Further study of the intrinsic safety of internally shorted lithium and lithium-ion cells within methane-air

National Institute for Occupational Safety and Health (NIOSH) researchers continue to study the potential for lithium and lithium-ion battery thermal runaway from an internal short circuit in equipment for use in underground coal mines. Researchers conducted cell crush tests using a plastic wedge within a 20-L explosion-containment chamber filled with 6.5% CH₄-air to simulate the mining hazard. The present work extends earlier findings to include a study of LiFePO₄ cells crushed while under charge, prismatic form factor LiCoO₂ cells, primary spiral-wound constructed LiMnO₂ cells, and crush speed influence on thermal runaway susceptibility. The plastic wedge crush was a more severe test than the flat plate crush with a prismatic format cell. Test results indicate that prismatic Saft MP 174565 LiCoO₂ and primary spiral-wound Saft FRIWO M52EX LiMnO₂ cells pose a CH₄-air ignition hazard from internal short circuit. Under specified test conditions, A123 systems ANR26650M1A LiFePO₄ cylindrical cells produced no chamber ignitions while under a charge of up to 5 A. Common spiral-wound cell separators are too thin to meet intrinsic safety standards provisions for distance through solid insulation, suggesting that a hard internal short circuit within these cells should be considered for intrinsic safety evaluation purposes, even as a non-countable fault. Observed flames from a LiMnO₂ spiral-wound cell after a chamber ignition within an inert atmosphere indicate a sustained exothermic reaction within the cell. The influence of crush speed on ignitions under specified test conditions was not statistically significant.     

Comparison of explosion parameters for Methane–Air mixture in different cylindrical flameproof enclosures

Flameproof enclosures having internal electrical components are generally used in classified hazardous areas such as underground coalmines, refineries and places where explosive gas atmosphere may be formed. Flameproof enclosure can withstand the pressure developed during an internal explosion of an explosive mixture due to electrical arc, spark or hot surface of internal electrical components. The internal electrical component of a flameproof enclosure can form ignition source and also work as an obstacle in the explosion wave propagation. The ignition source position and obstacle in a flameproof enclosure have significant effect on explosion pressure development and rate of explosion pressure rise. To study this effect three cylindrical flameproof enclosures with different diameters and heights are chosen to perform the experiment. The explosive mixture used for the experiment is stoichiometric composition of methane in air at normal atmospheric pressure and temperature.It is observed that the development of maximum explosion pressure (P_max) and maximum rate of explosion pressure rise (dp/dt)_ex in a cylindrical flameproof enclosure are influenced by the position of ignition source, presence of internal metal or non-metal obstacles (component). The severity index, K_G is also calculated for the cylindrical enclosures and found that it is influenced by position of ignition source as well as blockage ratios (BR) of the obstacles in the enclosures.     

锂枝晶导致的锂离子电池内短路模拟研究

锂离子电池内短路是导致其热失控的主要原因之一,机械撞击、集流体边缘毛刺和锂枝晶生长等都可刺穿隔膜导致电池内短路。采用有限元数值模拟方法,对锂枝晶引起的锂离子电池内短路进行了研究,比较分析了不同锂枝晶半径、数量和中心距情况下电池的热响应特征。结果表明锂枝晶导致的电池内短路产热来源主要是正负极可逆和不可逆热。短路电流、产热功率和电池最高温度等都随锂枝晶半径的增大而增大。锂枝晶中心距增大时,短路电流和产热功率也随之变大,但由于受到电解液锂离子浓度的影响二者增加的幅度越来越小。锂枝晶中心距越大时虽然电池总产热量越大,电池平均温度更高,但由于此时短路点分布较分散,电池最高温度却较反而较小。     

Minimum ignition energy theoretical model for flammable gas based on flame propagation layer by layer

To achieve the rapid prediction of minimum ignition energy (MIE) for premixed gases with wide-span equivalence ratios, a theoretical model is developed based on the proposed idea of flame propagation layer by layer. The validity and high accuracy of this model in predicting MIE have been corroborated against experimental data (from literature) and traditional models. In comparison, this model is mainly applicable to uniform premixed flammable mixtures, and the ignition source needs to be regarded as a punctiform energy source. Nevertheless, this model can exhibit higher accuracy (up to 90%) than traditional models when applied to premixed gases with wide-span equivalence ratios, such as C₃H₈-air mixtures with 0.7–1.5 equivalence ratios, CH₄-air mixtures with 0.7–1.25 equivalence ratios, H₂-air mixtures with 0.6–3.15 equivalence ratios et al. Further, the model parameters have been pre-determined using a 20 L spherical closed explosion setup with a high-speed camera, and then the MIE of common flammable gases (CH₄, C₂H₆, C₃H₈, C₄H₁₀, C₂H₄, C₃H₆, C₂H₂, C₃H₄, C₂H₆O, CO and H₂) under stoichiometric or wide-span equivalence ratios has been calculated. Eventually, the influences of model parameters on MIE have been discussed. Results show that MIE is the sum of the energy required for flame propagation during ignition. The increase in exothermic and heat transfer efficiency for fuel molecules can reduce MIE, whereas prolonging the flame induction period can increase MIE.     

