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Research on the impact of high-temperature aging on the thermal safety of lithium-ion batteries

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Journal of Energy Chemistry 2023年第12期87卷 378-389,I0010页

作者： Guangxu Zhang Xuezhe Wei Siqi Chen Gang Wei Jiangong Zhu Xueyuan Wang Guangshuai Han Haifeng Dai Clean Energy Automotive Engineering Center Tongji UniversityShanghai 201804China School of Automotive Studies Tongji UniversityShanghai 201804China Institute for Advanced Study Tongji UniversityShanghai 200092China Shanghai AI NEV Innovative Platform Co. Ltd.Shanghai 201804China

Understanding the thermal safety evolution of lithium-ion batteries during high-temperature usage conditions bears significant implications for enhancing the safety management of aging batteries.This work investigates the thermal safety evolution mechanism of lithium-ion batteries during high-temperature aging.Similarities arise in the thermal safety evolution and degradation mechanisms for lithium-ion batteries undergoing cyclic aging and calendar aging.Employing multi-angle characterization analysis,the intricate mechanism governing the thermal safety evolution of lithium-ion batteries during high-temperature aging is clarified.Specifically,lithium plating serves as the pivotal factor contributing to the reduction in the self-heating initial temperature.Additionally,the crystal structure of the cathode induced by the dissolution of transition metals and the reductive gas generated during aging attacking the crystal structure of the cathode lead to a decrease in thermal runaway triggering temperature.Furthermore,the loss of active materials and active lithium during aging contributes to a decline in both the maximum temperature and the maximum temperature rise rate,ultimately indicating a decrease in the thermal hazards of aging batteries.

关键词： Lithium-ion batteries High-temperature aging thermal safety Degradation Lithium plating

A holistic approach to improving safety for battery energy storage systems

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Journal of Energy Chemistry 2024年第5期92卷 422-439页

作者： James Close Jonathan E.Barnard Y.M.John Chew Semali Perera Department of Chemical Engineering Centre for DigitalManufacturing&DesignUniversity of BathBath BA27AYUK ioMosaic International Limited 16-18 Queen SquareBath BA12HNUK

The integration of battery energy storage systems(BESS)throughout our energy chain poses concerns regarding safety,especially since batteries have high energy density and numerous BESS failure events have occurred.Wider spread adoption will only increase the prevalence of these failure events unless there is a step change in the management and design of BESS.To understand the causes of failure,the main challenges of BESS safety are summarised.BESS consequences and failure events are discussed,including specific focus on the chain of events causing thermal runaway,and a case study of a BESS explosion in Surprise Arizona is analysed.Based on the technology and past events,a paradigm shift is required to improve BESS safety.In this review,a holistic approach is proposed.This combines currently adopted approaches including battery cell testing,lumped cell mathematical modelling,and calorimetry,alongside additional measures taken to ensure BESS safety including the requirement for computational fluid dynamics and kinetic modelling,assessment of installation level testing of the full BESS system and not simply a single cell battery test,hazard and layers of protection analysis,gas chromatography,and composition testing.The holistic approach proposed in this study aims to address challenges of BESS safety and form the basis of a paradigm shift in the safety management and design of these systems.

关键词： Energy storagesystems Process safety Battery safety thermal safety

Superior and safer lithium sulfur batteries realized by robust polysulfides-retarding dam with high flame retardance

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Journal of Energy Chemistry 2024年第2期89卷 471-486,I0011页

作者： Junling Wang Yanfang Cao Zhirong Wang Yinquan Zhao Chuang He Fudong Zhao Chaoling Han Shui Yu Jiangsu Key Laboratory of Hazardous Chemicals safety and Control College of Safety Science and EngineeringNanjing Tech UniversityNanjing 211816JiangsuChina Department of Architecture and Civil Engineering City University of Hong KongHong Kong 999077China School of Mechanical and Power Engineering Nanjing Tech UniversityNanjing 211816JiangsuChina

The unparalleled energy density has granted lithium-sulfur batteries(LSBs)with attractive usages.Unfortunately,LSBs still face some unsurpassed challenges in industrialization,with polysulfides shuttling,dendrite growth and thermal hazard as the major problems triggering the cycling instability and low safety.With the merit of convenience,the method of designing functional separator has been adapted.Concretely,the carbon aerogel confined with CoS_(2)(CoS_(2)-NCA)is constructed and coated on Celgard separator surface,acquiring CoS_(2)-NCA modified separator(CoS_(2)-NCA@C),which holds the promoted electrolyte affinity and flame retardance.As revealed,CoS_(2)-NCA@C cell gives a high discharge capacity 1536.9 mAh/g at 1st cycle,much higher than that of Celgard cell(987.1 mAh/g).Moreover,the thermal runaway triggering time is dramatically prolonged by 777.4 min,corroborating the promoted thermal safety of cell.Noticeably,the higher coulombic efficiency stability and lower overpotential jointly confirm the efficacy of CoS_(2)-NCA@C in suppressing the lithium dendrite growth.Overall,this work can provide useful inspirations for designing functional separator,coping with the vexing issues of LSBs.

