Understanding the battery safety improvement enabled by a quasi-solid-state battery design

The rapid development of lithium-ion batteries(LIBs)is faced with challenge of its safety bottleneck,calling for design and chemistry innovations.Among the proposed strategies,the development of solid-state batteries(SSBs)seems the most promising solution,but to date no practical SSB has been in large-scale application.Practical safety performance of SSBs is also challenged.In this article,a brief review on LIB safety issue is made and the safety short boards of LIBs are emphasized.A systematic safety design in quasi-SSB chemistry is proposed to conquer the intrinsic safety weak points of LIBs and the effects are accessed based on existing studies.It is believed that a systematic and targeted solution in SSB chemistry design can effectively improve the battery safety,promoting larger-scale application of LIBs.

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

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.

A holistic approach to improving safety for battery energy storage systems

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.

Adaptive battery thermal management systems in unsteady thermal application contexts

With the increasing attention paid to battery technology,the microscopic reaction mechanism and macroscopic heat transfer process of lithium-ion batteries have been further studied and understood from both academic and industrial perspectives.Temperature,as one of the key parameters in the physical fra mework of batteries,affects the performa nce of the multi-physical fields within the battery,a nd its effective control is crucial.Since the heat generation in the battery is determined by the real-time operating conditions,the battery temperature is essentially controlled by the real-time heat dissipation conditions provided by the battery thermal management system.Conventional battery thermal management systems have basic temperature control capabilities for most conventional application scenarios.However,with the current development of la rge-scale,integrated,and intelligent battery technology,the adva ncement of battery thermal management technology will pay more attention to the effective control of battery temperature under sophisticated situations,such as high power and widely varied operating conditions.In this context,this paper presents the latest advances and representative research related to battery thermal management system.Firstly,starting from battery thermal profile,the mechanism of battery heat generation is discussed in detail.Secondly,the static characteristics of the traditional battery thermal management system are summarized.Then,considering the dynamic requirements of battery heat dissipation under complex operating conditions,the concept of adaptive battery thermal management system is proposed based on specific research cases.Finally,the main challenges for battery thermal management system in practice are identified,and potential future developments to overcome these challenges are presented and discussed.

Thermal runaway evolution of a 280 Ah lithium-ion battery with LiFePO_(4) as the cathode for different heat transfer modes constructed by mechanical abuse

Lithium iron phosphate batteries have been increasingly utilized in recent years because their higher safety performance can improve the increasing trend of recurring thermal runaway accidents.However,the safety performance and mechanism of high-capacity lithium iron phosphate batteries under internal short-circuit challenges remain to be explored.This work analyzes the thermal runaway evolution of high-capacity LiFePO_(4) batteries under different internal heat transfer modes,which are controlled by different penetration modes.Two penetration cases involving complete penetration and incomplete penetration were detected during the test,and two modes were performed incorporating nails that either remained or were removed after penetration to comprehensively reveal the thermal runaway mechanism.A theoretical model of microcircuits and internal heat conduction is also established.The results indicated three thermal runaway evolution processes for high-capacity batteries,which corresponded to the experimental results of thermal equilibrium,single thermal runaway,and two thermal runaway events.The difference in heat distribution in the three phenomena is determined based on the microstructure and material structure near the pinhole.By controlling the heat dissipation conditions,the time interval between two thermal runaway events can be delayed from 558 to 1417 s,accompanied by a decrease in the concentration of in-situ gas production during the second thermal runaway event.

A perspective on the key factors of safety for rechargeable magnesium batteries

Rechargeable Mg batteries(RMBs)have become one of the best subsitutes for lithium-ion batteries due to the high volumetric capacity,abundant resources,and uniform plating behavior of Mg metal anode.However,the safety hazard induced by the formation of high-modulue Mg dendrites under a high current density(10 mA cm^(-1))was still revealed in recent years.It has forced researchers to re-examine the safety of RMBs.In this review,the intrinsic safety factors of key components in RMBs,such as uneven plating,pitting and flammability of Mg anode,heat release and crystalline water decomposition of cathode,strong corrosion,low oxidition stability and flammability of electrolytes,and soforth,are systematacially summarized.Their origins,formation mechanisms,and possible safety hazards are deeply discussed.To develop high-performance Mg anode,current strategies including designing artificial SEI,three-dimensional substrates,and Mg alloys are summarized.For practical electrolytes,the configurations of boron-centered anions and simple Mg salts and the functionalized solvent with high boiling point and low flammability are suggested to comprehensively design.In addition,the future study should more focus on the investigation on the thermal runaway and decomposition of cathode materials and separa-tors.This review aims to provide fundamental insights into the relationship between electrochemistry and safety,further promoting the sustainable development of RMBs.