Lithium-ion energy storage battery explosion incidents

Utility-scale lithium-ion energy storage batteries are being installed at an accelerating rate in many parts of the world. Some of these batteries have experienced troubling fires and explosions. There have been two types of explosions; flammable gas explosions due to gases generated in battery thermal runaways, and electrical arc explosions leading to structural failure of battery electrical enclosures. The thermal runaway gas explosion scenarios, which can be initiated by various electrical faults, can be either prompt ignitions soon after a large flammable gas mixture is formed, or delayed ignitions associated with late entry of air and/or loss of gaseous fire suppression agent. The electrical explosions have entailed inadequate electrical protection to prevent high energy arcs within electrical boxes vulnerable to arc induced high pressures and thermal loads. Estimates of both deflagration pressures and arc explosion pressures are described along with their incident implications.     

A review of hazards associated with primary lithium and lithium-ion batteries

Primary lithium batteries contain hazardous materials such as lithium metal and flammable solvents, which can lead to exothermic activity and runaway reactions above a defined temperature. Lithium-ion batteries operating outside the safe envelope can also lead to formation of lithium metal and thermal runaway. Despite protection by battery safety mechanisms, fires originating from primary lithium and lithium-ion batteries are a relatively frequent occurrence.This paper reviews the hazards associated with primary lithium and lithium-ion cells, with an emphasis on the role played by chemistry at individual cell level. Safety mechanisms to prevent the occurrence and limit the consequences of incidents are reviewed, together with safety tests to monitor compliance with battery safety regulations and standards. Incident information from news accounts and open literature sources are reviewed to extract causal information.It is concluded that the potential severity of incidents during storage, transport and recycling of waste batteries can be significantly higher than in end-use applications. Safe storage, packaging and labelling practices, as well as communication among the parties involved, are essential to ensure safety across the battery lifecycle. It is recommended that a database of lithium battery incidents would be valuable to improve the evidence base for informing accident prevention measures.     

Gas flame acceleration in long ducts

In many practical situations, a flame may propagate along a pipe, accelerate and perhaps transform into a devastating detonation. This phenomenology has been known, more or less qualitatively, for a long time and mitigation techniques were proposed to try and avoid this occurrence (flame arresters, vents,...). A number of parameters need to be known and in particular the “distance to detonation” and more generally the flame acceleration characteristic scales. Very often, the ratio between the detonation run-up distance and the pipe diameter is used without any strong justification other that using a non-dimensional parameter (L/D). In this paper, novel experimental evidence is presented on the basis of relatively large scale experiments using 10 cm and 25 cm inner diameter duct with a length between 7 and 40 m. Homogeneous C₂H₄-air, CH₄-air, C₃H₈-air and H₂-air mixtures were used and different ignition sources. The interpretation suggests that the self-acceleration mechanism of the flame may be much better represented by flame instabilities than by turbulence build-up. One consequence would be that the maximum flame velocity and, following, the maximum explosion overpressure, would be rather linked with the run-up distance than with the L/D ratio.     

Effects of a carbon monoxide-dominant gas mixture on the explosion and flame propagation behaviors of methane in air