关键词： Lithium-sulfur batteries thermal safety Flame retardancy Separator

Crystal Structures, thermal Behavior Analysis and thermal safety of Two Energetic Salts of Hydrazinyl-1,2,4,5-tetrazine with 3,5-Dinitrosalicylic Acid

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Chemical Research in Chinese Universities 2018年第6期34卷 959-964页

作者： CHEN Xiang ZENG Tian GUO Zhaoqi LI Shuailei MAI Tao GAO Rong MA Haixia School of Chemieal Engineering Northwest University Xi 'an 710069 P. R. China College of Chemistry and Materials Science Northwest University Xi 'an 710069 P. R. China

Two energetic salts, DPHT.DNS-H20（1） and DHT.2DNS.2H20（2）[DPHT=3-（3,5-dimethyl-lH-pyrazol- 1-yl）-6-hydrazinyl-1,2,4,5-tetrazine; DHT=3,6-dihydrazinyl-l,2,4,5-tetrazine], were synthesized from S-tetrazine with 3,5-dinitrosalicylic acid（DNS）. Compounds 1 and 2 were structurally characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction. The thermal behavior of the title compounds was studied by differential scanning calorimetry（DSC） and thermogravimetry（TG）. The non-isothermal decomposition kinetics of compound 2 were investigated. The self-accelerating decomposition temperature, thermal ignition temperature, and critical temperatures of thermal explosion were obtained to evaluate the thermal safety of compound 2. The results show compounds 1 and 2 decompose at 150.8 and 179.2℃, respectively. The TSADT and Tb of compound 2 are higher than those of DHT, which indicates compound 2 is a potential candidate for energetic materials that have good thermal stability. Keywords Tetrazine compound; Dinitrosalicylic acid（DNS）; Crystal structure; thermal behavior; thermal safety

关键词： Tetrazine compound Dinitrosalicylic acid（DNS） Crystal structure thermal behavior thermal safety

Influence of Ambient Temperature on the thermal safety of Fireworks Products in Civil Aviation Transportation

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Proceedings of Business and Economic Studies 2023年第2期6卷 45-54页

作者： Lingling Ji Shanghai Civil Aviation College ShanghaiChina

Fireworks products are energy-containing materials and are hazardous during production,storage,transportation,and use.By analyzing the range of civil aviation ground ambient temperature and civil aviation cabin ambient temperature in storage and ground operation as well as establishing a spontaneous combustion mathematical model for cylindrical fireworks products based on the spontaneous combustion theory,we identified the critical temperature for spontaneous combustion of a single spray and analyzed the thermal safety of fireworks products under the civil aviation ambient temperature by example to provide theoretical support for the feasibility study of transporting fireworks products by civil aviation.

关键词： Civil aviation ambient temperature Fireworks Spontaneous combustion theory thermal safety

Novel Magnesium Salt Based on BTATz： Crystal Structure, thermal Behavior and thermal safety

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Chemical Research in Chinese Universities 2013年第4期29卷 627-631页

作者： ZHANG Xian-bo REN Ying-hui LI Wen ZHAO Feng-qi WANG Bo-zhou SONG Ji-rong Shaanxi Key Laboratory of Physico-inorganic Chemistry School of Chemical Engineering Northwest University Xi 'an 710069 P. R. China" Science and Technology on Combustion and Explosion Laboratory Xi 'an Modern Chemistry Research Institute Xi 'an 710065 P. R. China Conservation Technology Department The Palace Museum Beijing 100009 P. R. China

A new high-energy organic magnesium salt [Mg（H2O）6]（BTATz）·2H2O[BTATz=3,6-bis（1H-1,2,3,4-tetrazol-5-yl-amino）-1,2,4,5-tetrazine] was synthesized and characterized by elemental analysis and Fourier transform infrared（FTIR） spectrometry.Its crystal structure was determined by X-ray single crystal diffraction.The crystal belongs to monoclinic system with space group C2/c and a=2.1329（7） nm,b=0.52275（16） nm,c=1.5909（5） nm,β=100.471（6）°,V=1.7443（9） nm3,Z=4,μ=0.361 mm-1,F（000）=900 and Dc=1.644 g/cm3.Meanwhile,the thermal behavior of [Mg（H2O）6]（BTATz）·2H2O was studied under the non-isothermal conditions by differential scanning calorimetry（DSC） and thermalgravity-differential thermalgravity（TG-DTG） methods.The enthalpy,apparent activation energy and per-exponential factor of the main exothermic decomposition reaction are 898.88 J/g,139.2 kJ/mol and 1010.48 S-1,respectively.The values of the self-accelerating decomposition temperature（TsADT）,the thermal ignition temperature（TTIT） and the critical temperature of thermal explosion（Tb） for [Mg（H2O）6]（BTATz）.2H2O are 515.13,532.08 and 565.99 K,respectively.

