Thermal runaway behavior and features of LiFePO4/graphite aged batteries under overcharge

In this paper, the overcharge tests of 25 Ah LiFePO₄/graphite batteries are conducted in an open environment and the overcharge-to-thermal-runaway characteristics are studied. The effects of current rates (C-rates: 2C, 1C, 0.5C, and 0.3C) and states of health (SOHs: 100%, 80%, 70%, and 60%) on thermal runaway features are discussed in detail. The overcharge process can be summarized into five stages based on the experimental phenomena (C-rate ≥ 1 and SOH ≥ 80%): expansion, fast venting after safety valve rupture, slow venting, intense jet smoke, and explosion, while the battery cannot explode at lower C-rates and SOHs. The maximum pressure increases with the increase in C-rate or SOH. There are five obvious inflection points in the voltage curve during overcharge process. The V₁ (point B) of aged battery, corresponding to lithium plating on the anode, changes little with C-rates. It is slightly lower than that of the new battery. A sharp drop in voltage (point E) is probably due to the internal short circuit (ISC), caused by the local melting and rupture of the separator. It takes more than 2 minutes from the moment of ISC to thermal runaway regardless of the SOH, indicating that there are a few minutes to take safety measures if the voltage is an indication parameter. The onset temperature of thermal runaway decreases first and then increases as the SOH decreases from 100% to 60% during 1C constant overcharge tests. These results can provide guidance for the thermal management of the whole battery life cycle and the reuse of retired batteries.     

Research on thermal runaway test platform design for energy-storage lithium-ion batteries

介绍了锂离子储能电池热失控研究的目的和意义,探讨了储能电池与动力电池在热失控检测实验研究关注上的异同,从理论分析和实验研究两方面归纳了影响储能电池热失控的促发条件及对应的关键阈值.在此基础上,完成了模拟热失控促发条件和满足阈值要求的检测实验平台设计及功能验证,并对此平台的应用前景进行了展望.     

Recent progress on thermal runaway propagation of lithium-ion battery

简述了电动汽车锂离子动力电池热失控蔓延机理、建模与抑制技术的最新研究进展。为了满足汽车高能量的要求,需要动力电池进行串并联成组来提供动力。电池组成组安全问题成为电动汽车大规模应用的重要技术问题。电池组中的某一个电池单体发生热失控后产生大量热,导致周围电池单体受热产生热失控。因而,电池组成组安全问题的重要关注点是电池组内的热失控蔓延问题。本文对锂离子电池热失控蔓延问题的国内外研究进展进行了综述,分析了对于不同种类锂离子动力电池影响其热失控蔓延特性的主要因素。总结了文献中的热失控蔓延建模方法,并指出了已有方法的不足。从电池系统热安全管理的角度,阐述并分析了热失控蔓延防控技术的研究成果与方向。最后对锂离子电池热失控蔓延研究进行了展望。     

Prediction of thermal runaway and thermal management requirements in cylindrical Li‐ion cells in realistic scenarios

Li‐ion cells suffer from significant safety and performance problems due to overheating and thermal runaway. Effective thermal management can lead to increased energy conversion efficiency and energy storage density. Critical needs towards these goals include the capability to predict thermal behavior in extreme conditions and determine thermal management requirements to prevent thermal runaway. This paper presents an experimentally validated theoretical model to predict the temperature distribution in a cell in response to nonlinear heat generation rate that is known to occur during thermal runaway. This problem is solved by linearization of the nonlinear term over successive time intervals. Experimental measurements carried out on a thermal test cell in conditions similar to thermal runaway show good agreement with the theoretical model. Experimental measurements and model predictions indicate strong dependence of the fate of the cell on its reaction kinetics, thermal properties, and ambient conditions. Specifically, a sudden change in thermal runaway behavior is predicted once the ambient temperature crosses a certain threshold, consistent with past experimental observations. The impact of increasing cell thermal conductivity on improved thermal runaway performance is quantified. Results presented here provide a fundamental understanding of thermal runaway, and may lead to improved performance and safety of Li‐ion–based energy conversion and storage systems.     

Experimental investigation on the effect of ambient pressure on thermal runaway and fire behaviors of lithium‐ion batteries

To investigate the impacts of ambient pressure on thermal runaway and fire behaviors of lithium‐ion battery (LIB), experimental measurement and theoretical analysis with serial conditions are conducted at two altitudes. The well‐designed experimental equipment and operating conditions have enabled the accurate evaluation of ambient pressure effects. Results show that the first abrupt temperature change in Hefei (ambient pressure 100.8 kPa) is higher than that in Lhasa (64.3 kPa). The difference in ambient pressure at two altitudes leads to different relief valve crack temperature and time. The average burning rate in Hefei is larger than that in Lhasa, and the estimated pressure effect factor is quite different for detailed pack conditions and varies within the range of 0.083‐1.39. The ambient pressure has a greater effect on the heat release rate and total heat release than the mass loss, and the effective combustion heat under the low pressure is lower than that in normal condition. This work can provide more comprehensive and useful data for the safety management of LIBs at low pressure environments.     

