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 propaga...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.展开更多
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 ...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.展开更多
Developing technologies that can be applied simultaneously in battery thermal management(BTM)and thermal runaway(TR)mitigation is significant to improving the safety of lithium-ion battery systems.Inorganic phase chan...Developing technologies that can be applied simultaneously in battery thermal management(BTM)and thermal runaway(TR)mitigation is significant to improving the safety of lithium-ion battery systems.Inorganic phase change material(PCM)with nonflammability has the potential to achieve this dual function.This study proposed an encapsulated inorganic phase change material(EPCM)with a heat transfer enhancement for battery systems,where Na_(2)HPO_(4)·12H_(2)O was used as the core PCM encapsulated by silica and the additive of carbon nanotube(CNT)was applied to enhance the thermal conductivity.The microstructure and thermal properties of the EPCM/CNT were analyzed by a series of characterization tests.Two different incorporating methods of CNT were compared and the proper CNT adding amount was also studied.After preparation,the battery thermal management performance and TR propagation mitigation effects of EPCM/CNT were further investigated on the battery modules.The experimental results of thermal management tests showed that EPCM/CNT not only slowed down the temperature rising of the module but also improved the temperature uniformity during normal operation.The peak battery temperature decreased from 76℃to 61.2℃at 2 C discharge rate and the temperature difference was controlled below 3℃.Moreover,the results of TR propagation tests demonstrated that nonflammable EPCM/CNT with good heat absorption could work as a TR barrier,which exhibited effective mitigation on TR and TR propagation.The trigger time of three cells was successfully delayed by 129,474 and 551 s,respectively and the propagation intervals were greatly extended as well.展开更多
Early warning of thermal runaway(TR)of lithium-ion batteries(LIBs)is a significant challenge in current application scenarios.Timely and effective TR early warning technology is urgently required considering the curre...Early warning of thermal runaway(TR)of lithium-ion batteries(LIBs)is a significant challenge in current application scenarios.Timely and effective TR early warning technology is urgently required considering the current fire safety situation of LIBs.In this work,we report an early warning method of TR with online electrochemical impedance spectroscopy(EIS)monitoring,which overcomes the shortcomings of warning methods based on traditional signals such as temperature,gas,and pressure with obvious delay and high cost.With in-situ data acquisition through accelerating rate calorimeter(ARC)-EIS test,the crucial features of TR were extracted using the RReliefF algorithm.TR mechanisms corresponding to the features at specific frequencies were analyzed.Finally,a three-level warning strategy for single battery,series module,and parallel module was formulated,which can successfully send out an early warning signal ahead of the self-heating temperature of battery under thermal abuse condition.The technology can provide a reliable basis for the timely intervention of battery thermal management and fire protection systems and is expected to be applied to electric vehicles and energy storage devices to realize early warning and improve battery safety.展开更多
In recent years,the new energy storage system,such as lithium ion batteries(LIBs),has attracted much attention.In order to meet the demand of industrial progress for longer cycle life,higher energy density and cost ef...In recent years,the new energy storage system,such as lithium ion batteries(LIBs),has attracted much attention.In order to meet the demand of industrial progress for longer cycle life,higher energy density and cost efficiency,a quantity of research has been conducted on the commercial application of LIBs.However,it is difficult to achieve satisfying safety and cycling performance simultaneously.There may be thermal runaway(TR),external impact,overcharge and overdischarge in the process of battery abuse,which makes the safety problem of LIBs more prominent.In this review,we summarize recent progress in the smart safety materials design towards the goal of preventing TR of LIBs reversibly from different abuse conditions.Benefiting from smart responsive materials and novel structural design,the safety of LIBs can be improved a lot.We expect to provide a comprehensive reference for the development of smart and safe lithium-based battery materials.展开更多
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 quantita...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.展开更多
Lithium-ion batteries are widely used in electric vehicles and electronics, and their thermal safety receives widespread attention from consumers. In our study, thermal runaway testing was conducted on the thermal sta...Lithium-ion batteries are widely used in electric vehicles and electronics, and their thermal safety receives widespread attention from consumers. In our study, thermal runaway testing was conducted on the thermal stability of commercial lithium-ion batteries, and the internal structure of the battery was analyzed with an in-depth focus on the key factors of the thermal runaway. Through the study of the structure and thermal stability of the cathode, anode, and separator, the results showed that the phase transition reaction of the separator was the key factor affecting the thermal runaway of the battery for the condition of a low state of charge.展开更多