This work aimed to experimentally evaluate the effects of a carbon monoxide-dominant gas mixture on the explosion characteristics of methane in air and report the results of an experimental study on explosion pressure measurement in closed vessel deflagration for a carbon monoxide-dominant gas mixture over its entire flammable range. Experiments were performed in a 20-L spherical explosion tank with a quartz glass window 110 mm in diameter using an electric spark (1 J) as the ignition source. All experiments were conducted at room temperature and at ambient pressure, with a relative humidity ranging from 52 to 73%. The peak explosion pressure (P_max), maximum pressure rise rate ((dp/dt)_max), and gas deflagration index (K_G) were observed and analyzed. The flame propagation behavior in the initial stage was recorded using a high-speed camera. The spherical outward flame front was determined on the basis of a canny method, from which the maximum flame propagation speed (S_n) was calculated. The results indicated that the existence of the mixture had a significant effect on the flame propagation of CH₄-air and increased its explosion risk. As the volume fraction of the mixed gas increases, the P_max, (dp/dt)_max, K_G and S_n of the fuel-lean CH₄-air mixture (7% CH₄-air mixture) increase nonlinearly. In contrast, addition of the mixed gas negatively affected the fuel-rich mixture (11% CH₄-air mixture), exhibiting a decreasing trend. Under stoichiometric conditions (9.5% CH₄-air mixture), the mixed gas slightly lowered P_max, (dp/dt)_max, K_G, and S_n. The P_max of CH₄-air mixtures at volume fractions of 7%, 9.5%, and 11% were 5.4, 6.9, and 6.8 bar, respectively. The S_n of CH₄-air mixtures at volume fractions of 7%, 9.5%, and 11% were 1.2 m/s, 2.0 m/s, and 1.8 m/s, respectively. The outcome of the study is comprehensive data that quantify the dependency of explosion severity parameters on the gas concentration. In the storage and transportation of flammable gases, the information is required to quantify the potential severity of an explosion, design vessels able to withstand an explosion and design explosion safety measures for installations handling this gas.     

Lithium ion battery energy storage systems (BESS) hazards

There has been an increase in the development and deployment of battery energy storage systems (BESS) in recent years. In particular, BESS using lithium-ion batteries have been prevalent, which is mainly due to their power density, performance, and economical aspects. BESS have been increasingly used in residential, commercial, industrial, and utility applications for peak shaving or grid support. As the number of installed systems is increasing, the industry has also been observing more field failures that resulted in fires and explosions. Lithium-ion batteries contain flammable electrolytes, which can create unique hazards when the battery cell becomes compromised and enters thermal runaway. The initiating event is frequently a short circuit which may be a result of overcharging, overheating, or mechanical abuse. During the exothermic reaction process (i.e., thermal runaway), large amounts of flammable and potentially toxic battery gas will be generated. The released gas largely contains hydrogen, which is highly flammable under a wide range of conditions. This may create an explosive atmosphere in the battery room or storage container. As a result, a number of the recent incidents resulted in significant consequences highlighting the difficulties on how to safely deal with the hazard. This paper identifies fire and explosion hazards that exist in commercial/industrial BESS applications and presents mitigation measures. Common threats, barriers, and consequences are conceptually shown and how they would be identified in a hazard mitigation analysis (HMA). Mitigation measures that can be implemented to reduce the risk of a fire or an explosion are discussed. The presented information is intended to provide practical information to professionals and authorities in this fairly new industry to assure that prevention and mitigation strategies can be effectively implemented and that the regulatory requirement of the HMA can be met.     

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。     

Ignitability assessment of shredder dusts of refrigerator and the prevention of the dust explosion

Explosibility of polyurethane dusts produced in the recycling process of refrigerator and the ways to prevent the dust explosion were studied. In recent years, cyclopentane is often used as the foaming agent and this produces explosive atmosphere in the shredding process. The minimum explosive concentration of polyurethane dust, influence of coexisting cyclopentane gas on the explosibility, effect of relative humidity on the minimum explosive concentration of polyurethane dusts, the minimum ignition energy, influence of cyclopentane mixture on the explosion severity, etc. were investigated.The minimum explosive dust concentration decreased with the increase of cyclopentane concentration and increased with the increase of relative humidity. The minimum ignition energy was about 11 mJ. The ignition energy decreased with the increase of the cyclopentane gas concentration. The cyclopentane gas concentration up to about 5300 ppm did not influence too much on the explosion index (K_st) and maximum explosion pressure. From these, it would be a good way to increase the relative humidity and to regulate the cyclopentane concentration in the shredding process to prevent the dust explosion hazard.     

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...     

Acceleration sensitivity of piezoelectric pressure sensors and the influence on the measurement of explosion pressures