关键词： 3,6-Bis（1H-1,2,3,4-tetrazol-5-yl-amino）-1,2,4,5-tetrazine Magnesium salt Crystal structure thermal behavior thermal safety

New insight on correlation between the electrochemical stability and the thermal stability of high nickel cathode materials

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Journal of Energy Chemistry 2022年第9期31卷 265-275,I0008页

作者： Lifan Wang Rui Wang Cong Zhong Liangtao Lu Danya Gong Qinling Shi Yujie Fan Xindong Wang Chun Zhan Guicheng Liu Department of Physical Chemistry School of Metallurgical and Ecological EngineeringUniversity of Science and Technology BeijingBeijing 100083China Department of Physics Dongguk UniversitySeoul 04620Republic of Korea

Cycle stability and thermal safety are critical to the commercialization of nickel-rich layered materials,yet whether there is a potential correlation between these two factors is still controversial. Herein, the relationship between the cycle stability and thermal stability of nickel-rich cathode materials have been systematically studied through five different calcination temperatures of Li[NiCoMn]O(NCM83) cathode materials. The research results confirm that the cycle stability and thermal safety of nickel-rich cathode materials do not necessarily show a positive correlation. Actually, with the calcination temperature elevated, the thermal stability of the NCM83 is enhanced, while the cycle stability is degraded. This opposite correlation is not commonly reported in previous literatures. In this work, systematical characterizations demonstrate that under the experimental conditions, the capacity retention of NCM83 is mainly determined by the Li/Ni cation disorder and H2-H3 irreversible phase transition,which is optimal at lower calcination temperature. Meanwhile, the thermal stability is mainly impacted by thermal expansion characteristics and interfacial stability of cathode material, and it is dramatically improved by the mechanical strength of the secondary particles reinforced at high calcinated temperature. This study provides some new insights on understanding and designing of the high-energy cathode materials with long cycle-life and superior safety.

关键词： Nickel-rich layered materials Cycle stability thermal safety Calcination temperatures thermal expansion Interfacial stability

Composite separator based on PI film for advanced lithium metal batteries

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Journal of Materials Science & Technology 2022年第7期102卷 264-271页

作者： Bin Sun Zili Zhang Jing Xu Yanpeng Lv Yang Jin Research Center of Grid Energy Storage and Battery Application School of Electrical EngineeringZhengzhou UniversityZhengzhou 450001China

Lithium(Li) metal batteries have received extensive research focusing on the dendrite growth issue on account of the high chemical activity of Li anode. While, thermal safety, as one of the important security concerns facing the further application, gets little attention. Here, the high-performance polyimide film is successfully developed to enhance the safety margin based on the excellent mechanical strength and heat resistance corresponding to the traditional separator. And, the polyimide film with the Mo S2 coating made by spraying method as the composite separator can not only improve the wettability to the electrolyte, but also in-situ form an artificial layer with the low nucleation barrier for the Li ions. When used in both the coin cell and the pouch cell, all achieve the outstanding cycling stability and the coulombic efficiency. Specially, the in-situ Li ions nucleation behaviors are investigated by optical microscopy in the capillary cell. The electric field intensity at the Li anode surface is also simulated by COMSOL Multiphysics to further elucidate the effect of the coating.

关键词： Polyimide film Composite separator Lithium anode Molybdenum sulfide thermal safety

Effects ofmodulenumberand firing conditiononchargethermal safetyingunchamber

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Defence Technology（防务技术） 2022年第1期18卷 27-37页

作者： Huan-yu Qian Yong-gang Yu Jing Liu School of Energy and Power Engineering Nanjing University of Science and Technology Narjing 21094 China Acudemny of Opto-Electroric China Electronis Technology Group Corporation(AOE CETC)Tianjin300308China

thermal safety of modular charge which is fed into and retained in the chamber after gun fires consecutively is first investigated with cook-off method,A two-dimensional cook-off model of modular charge in gun chamber is established and the cook-off process of modular charge in gun chamber is numerically simulated.Then the effects of module number and firing condition on charge thermal safety are evaluated by researching the cook-off response characteristics of modules.The results show that under conditions of different module numbers the cook-off responses all occur on the module closest to the boundary of missile,and the single-base propellants located at the inner surface of cartridge ignite first.When the number of loaded module changes from 1 to 6,the cook-off response temperatures vary little,only in a small range of 478.1 K-482.4 K.The cook-off response times decrease logarithmically in the range of 211.25-166.7 s with the increasing length of residual air gap in gun chamber.The simulation results are well matched with the experimental data.Furthermore,different firing conditions have greatinfluence on the cook-off response time,minor influence on the initial response position and little in-fluence on the response temperature.Under the three conditions of consecutive 32 launches with 5 rounds/min,43 launches with 1 round/min,and 41 launches with different firing frequencies,the cook off response temperatures are 479.2 K,481.1 K and 479.9 K respectively and the response times are 709.25,211.2 s and 214.4 s respectively.The response position is near the middle area of the inner cartridge surface in the former condition and near the right area in the latter two conditions.

关键词： thermal safety Modular charge Cook-off Firing condition