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-pac...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.展开更多
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 batter...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.展开更多
This study examines the thermal runaway of a lithium ion battery caused by poor heat dissipation performances.The heat transfer process is analyzed on the basis of standard theoretical concepts.Water mist additives ar...This study examines the thermal runaway of a lithium ion battery caused by poor heat dissipation performances.The heat transfer process is analyzed on the basis of standard theoretical concepts.Water mist additives are considered as a tool to suppress the thermal runaway process.The ensuing behaviour of the battery in terms of surface temperature and heat generation is analyzed for different charge and discharge rates.It is found that when the remaining charge is 100%,the heat generation rate of the battery is the lowest,and the surface temperature with a 2C charge rate is higher than that obtained for a 0.5C charge rate.The experimental results show that when the additive concentration is 20%NaCl,its ability to inhibit the thermal runaway is the strongest.展开更多
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 att...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.展开更多
To improve the safety of electric vehicles and battery energy storage systems,early prediction of thermal runaway(TR)is of great significance.This work proposes a novel method for early warning and short-term predicti...To improve the safety of electric vehicles and battery energy storage systems,early prediction of thermal runaway(TR)is of great significance.This work proposes a novel method for early warning and short-term prediction of the TR.To give warning of TR long time in advance,a variety of battery models are established to extract key features,such as Pauta feature and Shannon entropy of voltage deviation,and then local outlier factor algorithm is used for feature fusion to detect abnormal cells.For the short-term prediction,the predefined threshold and variation rates are used.By measuring the real-time signals,such as voltage and temperature,their variation rates are calculated,based on which TR can be predicted exactly.The real data including TR from an electric vehicle are used to verify the method that it can give a warning on TR long time before it happens up to 74 days.This is remarkable for providing replacement recommendations for abnormal cells.It can also predict the occurrence of TR 33 seconds in advance to ensure the safe use of batteries.展开更多
Lithium-ion batteries have been widely used in transportation,power equipment,aerospace,and other fields.However,the complex electrochemical reactions inside the battery cause excessive heat generation rate due to the...Lithium-ion batteries have been widely used in transportation,power equipment,aerospace,and other fields.However,the complex electrochemical reactions inside the battery cause excessive heat generation rate due to thermal,mechanical,and electrical abuse conditions,and even lead to thermal runaway.The problem of thermal runaway has become an important factor limiting its use.This review summarizes the intrinsic safety of batteries,thermal management,early monitoring and warning for thermal runaway,fire prevention and fire suppression technologies.The intrinsic safety technologies were summarized from the aspects of electrolyte flame retardancy,improvement of thermal stability of battery materials,and ceramic separators.To effectively control battery temperature,thermal management technologies were elaborated from the perspectives of air cooling,liquid cooling,heat pipes,phase change materials,and coupled thermal management.Single parameter detection,multi parameter composite detection,and new detection technologies were also discussed.In-situ monitoring of batteries based on fiber optic sensors helps to achieve early warning of thermal runaway.After thermal runaway occurs,fire prevention and fire extinguishing technology can effectively reduce the harm of thermal runaway,which should be given sufficient attention.This work provides important references value and research ideas for the prevention and mitigation of thermal runaway in lithium-ion batteries.展开更多
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 characteristi...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.展开更多
