其传播行为特征,选用86Ah方形磷酸铁锂(LiFePO4)电池,对其在热滥用触发方式下的热失控行为及模组箱体空间与开放空间中的传播行为规律进行了实验研究。单体实验结果表明,电池热失控产生的高温烟气会导致模组箱体内沿高度方向出现明显温度梯度,模组底部与顶部温度测点的最大温差达118.4 ℃。传播实验结果表明,模组箱体空间内热失控电池通过产气及喷出高温电解液向其他电池传热,在热失控电池影响下,模组箱体空间内3块电池上表面所能达到的最高温度均高于开放空间实验12 ℃~150 ℃,模组空间内热失控电池向同侧两块电池的传热量高于开放空间实验225 kJ和44.4 kJ。但箱体环境中有限的氧气供给会减缓电池在热失控时的内部放热反应进程,模组箱体空间实验中电池热失控峰值温度较开放空间实验低33 ℃~145 ℃,并且模组箱体空间实验中热失控完全传播所用时间较开放空间实验滞后213 s。研究结果对于锂离子电池模组的安全设计和热失控传播阻隔具有一定的参考价值与指导意义。     

航空压力环境对锂离子电池热解气体爆炸极限影响*

针对航空锂离子电池热失控释放气体安全性研究不足的问题,采用气体拉曼光谱技术、气相色谱仪(Gas Chromatography,GC)和质谱(Mass Spectroscopy,MS)耦合来探究压力和荷电状态(State of Charge,SOC)对锂离子电池早期故障气体类型、气体动态演变及气体潜在危险性等特征的影响规律,同时综合考虑压力、电压和电池温度等多种因素分析锂离子电池热失控危害。研究结果表明:电池SOC越高且环境压力越低,电池越早触发热失控,爆炸极限越宽,其中30 kPa下100%SOC电池热解气体爆炸极限为8.01%~53.35%;SOC和环境压力越高,电池热失控越危险,释放的气体体积越多;CO,CO2,PF3,C2H4及电解液（C3H6O2、C3H6O3、C4H8O2）等气体可作为航空锂离子电池早期故障诊断特征。研究结果对保障锂离子电池在航空领域的安全运输及应用具有重要意义。     

Experimental study on thermal runaway risk of 18650 lithium ion battery under side-heating condition

To simulate the heat transfer process between lithium-ion batteries (LIBs), an electric heater with the same size and shape as LIB in this work is used to trigger thermal runaway event. The effect of state of charge (SOC), the power of heater, the cell spacing on thermal behavior of LIB was investigated as well the amount of transferred heat between the heater and LIB was calculated. The results indicate that 50% SOC is an unstable state for LIB, that a stronger jet flame becomes more likely when the SOC of LIB is higher than 50%. Additionally, the increased spacing, lower heating power and SOC can contribute to mitigate the severity of thermal runaway behavior. Further, the dominant path of heat transfer between the heater and LIB will also vary with operating conditions. The heat conduction through air is the main heat transfer path in tests with lower heating power. However, heat radiation will replace heat conduction as the primary heat transfer mode when there is a large temperature difference between the heater and LIB in tests with higher heating power. Understanding the leading heat transfer path between LIBs can provide valuable guidelines for the safety design of lithium-ion battery modules.     

钛酸锂电池在绝热环境中循环的热响应特性

钛酸锂电池广泛应用于储能系统,其安全性也备受关注。采用加速量热仪与电池循环仪联用技术,对钛酸锂电池在循环过程中的热响应情况进行了研究。研究表明,测试电池在放电和充电阶段均有明显的小幅度温升现象。通过测试电池在不同倍率下的产热情况,发现电池在各循环阶段的绝热产热量与循环倍率成正比,其热失控危险性也随着循环倍率的增大而增加。     

