Effects of environmental temperature on the thermal runaway of lithium-ion batteries during charging process

Lithium-ion batteries with relatively narrow operating temperature range have provoked concerns regarding the safety of LIBs. In this work, a series of experiments were conducted to explore the thermal runaway (TR) behaviors of charging batteries in a high/low temperature test chamber. The effects of charging rates (0.5 C, 1 C, 2 C, and 3 C), and ambient temperature (2 °C, 32 °C and 56 °C) are comprehensively investigated.The results indicate that the cell exhibited greater thermal hazard at the high charging rate and ambient temperature conditions. As the charging rate increased from 0.5 C to 3 C, more lithium intercalated in the anode prompt the TR triggered in advance, the TR onset temperature decreased from 297.5 °C to 264.7 °C. In addition, the charging time decreased with the elevated ambient temperature, resulting in a relatively higher TR onset temperature and lower maximum temperature, and the average TR critical time declined by 115–143 s. Finally, the TR required less heat accumulation with increasing of charging rate and ambient temperature, and the heat generation of side reaction played a substantial role that accounted for approximately 54%∼63%. These results provide an insight into the charging cell thermal runaway behaviors in complex operation environments and deliver valuable guidance for improving the safety of cell operation.     

Evaluative comparison of two methods for SADT determination (UN H.1 and H.4)

We present our results on the comparison of two methods for the SADT determination. Both methods, UN test H.1 and UN test H.4 are recommended by the international transport regulations from the UN. But during the last years the applicability of the UN test H.4 has been questioned for solid substances. Therefore, three organic peroxides and one self-reactive substance have been investigated in 5 kg and 20 kg packages as well as in the UN test H.4 in a 500 mL Dewar vessel. The SADT values determined with the different methods match. The UN test H.4 seems to be well suited for solid organic peroxides and self-reactive substances of at least 20 kg or 60 L.     

Study on the early stage of runaway reaction using Dewar vessels

In this paper, compared with a UN cylindrical 500 mL Dewar (H.4 in the UN tests), a spherical 1 L Dewar vessel was used to study the early stages of runaway reactions of several liquid and solid samples, including three organic peroxides and a reactive material. The samples were filled in the vessels and the temperature profiles versus times at different positions of the samples were measured. As a result, the minimum temperatures, defined as the SADT, were averagely 10 K lower than those measured in the cylindrical Dewar vessels. At the same time, the temperature profiles of solids in the spherical Dewars tended to be homogeneous. The heat transfer coefficient of a spherical Dewar is only 0.18 W/K/m, one-eighth of a conventional cylindrical Dewar vessel. Meanwhile it has a low phi factor. These factors are essential to simulate low heat loss bulk conditions in the equilibrium process and at the early stage of a runaway reaction. To characterize the ability of the adiabaticity of a storage vessel, it can be seen that a spherical Dewar could simulate the plant process having critical storage size of a reactive-material, r₀, approximately 0.6 m. It is recommended that such a technique is used to investigate the SADT of an unstable material in larger scale packaging or a material with very weak heat release in industry.     

Green thermal analysis for predicting thermal hazard of storage and transportation safety for tert-butyl peroxybenzoate

Liquid organic peroxides, such as tert-butyl peroxybenzoate (TBPB), have been widely employed in the petrifaction industry as a polymerization formation agent. This study investigated the thermokinetic parameters of TBPB by isothermal kinetic algorithms and non-isothermal kinetic equations, using thermal activity monitor III (TAM III) and differential scanning calorimetry (DSC), respectively. Simulations of 0.5 L, 25 kg, 55 gallon, and 400 kg reactors in liquid thermal explosion models were performed and compared to the results in the literature. A green thermal analysis was developed for a reactor containing TBPB to prevent pollution and reduce the energy consumption by thermal decomposition. It is based on the thermal hazard properties, such as the heat of decomposition (ΔH_d), activation energy (E_a), self-accelerating decomposition temperature (SADT), control temperature (CT), emergency temperature (ET), and critical temperature (TCR). From the experimental results, the optimal conditions to avoid violent runaway reactions during the storage and transportation of TBPB were determined.     

