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。     

常压及低压下锂电池热失控随数量变化特性

为明确在地面常压环境和商用飞机巡航高度低气压环境下锂电池热失控火灾危险特性随电池数量的变化关系,分别于95 kPa地面常压环境和20 kPa低压环境下,开展不同电池数量梯度的热失控试验,测量热释放速率,总热释放量,烟气温度,CO、CO2和碳氢等气体的实时体积分数.结果表明:最高热释放速率和总热释放量与电池数量均呈幂函数...     

Experimental hazardous risk investigation of energetic styphnic acid analytical reagent in calorimetric analysis

Analytical reagents identify and manage metal pollution, a major environmental issue. Regrettably, these compounds' safety concerns, especially when heated, have been neglected. This research examines the thermal hazard of the extremely reactive analytical reagent styphnic acid. Differential scanning calorimetry, thermogravimetric analysis, and accelerating rate calorimetry examined styphnic acid's thermodynamics. Thermogravimetric analysis showed weight loss reactions starting at 127 °C and peaking at 208 °C. Differential scanning calorimetry showed an endothermic peak at 176 °C. The accelerating rate calorimetry test showed that styphnic acid self-accelerates at 237 °C after 196.5 °C. Kissinger, Ozawa-Flynn-Wall, and Kissinger-Akahira-Sunose thermokinetic models calculated apparent activation energy from 131.677 to 155.718 kJ/mol. A nonlinear regression analysis showed that styphnic acid undergoes a two-step autocatalytic reaction during heat degradation. Thermal safety was assessed by measuring time to conversion limit, maximum rate, total energy release, self-accelerating decomposition temperature, and adiabatic temperature rise. Styphnic acid is less stable at higher temperatures and its thermal hazards depend on heating rate. The computed SADT was 109.04 °C, with alarm and control temperatures of 104.04 and 99.04 °C, respectively. The risk matrix analysis based on T_ad and TMR_ad suggests reducing thermal instability. This study on styphnic acid's thermal risks and safe storage and transit during analytical applications is beneficial.     

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。     

Evaluation of thermal properties and process hazard of three ionic liquids through thermodynamic calculations and equilibrium methods

Industrial and new energy applications of ionic liquids (ILs) may have to be used at high temperatures conditions, such as in batteries and fuel applications, which may cause thermal hazards. However, there are few studies on the thermal hazards of ILs. To ensure the thermal safety of ILs processes, three commonly used ILs were selected for analysis: 1-butyl-3-methylimidazolium nitrate ([Bmim]NO₃), 1-butyl-2,3-dimethylimidazolium nitrate ([Bmmim]NO₃), and 1,3-dimethylimidazolium nitrate ([Mmim]NO₃). The process hazards under adiabatic conditions demonstrated that [Bmmim]NO₃ and [Mmim]NO₃ have extensive explosion hazards. The self-reaction characteristics determined by the isothermal test indicated that the ILs are nth reactions, and the thermal decomposition features were also determined by thermogravimetric analysis. The data were obtained with a nonlinear thermodynamic model and used to establish the basic thermal hazards of the three ILs. In addition, based on the thermal equilibrium theory, the critical safety parameters can be inferred. The effects of heat transfer in 25.0 g and 50.0 g containers were discussed. The results show that [Mmim]NO₃ will produce a thermal runaway reaction at a lower temperature (<100 °C) and has the shortest reaction time (<1 day), which means [Mmim]NO₃ is considered to be the most hazardous material among the three ILs studied.     

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。     

Thermal hazard assessment for synthesis of 3-methylpyridine-N-oxide

The exothermic oxidation of 3-methylpyridine with hydrogen peroxide was analyzed by Reaction Calorimeter (RC1e) in semi-batch operation. Heat releasing rate and heat conversion were studied at different operating conditions, such as reaction temperature, feeding rate, the amount of catalyst and so on. The thermal hazard assessment of the oxidation was derived from the calorimetric data, such as adiabatic temperature rise (ΔT_ad) and the maximum temperature of synthesis reaction (MTSR) in out of control conditions. Along with thermal decomposition of the product, the possibility of secondary decomposition under runaway conditions was analyzed by time to maximum rate (TMR_ad). Also, risk matrix was used to assess the risk of the reaction. Results indicated that with the increase of the reaction temperature, the reaction heat release rate increased, while reaction time and exotherm decreased. With the increase of feeding time, heat releasing rate decreased, but reaction time and exotherm increased. With the amount of the catalyst increased, heat releasing rate increased, reaction time decreased and exothermic heat increased. The risk matrix showed that when the reaction temperature was 70 °C, feeding time was 1 h, and the amount of catalyst was 10 g and 15 g, respectively, the reaction risk was high and must be reduced.     

