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.     

Low temperature autoignition of Jet A and surrogate jet fuel

An experimental study of the low-temperature and low-pressure autoignition of Jet A and surrogate fuels was conducted using the ASTM-E659 standardized test method. Two surrogate fuels (Aachen and JI mixtures), their individual components and two batches (POSF-4658 and POSF-10325) of standardized Jet A were tested using the ASTM-E659 method for a range of fuel concentrations and temperatures. The ignition behaviors were categorized into four distinct ignition modes. The individual hydrocarbon components had a wide range of ignition behaviors and minimum autoignition temperatures (AIT) values depending on the molecular structure. The two Jet A batches showed similar ignition behavior with measured AITs of 229 ±3°C and 225 ±3°C respectively. Both surrogates exhibited similar ignition behavior to Jet A with comparable AITs of 219 ±3.1°C (Aachen) and 228 ±3°C (JI) with the JI mixture proving to be a more suitable surrogate to Jet A in the low-temperature thermal ignition regime.     

Limiting explosible concentration of hydrogen–oxygen–helium mixtures related to the practical operational case

This paper presents data on the limiting (minimum) concentrations of hydrogen in oxygen, in the presence of added helium, at elevated temperature and pressure related to the practical operational case. A 5 L explosion vessel, an ignition sub-system and a transient pressure measurement sub-system were used. Through a series of experiments carried out using this system, the limiting concentrations of hydrogen in oxygen and helium at different initial pressures and temperatures for the practical operational case were studied, and the influence of ignition energy and initial temperature on the limiting concentration of hydrogen in oxygen and helium was analyzed and discussed. The variation of ignition energy within the studied range is found to have a significant effect on the limiting concentration of hydrogen in oxygen and helium at lower initial temperature. However, when the ignition energy is higher than 32 mJ, the limiting hydrogen concentration remains almost changeless as the initial temperature increases from 21 °C to 90 °C. The limiting explosible concentration of hydrogen–oxygen–helium mixture decreases as the ignition energy increases when the initial temperature is lower. When the initial temperature is higher, the ignition energy has little effect on the limiting hydrogen concentration of hydrogen–oxygen–helium mixtures. When the initial temperature reaches 90 °C, the limiting hydrogen concentration remains almost changeless with an increase in ignition energy. The limiting explosible concentration of hydrogen in the mixtures, at the initial temperature of 21 °C and the ignition energy of 0.5 mJ, is 8.5% and that of oxygen is 11.25%.     

Analysis of the chosen thermal and flammability parameters of dried sewage dust

The hazardous sludge disposal process in the form of landfills requires the determination inter alia of the flammable and explosion properties of dried sewage sludge dust, which has the ability to ignite and spontaneously combust when stored in silos. At a constant furnace surface temperature, the minimum ignition temperature of the sludge dust layer with a layer thickness of 5 mm is 270 °C, and for a layer thickness of 12.5 mm it is 250 °C. Two selected fire extinguishing powders for Class A, B, C and D fires were used in the study to determine the possibility of reducing the susceptibility of dried wastewater to ignition from heated surface, self-ignition and explosion parameters. The most effective extinguishing powder was ABC Favorit, which increased the value of the minimum ignition temperature of the layer (5 mm thick) to 360 °C and the spontaneous ignition temperature of the sludge with this powder increased by 22 °C at 169.6 cm³ in comparison to the sludge without extinguishing powder, respectively. The lowest self-ignition temperature of 136 °C was recorded for the largest tested volume (169.6 cm³) for dried sewage dust without any fire extinguishing powders. The biggest values of p_max and (dp/dt)_max dried sewage dust were recorded 4.8 bar and 113 bar/s respectively. By analysing the obtained test results, it can be assumed that dried sewage dust is a combustible material with properties similar to biomass.     

Determination of explosion limits – Criterion for ignition under non-atmospheric conditions

Many industrial processes are run at non-atmospheric conditions (elevated temperatures and pressures, other oxidizers than air). To judge whether and if yes to what extent explosive gas(vapor)/air mixtures will occur or may be generated during malfunction it is necessary to know the safety characteristic data at the respective conditions. Safety characteristic data like explosion limits, are depending on pressure, temperature and the oxidizer. Most of the determination methods are standardized for ambient conditions. In order to obtain determination methods for non-atmospheric conditions, particularly for higher initial pressures, reliable ignition criteria were investigated. Ignition tests at the explosion limits were carried out for mixtures of methane, propane, n-butane, n-hexane, hydrogen, ammonia and acetone in air at initial pressures up to 20 bar. The tests have been evaluated according to different ignition criteria: visual flame propagation, temperature and pressure rising. It could be shown that flame propagation and occasionally self-sustained combustion for several seconds occurred together with remarkable temperature rise, although the pressure rise was below 3%. The results showed that the combination of a pressure rise criterion of 2% and a temperature rise criterion of 100 K seems to be a suitable ignition criterion for the determination of explosion limits and limiting oxidizer concentration at higher initial pressures and elevated temperatures. The tests were carried out within the framework of a R&D project founded by the German Ministry of Economics and Technology.     