An upgraded polymeric composite with interparticle chemical bonding microstructure toward lithium-ion battery separators with enhanced safety and electrochemical performances

A composite separator of SiC/PVDF-HFP was synthesized for lithium-ion batteries with high thermal and mechanical stabilities.Benefiting from the nanoscale,high hardness,and melting point of SiC,SiC/PVDFHFP with highly uniform microstructure was obtained.This polarization caused by barrier penetration was significantly restrained.Due to the Si-F bond between SiC and PVDF-HFP,the structural stability has been obviously enhanced,which could suppress the growth of lithium(Li) dendrite.Furthermore,some 3D reticulated Si nanowires are found on the surface of Li anode,which also greatly inhibit Li dendrites and result in irregular flakes of Li metal.Especially,the shrinkage of 6% SiC/PVDF-HFP at 150℃ is only 5%,which is notably lower than those of PVDF-HFP and Celgard2500.The commercial LiFePO_(4) cell assembled with 6% SiC/PVDF-HFP possesses a specific capacity of 157.8 mA h g^(-1) and coulomb efficiency of 98% at 80℃.In addition,the tensile strength and modulus of 6% SiC/PVDF-HFP could reach 14.6 and 562 MPa,respectively.And a small deformation(1000 nm) and strong deformation recovery are obtained under a high additional load(2.3 mN).Compared with PVDF-HFP and Celgard2500,the symmetric Li cell assembled with 6% SiC/PVDF-HFP has not polarized after 900 cycles due to its excellent mechanical stabilities.This strategy provides a feasible solution for the composite separator of high-safety batteries with a high temperature and impact resistance.

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

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.

Electrolyte induced synergistic construction of cathode electrolyte interphase and capture of reactive free radicals for safer high energy density lithium-ion battery

As the energy density of battery increases rapidly,lithium-ion batteries(LIBs)are facing serious safety issue with thermal runaway,which largely limits the large-scale applications of high-energy-density LIBs.It is generally agreed that the chemical crosstalk between the cathode and anode leads to thermal runaway of LIBs.Herein,a multifunctional high safety electrolyte is designed with synergistic construction of cathode electrolyte interphase and capture of reactive free radicals to limit the intrinsic pathway of thermal runaway.The cathode electrolyte interphase not only resists the gas attack from the anode but suppresses the parasitic side reactions induced by electrolyte.And the function of free radical capture has the ability of reducing heat release from thermal runaway of battery.The dual strategy improves the intrinsic safety of battery prominently that the triggering temperature of thermal runaway is increased by 24.4℃and the maximum temperature is reduced by 177.7℃.Simultaneously,the thermal runaway propagation in module can be self-quenched.Moreover,the electrolyte design balances the trade-off of electrochemical and safety performance of high-energy batteries.The capacity retention of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)|graphite pouch cell has been significantly increased from 53.85%to 97.05%with higher coulombic efficiency of 99.94%at operating voltage extended up to 4.5 V for 200 cycles.Therefore,this work suggests a feasible strategy to mitigate the safety risk of high-energy-density LIBs without sacrificing electrochemical performances.

Non-flammable long chain phosphate ester based electrolyte via competitive solventized structures for high-performance lithium metal batteries