Thermal decomposition kinetic of liquid organic peroxides

This study demonstrates the application of isothermal calorimeter for investigating the thermal decomposition of several liquid organic peroxides, such as t-Butyl peroxy acetate (TBPA), Di-tert butyl peroxide (DTBP), and Cumene hydroperoxide (CHP). The decomposition mechanism and kinetic can be identified from case to case. TBPA and DTBP undergo first order reaction, whereas CHP occurs autocatalysis. Accurate kinetic can be assessed on the basis of discerning these various schemes of given samples. Consequently, the thermal runaway or reactive hazards potential of organic peroxides can be determined, for instance as a self accelerating decomposition temperature (SADT).     

The thermal hazard evaluation of 1,1-di (tert-butylperoxy) cyclohexane by DSC using non-isothermal and isothermal-kinetic simulations

1,1-Di (tert-butylperoxy) cyclohexane (DTBPH) has been widely employed in the chemical industry. Unfortunately, organic peroxides have been involved in many serious fires and explosions in manufacturing processes, storage, and transportation. This study investigated the thermokinetic parameters by isothermal kinetic and non-isothermal-kinetic simulation, using differential scanning calorimetry (DSC) tests. DSC was applied to assess the kinetic parameters, such as kinetic model, frequency factor (ln k₀), activation energy (E_a), reaction order, and heat of reaction (ΔH_d). Comparisons of non-isothermal and isothermal-kinetic model simulation led to a beneficial kinetic model of thermal decomposition to predict the thermal hazard of DTBPH. Simulations of a 0.5 L Dewar vessel and 25 kg barrel commercial package in liquid thermal explosion models were performed and compared to the results in the literature. From the results, the optimal conditions for use of DTBPH to avoid violent runaway reactions during the storage and transportation were determined. This study established the features of thermal decomposition that could be executed as a reduction of energy potential and storage conditions in view of loss prevention.     

The effect of ventilation on spontaneous heating of coal

Ventilation plays an important role in the spontaneous heating of coal in an underground coal mine. If the ventilation rate is too high, heat is carried away by convection. If the ventilation rate is too low, the reaction rate becomes oxygen-limited. The effect of ventilation on the spontaneous heating of coal was investigated in an isothermal oven in this study. Experiments were conducted on three U.S. coal samples with ventilation rates ranging from 100 to 500 cm³/min. Experiments under ventilation were conducted to determine the critical ambient temperature, which is the minimum oven temperature required for a coal sample to achieve thermal runaway. Spontaneous heating tests were then conducted at various ventilation rates at the critical ambient temperature and the results were compared with spontaneous heating tests without ventilation. It was found that there is an optimum ventilation flow to produce the maximum rate of temperature rise at the critical ambient temperature. When the coal sample particle size was increased, a higher critical ambient temperature was required. The results in this study have application in the prevention of spontaneous combustion in underground coal mines.     

Diphenylmethane diisocyanate self-polymerization: Thermal hazard evaluation and proof of runaway reaction in gram scale

Thermal analysis by differential scanning calorimetry and thermogravimetric/differential thermal analysis mass spectrometry, adiabatic calorimetry, a gram-scale heating test, and infrared spectroscopy were performed to evaluate the thermal hazards of diphenylmethane diisocyanate (MDI) and prove the occurrence of a runaway reaction. The self-polymerization of MDI was found to occur at about 340 °C under rapid heating conditions. Carbon dioxide was eliminated and heat was generated to allow polymerization. Under adiabatic and closed conditions, the runaway reaction of MDI can begin at least from 220 °C. Besides it is highly probable that the runaway reaction of MDI can begin from a lower temperature in an actual process scale. More heat was generated than in the previous case and the pressure rose rapidly. A closed 2-mm-thick glass vessel exploded because of the runaway reaction of MDI even if the temperature was lower than 300 °C. Therefore, MDI could cause fatal runaway reactions below 300 °C, where MDI had been assumed to self-polymerize by eliminating carbon dioxide previously.     