In this paper,overcharge behaviors and thermal runaway(TR)features of large format lithium-ion(Liion)cells with different cathode materials(LiFePO4(LFP),Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_(2)(NCM111),Li[Ni_(0.6)Co_(0.2)Mn_...In this paper,overcharge behaviors and thermal runaway(TR)features of large format lithium-ion(Liion)cells with different cathode materials(LiFePO4(LFP),Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_(2)(NCM111),Li[Ni_(0.6)Co_(0.2)Mn_(0.2)]O_(2)(NCM622)and Li[Ni_(0.8)Co_(0.1)Mn_(0.1)]O_(2)(NCM811))were investigated.The results showed that,under the same overcharge condition,the TR of LFP Li-ion cell occurred earlier compared with the NCM Li-ion cells,indicating its poor overcharge tolerance and high TR risk.However,when TR occurred,LFP Li-ion cell exhibited lower maximum temperature and mild TR response.All NCM Liion cells caught fire or exploded during TR,while the LFP Li-ion cell only released a large amount of smoke without fire.According to the overcharge behaviors and TR features,a safety assessment score system was proposed to evaluate the safety of the cells.In short,NCM Li-ion cells have better performance in energy density and overcharge tolerance(or low TR risk),while LFP Li-ion cell showed less severe response to overcharging(or less TR hazards).For NCM Li-ion cells,as the ratio of nickel in cathode material increases,the thermal stability of the cathode materials becomes poorer,and the TR hazards increase.Such a comparison study on large format Li-ion cells with different cathode materials can provide deeper insights into the overcharge behaviors and TR features,and provide guidance for engineers to reasonably choose battery materials in automotive applications.展开更多
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 o...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.展开更多
As the global energy policy gradually shifts from fossil energy to renewable energy,lithium batteries,as important energy storage devices,have a great advantage over other batteries and have attracted widespread atten...As the global energy policy gradually shifts from fossil energy to renewable energy,lithium batteries,as important energy storage devices,have a great advantage over other batteries and have attracted widespread attention.With the increasing energy density of lithium batteries,promotion of their safety is urgent.Thermal runaway is an inevitable safety problem in lithium battery research.Therefore,paying attention to the thermal hazards of lithium battery materials and taking corresponding preventive measures are of great significance.In this review,the heat source and thermal hazards of lithium batteries are discussed with an emphasis on the designs,modifications,and improvements to suppress thermal runaway based on the inherent structure of lithium batteries.According to the source of battery heat,we divide it into reversible heat and irreversible heat.Additionally,superfluous heat generation has profound effects,including thermal runaway,capacity loss,and electrical imbalance.Thereafter,we emphatically discuss the design and modification strategies for various battery components(anodes,cathodes,electrolytes,and separators)to suppress thermal runaway.Preparation of solid electrolyte interphase layers with excellent thermal stability and mechanical properties is the core of the modification strategy for anode materials.Additives,stable coatings,elemental substitution,and thermally responsive coating materials are commonly used to improve the safety of cathodes.Novel electrolyte additives,solid-state electrolytes,and thermally stable separators provide a good opportunity to solve the thermal runaway problem of next-generation high-performance electrochemical storage devices.展开更多
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 ther...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.展开更多
By adding 1 wt% damage homogenizer(DH), i.e. carbon black microparticles, into the electrodes of lithiumion batteries, thermal runaway can be mitigated as the battery cells are subjected to impact loadings. In a dro...By adding 1 wt% damage homogenizer(DH), i.e. carbon black microparticles, into the electrodes of lithiumion batteries, thermal runaway can be mitigated as the battery cells are subjected to impact loadings. In a drop tower test, the generated heat of the modified cells is reduced by nearly 40%, compared with the reference cells. This phenomenon may be attributed to the weakening effect of the carbon black fillers.The shape of the filler grains does not have a pronounced influence on the temperature profile.展开更多
Safe batteries are the basis for next-generation application scenarios such as portable energy storage devices and electric vehicles,which are crucial to achieving carbon neutralization.Electrolytes,separators,and ele...Safe batteries are the basis for next-generation application scenarios such as portable energy storage devices and electric vehicles,which are crucial to achieving carbon neutralization.Electrolytes,separators,and electrodes as main components of lithium batteries strongly affect the occurrence of safety accidents.Responsive materials,which can respond to external stimuli or environmental change,have triggered extensive attentions recently,holding great promise in facilitating safe and smart batteries.This review thoroughly discusses recent advances regarding the construction of high-safety lithium batteries based on internal thermal-responsive strategies,together with the corresponding changes in electrochemical performance under external stimulus.Furthermore,the existing challenges and outlook for the design of safe batteries are presented,creating valuable insights and proposing directions for the practical implementation of safe lithium batteries.展开更多
基金supported by the National Key R&D Program-Strategic Scientific and Technological Innovation Cooperation(Grant No.2022YFE0207900)the National Natural Science Foundation of China(Grant Nos.51706117,52076121)。
文摘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.