Venting process of lithium-ion power battery during thermal runaway under medium state of charge

以电动汽车用方壳型镍钴锰（NCM）锂离子动力电池为研究对象,以氮气为惰性保护,采用高速摄影的方法,在密闭容器内开展了电池热失控产物喷发过程的试验研究。检测压力突变表明,中等荷电状态下的电池热失控后的喷发过程出现了2次剧烈喷射,分别导致了喷发物射流区温度的突然降低和快速升高。借助辅助光源,捕捉到了热失控产物首次喷发演变过程的高速影像,进一步分析发现,首次喷发经历了初期的带状和锥形喷发,然后进入较长时间的无定形喷发和后期的倒锥形喷发;同时,在影像中还观察到了气-液-固三相共存的特征。     

Electrochemical thermal stability of the LiFePO4/LiNi0.8Co0.15Al0.05O2 blend cathode material for lithium ion batteries

为了改善LiNi_0.8Co_0.15Al_0.05O₂正极材料的电化学热稳定性能,加入LiFePO₄共混制成了LiFePO₄/LiNi_0.8Co_0.15Al_0.05O₂锂离子电池用混合正极材料。使用X射线衍射（XRD）和扫描电子显微镜（SEM）表征了结构和形貌,测试了电化学性能。结果显示,简单球磨的混合LiFePO₄/LiNi_0.8Co_0.15Al_0.05O₂正极材料中,纳米LiFePO₄粒子包覆在LiNi_0.8Co_0.15Al_0.05O₂粒子表面提高了混合正极材料在充放电过程中的电化学稳定性和结构稳定性。LiFePO₄/LiNi_0.8Co_0.15Al_0.05O₂混合正极材料在50 ℃下循环100周容量保持率为82.0%,明显地优于单一LiNi_0.8Co_0.15Al_0.05O₂材料的72.9%。     

Recent progress on mechanism and detection of internal short circuit in lithium-ion batteries

锂离子电池内短路是锂离子电池热失控事故中最常见的诱因之一,也是机械滥用、电滥用、热滥用的共性环节,是潜在的安全威胁。本文从锂离子电池内短路安全问题出发,综述了内短路机理的研究进展,归纳了内短路替代实验方法,介绍了内短路演化过程,指出了内短路检测需在其发展初期和中期完成。进而,总结了多种内短路检测方法,最后,对内短路问题下一步研究进行了展望。     

石墨负极材料形态对LiFePO4动力电池性能的影响

本文分别以树脂包覆天然石墨（RCNG）、人造石墨（AG）和中间相碳微球（MCMB）为负极材料,制备了三种不同的圆柱形磷酸铁锂（LiFePO4）动力电池。通过X射线衍射分析仪（XRD）和扫描电子显微镜（SEM）对材料的晶体结构与形貌进行表征,并采用多种手段测试了各动力电池的电化学性能。结果显示,磷酸铁锂/中间相碳微球（LFP/MCMB）电池表现出较为优异的电化学低温、倍率和循环性能,其在 −20℃下的1 C容量保持率为61.04%,6 C高倍率容量保持率和温升分别为87.52%和24.8℃,3 C循环1 000次后容量保持率为93.81%。     

Experimental study on fire extinguishing of large-capacity lithium-ion batteries by various fire extinguishing agents

为研究不同灭火介质对大容量动力锂离子电池火灾的有效性,搭建了适用于多种灭火介质的灭火测试平台。在灭火测试平台上以功率为300 W的电热管作为外热源引发单电池热失控,通过改变灭火介质,研究了不同灭火介质的灭火行为及灭火效率。研究结果表明,对于38 A·h单体动力电池火灾,ABC干粉、七氟丙烷（HFC）、水、全氟己酮和CO₂灭火剂均能快速熄灭电池明火,但CO₂灭火剂灭火后电池出现了复燃;电池灭火过程中,不同的灭火剂在抑制电池温度上升表现出明显差异,其中,抑制温升效果优劣依次为水、全氟己酮、HFC、ABC干粉和CO₂。本研究的结果可为工程应用及电池灭火规范制定提供实验支撑。     

Thermal analysis for LiFePO4 power battery based on finite element analysis

针对新能源车用磷酸铁锂动力电池的温度分布问题,本文以本公司生产的磷酸铁锂动力电池为研究对象,基于电池热分析的数学模型和有限元分析方法,利用ANSYS软件对单体电池的温度分布进行了仿真计算。结果表明,在1 C、2 C和3 C放电倍率下,单体电池的最高温度分别为34.3629℃、53.7926℃和83.3099℃。在冷却方式中,水冷的冷却效果最佳。本文为电池设计和测定电池实际温度分布提供了依据。     

