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Mechanism of internal thermal runaway propagation in blade batteries

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

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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

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Parameter-independent error correction for potential measurements by reference electrode in lithium-ion batteries

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Journal of Energy Chemistry 2022年第4期31卷 34-45页

作者： Yalun Li Xinlei Gao xuning feng Xuebing Han Jiuyu Du Languang Lu Minggao Ouyang State Key Laboratory of Automotive Safety and Energy Tsinghua UniversityBeijing 100084 China School of Transportation Science and Engineering Beihang UniversityBeijing 100191China

The safety monitoring of lithium-ion batteries(LIBs) is of great significance for realizing all-climate and full-lifespan battery management. In-situ measurement of anode potential with implanted reference electrodes(REs) has proven to be effective to monitor and avoid the occurrence of severe side reactions like Li plating to ensure the safe and fast charging. However, the intrinsic measurement errors caused by local blocking effects, which also can be referred to as potential artefacts, are seldom taken into consideration in existing studies, yet they highly dominate the correctness of conclusions inferred from REs. In this study, aiming at exploring the physical origin of the measurement errors and ensure reliable potential monitoring, electrochemical and post-mortem tests are conducted using commercial pouch cells with implanted REs. Corresponding electrochemical model which describes the blocking effects, is established to validate the abnormal absence of lithium plating that predicted by measured anode potentials under various charging rates. Theoretical derivation is further presented to explain the error sources, which can be attributed to increased local liquid potential of the RE position. Most importantly, with the guidance of error analysis, a novel parameter-independent error correction method for RE measurements is proposed for the first time, which is proven to be adequate to estimate the real anode potentials and deduce the critical C-rate of Li plating with extra safety margin. After error correction, the resulting critical C-rates are all within the range of 0.55 ± 0.03 C, which is close to the C-rate of 0.6–0.7 C obtained from experiments. In addition, this error correction method can be performed conveniently with only some simple RE measurements of polarization voltages, totally independent of battery electrochemical and geometric parameters. This study provides highly practical error correction method for RE measurements in real LIBs, substantially facilitating the fast diagnosis and safety

关键词： Reference electrode Lithium-ion battery Potential artefacts Measurement error correction

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Experimental Study on the Effect of State of Charge on Failure Propagation Characteristics within Battery Modules

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Chinese Journal of Electrical Engineering 2023年第3期9卷 3-14页

作者： Kuijie Li Yalun Li Xinyu Rui Yuancheng Cao Liyun Fan xuning feng School of Electrical and Electronic Engineering Huazhong University of Science and TechnologyWuhan 430074China State Key Laboratory of Automotive Safety and Energy Tsinghua UniversityBeijing 100086China College of Power and Energy Engineering Harbin Engineering UniversityHarbin 150001China Department of Electrical Engineering Tsinghua UniversityBeijing 100086China

To investigate the effect of different states of charge(SOC)on the thermal runaway(TR)propagation behaviors within lithium-ion-batteries based energy storage modules,an experimental setup was developed to conduct failure propagation tests on battery modules at an SOC of 97%,85%,and 50%.The result indicates that an increase in the SOC of batteries can decrease the TR trigger temperature,making batteries trigger TR earlier and reducing the average failure propagation time between two adjacent cells.In addition,the failure propagation tests reveal that at higher SOCs,the TR reaction becomes more violent,the maximal reaction temperature is also much higher,and the damage to the battery module is severe.Compared to the battery module with 97%SOC,the TR trigger time of the battery module with 50%SOC was postponed by approximately 57.8%.Meanwhile,the average failure propagation time got prolonged by approximately 36.0%.Thus,this study can provide references for the thermal safety design of energy-storage battery modules.

关键词： Energy storage battery module thermal runaway failure propagation state of charge battery safety

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In-depth investigation of the exothermic reactions between lithiated graphite and electrolyte in lithium-ion battery

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Journal of Energy Chemistry 2022年第6期31卷 593-600,I0017页

作者： Yuejiu Zheng Zhihe Shi Dongsheng Ren Jie Chen Xiang Liu xuning feng Li Wang Xuebing Han Languang Lu Xiangming He Minggao Ouyang College of Mechanical Engineering University of Shanghai for Science and TechnologyShanghai 200093China State Key Laboratory of Automotive Safety and Energy Tsinghua UniversityBeijing 100084China Institute of Nuclear and New Energy Technology Tsinghua UniversityBeijing 100084China College of Electrical Engineering University of Beijing JiaotongBeijing 100044China

Thermal runaway is a critical issue for the large application of lithium-ion batteries.Exothermic reactions between lithiated graphite and electrolyte play a crucial role in the thermal runaway of lithium-ion batteries.However,the role of each component in the electrolyte during the exothermic reactions with lithiated graphite has not been fully understood.In this paper,the exothermic reactions between lithiated graphite and electrolyte of lithium-ion battery are investigated through differential scanning calorimetry(DSC) and evolved gas analysis.The lithiated graphite in the presence of electrolyte exhibit three exothermic peaks during DSC test.The reactions between lithiated graphite and LiPF_(6) and ethylene carbonate are found to be responsible for the first two exothermic peaks,while the third exothermic peak is attributed to the reaction between lithiated graphite and binder.In contrast,diethylene carbonate and ethyl methyl carbonate contribute little to the total heat generation of graphite-electrolyte reactions.The reaction mechanism between lithiated graphite and electrolyte,including the major reaction equations and gas products,are summarized.Finally,DSC tests on samples with various amounts of electrolyte are performed to clarify the quantitative relationship between lithiated graphite and electrolyte during the exothermic reactions.2.5 mg of lithiated graphite (Li_(0.8627)C_(6)) can fully react with around 7.2 mg electrolyte,releasing a heat generation of 2491 J g^(-1).The results presented in this study can provide useful guidance for the safety improvement of lithium-ion batteries.

关键词： Lithium-ion battery Battery safety Thermal runaway Exothermic reaction Li-intercalated graphite Electrolyte

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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

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基于间苯三酚的电池热失效自毁机制研究

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工程热物理学报 2024年第6期45卷 1663-1670页

作者：侯博文彭勇冯旭宁清华大学车辆与运载学院北京100084

高比能锂离子电池的热失控问题是限制其大规模应用的关键原因。本文从自毁电池的角度出发,以间苯三酚为自毁剂,阻断负极和电解液的反应,避免大量还原性气体的产生,减少气体串扰的反应热释放,最终降低热失控灾害程度。结果表明,间苯三酚... 详细信息

高比能锂离子电池的热失控问题是限制其大规模应用的关键原因。本文从自毁电池的角度出发,以间苯三酚为自毁剂,阻断负极和电解液的反应,避免大量还原性气体的产生,减少气体串扰的反应热释放,最终降低热失控灾害程度。结果表明,间苯三酚的引入使热失控反应提前至120℃,且消除了200℃时的剧烈放热,实现了热失控反应时序的调控和热失控反应焓值的降低,提高了电池的安全性。本文为高安全电池设计提供了新的思路,具有一定的指导意义。

关键词：锂离子电池自毁电池热失控反应时序调控间苯三酚

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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

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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

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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

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