Thermal safety assessment for solid organic peroxides

The thermal hazards of dicumyl peroxide (DCP) and benzoyl peroxide (BPO), self-reactive chemicals are identified and characterized using high-pressuredifferential scanning calorimeter, and simultaneous thermogravimetric analyzer, a C80 micro-calorimeter is used. The apparent exothermic onset temperature of DCP is found to be between the range of 112–122 °C for different heating rates in DSC tests. There are two coupled peaks of BPO around 105 °C at both the heating rates of 4.0 and 8.0 °C/min while no endothermic peak showed at lower heating rates. Furthermore, another endothermic peak appears immediately after the exothermic peak at about 211 °C of DCP under high-pressure conditions. For BPO, the endothermic peak before the exothermic peak disappears as the pressure increases to 1.0 and 1.5 MPa. The average values of apparent activation energy calculated by Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods during the conversion rate between 15 and 75% of DCP are 80.69 and 74.05 kJ/mol, and that of BPO are 119.96 and 112.93 kJ/mol, respectively. According to the isothermal tests, the thermal decomposition of DCP behaviors is an n-th order reaction while BPO conforms to the laws of autocatalytic reaction.     

低压环境对锂电池热失控释放温度影响

为研究锂电池在民航飞行低压特殊环境的安全性及发生热失控灾害后的高温危险性,通过可模拟飞行变动条件的动压变温实验舱开展系列实验,研究锂电池在不同低压环境下的（101,60,30 kPa）多节18650型锂离子电池热失控温度特性,采集电池池体温度及热失控喷射释放温度等参数。研究结果表明:随环境压力降低,圆柱锂电池间的热失控传播并不能被阻断,但锂电池热失控灾害所释放产生的高温区域减少,且高温持续时间变短,释放所产生温度的高温危险性随环境压力的降低而有所降低。     

Effects of workplace thermal conditions on safe work behavior

The effect of workplace thermal conditions on worker safety has not previously been adequately investigated, due in part to the difficulty of defining a suitable safety performance measure. This report describes a study conducted in two industrial plants to determine if a correlation exists between the safety-related behavior of workers and workplace thermal conditions. Both heat exposure measurements and behavioral observations were taken over a 14-month period, for a total of over 17,000 observations. The results indicate that temperatures below and above those typically preferred by most people have a significantly detrimental effect on the safety-related behavior of workers. This is demonstrated by an index based on the ratio of observed unsafe behaviors to the total number of observed behaviors. The relationship between this index of unsafe behavior and the ambient temperature formed a U-shaped curve. The minimum unsafe behavior index occurred within the zone of preferred temperature (approximately 17°C to 23°C, WBGT). Other factors such as metabolic workload and time during the shift also had significant effects on worker safety-related behavior.     

锂离子电池组热失控蔓延热传递机制的影响研究

分析通风和电池组数量对电池组热失控发展蔓延热传递机制的影响。选择荷电状态(SOC)为100%的镍钴锰(NCM523)三元锂离子动力电池组作为研究对象,改变电池组底部外加热源的热流量和加热时间,利用多物理场仿真软件COMSOL,进行热滥用导致不同风速通风环境和不同电池数量电池组热失控过程的模拟。结果表明:随着风速不断增大,电池组和周围环境的对流换热损失增强,电池组热失控蔓延进程受到了有效抑制。受热传导模式的影响,电池组数量和排列方式不同,电池组热失控蔓延的路线不同。越靠近外部热源的电池,触发热失控越早,触发热失控的起始温度越高;电池组所含电池数量越多,触发电池组热失控所需的热流量越大,但第一块电池热失控以后,后续电池触发热失控的时间间隔急剧缩短,电池组热失控后果的严重度增加。     

