金属锂电池的热失控与安全性研究进展

锂离子电池在便携式储能器件及电动汽车领域得到了广泛应用,然而频繁发生的电池起火爆炸事故,使热失控和热安全问题备受人们关注,目前已有多篇综述报道了缓解锂离子电池热失控的措施。相比于已经接近理论比能极限的锂离子电池,金属锂负极具有更高的比容量、更低的电势和高反应活性,但是不可控的锂枝晶生长,使得金属锂电池的热失控问题更为复杂和严重。针对金属锂电池的热失控问题,本文首先介绍了热失控的诱因及基本过程和阶段,其次从材料层面综述了提高电池热安全性的多种策略,包括使用阻燃性电解质、离子液体电解质、高浓电解质和局域高浓电解质等不易燃液态电解质体系,开发高热稳定性隔膜、热响应隔膜、阻燃性隔膜和具有枝晶检测预警与枝晶消除功能的新型智能隔膜,以及研究热响应聚合物电解质,最后对金属锂电池热失控在未来的进一步研究进行了展望。     

Thermal runaway and fire behavior investigation of lithium ion batteries using modified cone calorimeter

The lithium ion battery has been widely used, but it has high fire risk due to its flammable materials. In this study, a series of combustion tests are conducted on the 18650-type lithium ion batteries using the modified cone calorimeter. The temperature and voltage variation of the battery, heat release rate and gas generation during combustion are measured in this study. The battery is heated evenly by the self-made heater, and the reliable trigger temperatures of thermal runaway are obtained for different states of charge (SOCs) batteries in this study. The fire behavior of the 100% SOC batteries is shown in this paper. The net heat absorption by the battery before thermal runaway is calculated based on the heat transfer theory. It ranges from 56.81 to 64.05 kJ for 0 to 100% SOC batteries, which shows a decreasing trend as SOC increases. The peak combustion heat release rate of 100% SOC batteries is 3.747?±?0.858 kW. CH₄ and CO gases are detected before and after thermal runaway. The generation of CO shows an increasing trend as SOC increases. Some suggestions on the early warning system of battery thermal runaway are proposed based on this study.

     

Thermal Behavior Investigation of LiNi1/3Co1/3Mn1/3O2-Based Li-ion Battery under Overcharged Test

Thermal behavior of its components such as separator, electrolyte, cathode, anode, and each binder were investigated by differential scanning calorimetry and thermal gravimetric (DSC/TG) to explain thermal runaway mechanism of Li‐ion battery under overcharged test. DSC results indicated the decomposition reaction temperature of SEI (solid electrolyte interface) layer in anode was at about 126°C. It was found that heat generation in anode under normal charged state increased obviously with the increasing of charged voltage. When the battery was overcharged to 4.6 V or 5.0 V, the onset temperature and heat generation of thermal reaction in anode changed a little, while those in cathode had large increase. It was proposed that thermal behavior in cathode mainly caused by the reaction of electrolyte with evolutional oxygen played a key role to thermal runaway for the studied Li‐ion battery under overcharged test.     

电压敏感性聚三苯胺修饰隔膜用于锂硫电池过充保护

本文以三苯胺为原料,通过化学氧化法制备了具有电压敏感性的聚三苯胺(PTPAn)并将其成功应用到锂硫电池隔膜上。电导率测试结果表明,PTPAn/聚丙烯(PP)隔膜的离子电导率达1.56 mS·cm^-1;循环伏安(CV)测试结果表明,PTPAn/PP隔膜在3.5–4.2 V内具有氧化还原峰。在0.1C倍率下,采用PTPAn/PP隔膜和空白PP隔膜的锂硫电池在经200周循环后,放电比容量分别为424.8和407.2 mAh·g^-1,库伦效率分别为99.38%和98.59%,倍率测试表明(0.1C、0.2C、0.5C、1C),采用PTPAn/PP隔膜的锂硫电池在不同倍率下放电比容量均高于采用空白PP隔膜的锂硫电池。与此同时,对采用PTPAn/PP隔膜的锂硫电池进行过充实验,在第4周过充时,充电比容量为843.1 mAh·g^-1,放电比容量为839.8 mAh·g^-1;第10周过充时,充电比容量为690.2 mAh·g^-1,放电比容量为669.2 mAh·g^-1。第16周过充时,电池的充电比容量为538.7 mAh·g^-1,放电比容量为512.9 mAh·g^-1。倍率过充测试表明,经过不同倍率过充实验后,采用PTPAn/PP隔膜的锂硫电池仍能正常工作,在1C倍率下过充,电池电压稳定保持在3.9 V,充电比容量为349.8 mAh·g^-1,放电比容量为328.7 mAh·g^-1。     

Electrolyte additives for improved lithium-ion battery performance and overcharge protection

Much effort is being expended on the development of smart, safe, high-power lithium-ion batteries that are also environmentally friendly. Scaled-up lithium-ion batteries still raise safety concerns, especially when they are overcharged. Therefore, efforts continue to improve the thermal and chemical stability of positive electrodes, negative electrodes, separators, and electrolytes within the battery to counter thermal runaway. This opinion discusses highlights of research on additives for nonaqueous electrolytes published during 2018 and 2019.     