火场环境下无人机热损伤试验研究

无人机(UAV)逐步运用于火场搜救,但同时会因为火场高温而受损,为提高UAV在火场救援中的工作效率,设计一种UAV动态测试平台,开展UAV火场飞行试验;分析火场环境下UAV的热损伤情况,探究UAV在火场中的机身温度变化特征和UAV火场飞行安全距离。结果表明:火场热辐射和热对流是造成UAV热损伤的主要形式;旋翼产生的气流场对UAV机身有较为明显的降温效应,在试验工况下最高有25.6℃的降温作用;UAV与火焰的相对距离减少会增加机身的热损伤,在距离0.8 m处开始发生不可逆热损坏,试验工况下UAV火场飞行的安全距离为0.8 m。     

Research on thermal decomposition characteristics of H foaming agent with different moisture contents

N, N-Dinitroso pentamethylene tetramine, also known as H foaming agent, is a self-reactive chemical substance commonly used in the rubber industry. Decomposition, explosion and combustion may be caused by the presence of fire or high temperature. As a high-risk chemical that is strictly regulated in China, H foaming agent has ever triggered multiple accidents. During the study of the decomposition thermal process of H foaming agent, it was found that the presence of moisture content at different levels had a significant effect on its thermal stability. The thermal characteristics of H foaming agent under different moisture contents was studied through the test means such as adiabatic calorimetry and high-pressure differential scanning calorimetry. Through isothermal calorimetry experiment, it was found that the decomposition of H foaming agent had obvious auto-catalytic characteristics. In the moisture content within the range of 0–40%, with the increase of moisture content, the initial exothermic temperature T_onset of the mixture system of H foaming agent and water decreased, while the time from initial heat release to rapid temperature rise of the reaction system (induction period) was gradually prolonged, and the temperature increment of the reaction system was increased gradually. As the proportion of moisture content in the system increased, the adiabatic temperature rise ΔT_ad of the mixture system of H foaming agent and water gradually decreased, meanwhile the time to maximum rate under adiabatic condition (TMR_ad) gradually decreased. The research results have guiding significance for finding the reasonable moisture content of H foaming agent in the drying process and determining the upper temperature limit during storage and transportation.     

一种新型煤层气旋转控制头旋转总成的温升影响因素分析

可靠有效的冷却润滑系统是旋转控制头安全、高效工作的保证。结合现有成熟技术,设计出一种集冷却润滑系统与旋转总成为一体的新型旋转控制头。为确保其旋转总成冷却润滑的要求,建立1/2实体三维数值模型,分析了密封井压、钻杆转速、井口偏心距对其温升的影响。结果表明:三影响因素均是旋转总成温升的主要因素,随三者的增大旋转总成的热平衡最高温升呈非线性增大,但在其运转所允许的温升范围内;三影响因素对旋转总成的动密封系统温升的影响最为明显,说明动密封系统是旋转总成的主要热源点;井口偏心距的增大较另外两种影响因素的增大,对旋转总成的热平衡最高温升值影响更大,进一步证实了旋转控制头安装过程中减少井口偏心距的重要性。     

Lower explosion limit of the vented gases from Li-ion batteries thermal runaway in high temperature condition

The thermal runaway of lithium-ion battery (or Li-ion battery, LIB) results in scrap of battery and fire, with the toxic and flammable gases generated. In this work, a self-made device was to collect gases from LIB thermal runaway, when the batteries were under different states of charge (SOC), temperatures of the environment and powers of external heating. Three samples of the collected gases were analyzed to get the results of the composition and content by chromatography-mass spectrometry system (GC-MS). The lower explosion limits (LELs) of the gases was tested by FRTA explosion limit instrument. And then the LEL of three analyzed samples whose composition and content were known by GC-MS were calculated via theoretical formulas. The calculated LELs were compared with those of the instrument test. The errors of the two results of three samples are 2.1%, 1.9%, and 0.4%. The Le Chatelier Formula and empirical formula provide a way to evaluate the LEL of the battery runaway gas more quickly.     