分布式光纤测温系统在公路隧道火灾探测中 响应特性研究

随着交通运输的快速发展,公路隧道火灾监测与报警越来越重要。目前分布式光纤测温系统已被广泛应用到隧道火灾的监测中,外界风速和隧道断面对火灾监测有一定的影响。该文通过FDS数值模拟和全尺寸实验模拟不同高度的公路隧道发生火灾时,分布式光纤测温系统的报警响应情况。结果表明：在外界风力作用下,传感器的报警位置发生显著偏移;随着隧道高度的增加,分布式光纤感温火灾探测系统报警响应时间延长,可能会不报警。     

Differences in physical properties and CO2 gasification reactivity between coal char and petroleum coke

This paper mainly investigated the physical properties and gasification reactivity of coal char and petroleum coke, separately at the high temperature pyrolysis (950–1400 °C) with slow heating rate and pyrolysis pressure of the atmospheric pressure and at the pressurized pyrolysis (the atmospheric pressure to 3 MPa) with rapid heating rate and the pyrolysis temperature of 950 °C. Some significant differences in those between coal chars and petroleum coke were found. The high temperature pyrolysis caused more easily the graphitization of petroleum coke than that of coal char, especially in the higher temperature range. The increasing pyrolysis temperature resulted in the decrease of surface areas of coal char and the increase of surface areas of petroleum coke. As the pyrolysis pressure was elevated from the atmospheric pressure to 3 MPa, surface areas of petroleum coke initially increased and then decreased, while those of coal chars presented an opposite tendency. The increasing pyrolysis temperature was adverse to the gasification activity of coal chars and was favorable for the gasification activity of petroleum coke. Also, the effects of the pyrolysis pressure on the gasification activity of coal char and petroleum coke were significantly different. The gasification activity of petroleum coke was obviously lower than that of coal chars, and even lower than that of the natural graphite.     

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...     

Experimental research in the fire resistance of the double-frame container

During the road transportation of hazardous materials (hazmat), container was usually used to protect the inner package from accidents. The conventional container is a sandwich-framed construction. When it was subjected to car fire, the combustible materials such as poly-foam interlayer would burn up in few minutes. Once the hazmat leaked out, it could result in the great loss of the public and environment. In this paper, a double-frame container mechanism was firstly proposed for loss prevention. In order to investigate the heat conduction pattern and the effect of interlayer thickness, the two-dimensional (2D) Finite Element (FE) model was developed. Based on the numerical results, the interlayer thickness was defined as 155 mm considering the ignorance of sealing. Furthermore, two small-scale containers whose interlayer were ceramic fiber and phenolic foam separately were manufactured. Pool fire experiments were carried out to evaluate the fire resistance of the mechanism and compare the insulation of the interlayer. Results show that the construction of the container remained complete after about 30-min fire exposure. The maximum temperature inside was below 100 °C during the burning process. When the fire burnt down, the temperature inside increased to 110 °C and then declined gradually during the 1000-min cooling process. Additionally, although the thermal insulation of the container with phenolic foam is relatively better, the ceramic fiber is much more suitable for the interlayer considering the sealing of the container and the stability in heat. In summary, the double-frame container could protect the product inside from car fire. It could be beneficial for the fire-resistant design of much bigger containers, which might be widely used for loss prevention in hazmat transport.     

反应失控型火灾爆炸事故预测

介绍了一种预测反庆失控灾害的方法,通过实验测定容器的时间常数,预测能够引起反应失控的最低环境温度,发生反应失控时的危险温度,以及达到最大反应速度反需的时间,预测结果与实际情况具有良好的一致性。     

Theoretical estimation of the lower flammability limit of fuel-air mixtures at elevated temperatures and pressures

