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Journal of Energy Chemistry 2024年第2期89卷 195-207,I0006页

作者： Zhuangzhuang Jia Yuanyuan Min Peng Qin Wenxin Mei Xiangdong Meng Kaiqiang Jin Jinhua Sun Qingsong Wang State Key Laboratory of Fire Science University of Science and Technology of ChinaHefei 230026AnhuiChina Gotion High-Tech Co. Ltd.Hefei 230012AnhuiChina

The safety valve is an important component to ensure the safe operation of lithium-ion batteries(LIBs).However,the effect of safety valve type on the thermal runaway(TR)and gas venting behavior of LIBs,as well as the TR hazard severity of LIBs,are not known.In this paper,the TR and gas venting behavior of three 100 A h lithium iron phosphate(LFP)batteries with different safety valves are investigated under overheating.Compared to previous studies,the main contribution of this work is in studying and evaluating the effect of gas venting behavior and TR hazard severity of LFP batteries with three safety valve types.Two significant results are obtained:(Ⅰ)the safety valve type dominates over gas venting pressure of battery during safety venting,the maximum gas venting pressure of LFP batteries with a round safety valve is 3320 Pa,which is one order of magnitude higher than other batteries with oval or cavity safety valve;(Ⅱ)the LFP battery with oval safety valve has the lowest TR hazard as shown by the TR hazard assessment model based on gray-fuzzy analytic hierarchy process.This study reveals the effect of safety valve type on TR and gas venting,providing a clear direction for the safety valve design.

关键词： Lithium iron phosphate battery Safety valve thermal runaway Gas venting behavior thermal runaway hazard severity Gray-fuzzy analytic hierarchy process

Mechanism of internal thermal runaway propagation in blade batteries

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Journal of Energy Chemistry 2024年第2期89卷 184-194,I0005页

作者： Xuning Feng Fangshu Zhang Wensheng Huang Yong Peng Chengshan Xu Minggao Ouyang School of Vehicle and Mobility Tsinghua UniversityBeijing 100084China

Blade batteries are extensively used in electric vehicles,but unavoidable thermal runaway is an inherent threat to their safe use.This study experimentally investigated the mechanism underlying thermal runaway propagation within a blade battery by using a nail to trigger thermal runaway and thermocouples to track its propagation inside a cell.The results showed that the internal thermal runaway could propagate for up to 272 s,which is comparable to that of a traditional battery module.The velocity of the thermal runaway propagation fluctuated between 1 and 8 mm s^(-1),depending on both the electrolyte content and high-temperature gas diffusion.In the early stages of thermal runaway,the electrolyte participated in the reaction,which intensified the thermal runaway and accelerated its propagation.As the battery temperature increased,the electrolyte evaporated,which attenuated the acceleration effect.Gas diffusion affected thermal runaway propagation through both heat transfer and mass transfer.The experimental results indicated that gas diffusion accelerated the velocity of thermal runaway propagation by 36.84%.We used a 1D mathematical model and confirmed that convective heat transfer induced by gas diffusion increased the velocity of thermal runaway propagation by 5.46%-17.06%.Finally,the temperature rate curve was analyzed,and a three-stage mechanism for internal thermal runaway propagation was proposed.In Stage I,convective heat transfer from electrolyte evaporation locally increased the temperature to 100℃.In Stage II,solid heat transfer locally increases the temperature to trigger thermal runaway.In StageⅢ,thermal runaway sharply increases the local temperature.The proposed mechanism sheds light on the internal thermal runaway propagation of blade batteries and offers valuable insights into safety considerations for future design.

关键词： Lithium-ion battery Blade battery thermal runaway Internal thermal runaway propagation

thermal runaway Characteristics and Modeling of LiFePO4 Power Battery for Electric Vehicles

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Automotive Innovation 2023年第3期6卷 414-424页

作者： Tao Sun Luyan Wang Dongsheng Ren Zhihe Shi Jie Chen Yuejiu Zheng Xuning Feng Xuebing Han Languang Lu Li Wang Xiangming He Minggao Ouyang School of Mechanical Engineering University of Shanghai for Science and TechnologyShanghai 200093China Institute of Nuclear and New Energy Technology Tsinghua UniversityBeijing 100084China State Key Laboratory of Automotive Safety and Energy Tsinghua UniversityBeijing 100084China

LiFePO_(4)(LFP)lithium-ion batteries have gained widespread use in electric vehicles due to their safety and longevity,but thermal runaway(TR)incidents still have been reported.This paper explores the TR characteristics and modeling of LFP batteries at different states of charge(SOC).Adiabatic tests reveal that TR severity increases with SOC,and five stages are identified based on battery temperature evolution.Reaction kinetics parameters of exothermic reactions in each TR stage are extracted,and TR models for LFP batteries are established.The models accurately simulate TR behaviors at different SOCs,and the simulated TR characteristic temperatures also agree well with the experimental results,with errors of TR characteristic temperatures less than 3%.The prediction errors of TR characteristic temperatures under oven test conditions are also less than 1%.The results provide a comprehensive understanding of TR in LFP batteries,which is useful for battery safety design and optimization.