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.     

Influence of the ignition source location on the determination of the explosion pressure at elevated initial pressures

Explosion pressures are determined for rich methane–air mixtures at initial pressures up to 30 bar and at ambient temperature. The experiments are performed in a closed spherical vessel with an internal diameter of 20 cm. Four different igniter positions were used along the vertical axis of the spherical vessel, namely at 1, 6, 11 and 18 cm from the bottom of the vessel. At high initial pressures and central ignition a sharp decrease in explosion pressures is found upon enriching the mixture, leading to a concentration range with seemingly low explosion pressures. It is found that lowering the ignition source substantially increases the explosion pressure for mixtures inside this concentration range, thereby implying that central ignition is unsuitable to determine the explosion pressure for mixtures approaching the flammability limits.     

Effect of particle size and dust layer size on ignition characteristics of PMMA dust layer on hot surface

Deposition of combustible dust on a hot surface is a hidden danger of fire. In this work, polymethylmethacrylate (PMMA) dust was selected to analyse the influence of dust layer diameter, dust particle size and dust layer thickness on the ignition characteristics of PMMA dust layer. Critical heating temperatures and ignition time had been measured. The STA-GC/MS-FTIR analysis was used to determine that the main products of PMMA pyrolysis were MMA, CO, CO₂, and C₂H₄, of which CO and C₂H₄ were transported to the ambient to cause gas phase combustion on the surface of the dust layer. For 10 mm thick dust layer, the critical heating temperatures of 5 μm PMMA, 100 nm PMMA, and 30 μm PMMA were 300 °C, 330 °C, and 320 °C. As the thickness of the dust layer increased, the gas transport path became longer, the critical heating temperature and ignition time increased. The characteristic particle size (D [3,2]) was utilized to represent the true particle size, and the ignition time increased with the increase of the characteristic particle size. The increase in the diameter of the dust layer had a slight effect on the temperature history and ignition time of the dust layer.     

Influence of coal particles on methane/air mixture ignition in a heated environment

The temperature at which coal dust glows is normally much lower than the auto-ignition temperature (AIT) of methane/air mixtures, and thus a better understanding is needed regarding methane/air ignition in a heated environment in the presence of coal particles. A horizontal tube apparatus was used to test the effect of brown coal and two kinds of bituminous and anthracite on methane/air combustibility. For the four coal samples tested, the presence of coal particles significantly reduced the minimum temperature for ignition of methane/air mixtures in a heated environment. No. 1 bituminous coal with 12 mm diameter decreased the ignition temperature value from 595 to 500 °C. It is thought that pre-ignition of low-AIT volatiles emitted from the heated coal particles ignited the methane/air mixtures. Volatiles, sulfur content, and large porosity of piled coal particles all enhanced ignition of methane/air mixtures in a hot environment, while water content and small particle size reduced ignition. For anthracite, no ignition occurred when temperatures of the heated environment were lower than the AIT of methane (595 °C), except for the 12-mm-diameter sample. Anthracite did not readily ignite methane/air mixtures and the ignition mechanism was somewhat similar to that of a burning cigarette.     

20L近球形容器中甲醇喷雾液滴爆炸特性实验研究*

为了评估易燃液体喷雾的爆炸风险,借助喷雾粒度仪、高速相机以及喷雾爆炸实验系统,围绕2种粒径(表面积平均粒径:2.0 μm±0.5 μm;18.0 μm±0.5 μm)的甲醇喷雾,研究点火位置和延迟时间等因素对甲醇喷雾爆炸特性的影响。结果表明:甲醇喷雾粒径均随环境温度的增加而减小,当甲醇喷雾浓度较大时,环境温度对于甲醇喷雾粒径的影响更为显著;甲醇物料温度的改变对于其粒径的影响很小。随着点火延迟时间的增大,甲醇喷雾爆炸特性参数均呈现先增加后减小的趋势,在τ=120 ms时最大。受限空间内甲醇喷雾采用中心或上部点火方式,当甲醇喷雾浓度为356.4 g/m3(φ=1.8)时,甲醇喷雾爆炸特性参数均取得最大值;与上部位置点火相比,中心位置点火的甲醇喷雾爆炸特性参数值较大。     