基金supported by the National Key R&D Program of China(No.2021YFB2402001)the Postgraduate Innovation and Entrepreneurship Practice Project of Anhui Province(No.2022cxcysj013)+2 种基金the China Postdoctoral Science Foundation(No.2022T150615)the Fundamental Research Funds for the Central Universities(No.WK5290000002)supported by Youth Innovation Promotion Association CAS(No.Y201768)。
文摘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.
基金financially supported by the National Key Research and Development Program(Grant No.2022YFE0207400)the National Natural Science Foundation of China(Grant No.U22A20168 and 52174225)。
文摘Developing technologies that can be applied simultaneously in battery thermal management(BTM)and thermal runaway(TR)mitigation is significant to improving the safety of lithium-ion battery systems.Inorganic phase change material(PCM)with nonflammability has the potential to achieve this dual function.This study proposed an encapsulated inorganic phase change material(EPCM)with a heat transfer enhancement for battery systems,where Na_(2)HPO_(4)·12H_(2)O was used as the core PCM encapsulated by silica and the additive of carbon nanotube(CNT)was applied to enhance the thermal conductivity.The microstructure and thermal properties of the EPCM/CNT were analyzed by a series of characterization tests.Two different incorporating methods of CNT were compared and the proper CNT adding amount was also studied.After preparation,the battery thermal management performance and TR propagation mitigation effects of EPCM/CNT were further investigated on the battery modules.The experimental results of thermal management tests showed that EPCM/CNT not only slowed down the temperature rising of the module but also improved the temperature uniformity during normal operation.The peak battery temperature decreased from 76℃to 61.2℃at 2 C discharge rate and the temperature difference was controlled below 3℃.Moreover,the results of TR propagation tests demonstrated that nonflammable EPCM/CNT with good heat absorption could work as a TR barrier,which exhibited effective mitigation on TR and TR propagation.The trigger time of three cells was successfully delayed by 129,474 and 551 s,respectively and the propagation intervals were greatly extended as well.
基金supported by the National Natural Science Foundation of China(U2033204,51976209)the Natural Science Foundation of Hefei(2022019)supported by Youth Innovative Promotion Association CAS(Y201768)。
文摘Early warning of thermal runaway(TR)of lithium-ion batteries(LIBs)is a significant challenge in current application scenarios.Timely and effective TR early warning technology is urgently required considering the current fire safety situation of LIBs.In this work,we report an early warning method of TR with online electrochemical impedance spectroscopy(EIS)monitoring,which overcomes the shortcomings of warning methods based on traditional signals such as temperature,gas,and pressure with obvious delay and high cost.With in-situ data acquisition through accelerating rate calorimeter(ARC)-EIS test,the crucial features of TR were extracted using the RReliefF algorithm.TR mechanisms corresponding to the features at specific frequencies were analyzed.Finally,a three-level warning strategy for single battery,series module,and parallel module was formulated,which can successfully send out an early warning signal ahead of the self-heating temperature of battery under thermal abuse condition.The technology can provide a reliable basis for the timely intervention of battery thermal management and fire protection systems and is expected to be applied to electric vehicles and energy storage devices to realize early warning and improve battery safety.