关键词： Lithium-ion battery Safety thermal runaway thermal runaway model State of charge

thermal runaway of Lithium-Ion Batteries Employing Flame-Retardant Fluorinated Electrolytes

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Energy & Environmental Materials 2023年第1期6卷 333-339页

作者： Junxian Hou Li Wang Xuning Feng Junpei Terada Languang Lu Shigeaki Yamazaki Anyu Su Yoshiko Kuwajima Yongjiang Chen Tomoya Hidaka Xiangming He Hewu Wang Minggao Ouyang State Key Laboratory of Automotive Safety and Energy Tsinghua UniversityBeijing 100084China Institute of Nuclear and New Energy Technology Tsinghua UniversityBeijing 100084China Daikin Industries Ltd.1-1Nishi-HitotsuyaSettsu Osaka 566-8585Japan Sichuan New Energy Vehicle Innovation Center Yibin 644002China

Fluorinated electrolytes possess good antioxidant capacity that provides high compatibility to high-voltage cathode and flame retardance;thus,they are considered as a promising solution for advanced lithium-ion batteries carrying both high-energy density and high safety.Moreover,the fluorinated electrolytes are widely used to form stable electrolyte interphase,due to their chemical reactivity with lithiated graphite or lithium.However,the influence of this reactivity on the thermal safety of batteries is seldom discussed.Herein,we demonstrate that the flame-retardant fluorinated electrolytes help to reduce the flammability,while the lithium-ion batteries with flame-retardant fluorinated electrolytes still undergo thermal runaway and disclose their different thermal runaway pathway from that of battery with conventional electrolyte.The reduction in fluorinated components(e.g.,LiPF 6 and fluoroethylene carbonate(FEC))by fully lithiated graphite accounts for a significant heat release during battery thermal runaway.The 13%of total heat is sufficient to trigger the chain reactions during battery thermal runaway.This study deepens the understanding of the thermal runaway mechanism of lithium-ion batteries employing flame-retardant fluorinated electrolytes,providing guidance on the concept of electrolyte design for safer lithium-ion batteries.

关键词： battery safety flame retardance fluorinated electrolytes lithium-ion battery thermal runaway

thermal runaway propagation behavior of the Cell-to-Pack battery system

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Journal of Energy Chemistry 2023年第9期84卷 162-172页

作者： Huaibin Wang Qinzheng Wang Zhenyang Zhao Changyong Jin Chengshan Xu Wensheng Huang Zhuchen Yuan Shuyu Wang Yang Li Yanhong Zhao Junli Sun Xuning Feng China People’s Police University LangFang 065000HebeiChina State Key Laboratory of Intelligent Green Vehicle and Mobility Tsinghua UniversityBeijing 100084China Laboratory of Explosion Science and Technology Beijing Institute of TechnologyBeijing 100084China Beijing Electric Vehicle Co.Ltd Beijing 100176China College of Mechanical Engineering University of Shanghai for Science and TechnologyShanghai 200093China

Structurally compact battery packs significantly improve the driving range of electric vehicles.Technologies like Cell-to-Pack increase energy density by 15%-20%.However,the safety implications of multiple tightly-packed battery cells still require in-depth research.This paper studies thermal runaway propagation behavior in a Cell-to-Pack system and assesses propagation speed relative to other systems.The investigation includes temperature response,extent of battery damage,pack structure deformation,chemical analysis of debris,and other considerations.Results suggest three typical patterns for the thermal runaway propagation process:ordered,disordered,and synchronous.The synchronous propagation pattern displayed the most severe damage,indicating energy release is the largest under the synchronous pattern.This study identifies battery deformation patterns,chemical characteristics of debris,and other observed factors that can both be applied to identify the cause of thermal runaway during accident investigations and help promote safer designs of large battery packs used in large-scale electric energy storage systems.