锂离子电池隔膜的功能化改性及表征技术

随着锂离子电池在动力和规模化储能等新能源领域应用的不断拓展,具有特殊功能且满足特定使用需求隔膜的设计准则、制备/改性方法及表征技术亟需系统深入研究。针对锂离子电池高性能和高安全性的要求,研究人员已通过结构设计和表面化学改性等策略优化了隔膜的本征特性,并通过系列表征技术探讨了隔膜的功能化改性对锂离子电池电化学性能的影响。基于以上背景,本文从离子传输、枝晶形核与生长、及安全性能三个方面详细探讨了隔膜对电池性能影响的关键因素及其改性方法,并系统总结了隔膜结构、物化特性、力学性能、热学性能以及电化学性能的表征技术,以期为功能隔膜的合理设计,从而优化锂离子电池性能提供理论和实践指导。同时,本文对隔膜未来的进一步研究和发展提出了展望。     

Thermal hazard evaluations of 18650 lithium-ion batteries by an adiabatic calorimeter

In this study, the thermal hazard features of various lithium-ion batteries, such as LiCoO₂ and LiFePO₄, were assessed properly by calorimetric techniques. Vent sizing package 2 (VSP2), an adiabatic calorimeter, was used to measure the thermal hazards and runaway characteristics of the 18650 lithium-ion batteries under an adiabatic condition. The thermal behaviors of the lithium-ion batteries were obtained at normal and abnormal conditions in this study. The critical parameters for thermal hazardous behavior of lithium-ion batteries were obtained including the exothermic onset temperature (T ₀), heat of decomposition (ΔH), maximum temperature (T _max), maximum pressure (P _max), self-heating rate (dT/dt), and pressure rise rate (dP/dt). Therefore, the result indicates the thermal runaway situation of the lithium-ion battery with different materials and voltages in view the of TNT-equivalent method by VSP2. The hazard gets greater with higher voltage. Without the consideration of other anti-pressure measurements, different voltages involving 3.3, 3.6, 3.7, and 4.2 V are evaluated to 0.11, 0.23, 0.88, and 1.77 g of TNT. Further estimation of thermal runaway reaction and decomposition reaction of lithium-ion battery can also be confirmed by VSP2. It shows that the battery of a fully charged state is more dangerous than that of a storage state. The technique results showed that VSP2 can be used to strictly evaluate thermal runaway reaction and thermal decomposition behaviors of lithium-ion batteries. The loss prevention and thermal hazard assessment are very important for development of electric vehicles as well as other appliances in the future. Therefore, our results could be applied to define important safety indices of lithium-ion batteries for safety concerns.     

Evaluation of thermal hazard for commercial 14500 lithium-ion batteries

Commercial lithium-ion batteries ranged from different sizes, shapes, capacities, electrolytes, anode and cathode materials, etc. have recently caused many incidents under abusive or normal operating conditions worldwide. Inherently safer designs with active or passive protections have became the captious issues that need more attentions paid to. In this study, the worst scenarios on thermal runaway of four commercial batteries were conducted and compared. A customized-made closed testing instrument was utilized to measure and track thermal behaviors of four brands of cylindrical lithium-ion batteries under maximum open circuit voltage condition. Characteristics on thermal hazards of lithium-ion batteries such as onset temperature, maximum temperature, maximum self-heat rate, maximum pressures, battery mass loss, etc. were measured and evaluated. Results point out that one brand of cells reached the maximum temperature and maximum self-heat rate of 590.9 K and 1,130.4 K min^?1, respectively. In conclusion, in case of thermal runaway all the lithium-ion batteries will rupture the cell and catch fire automatically owing to the maximum temperatures over the auto-ignition temperature of electrolytes and the maximum pressure higher than four times of maximum allowable working pressure, respectively. In addition, Lithium-ion battery with cathode material of LiFePO₄ was verified to be more stable than the lithium-ion battery with cathode material of LiMn₂O₄ or LiCoO₂.     