基金support by,National Key Research and Development Program(2023YFB2503700 and 2023YFC3008804)the Beijing Municipal Science&Technology Commission No.Z231100006123003+1 种基金the National Science Foundation of China(22071133)the Beijing Natural Science Foundation(No.Z220020).
文摘In recent years,the new energy storage system,such as lithium ion batteries(LIBs),has attracted much attention.In order to meet the demand of industrial progress for longer cycle life,higher energy density and cost efficiency,a quantity of research has been conducted on the commercial application of LIBs.However,it is difficult to achieve satisfying safety and cycling performance simultaneously.There may be thermal runaway(TR),external impact,overcharge and overdischarge in the process of battery abuse,which makes the safety problem of LIBs more prominent.In this review,we summarize recent progress in the smart safety materials design towards the goal of preventing TR of LIBs reversibly from different abuse conditions.Benefiting from smart responsive materials and novel structural design,the safety of LIBs can be improved a lot.We expect to provide a comprehensive reference for the development of smart and safe lithium-based battery materials.
基金the support given by National Natural Science Foundation of China(51874184)the Key Natural Science Foundation in Jiangsu Province(18KJA620003)Jiangsu Project Plan for Outstanding Talents Team in Six Research Fields(TD-XNYQC-002)。
文摘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.
基金financial supports from National Key R&D Program of China (2018YFC1902200)the key technologies R&D program of Tianjin (18YFZCGX00240)key R&D Program of China Automotive Technology and Research Center Co., Ltd. (18200116)。
文摘Lithium-ion batteries are widely used in electric vehicles and electronics, and their thermal safety receives widespread attention from consumers. In our study, thermal runaway testing was conducted on the thermal stability of commercial lithium-ion batteries, and the internal structure of the battery was analyzed with an in-depth focus on the key factors of the thermal runaway. Through the study of the structure and thermal stability of the cathode, anode, and separator, the results showed that the phase transition reaction of the separator was the key factor affecting the thermal runaway of the battery for the condition of a low state of charge.
基金supported by the Natural Science Foundation of Hebei Province (B2021507001)the National Natural Science Foundation of China (52106284, 52076121)+2 种基金the Ministry of Science and Technology (2022YFE0207900)the support of the Science and Technology Project of Langfang (2021011017)the Project to Promote Innovation in Doctoral Research at CPPU (BSKY202302)。
文摘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.
基金This work is funded by National Natural Science Foundation of China(Grant No.52006115)Ministry of Science and Technology of China(Grant No.2019YFE0100200)+3 种基金National Natural Science Foundation of China(Grant No.52076121)China National Postdoctoral Program for Innovative Talents(Grant No.BX20190162)China Postdoctoral Science Foundation(Grant No.2019M660631)the Tsinghua University Initiative Scientific Research Program(Grant No.2019Z02UTY06).
文摘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.
文摘This study examines the thermal runaway of a lithium ion battery caused by poor heat dissipation performances.The heat transfer process is analyzed on the basis of standard theoretical concepts.Water mist additives are considered as a tool to suppress the thermal runaway process.The ensuing behaviour of the battery in terms of surface temperature and heat generation is analyzed for different charge and discharge rates.It is found that when the remaining charge is 100%,the heat generation rate of the battery is the lowest,and the surface temperature with a 2C charge rate is higher than that obtained for a 0.5C charge rate.The experimental results show that when the additive concentration is 20%NaCl,its ability to inhibit the thermal runaway is the strongest.
基金supported by the National Natural Science Foundation of China (52076121, 51977131, and 51877138)the Natural Science Foundation of Shanghai (19ZR1435800)+1 种基金the State Key Lab-oratory of Automotive Safety and Energy under Project No. KF2020the Shanghai Science and Technology Development Fund(19QA1406200)。
文摘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.
基金supported by the National Key R&D Program of China(2021YFB2402002).