关键词： Energy storage Cell-to-Pack Lithium-ion battery thermal runaway Battery safety

Influences of multi factors on thermal runaway induced by overcharging of lithium-ion battery

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Journal of Energy Chemistry 2022年第7期31卷 531-541,I0014页

作者： Jialong Liu Zhirong Wang Jinlong Bai Jiangsu Key Laboratory of Hazardous Chemicals Safety and Control College of Safety Science and EngineeringNanjing Tech UniversityNanjing 21009JiangsuChina

thermal runaway caused by overcharging results in catastrophic disasters. The influences of charging rate, ambient temperature and aging on thermal runaway caused by overcharging are studied qualitatively and quantitatively in this manuscript. The results of overcharging tests indicate that high charging rate and ambient temperature increase thermal runaway risk. Aging in 40 ℃ decreases thermal runaway risk. The risk increase of battery with high overcharging rate and in high ambient temperature is due to fast lithium plating reaction and accelerated SEI decomposition, respectively. The risk decrease of aged battery is due to the occurrence of SEI before overcharging tests. SEI suppresses the side reactions between lithium plating and electrolyte. The results of orthogonal tests indicate that the rank of effect is: discharging rate > ambient temperature > aging. The heat generation is calculated based on the results of overcharging tests. The calculation results indicate that heat generated by side reactions contributes more to the total heat generation. Although thermal runaway does not occur during overcharging with low current, the heat dissipation of the lithium-ion battery is the most and deserves focus. The results are important to the design of battery management system and thermal management system to prevent thermal runaway induced by overcharging in total lifespan of battery.

关键词： Lithium-ion battery safety Overcharging Aging thermal runaway

Higher-order polysulfides induced thermal runaway for 1.0 Ah lithium sulfur pouch cells

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Particuology 2023年第8期79卷 10-17页

作者： Feng-Ni Jiang Shi-Jie Yang Zi-Xian Chen He Liu Hong Yuan Lei Liu Jia-Qi Huang Xin-Bing Cheng Qiang Zhang College of Chemical Engineering and Technology Taiyuan University of TechnologyTaiyuan030024ShanxiChina Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology Department of Chemical EngineeringTsinghua UniversityBeijing100084China Advanced Research Institute of Multidisciplinary Science Beijing Institute of TechnologyBeijing100081China Key Laboratory of Energy thermal Conversion and Control of Ministry of Education School of Energy and EnvironmentSoutheast UniversityNanjing211189JiangsuChina School of Chemistry and Materials Science Nanjing University of Information Science and TechnologyNanjing210044JiangsuChina

Comprehensive analyses on thermal runaway mechanisms are critically vital to achieve the safe lithium-sulfur(Li-S)batteries.The reactions between dissolved higher-order polysulfides and Li metal were found to be the origins for the thermal runaway of 1.0 Ah cycled Li-S pouch cells.16-cycle pouch cell indicates high safety,heating from 30 to 300 ℃ without thermal runaway,while 16-cycle pouch cell with additional electrolyte undergoes severe thermal runaway at 147.9 ℃,demonstrating the key roles of the electrolyte on the thermal safety of batteries.On the contrary,thermal runaway does not occur for 45-cycle pouch cell despite the addition of the electrolyte.It is found that the higher-order polysulfides(Li_(2)S_(x) ≥ 6)are discovered in 16-cycle electrolyte while the sulfur species in 45-cycle electrolyte are Li_(2)S_(x) ≤ 4.In addition,strong exothermic reactions are discovered between cycled Li and dissolved higher-order polysulfide(Li_(2)S_(6) and Li_(2)S_(8))at 153.0 ℃,driving the thermal runaway of cycled Li-S pouch cells.This work uncovers the potential safety risks of Li-S batteries and negative roles of the polysulfide shuttle for Li-S batteries from the safety view.

关键词： Lithium-sulfur batteries thermal runaway Polysulfides Pouch cell Polysulfide shuttle

Mitigating thermal runaway hazard of high-energy lithium-ion batteries by poison agent

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能源化学:英文版 2023年第8期83卷 3-15,I0002页

作者： Xin Lai Zheng Meng Fangnan Zhang Yong Peng Weifeng Zhang Lei Sun Li Wang Fei Gao Jie Sheng Shufa Su Yuejiu Zheng Xuning Feng School of Mechanical Engineering University of Shanghai for Science and TechnologyShanghai 200093China svoLT Energy Technology Co.Ltd Changzhou 213200JiangsuChina State Key Laboratory of Automotive Safety and Energy Tsinghua UniversityBeijing 100084China State Grid Jiangsu Electric Power Co. LtdNanjing 211103JiangsuChina