不同外热部位下18650型锂离子电池热失控研究

为探究不同外热部位对18650型锂离子电池热失控特性的影响,通过自主设计的试验平台对电荷量为100%的18650型锂离子电池开展不同外热部位下热失控试验,探讨不同部位外热源对电池热失控行为过程、热失控响应时间、温度特性、电池破裂部位的影响。结果表明:在相同热源功率条件下,外热源位置对电池热失控过程中初爆与二次燃爆间的时间间隔存在影响,顶部加热时安全阀打开瞬间便发生二次燃爆,底部和中部加热工况下,时间间隔分别延迟至18 s和40 s;中部加热时池体温升速率最慢,为0.873℃/s,分别为顶部和底部加热时的77.5%和77.8%;中部加热时热失控响应时间最长达290 s,顶部和底部加热时分别缩短12.4%和30.0%;顶部和底部加热时,热失控破裂部位集中于顶部"褶皱处"和底部防爆阀,但在中部加热工况下,电池发生破裂部位的随机性增加,其外壳破坏程度也有增加。     

Validation of the UN criteria for the uncooled sea transport of liquid organic peroxides: Full-scale test and modeling

In the years 1987 and 1988 TNO and Akzo Nobel investigated the thermal safety of non-temperature-controlled sea transport of organic peroxides, by modeling and experimenting on several scales. A full-scale test was organised in the summer of 1989, in co-operation with the former Nedlloyd company, in which a sea container with palletised packages, filled with soybean oil as inert liquid and fully equipped with temperature measuring equipment, was transported from Rotterdam, The Netherlands, to Beira, Mozambique, and back. The trip took 2 months.To answer questions stated by the workgroup International Group of Experts on the Explosion Risk of Unstable Substances—subgroup on Energetic and Oxidising Substance (IGUS-EOS) during its meeting in Washington, DC, USA, April 2006, the original data of the sea-container trip were reviewed and applied in a new mathematical model of the sea-container filled with packages, and traveling through tropical sea areas.Analysis of the data from the full-scale test led to defining a worst combination of adverse temperature conditions: constant dead sailing of the wind (wind direction and speed equal to that of the ship), and sunny weather 12 h/day and a mean ambient temperature of 30 °C during 28 days.The effect of sunny weather was put into the model by assigning 24 h averaged excess temperatures to the sun-exposed surfaces. New simulations showed no runaway for the sea container, if filled with an organic peroxide having an self-accelerating decomposition temperature (SADT) of exactly 55 °C.The exaggerated worst case with an improbable mean ambient temperature of 33 °C also does not lead to a runaway.Therefore, the UN criteria for temperature control for organic peroxides are appropriate.     

基于火探管式的锂离子电池灭火技术研究

为研究锂离子电池灭火方案,基于火探管灭火技术同时利用新型清洁灭火剂Novec 1230,组装成火探管灭火系统。在灭火测试平台上以功率为200 W的电热管作为外热源引发单电池或电池模组热失控,通过改变火探管的布置位置,记录相应的灭火行为以及灭火效率,并对实验结果进行了分析。研究结果表明,当火探管灭火系统直接布置在电池正上方时,在起火后的5.6s内控制火情;随着灭火剂用量增加可以显著降低体系温度,防止电池复燃以及连锁热失控现象发生;火探管有效覆盖区域外的失控电池作为热源将继续加热临近电池,引发连锁热失控,造成灭火系统失效;根据电池热失控后的燃烧行为以及传热行为,提出相应的火探管灭火系统复合方案。     

Thermal hazard evaluation for γ-valerolactone production by using formic acid as hydrogen donor

Aiming at the green and sustainable energy substitution and supply, biomass valorization has become a potential strategy to face the energy crisis and increasing demand all over the world from long-term perspectives. Among the bio-based chemicals, γ-valerolactone (GVL) production from hydrogenation of levulinic acid (LA) and its esters has attracted great interests due to its wide applications, such as fuel, solvent, and additives. However, the safety evaluation for this hydrogenation reaction has received few attentions. To fill this gap, thermal hazard evaluation for GVL production from LA hydrogenation by using formic acid (FA) as hydrogen donor was first performed. The process conditions were optimized by using orthogonal experimental method for further calorimetry study. Thermal stability of chemicals and thermal risk of reaction process under adiabatic conditions were investigated by applying differential scanning calorimetry and accelerating rate calorimeter Phi-Tec II, respectively. The results revealed that the chemicals were stable in temperature range from 30 to 250 °C except FA due to its evaporation and decomposition with endothermic behaviors. The reaction process under isothermal and adiabatic conditions demonstrates that the decomposition of FA was rapid and followed by the hydrogenation of LA to GVL. Based on kinetic model under adiabatic conditions and risk matrix, the thermal runaway risk was found to be medium, indicating that certain safety measures should be properly designed and taken for loss prevention. This work could benefit the safety design and thermal risk prevention for GVL production by using FA as hydrogen donor.     