Charge/discharge characteristics of Li‐ion batteries with two‐phase active materials: a comparative study of LiFePO4 and LiCoO2 cells

A comparative study of LiFePO₄ and LiCoO₂ cells was conducted using two mathematical models to identify the physical characteristics of the two‐phase electrode compared with the single‐phase electrode under both charge and discharge conditions. First, the electrical conductivity of the LiFePO₄ electrode was examined applying a two‐dimensional electrical conduction model. The calculation results showed that the electrical conductivity of the LiFePO₄ electrode could be improved significantly by coating the LiFePO₄ particles with a conductive substance. Second, a modified physics‐based cell model was applied to simulate the phase‐change phenomena at the equilibrium boundary inside the LiFePO₄ particles. The cell performance using LiFePO₄ electrode was degraded significantly owing to the increase in ohmic loss and concentration loss caused by the low electrical conductivity and phase‐change characteristics of LiFePO₄ under high C‐rate conditions. The present model was validated with experimental data and showed good agreement. Copyright © 2016 John Wiley & Sons, Ltd.     

Electrical‐thermal behaviors of a cylindrical graphite‐NCA Li‐ion battery responding to external short circuit operation

Large amount of heat generated during an external short circuit (ESC) process may cause battery safety events. An experimental platform is established to explore the battery electrothermal characteristics during ESC faults. For 18650‐type nickel cobalt aluminum (NCA) batteries, ESC fault tests of different initial state of charge (SOC) values, different external resistances, or different ambient temperatures are carried out. The test case of a smaller external resistance is characterized by a shorter ESC duration with a faster cell temperature rise, whereas the case of a larger external resistance will last for a longer duration, discharge more electricity, and terminate in a slightly higher temperature. The tested batteries of high initial SOCs generally have higher temperature rise rates, smoother changes at the output current/voltage curves, but a smaller discharged capacity. The batteries of low initial SOCs can be overdischarged by the ESC operations. At low temperatures, say 0°C, the ESC process outputs much less electricity than the process at high temperatures, eg, 30°C. The initial low temperature has little effect on reducing the battery overheat due to ESC operations. The battery thermal behavior is of hysteresis property; analysis of heat generations reveals the subsequent increase of battery surface temperature after the completion of ESC discharge is due to the battery material abusive reaction heats. It is found from analytical and numerical analyses that there can have approximately 30°C temperature difference between the battery core and its surface during ESC operations. The interruption of ESC operation is very probably caused by the high battery core temperature, which leads to the destruction of solid‐electrolyte interface (SEI) film.     

Prediction of vortex penetration depth at thermal stratification by cavity flow in a branch pipe with closed end (effect of heat radiation condition on temperature fluctuations)

In a branch pipe with one closed end, the cavity flow penetrates into the branch pipe from the main loop and a thermal boundary layer occurs because the cavity flow is a hot fluid, but heat removal causes a colder fluid in the branch pipe. This thermal stratification may affect the structural integrity. Therefore, a pipe design standard to suppress thermal fatigue should be established. The pipe design standard consists of the maximum penetration depth L_sv and the minimum penetration depth L_sh. In order to establish an evaluation method for L_sh, a visualization test and a temperature fluctuation test were carried out. A theoretical formula for thermal stratification was introduced from the heat balance model. Then the model was used to obtain an empirical equation from the map of fluid temperature fluctuation. This method can predict the vortex penetration depth by cavity flow in horizontal branch pipes. © 2006 Wiley Periodicals, Inc. Heat Trans Asian Res, 36(1):38–55, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.20135     

Effect of mixed LiBOB and LiPF6 salts on electrochemical and thermal properties in LiMn2O4 batteries

The effects of mixed LiBOB and LiPF₆ salts as electrolyte for lithium ion batteries are investigated by electrochemical testing and thermal stability analysis. Elevated temperature cycle, specific power, DCIR and EIS tests reveal that mixed salts electrolyte has a distinct effect on cycle life and effectively stabilize impedance increase, as optimum concentration of LiBOB is between 0.1 and 0.25 M. Fading mechanism analyses demonstrate that the mixed salts system could decrease Mn dissolution and LiBOB decomposition at elevated temperature application. Accelerating rate calorimetry (ARC) shows that the thermal stability of mixed salts electrolyte is also acceptable. In short, the mixed salts of LiBOB and LiPF₆ provide a possible solution to improve the instability of LiMn₂O₄ as cathode in lithium ion batteries at elevated temperature conditions and show a promising capability in high current discharge for high power application such as hybrid electrical vehicles.