低压环境下不同三元圆柱锂电池热失控危险特性对比研究

为研究21700和18650新旧2型多用途锂离子电池在航空运输低压环境下的热失控特性差异，采用动压变温实验舱搭建实验平台开展实验。将实验环境压力设定为飞机巡航时的环境压力30 kPa，对比常压101 kPa，使用外部热源加热的方式触发锂电池热失控，利用热传播引发相邻电池热失控，分别从热失控温度变化特性、热释放速率和热解气体组分浓度变化进行分析。研究结果表明:能量密度更高的21700电池热失控峰值温度更高，高温危险性要高于18650电池，但触发热失控所需的热量更多，电池间热传播时间会延长；低压环境有利于降低锂电池热失控燃爆峰值温度，减小燃爆热释放速率，但会产生更多CxHy和CO等具有燃爆性的热解气体，可能会在有限空间内与氧气混合引起二次燃爆。     

过氧化苯甲酰合成工艺热危险性分析

采用RC1e反应量热仪对过氧化苯甲酰(BPO)合成工艺危险性进行研究,测试不同Na OH溶液初始浓度(1.96 mol/L、3.93 mol/L、7.14 mol/L)下反应的放热历程,获得BPO合成反应过程中的热危险性参数,并采用PHI-TECⅡ绝热加速量热仪对产物进行热稳定性分析,最后评估该反应热风险。结果表明,Na OH浓度为7.14 mol/L时,反应初期放热速率慢,热累积度大,后期反应剧烈,绝热温升(ΔTad)及热失控时工艺反应达到的最高温度(MTSR)最大。热稳定性试验表明,合成的粗产物BPO初始分解温度、活化能、指前因子、最大放热速率到达时间为24 h时的对应温度(TD24)均低于纯BPO。利用合成粗产物BPO的TD24对反应进行危险度评估,该工艺热危险性等级均为5级,工艺危险性大。     

Reaction hazard and mechanism study of H2O2 oxidation of 2-butanol to methyl ethyl ketone using DSC,Phi-TEC II and GC-MS

Methyl ethyl ketone (MEK) oxidation via H₂O₂ with tungsten-based polyoxometalate catalysts has gained much attention with an ever-growing body of knowledge focusing on the development of environmentally benign processes in chemical industry. In this study, two calorimetry techniques, differential scanning calorimetry (DSC) and Phi-TEC II adiabatic calorimetry, were employed to analyze the thermal hazards associated with the 2-butanol oxidation reaction system. Hydrogen peroxide was the oxidant and a tungsten-based polyoxometalate as the catalyst. Gas chromatography-mass spectrometry was used for identification of the organic products. Important thermal kinetic data were obtained including “onset” temperature, heat of reaction, adiabatic temperature rise and self-heat rate. From DSC results, three exothermic peaks were detected with a total heat generation of approximately 1.26 kJ/g sufficiently to induce a thermal runaway. Possible reaction pathway for three stages were proposed based on both DSC and GC-MS results. One exotherm was detected by Phi-TEC II calorimeter and the pressure versus temperature profile together with the DSC and GC-MS data demonstrate the complexity of 2-butanol reaction system under both thermal screening and adiabatic conditions.     

硝酸甲胺反应过程的安全性研究

用反应量热仪(RC1e)对硝酸溶液与一甲胺溶液在反应过程中的热安定性进行初步研究,分别测试不同反应温度、加料速度和初始硝酸浓度下反应的放热情况。实验结果表明:该中和过程反应迅速,在室温就能进行;与反应温度、加料速度相比,起始硝酸浓度对反应安全性影响最大,且硝酸浓度越高,反应的速度和反应的完全程度也越高。实验还表明:RC1e是研究反应过程中热安定性情况的有效工具,能通过反应过程的热量变化体现反应速率,所得结果对硝酸甲胺的工业化生产具有重要的参考价值。