We present an approach for predicting the lower flammability limits of combustible gas in air. The influence of initial pressure and temperature on lower flammability limit has been examined in this study. The lower flammability limits of methane, ethylene and propane in air are estimated numerically at the pressure from one to 100 bar and the temperature from ambient to 1200 K. It was found that the predicted LFLs of methane, ethylene and propane decrease slightly with the elevated pressure at the high temperature. The LFLs variation for methane-air mixture is 0.17, 0.18, 0.18 volume% with the initial pressure from one to 100  bar at the initial temperature of 800 K, 1000 K and 1200 K respectively, which is significantly higher than that at lower temperature. And the LFL of methane-air mixture at 1200 K and 100 bar reaches 1.03 volume% which is much lower than that at 1 bar and ambient temperature. On the other hand, the LFLs variation is 0.11–0.12 volume% for ethylene-air mixture and 0.06–0.07 volume% for propane-air mixture with the initial temperature from 800 K to 1200 K at the same range of pressure. The LFL values at high temperatures and pressures represent higher risk of explosion.     

BIPB的热分解动力学和失控反应模拟

为了评估双(叔丁过氧基)二异丙苯(BIPB)的热危害,对其热分解过程进行多速率的动态扫描C80热分析,用几种简单的热危害评估方法分析其热危害。然后应用模式法、无模式法(Friedman微分等转化率法)分别对试验结果进行处理,得到分解动力学数据,并用ASTM E 698法得到活化能数据,同时用C80、ARC和DSC的试验数据验证分解动力学数据的可靠性。最后利用无模式法的分解动力学数据进行BIPB绝热条件下和非绝热的2m3球形容器中的失控反应模拟,得到类似工艺条件下BIPB的安全控制温度。     

Removal of Zn and Ni by adsorption in a fixed bed of wheat straw

Zn⁺² and Ni⁺² in a solution were removed by biosorption in a fixed bed of wheat straw Triticum aestivum. The removal rate and the mass transfer coefficient for Zn⁺² and Ni⁺² were found to be proportional to the liquid superficial velocity to the power of 0.31 for the range of the particle Reynolds number from 18 to 445 (equivalent liquid rates of 0.00070–0.0175 m³ m⁻² s⁻¹). This agrees well with reported literature for mass transfer in a packed bed of solid particles under a laminar flow regime. Effect of the solution pH, temperature and the particle size (0.5, 1.0, 1.5 and 2.0 in.) on biosorption of Zn⁺² and Ni⁺² was also investigated. Biosorption of both Zn⁺² and Ni⁺² increased significantly with the solution pH from 4.0 to 7.0. On the other hand, Zn⁺² and Ni⁺² removal appeared to be insensitive to liquid temperature from 25 to 30 °C. Nevertheless, a 25% increase in the percentage removal of metal ions was observed with further increase of liquid temperature from 30 to 35 °C. However, the biosorbent particle size did not seem to have a systematic effect on the biosorption of Zn⁺² and Ni⁺². In addition, biosorption of Zn⁺² was not affected considerably by co-adsorption of the bimetal solution while biosorption of Ni⁺² decreased about 14%.     

Probe into effect of the initiator on the thermal runaway hazards of methyl methacrylate bulk polymerization

The bulk polymerization of methyl methacrylate (MMA) is of great importance in chemical industry, but the polymerization process is highly hazardous, and few reports have focused on the effect of initiators on its thermal hazards. In this work, to thoroughly explore the thermal hazard characteristics, the runaway behavior of MMA bulk polymerization is investigated by a combination of thermodynamics experimental and kinetics theoretical methods. The results indicate that the presence of initiator exhibits an undesirable thermal hazard to the MMA bulk polymerization, and its exothermic behavior is also greatly influenced by the type and concentration of initiator. For azobisisoheptanenitrile (ABVN), azodiisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO) initiators as examples, the AIBN-initiated reaction has the shortest adiabatic induction period (39.51 min), whereas the BPO-initiated polymerization exhibits the strongest maximum temperature-rising rate and maximum pressure-rising rate. Under adiabatic runaway, the temperature and pressure change significantly with increasing AIBN concentration, revealing a great potential risk of thermal runaway. Kinetic parameters are calculated to further understand the thermal runaway mechanisms, showing a strong agreement with the adiabatic experimental data. Finally, based on the cooling failure scenario, severity grading is determined by the evaluation criteria. The current work provides extensive data as a reference and guidance for the process design and optimization of MMA bulk polymerization from the perspective of safety.