文摘To improve the safety of electric vehicles and battery energy storage systems,early prediction of thermal runaway(TR)is of great significance.This work proposes a novel method for early warning and short-term prediction of the TR.To give warning of TR long time in advance,a variety of battery models are established to extract key features,such as Pauta feature and Shannon entropy of voltage deviation,and then local outlier factor algorithm is used for feature fusion to detect abnormal cells.For the short-term prediction,the predefined threshold and variation rates are used.By measuring the real-time signals,such as voltage and temperature,their variation rates are calculated,based on which TR can be predicted exactly.The real data including TR from an electric vehicle are used to verify the method that it can give a warning on TR long time before it happens up to 74 days.This is remarkable for providing replacement recommendations for abnormal cells.It can also predict the occurrence of TR 33 seconds in advance to ensure the safe use of batteries.
基金supported by supported by National Natural Science Foundation of China(NO:U2033206)in study designCivil Aviation Safety Capacity Building Project(NO:MHAQ2024035)in study design+1 种基金Sichuan Science and Technology Program(NO:2022YFG0215)in data analysisFundamental Research Funds for the Central Universities(NO:24CAFUC01008,XKJ2022-8)in collection and interpretation of data.
文摘Lithium-ion batteries have been widely used in transportation,power equipment,aerospace,and other fields.However,the complex electrochemical reactions inside the battery cause excessive heat generation rate due to thermal,mechanical,and electrical abuse conditions,and even lead to thermal runaway.The problem of thermal runaway has become an important factor limiting its use.This review summarizes the intrinsic safety of batteries,thermal management,early monitoring and warning for thermal runaway,fire prevention and fire suppression technologies.The intrinsic safety technologies were summarized from the aspects of electrolyte flame retardancy,improvement of thermal stability of battery materials,and ceramic separators.To effectively control battery temperature,thermal management technologies were elaborated from the perspectives of air cooling,liquid cooling,heat pipes,phase change materials,and coupled thermal management.Single parameter detection,multi parameter composite detection,and new detection technologies were also discussed.In-situ monitoring of batteries based on fiber optic sensors helps to achieve early warning of thermal runaway.After thermal runaway occurs,fire prevention and fire extinguishing technology can effectively reduce the harm of thermal runaway,which should be given sufficient attention.This work provides important references value and research ideas for the prevention and mitigation of thermal runaway in lithium-ion batteries.
基金supported by the Key-Area Research and Development Program of Guangdong Province(2020B0909030001)the National Natural Science Foundation of China(52007099,52076121 and 52177217)+1 种基金China Postdoctoral Science Foundation(2020M680550)support from Young Elite Scientists Sponsorship Program by CAST[No.YESS20220063].
文摘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.
基金supported by the National Natural Science Foundation of China(Nos.U1564206,U1764258)the National Key R&D Program of China(No.2018YFB0105700)+1 种基金the support from China Scholarship Council(No.201806030115)supported by the Department of Energy(DOE),Office of Electricity(OE)at Oak Ridge National Laboratory managed by UL-Battelle LLC under contract DE-AC05-00OR22725。
文摘In this paper,overcharge behaviors and thermal runaway(TR)features of large format lithium-ion(Liion)cells with different cathode materials(LiFePO4(LFP),Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_(2)(NCM111),Li[Ni_(0.6)Co_(0.2)Mn_(0.2)]O_(2)(NCM622)and Li[Ni_(0.8)Co_(0.1)Mn_(0.1)]O_(2)(NCM811))were investigated.The results showed that,under the same overcharge condition,the TR of LFP Li-ion cell occurred earlier compared with the NCM Li-ion cells,indicating its poor overcharge tolerance and high TR risk.However,when TR occurred,LFP Li-ion cell exhibited lower maximum temperature and mild TR response.All NCM Liion cells caught fire or exploded during TR,while the LFP Li-ion cell only released a large amount of smoke without fire.According to the overcharge behaviors and TR features,a safety assessment score system was proposed to evaluate the safety of the cells.In short,NCM Li-ion cells have better performance in energy density and overcharge tolerance(or low TR risk),while LFP Li-ion cell showed less severe response to overcharging(or less TR hazards).For NCM Li-ion cells,as the ratio of nickel in cathode material increases,the thermal stability of the cathode materials becomes poorer,and the TR hazards increase.Such a comparison study on large format Li-ion cells with different cathode materials can provide deeper insights into the overcharge behaviors and TR features,and provide guidance for engineers to reasonably choose battery materials in automotive applications.