Safety remains a persistent challenge for high-energy-density lithium metal batteries(LMBs).The development of safe and non-flammable electrolytes is especially important in harsh conditions such as high temperatures.Herein,a flame-retardant,low-cost and thermally stable long chain phosphate ester based(tributyl phosphate,TBP)electrolyte is reported,which can effectively enhance the cycling stability of highly loaded high-nickel LMBs with high safety through co-solvation strategy.The interfacial compatibility between TBP and electrode is effectively improved using a short-chain ether(glycol dimethyl ether,DME),and a specially competitive solvation structure is further constructed using lithium borate difluorooxalate(LiDFOB)to form the stable and inorganic-rich electrode interphases.Benefiting from the presence of the cathode electrolyte interphase(CEI)and solid electrolyte interphase(SEI)enriched with LiF and Li_(x)PO_(y)F_(z),the electrolyte demonstrates excellent cycling stability assembled using a 50μm lithium foil anode in combination with a high loading NMC811(15.4 mg cm^(-2))cathode,with 88%capacity retention after 120 cycles.Furthermore,the electrolyte exhibits excellent high-temperature characteristics when used in a 1-Ah pouch cell(N/P=0.26),and higher thermal runaway temperature(238℃)in the ARC(accelerating rate calorimeter)demonstrating high safety.This novel electrolyte adopts long-chain phosphate as the main solvent for the first time,and would provide a new idea for the development of extremely high safety and high-temperature electrolytes.

The efficiency and toxicity of dodecafluoro-2-methylpentan-3-one in suppressing lithium-ion battery fire

Currently,the effective and clean suppression of lithium-ion battery(LIB)fires remains a challenge.The present work investigates the use of various inhibitor doses(Xin)of dodecafluoro-2-methylpentan-3-one(C_(6) F_(12)O)in 300 Ah LIBs,and systematically examines the thermal and toxic hazards of the extinguished batteries via real scale combustion and gas analysis.The inhibitor is shown to be completely effective.The inhibition mechanism involves a combination of chemical inhibition and physical cooling.While the chemical inhibition effect tends to saturate with increasing Xin,the physical cooling remains effective at higher inhibitor doses.However,extinguishing the battery fire with a high Xin of C_(6)F_(12)O is found to incur serious toxicity problems.These results are expected to provide a guideline for the design of inhibitor doses for the suppression of LIB fires.

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

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.

Thermal safety of dendritic lithium against non-aqueous electrolyte in pouch-type lithium metal batteries

A quantitative relationship between safety issues and dendritic lithium(Li) has been rarely investigated yet. Herein the thermal stability of Li deposits with distinct surface area against non-aqueous electrolyte in pouch-type Li metal batteries is probed. The thermal runaway temperatures of Li metal batteries obtained by accelerating rate calorimeter are reduced from 211 ℃ for Li foil to 111 ℃ for cycled Li.The initial exothermic temperature is reduced from 194 ℃ for routine Li foil to 142 ℃ for 49.5 m~2g^(-1) dendrite. Li with different specific surface areas can regulate the reaction routes during the temperature range from 50 to 300 ℃. The mass percent of Li foil and highly dendritic Li reacting with ethylene carbonate is higher than that of moderately dendritic Li. This contribution can strengthen the understanding of the thermal runaway mechanism and shed fresh light on the rational design of safe Li metal batteries.

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

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.

Advances in sodium-ion batteries at low-temperature: Challenges and strategies

With the continuing boost in the demand for energy storage,there is an increasing requirement for batteries to be capable of operation in extreme environmental conditions.Sodium-ion batteries(SIBs) have emerged as a highly promising energy storage solution due to their promising performance over a wide range of temperatures and the abundance of sodium resources in the earth's crust.Compared to lithiumion batteries(LIBs),although sodium ions possess a larger ionic radius,they are more easily desolvated than lithium ions.Fu rthermore,SIBs have a smaller Stokes radius than lithium ions,resulting in improved sodium-ion mobility in the electrolyte.Nevertheless,SIBs demonstrate a significant decrease in performance at low temperatures(LT),which constrains their operation in harsh weather conditions.Despite the increasing interest in SIBs,there is a notable scarcity of research focusing specifically on their mechanism under LT conditions.This review explores recent research that considers the thermal tolerance of SIBs from an inner chemistry process perspective,spanning a wide temperature spectrum(-70 to100℃),particularly at LT conditions.In addition,the enhancement of electrochemical performance in LT SIBs is based on improvements in reaction kinetics and cycling stability achieved through the utilization of effective electrode materials and electrolyte components.Furthermore,the safety concerns associated with SIBs are addressed and effective strategies are proposed for mitigating these issues.Finally,prospects conducted to extend the environmental frontiers of commercial SIBs are discussed mainly from three viewpoints including innovations in materials,development and research of relevant theoretical mechanisms,and intelligent safety management system establishment for larger-scale energy storage SIBs.