To measure the explosion pressure inside an enclosure, it is common to install a piezoelectric pressure sensor in the enclosure wall. The pressure wave of the internal explosion inevitably leads to vibrations of the enclosure walls. This unwanted but naturally occurring motion is also transmitted to the pressure sensor mounted in the enclosure wall and results in inertial forces affecting the piezoelectric element. During the measurement of the explosion pressure, this affects the output signal of the pressure sensor since an undesired signal due to the acceleration of the pressure sensor is superimposed on the desired pressure signal. This behaviour of the sensor is described as acceleration sensitivity. The level of acceleration sensitivity depends on the type and construction design of the pressure sensor. Even though this sensor behaviour is basically not a new phenomenon, the evaluation of an international comparison between Ex testing laboratories in the field of flameproof enclosures has shown that the consideration of this issue is a major challenge in daily practice concerning the measurement of explosion pressures and is even often completely neglected.This work evaluates the behaviour of various piezoelectric pressure sensors with respect to the influence of acceleration and investigates the specific impact on the explosion pressure measurement in the field of flameproof enclosures. For this purpose, explosions from typically used explosive mixtures such as hydrogen, propane and ethyne in air are examined. These investigations involve simple model enclosures with various specifications as well as a commercially available equipment for hazardous areas. By using blind holes and specially designed adapters, a practical method is applied to be able to detect the effect of acceleration on the sensor signal separately from the pressure signal. For this purpose, both the discrete-time pressure curves and the frequency components are analysed using Fast Fourier Transform. The use of signal filters as a practical and fast approach to address these unwanted signal components is discussed and evaluated.This paper provides guidelines for typical end-users in the field of flameproof enclosures how to handle acceleration of piezoelectric pressure sensors and the influence on the measurement of explosion pressures correctly.     

Experimental study on the influence of the nitrogen concentration in the air on the minimum ignition energies of combustible powders due to electrostatic discharges

As a useful method of preventing dust explosions, nitrogen (N₂), an incombustible gas, has been applied to an explosive atmosphere. This paper is a report that quantitatively determines whether the minimum ignition energy of powder depends on the nitrogen (or oxygen) concentration in the air. Hartman vertical-tube apparatus and six sample powders were used in this study. The results show that the minimum ignition energies of all of the powders used in this study increased with increased amounts of N₂ in the air. However, the effects were different in all of the sample powders. We finally suggest that the N₂ concentration of 84% (or above) prevents dust explosions due to electrostatic discharges in the industrial process with the sample powders used in this experiment.     

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。     

Consequence prediction for dust explosions involving interconnected vessels using computational fluid dynamics modeling

Combustible dust explosions continue to present a significant threat toward operating personnel and pneumatic conveyance equipment in a wide variety of processing industries. Following ignition of suspended fuel within a primary enclosure volume, propagation of flame and pressure fronts toward upstream or downstream interconnected enclosures can result in devastating secondary explosions if not impeded through an appropriate isolation mechanism. In such occurrences, an accelerated flame front may result in flame jet ignition within the secondary vessel, greatly increasing the overall explosion severity. Unlike an isolated deflagration event with quantifiable reduced pressures (vent sizing according to NFPA 68 guidance), oscillation of pressure between primary and secondary process vessels leads to uncertain overpressure effects. Dependent on details of the application such as relative enclosure volumes, relief area, fuel type, suspended concentration, duct size, and duct length, the maximum system pressure in both interconnected vessels can be unpredictable. This study proposes the use of FLame ACceleration Simulator (FLACS) computational fluid dynamics (CFD) modeling to provide reliable consequence predictions for specific case scenarios of dust deflagrations involving interconnected equipment. Required minimum supplement to the originally calculated relief area (A_v) was determined through iterative simulation, allowing for reduced explosion pressures (P_red) to be maintained below theoretical enclosure design strengths (P_es).     

Thermal evaluation of junction and connection boxes in explosion protection

To reliably avoid potential ignition sources and thus ignition of the potentially explosive atmosphere in junction and connection boxes of type of protection Increased Safety ‘e', the self-heating shall not exceed a specified level depending on the temperature class. For the conformity assessment of such products, complex thermal tests are necessary due to the great variety of mounting types and arrangements of terminal blocks in the enclosure, depending on the enclosure size. These tests are very time-consuming for the manufacturer of junction and connection boxes or for the testing laboratory and are therefore associated with considerable costs. To reduce this effort and to ensure a uniform assessment in the conformity evaluation by a certification body, it is therefore essential to create fitting charts depending on the enclosure size.This work introduces a calculation tool by means of systematic investigations on different enclosure sizes and with different assemblies, which enables the calculation of fitting charts with justifiable effort. For this purpose, the maximum temperature in the enclosure was determined as a function of the current and the assembly at 20 ± 5 °C ambient temperature. From this, electrical and enclosure-specific constants such as the maximum permissible current per conductor and a conductor specific factor were determined and combined with an exponential dependence of the power dissipation. It is shown that this relationship is valid for an overtemperature of 40 K for compliance with temperature class T6 up to an ambient temperature of +40 °C. Finally, to verify the reliability of the calculation tool, the results are compared with the enclosure-specific rated value of the maximum power dissipation according to IEC 60079-7, 5.7.     