基金supported by the National Key Research and Development Program(grant No.2021YFB2500300)National Natural Science Foundation of China(grant Nos.22179070,22075029,U1932220)+2 种基金Beijing Municipal Natural Science Foundation(grant No.Z200011)the Natural Science Foundation of Jiangsu Province(grant No.BK20220073)the Fundamental Research Funds for the Central Universities(grant No.2242022R10082).
文摘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.
基金the State Key Program of the National Natural Science Foundation of China(No.51633007)the National Natural Science Foundation of China(Nos.51773147 and 51973151).
文摘As the global energy policy gradually shifts from fossil energy to renewable energy,lithium batteries,as important energy storage devices,have a great advantage over other batteries and have attracted widespread attention.With the increasing energy density of lithium batteries,promotion of their safety is urgent.Thermal runaway is an inevitable safety problem in lithium battery research.Therefore,paying attention to the thermal hazards of lithium battery materials and taking corresponding preventive measures are of great significance.In this review,the heat source and thermal hazards of lithium batteries are discussed with an emphasis on the designs,modifications,and improvements to suppress thermal runaway based on the inherent structure of lithium batteries.According to the source of battery heat,we divide it into reversible heat and irreversible heat.Additionally,superfluous heat generation has profound effects,including thermal runaway,capacity loss,and electrical imbalance.Thereafter,we emphatically discuss the design and modification strategies for various battery components(anodes,cathodes,electrolytes,and separators)to suppress thermal runaway.Preparation of solid electrolyte interphase layers with excellent thermal stability and mechanical properties is the core of the modification strategy for anode materials.Additives,stable coatings,elemental substitution,and thermally responsive coating materials are commonly used to improve the safety of cathodes.Novel electrolyte additives,solid-state electrolytes,and thermally stable separators provide a good opportunity to solve the thermal runaway problem of next-generation high-performance electrochemical storage devices.
基金Beijing Municipal Natural Science Foundation(Z200011)National Key Research and Development Program(2021YFB2500300)National Natural Science Foundation of China(22179070,22075029,U1932220),the“Shuimu Tsinghua Scholar Program of Tsinghua University”,and Mercedes-Benz AG.Xiang-Qun Xu and Xin-Bing Cheng contributed equally to this work.
文摘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.
基金supported by the Advanced Research Projects Agency-Energy(ARPA-E)(No.DE-AR0000396)
文摘By adding 1 wt% damage homogenizer(DH), i.e. carbon black microparticles, into the electrodes of lithiumion batteries, thermal runaway can be mitigated as the battery cells are subjected to impact loadings. In a drop tower test, the generated heat of the modified cells is reduced by nearly 40%, compared with the reference cells. This phenomenon may be attributed to the weakening effect of the carbon black fillers.The shape of the filler grains does not have a pronounced influence on the temperature profile.
基金supported by the National Natural Science Foundation of China(22179070,U1932220)the Natural Science Foundation of Jiangsu Province(BK20220073)the Fundamental Research Funds for the Central Universities(RF1028623157)。
文摘Safe batteries are the basis for next-generation application scenarios such as portable energy storage devices and electric vehicles,which are crucial to achieving carbon neutralization.Electrolytes,separators,and electrodes as main components of lithium batteries strongly affect the occurrence of safety accidents.Responsive materials,which can respond to external stimuli or environmental change,have triggered extensive attentions recently,holding great promise in facilitating safe and smart batteries.This review thoroughly discusses recent advances regarding the construction of high-safety lithium batteries based on internal thermal-responsive strategies,together with the corresponding changes in electrochemical performance under external stimulus.Furthermore,the existing challenges and outlook for the design of safe batteries are presented,creating valuable insights and proposing directions for the practical implementation of safe lithium batteries.