Correlating electrochemical performance and heat generation of Li plating for lithium-ion battery with fluoroethylene carbonate additive

1.Introduction With the superior performance of high energy density,lightweight and long life span,lithium-ion battery(LIB)are perceived as an attractive and reliable power source for modern-used portable electronics,ecofriendly electric vehicles and power distribution,and thereby a remarkable solution to assuage energy dependence on fossil fuel and environmental concern.Nevertheless,the unexpected Li plating together with the Li dendrites growth on graphite anode surface has been a profound hindrance to the practical application of LIB,of which induces inferior Coulombic efficiency,poor lifespan and safety concern[1].

Scalable synthesis of Na_(3)V_(2)(PO_(4))_(3)/C with high safety and ultrahigh-rate performance for sodium-ion batteries

NASICON-type Na_(3)V_(2)(PO_(4))_(3) is a promising electrode material for developing advanced sodium-ion batteries.Preparing Na_(3)V_(2)(PO_(4))_(3) with good performance by a cost-effective and large-scale method is significant for industrial applications.In this work,a porous Na_(3)V_(2)(PO_(4))_(3)/C cathode material with excellent electrochemical performance is successfully prepared by an agar-gel combined with freeze-drying method.The Na_(3)V_(2)(PO_(4))_(3)/C cathode displayed specific capacities of 113.4 mAh·g^(-1),107.0 mAh·g^(-1) and 87.1 mAh·g^(-1) at 0.1 C,1 C and 10 C,respectively.For the first time,the 500-mAh soft-packed symmetrical sodium-ion batteries based on Na_(3)V_(2)(PO_(4))_(3)/C electrodes are successfully fabricated.The 500-mAh symmetrical batteries exhibit outstanding low temperature performance with a capacity retention of 83%at 0℃ owing to the rapid sodium ion migration ability and structural stability of Na_(3)V_(2)(PO_(4))_(3)/C.Moreover,the thermal runaway features are revealed by accelerating rate calorimetry(ARC)test for the first time.Thermal stability and safety of the symmetrical batteries are demonstrated to be better than lithium-ion batteries and some reported sodium-ion batteries.Our work makes it clear that the soft-packed symmetrical sodium ion batteries based on Na_(3)V_(2)(PO_(4))_(3)/C have a prospect of practical application in high safety requirement fields.

Thermal Runaway of Lithium-Ion Batteries Employing Flame-Retardant Fluorinated Electrolytes

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.

Progress on the Fault Diagnosis Approach for Lithium-ion Battery Systems:Advances,Challenges,and Prospects

Because of their advantages of high energy and power density,low self-discharge rate,and long lifespan,lithium-ion batteries(LIBs)have been widely used in many applications such as electric vehicles,energy storage systems,smart grids,etc.However,lithium-ion battery systems(LIBSs)frequently malfunction because of complex working conditions,harsh operating environment,battery inconsistency,and inherent defects in battery cells.Thus,safety of LIBSs has become a prominent problem and has attracted wide attention.Therefore,efficient and accurate fault diagnosis for LIBs is very important.This paper provides a comprehensive review of the latest re-search progress in fault diagnosis for LIBs.First,the types of battery faults are comprehensively introduced and the characteristics of each fault are analyzed.Then,the fault diagnosis methods are systematically elaborated,including model-based,data processing-based,machine learn-ing-based and knowledge-based methods.The latest re-search is discussed and existing issues and challenges are presented,while future developments are also prospected.The aim is to promote further researches into efficient and advanced fault diagnosis methods for more reliable and safer LIBs.Index Terms—Battery management system,battery safety,fault diagnosis,lithium-ion battery system.

Towards establishing uniform metrics for evaluating the safety of lithium metal batteries

Lithium metal batteries(LMBs)with ultra-high theoretical energy densities are regarded as excellent candidates for the next energy storage devices.Unfortunately,there are many factors can cause the temperature of LMBs to exceed a safe range and trigger thermal runaway.Countless effort has been invested in designing safe components of batteries to realize the application of LMBs.However,most studies only focus on one single aspect since there is no uniform metrics for evaluating the safety of LMBs.Herein,this review comprehensively summarizes all the trigger factors of thermal runaway and proposes the complete safety metrics of LMBs.A comprehensive overview of the development of safe LMBs is provided to discuss the gap between studies and practical applications.Finally,the future directions of academic research are proposed according to the challenges existing in current studies.