Thermal hazard and decomposition kinetics of 1-butyl-2,3-dimethylimidazolium nitrate via TGA/DSC and FTIR

1-Butyl-2,3-dimethylimidazolium nitrate ([Bmmim][NO₃]), a kind of versatile and novel ionic liquids, is widely applied in the modern petrochemical industry. Nevertheless, its thermal hazard safety data at high temperature or thermal disturbance conditions are currently unavailable. Therefore, this study aimed to characterize the thermal risk of [Bmmim][NO₃] through auto-ignition temperature measurements, flash point analysis, thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC), TGA-Fourier transform infrared spectroscopy (TGA-FTIR) and thermal decomposition kinetics analysis. Additionally, [Bmmim][NO₃] was examined using isothermal thermogravimetric analysis at different temperatures (220, 230, 240, 250, 260 and 270 °C). The experimental results show that the flash point of [Bmmim][NO₃] is 305.70 ± 9.30 °C and the auto-ignition temperature is 341.00 ± 21.60 °C with an ignition delay time of 8.6 s. In addition, using the nitrogen atmosphere TGA data to calculate the activation energy according to the Friedman, Kissinger and Flynn-Wall-Ozawa methods, roughly the same results were obtained. Finally, TGA-FTIR results show that [Bmmim][NO₃] produced acetylene, butane, butanol and carbon dioxide during the thermal decomposition process. This study could provide data support and some guidance for the thermal hazard assessment and safety control of [Bmmim][NO₃] during its use and storage.     

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.     

不同外热功率下18650锂离子电池热失控特性*

为探究不同外热功率（220,170,120,70 W）下锂离子电池的热失控特性,采用动压变温实验舱作为燃爆实验舱,并利用量热仪和ISO-9705烟气分析仪监测特征参数,对荷电状态（SOC）为100%的18650型锂离子电池进行高温热失控实验。结果表明:在不同的外热功率条件下,锂离子电池进入热失控的过程呈现出相似的趋势,但是各阶段的特性却存在差异。池体表面中心温度、HRR,THR和耗氧量均随外热功率的降低而降低。高外热功率下燃爆响应时间点明显提前,池体温度更高,220 W外热功率下,燃爆响时间点为176 s,池体温度为720.6 ℃,比70 W时提前366 s,高210.03 ℃,可见高外热功率时,电池热危害性更高。热解烟气CO的峰值体积百分比浓度随着外热功率的降低而升高,而CxHy的峰值质量百分比浓度降低,,CO2的峰值体积百分比浓度降低。在70 W外热功率时,CO峰值体积百分比浓度高达0.322%,220 W时CO峰值体积百分比浓度仅为0.165%,说明低外热功率时,电池毒危害性更高。     

Thermal hazards analysis of styrene in contact with impurities

Styrene is a reactive monomer commonly used to produce polystyrene and other copolymers. Unintended thermal runaway polymerization reactions of styrene keep reoccurring and have led to catastrophic consequences. One of the possible causes of these runaway incidents involves the contamination of the styrene monomer by incompatible species, which was not adequately investigated and documented. This study focuses on the quantification of thermal runaway hazards of styrene in contact with a series of contamination substances by adopting calorimetric analysis. Both Differential Scanning Calorimeter (DSC) and Advanced Reactive System Screening Tool (ARSST) were employed to examine the exothermic characteristics of styrene mixed with contaminating substances at different concentration levels and mixing conditions. Key safety parameters of the exothermic reaction, such as the onset temperature, the overall heat release, the maximum self-heating rate, as well as the activation energy, were obtained. The results indicated that the thermal runaway polymerization of purified styrene was significantly altered by the presence of contaminant species. Water effectively retarded and quenched the runaway polymerization at a higher temperature range. Alkaline had no substantial effect on the thermal runaway characteristics. The presence of acid solution under both static contact and vigorous mixing condition significantly promoted the thermal polymerization of styrene. A trace amount of concentrated acid initiated violent exothermic activity even at room temperature; and the severity of the reaction was profoundly impacted by the mass-transfer. Our study demonstrates significant implications in the prevention of runaway incidents during transportation and storage of styrene.