Experimental studies on the ignition behavior of pure silane released into air

Silane is a well known pyrophoric gas which normally ignites upon contact with air. However, a silane release from a pressure source may not always lead to prompt ignition and frequently the ignition occurs when the release is shutoff. In a confined space, significant quantities of silane can accumulate prior to autoignition leading to an explosion, causing significant damage. To date, the mechanism and condition of pure silane ignition upon release into air has not been completely explained. Thus there is a need for additional experimental investigations covering a wide range of release conditions to enable a full understanding of silane ignition and explosion characteristics.This work presents a series of tests that aims to uncover the precise condition for pure silane ignition upon release into air. Tests were performed for releases at controlled and steady velocities. Steady flow of silane to a burn box and nitrogen to the desired vent stub are first established through mass flow controllers. An electrically controlled four-way switching valve is used to switch the silane and nitrogen flow such that steady silane flow without acceleration to the vent stub can be established. With careful control of vent conditions, we are able to find a reproducible critical exit velocity for prompt ignition of steady silane releases for different vent diameters. If the releases are reduced to below the critical exit velocity, prompt ignition of silane release is ensured. Above this critical exit velocity, silane can be released indefinitely into air without any ignition. The critical exit velocity is found to vary with the vent diameter. This relationship between the critical exit velocity and the vent diameter suggests that the silane release without prompt ignition was most likely caused by quench of the reactive kernel from the scalar dissipation between the release gas and the ambient air. Analysis of locations where prompt ignition occurred from the clips from high speed video camera found that the most reactive ignition kernel occurs in the range when the ratio of volumetric flow rate of entrained air to the silane flow reaches 0.322 ± 0.076, which is equivalent to the most reactive silane concentration of 75.6% in air. The implications from these results are discussed with emphasis on the safety of silane supply systems and operation practices.     

3D simulation of hydrogen ignition in a rapid compression machine

Low-temperature (at T < 900–950 K) ignition delays of hydrogen–air mixtures are mainly measured in rapid compression machines (RCM). This communication is aimed at numerical simulation of ignition delays of hydrogen–air mixtures in the RCM by means of a coupled three-dimensional (3D) Unsteady Reynolds-Averaged Navier–Stokes (URANS) – Particle Method (PM) simulation of RCM operation capable of catching turbulence–chemistry interaction. The study indicates that the time history of piston motion in an RCM affects the final state of a test mixture at the end of compression stroke and therefore influences the phenomena relevant to test mixture ignition. More specifically, the calculations show that different laws of piston motion at a fixed average piston velocity (i.e., fixed piston displacement and fixed compression time) and fixed compression ratio result in different evolution of mean pressure, temperature and velocity fields in the RCM test section leading to different ignition behavior. The reasons for the arising differences lie in the fact that the local instantaneous piston velocity determines the roll-up vortex structure, strength and turbulence dissipation in it, heat transfer in test-section walls, and mass leakage through piston rings.     

Study of the explosion parameters of vapor–liquid diethyl ether/air mixtures

The knowledge of the vapor–liquid two-phase diethyl ether (DEE)/air mixtures (mist) on the explosion parameters was an important basis of accident prevention. Two sets of vapor–liquid two-phase DEE/air mixtures of various concentrations were obtained with Sauter mean diameters of 12.89 and 22.90 μm. Experiments were conducted on vapor–liquid two-phase DEE/air mixtures of various concentrations at an ignition energy of 40.32 J and at an initial room temperature and pressure of 21 °C and 0.10 MPa, respectively. The effects of the concentration and particle size of DEE on the explosion pressure, the explosion temperature, and the lower and upper flammability limits were analyzed. Finally, a series of experiments was conducted on vapor–liquid two-phase DEE/air mixtures of various concentrations at various ignition energies. The minimum ignition energies were determined, and the results were discussed. The results were also compared against our previous work on the explosion characteristics of vapor–liquid two-phase n-hexane/air mixtures.     

Experimental investigation of spark ignition energy in kerosene,hexane, and hydrogen

Quantifying the risk of accidental ignition of flammable mixtures is extremely important in industry and aviation safety. The concept of a minimum ignition energy (MIE), obtained using a capacitive spark discharge ignition source, has traditionally formed the basis for determining the hazard posed by fuels. While extensive tabulations of historical MIE data exist, there has been little work done on ignition of realistic industrial and aviation fuels, such as gasoline or kerosene. In the current work, spark ignition tests are performed in a gaseous kerosene–air mixture with a liquid fuel temperature of 60 °C and a fixed spark gap of 3.3 mm. The required ignition energy was examined, and a range of spark energies over which there is a probability of ignition is identified and compared with previous test results in Jet A (aviation kerosene). The kerosene results are also compared with ignition test results obtained in previous work for traditional hydrogen-based surrogate mixtures used in safety testing as well as two hexane–air mixtures. Additionally, the statistical nature of spark ignition is discussed.     