Lithium-ion batteries with high-energy density are extensively commercialized in long-range electric vehicles. However, they are poor in thermal stability and pose fire or explosion, which has attracted the global attention. This study describes a new route to mitigate the battery thermal runaway(TR) hazard by poison agents. First, the self-destructive cell is built using the embedded poison layer. Then, the poisoning mechanism and paths are experimentally investigated at the material, electrode, and cell levels. Finally, the proposed route is verified by TR tests. The results show the TR hazard can be significantly reduced in the self-destructive cell based on a new reaction sequence regulation. Specifically, the maximum temperature of the self-destructive cell is more than 300℃ lower than that of the normal cell during TR. The drop in maximum temperature can reduce total heat release and the probability of TR propagation in the battery system, significantly improving battery safety.

关键词： Energystorage Lithium-ionbatteries thermal runaway Self-poison Chemical reactions

Dendrite-accelerated thermal runaway mechanisms of lithium metal pouch batteries

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SusMat 2022年第4期2卷 435-444页

作者： Xiang-Qun Xu Xin-Bing Cheng Feng-Ni Jiang Shi-Jie Yang Dongsheng Ren Peng Shi HungJen Hsu Hong Yuan Jia-Qi Huang Minggao Ouyang Qiang Zhang Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology Department of Chemical EngineeringTsinghua UniversityBeijingChina School of Metallurgy and Environment Central South UniversityChangshaChina Key Laboratory of Energy thermal Conversion and Control of Ministry of Education School of Energy and EnvironmentSoutheast UniversityNanjingChina Advanced Research Institute of Multidisciplinary Science Beijing Institute of TechnologyBeijingChina State Key Laboratory of Automotive Safety and Energy Tsinghua UniversityBeijingChina Mercedes-Benz AG MercedesstraßeStuttgartGermany

High-energy-density lithium metal batteries(LMBs)are widely accepted as promising next-generation energy storage systems.However,the safety features of practical LMBs are rarely explored quantitatively.Herein,the thermal runaway behaviors of a 3.26 Ah(343 Wh kg^(−1))Li|LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)pouch cell in the whole life cycle are quantitatively investigated by extended volume-accelerating rate calorimetry and differential scanning calorimetry.By thermal failure analyses on pristine cell with fresh Li metal,activated cell with once plated dendrites,and 20-cycled cell with large quantities of dendrites and dead Li,dendrite-accelerated thermal runaway mechanisms including reaction sequence and heat release contribution are reached.Suppressing dendrite growth and reducing the reactivity between Li metal anode and electrolyte at high temperature are effective strategies to enhance the safety performance of LMBs.These findings can largely enhance the understanding on the thermal runaway behaviors of Li metal pouch cells in practical working conditions.

关键词： battery safety lithium metal dendrites lithium metal pouch cells solid electrolyte interphase thermal runaway whole life cycle

thermal safety boundary of lithium-ion battery at different state of charge

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Journal of Energy Chemistry 2024年第4期91卷 59-72页

作者： Hang Wu Siqi Chen Yan Hong Chengshan Xu Yuejiu Zheng Changyong Jin Kaixin Chen Yafei He Xuning Feng Xuezhe Wei Haifeng Dai Clean Energy Automotive Engineering Center Tongji UniversityShanghai 201804China College of Mechanical Engineering University of Shanghai for Science and TechnologyShanghai 200093China State Key Laboratory of Automotive Safety and Energy Tsinghua UniversityBeijing 100084China

thermal runaway(TR)is a critical issue hindering the large-scale application of lithium-ion batteries(LIBs).Understanding the thermal safety behavior of LIBs at the cell and module level under different state of charges(SOCs)has significant implications for reinforcing the thermal safety design of the lithium-ion battery module.This study first investigates the thermal safety boundary(TSB)correspondence at the cells and modules level under the guidance of a newly proposed concept,safe electric quantity boundary(SEQB).A reasonable thermal runaway propagation(TRP)judgment indicator,peak heat transfer power(PHTP),is proposed to predict whether TRP occurs.Moreover,a validated 3D model is used to quantitatively clarify the TSB at different SOCs from the perspective of PHTP,TR trigger temperature,SOC,and the full cycle life.Besides,three different TRP transfer modes are discovered.The interconversion relationship of three different TRP modes is investigated from the perspective of PHTP.This paper explores the TSB of LIBs under different SOCs at both cell and module levels for the first time,which has great significance in guiding the thermal safety design of battery systems.

关键词： Lithium-ion battery Battery safety thermal runaway State of charge Numerical analysis