Study on explosion characters of HDPE dust inerted by CaCO3 and NaHCO3

To prevent high density polyethylene (HDPE) dust explosions, this study evaluated HDPE's explosive sensitivity characteristics, and comparatively examined two inert dust types (CaCO₃ and NaHCO₃) to mitigate the explosive sensitivity of HDPE dust. In the serials of experiments, the 1.2 L Hartmann tube and Godbert-Greenwald furnace were used respectively to measure the minimum ignition energy (MIE) and minimum ignition temperature (MIT) of HDPE dust. The findings demonstrated that the MIE and MIT of HDPE are 56.8 mJ and 320 °C under the most sensitive situation. Second, both CaCO₃ and NaHCO₃ can inhibit the explosive sensitivity of HDPE with the variation of several parameters (i.e., quality percentage and particle sizes). Specially, as the quality percentage of 38–48 μm NaHCO₃ come to 70%, the HDPE/NaHCO₃ will not be explosive. Finally, NaHCO₃ had a better inerting effect than CaCO₃ in the reduction of explosive sensitivity of HDPE.     

Experimental investigation on the lower flammability limits of diethyl ether/ n-pentane/epoxypropane-air mixtures

Diethyl ether (DEE), epoxypropane (PO) and n-pentane have excellent ignition and combustion performance; hence, they have a wide variety of applications in industry and advanced aviation propulsion systems. As these fuels are flammable at normal temperature and pressure, their explosive characteristics need to be explored. In this study, the lower flammability limits (LFLs) of vapor mixtures of DEE/PO/n-pentane in air were measured in 20 L, closed, stainless steel spherical vessels. Experimental results were obtained at ambient atmospheric pressure and an initial temperature of 40 °C. The experimental results show that the LFLs of DEE-air, n-pentane -air, and PO-air are 1.81 vol%, 1.41 vol% and 2.44 vol%, respectively. The LFLs of binary/ternary fuel mixtures under different compositions were tested, and the experimental results are compared with the classical Le Chatelier's formula. The results show that, for the binary fuels (i.e., DEE/PO, DEE/n-pentane, PO/n-pentane)-air mixtures, the maximum difference of the LFLs between Le Chatelier's formula and the experimental results is 6.10%. For the ternary fuels (i.e., DEE/PO/n-pentane)-air mixtures, the maximum difference of the LFLs between the two results is 6.33%. Due to the adiabatic flame temperature of each single fuel mixture being close, the Le Chatelier's formula is applicable for an estimation of the LFL for DEE/PO/n-pentane-air mixtures.     

Explosibility of polyamide and polyester fibers

The current research is aimed at investigating the explosion behavior of hazardous materials in relation to aspects of particulate size. The materials of study are flocculent (fibrous) polyamide 6.6 (nylon) and polyester (polyethylene terephthalate). These materials may be termed nontraditional dusts due to their cylindrical shape which necessitates consideration of both particle diameter and length. The experimental work undertaken is divided into two main parts. The first deals with the determination of deflagration parameters for polyamide 6.6 (dtex 3.3) for different lengths: 0.3 mm, 0.5 mm, 0.75 mm, 0.9 mm and 1 mm; the second involves a study of the deflagration behavior of polyester and polyamide 6.6 samples, each having a length of 0.5 mm and two different values of dtex, namely 1.7 and 3.3. (Dtex or decitex is a unit of measure for the linear density of fibers. It is equivalent to the mass in grams per 10,000 m of a single filament, and can be converted to a particle diameter.) The explosibility parameters investigated for both flocculent materials include maximum explosion pressure (P_max), size-normalized maximum rate of pressure rise (K_St), minimum explosible concentration (MEC), minimum ignition energy (MIE) and minimum ignition temperature (MIT). ASTM protocols were followed using standard dust explosibility test equipment (Siwek 20-L explosion chamber, MIKE 3 apparatus and BAM oven). Both qualitative and quantitative analyses were undertaken as indicated by the following examples. Qualitative observation of the post-explosion residue for polyamide 6.6 indicated a complex interwoven structure, whereas the polyester residue showed a shiny, melt-type appearance. Quantitatively, the highest values of P_max and K_St were obtained at the shortest length and finest dtex for a given material. For a given length, polyester displayed a greater difference in P_max and K_St at different values of dtex than polyamide 6.6. Long ignition delay times were observed in the BAM oven (MIT measurements) for polyester, and video framing of explosions in the MIKE 3 apparatus (MIE measurements) enabled observation of secondary ignitions caused by flame propagation after the initial ignition occurring at the spark electrodes.