Numerical study on the spontaneous ignition of pressurized hydrogen during its sudden release into the tube with varying lengths and diameters

Fuel cell vehicles (FCV) and other hydrogen systems with pressurized hydrogen has a safety hazard of spontaneous ignition during its sudden release into the tube. Tube parameter is a key factor affecting the spontaneous ignition of pressurized hydrogen. In this paper, a numerical study on the spontaneous ignition of pressurized hydrogen during its sudden release into the tube with varying lengths and diameters is conducted. The models of Large Eddy Simulation (LES), Eddy Dissipation Concept (EDC), Renormalization Group (RNG), 10-step like opening process of burst disk and 18-step detailed hydrogen combustion mechanism are employed. 6 cases are simulated based on the previous experiments. Numerical results show that the possibility of spontaneous ignition of pressurized hydrogen increases inside the longer and thinner tubes, which agrees with the experimental results. The increasing of tube length has little influence on the shock wave formation and propagation inside the tube. However, there exists critical tube lengths for the generation of Mach disk and the normal shock wave: the maximum and minimum distances for the generation of the Mach disk in 10 mm diameter tube are 7.8 and 6.7 mm, respectively. As for the normal shock wave, these critical values are 22.1 and 19.4 mm, respectively. In addition, the formation times and initial positions of Mach disk and normal shock wave are delayed inside the thicker tube. Due to the shock-affected time increases with the increasing of tube length, the temperature could rise to the critical ignition temperature and triggers the spontaneous ignition due to the sufficient tube length even though the less hydrogen/air mixture and the contact surface with lower temperature is produced inside the thicker tube. Finally, a simple time scale analysis is conducted.     

Effect of superfine KHCO3 and ABC powder on ignition sensitivity of PMMA dust layer

In order to evaluate the flame-retardant capacity of KHCO₃ and ABC on the ignition of PMMA dust layer accumulation on hot surfaces, the ignition time and critical heating temperature of PMMA/KHCO₃ and PMMA/ABC dust layer were experimentally investigated. The thermal stability of the mixed dust, the condensed phase products and gas phase products of the mixed dust combustion were analyzed to reveal the flame-retardant mechanism. The ignition time of 30 μm PMMA was obviously longer than that of 5 μm PMMA, and the critical heating temperature was close to that of 5 μm PMMA. KHCO₃ and ABC could greatly extend the ignition time of the PMMA dust layer and increase the critical heating temperature of the dust layer. ABC was more effective than KHCO₃. The decomposition of KHCO₃ and ABC absorbed the heat and inhibits the pyrolysis of PMMA. The HPO₃ and P₂O₅ generated by the decomposition of ABC would cover the surface of PMMA aggregates or particles and act as a physical barrier. The main light combustible gas produced by PMMA pyrolysis were CO and C₂H₄. The CO₂ generated during the decomposition of KHCO₃ could dilute the combustible gas in the ambient to inhibit the combustion of PMMA.     

Flame propagation in lycopodium/air mixtures below atmospheric pressure

Industrial processes are often operated at conditions deviating from atmospheric conditions. Safety relevant parameters normally used for hazard evaluation and classification of combustible dusts are only valid within a very narrow range of pressure, temperature and gas composition. The development of dust explosions and flame propagation under reduced pressure conditions is poorly investigated. Standard laboratory equipment like the 20 l Siwek chamber does not allow investigations at very low pressures. Therefore an experimental device was developed for the investigations on flame propagation and ignition under reduced pressure conditions. Flame propagation was analysed by a video analysis system the actual flame speed was measured by optical sensors. Experiments were carried out with lycopodium at dust concentrations of 100 g/m³, 200 g/m³ and 300 g/m³. It was found that both flame shapes and flame speeds were quite different from those obtained at atmospheric pressure. Effects like buoyancy of hot gases during ignition and flame propagation are less strong than at atmospheric conditions. For the investigated dust concentrations the flame reaches speeds that are nearly an order of a magnitude higher than at ambient conditions.     

Propagation of ethylene–air flames in closed cylindrical vessels with asymmetrical ignition

A study of explosions in several elongated cylindrical vessels with length to diameter L/D = 2.4–20.7 and ignition at vessel's bottom is reported. Ethylene–air mixtures with variable concentration between 3.0 and 10.0 vol% and pressures between 0.30 and 1.80 bara were experimentally investigated at ambient initial temperature. For the whole range of ethylene concentration, several characteristic stages of flame propagation were observed. The height and rate of pressure rise in these stages were found to depend on ethylene concentration, on volume and asymmetry ratio L/D of each vessel. High rates of pressure rise were found in the early stage; in later stages lower rates of pressure rise were observed due to the increase of heat losses. The peak explosion pressures and the maximum rates of pressure rise differ strongly from those measured in centrally ignited explosions, in all examined vessels. In elongated vessels, smooth p(t) records have been obtained for the explosions of lean C₂H₄–air mixtures. In stoichiometric and rich mixtures, pressure oscillations appear even at initial pressures below ambient, resulting in significant overpressures as compared to compact vessels. In the stoichiometric mixture, the frequency of the oscillations was close to the fundamental characteristic frequency of the tube.     

The effects of phosphorus-free inhibitors on the ignition of lycopodium dust

The minimum ignition temperature of dust suspension (MIT) and the hot surface ignition temperature of the dust layer (LIT) are essential safety parameters for the process industry. However, the knowledge of the ignition behavior when solid mixtures of flammable fuels and phosphorous-free inhibitors are considered is still scarce and further experimental and theoretical analyses are requested. In this work, the ignition temperature of phosphorous-free inhibitors (coal fly ash and calcium carbonate) mixed with lycopodium dust have been studied in terms of LIT analysis (hot plate thickness: 5 mm, 12.5 mm and 15 mm), and by the Godbert-Greenwald test for the MIT. Both coal fly ash and calcium carbonate have been tested at different concentrations and particle sizes.Results show that the effects of the inhibitor can be counter-productive when layer ignition temperature is considered even if the minimum ignition temperature of the dust suspension shows a positive effect from the safety point of view. This behavior has been analyzed in the terms of thermal conductivity and diffusivity of the mixture, by using Maxwell's equation for two-phase solid mixtures. Standard empirical correlations for the ignition temperature of solid mixtures have been also tested, showing their weakness in reproducing mixture behavior.     

Explosion characteristics of micron- and nano-size magnesium powders

Explosion characteristics of micron- and nano-size magnesium powders were determined using CSIR-CBRI 20-L Sphere, Hartmann apparatus and Godbert-Greenwald furnace to study influence of particle size reduction to nano-range on these. The explosion parameters investigated are: maximum explosion pressure (P_max), maximum rate of pressure-rise (dP/dt)_max, dust explosibility index (K_St), minimum explosible concentration (MEC), minimum ignition energy (MIE), minimum ignition temperature (MIT), limiting oxygen concentration (LOC) and effect of reduced oxygen level on explosion severity. Magnesium particle sizes are: 125, 74, 38, 22, 10 and 1 μm; and 400, 200, 150, 100, 50 and 30 nm. Experimental results indicate significant increase in explosion severity (P_max: 7–14 bar, K_St: 98–510 bar·m/s) as particle size decreases from 125 to 1 μm, it is maximum for 400 nm (P_max: 14.6 bar, K_St: 528 bar·m/s) and decreases with further decrease of particle size to nano-range 200–30 nm (P_max: 12.4–9.4 bar, K_St: 460–262 bar·m/s) as it is affected by agglomeration of nano-particles. MEC decreases from 160 to 30 g/m³ on decreasing particle size from 125 to 1 μm, its value is 30 g/m³ for 400 and 200 nm and 20 g/m³ for further decrease in nano-range (150–30 nm). MIE reduces from 120 to 2 mJ on decreasing the particle size from 125 to 1 μm, its value is 1 mJ for 400, 200, 150 nm size and <1 mJ for 50 and 30 nm. Minimum ignition temperature is 600 °C for 125 μm magnesium, it varies between 570 and 450 °C for sizes 38–1 μm and 400–350 °C for size range 400–30 nm. Magnesium powders in nano-range (30–200 nm) explode less violently than micron-range powder. However, likelihood of explosion increases significantly for nano-range magnesium. LOC is 5% for magnesium size range 125–38 μm, 4% for 22–1 μm, 3% for 400 nm, 4% for 200, 150 and 100 nm, and 5% for 50 and 30 nm. Reduction in oxygen levels to 9% results in decrease in P_max and K_St by a factor of 2–3 and 4–5, respectively, for micron as well as nano-sizes. The experimental data presented will be useful for industries producing or handling similar size range micron- and nano-magnesium in order to evaluate explosibility of their magnesium powders and propose/design adequate safety measures.