A study on structure-performance relationship of overcharged 18650-size Li4Ti5O12/LiMn2O4 battery

The electrochemical properties and thermal generation behavior of 18650 Li₄Ti₅O₁₂/LiMn₂O₄ batteries were tested before and after overcharge. The experimental results showed that after overcharge, the specific capacity decreased obviously. The higher the current density was, the more obvious the capacity decreased. For instance, the overcharged battery had almost no capacity when the current density increased to 5C. At the same time, the overcharged battery presented a much more apparent thermal runaway trend compared to the normal battery. After measuring the electrochemical impedance spectroscopy of the batteries and characterizing the crystal structure/nanostructure of the electrode materials, these phenomena could be attributed to the following two reasons: (1) the decomposition of the electrolyte arisen from the overcharge process resulted in increased internal resistance; (2) the thermal runaway due to the increased internal resistance resulted in the damage to crystal structure/nanostructure and aggregation of the electrode materials, thus leading to the secondary decrease in capacity.     

Nonflammable pseudoconcentrated electrolytes for batteries

Electrolyte is essentially important for electrochemical and safety performance of batteries. The pseudoconcentrated electrolyte, with lean solvent but anion-involved solvation sheath and heterogeneous long-range structure, endows the electrolyte with superior interfacial properties and the bulk properties, enabling the high-voltage lithium-ion battery, lithium-metal battery, and sodium battery with outstanding electrochemical performances. Nonflammable solvents as diluent in the pseudoconcentrated electrolyte can reach 30–60% by volume share, making the electrolyte nonflammable and then showing great possibility in mitigating the thermal runaway of the battery. As a new family of liquid electrolyte, nonflammable pseudoconcentrated electrolyte is promising for high safety and high energy density secondary batteries.     

Recent Development of Polyolefin‐Based Microporous Separators for Li−Ion Batteries: A Review

Secondary Li?ion batteries have been paid attention to wide‐range applications of power source for the portable electronics, electric vehicle, and electric storage reservoir. Generally, lithium‐ion batteries are comprised of four components including anode, cathode, electrolyte and separator. Although separators do not take part in the electrochemical reactions in a lithium‐ion (Li?ion) battery, they conduct the critical functions of physically separating the positive and negative electrodes to prevent electrical short circuit while permitting the free flow of lithium ions through the liquid electrolyte that fill in their open porous structure. Hence, the separator is directly related to the safety and the power performance of the battery. Among a number of separators developed thus far, polyethylene (PE) and polypropylene (PP) porous membrane separators have been the most dominant ones for commercial Li?ion batteries over the decades because of their superior properties such as cost‐efficiency, good mechanical strength and pore structure, electrochemical stability, and thermal shutdown properties. However, there are main issues for vehicular storage, such as nonpolarity, low surface energy and poor thermal stability, although the polyolefin separators have proven dependable in portable applications. Hence, in this review, we decide to provide an overview of the types of polyolefin microporous separators utilized in Li?ion batteries and the methods employed to modify their surface in detail. The remarkable results demonstrate that extraordinary properties can be exhibited by mono‐ and multilayer polyolefin separators if they are modified using suitable methods and materials.     

纤维素微孔锂电隔膜的制备及性能研究

为了改善锂电隔膜的亲液性和耐高温性,以醋酸纤维素为成膜材料,利用相转化法制备了新型锂电隔膜,通过形貌和孔道结构表征、亲液性能和耐热性能测试对醋酸纤维素隔膜的基本性能进行研究,并将该隔膜装配成锂离子电池进行充放电性能测试. 结果表明,醋酸纤维素隔膜具有均匀的微孔结构,孔隙率达到65%,约为传统聚烯烃隔膜的1.5倍;纤维素材料的良好亲液性和高孔隙率结构改善了隔膜的吸液性能,其吸液率达到285%;该隔膜在150 ^oC、30 min的热处理条件下未发生明显的热收缩. 鉴于上述优点,相对于市售PE隔膜,醋酸纤维素隔膜所装配锂离子电池显示出更优的循环性能和倍率性能.     

Recent advances on battery separators based on poly(vinylidene fluoride) and its copolymers for lithium-ion battery applications

Lithium-ion batteries represent one of the most suitable systems for effective energy storage for a wide range of applications, such as smartphones, laptops, electric vehicles, or even home storage systems. Among the different battery components, the separator plays an essential role in the performance of the batteries; its most relevant characteristics are (micro)structure, wettability, thermal and mechanical properties, and ionic conductivity value. This work provides a comprehensive review of the current state of the art in lithium-ion battery separator membranes based on poly(vinylidene fluoride) (PVDF) and its copolymers. The most recent developments in the last two years are presented, focusing on the different separator types that have been developed with the aim of improving wettability, thermal characteristics, and cycling behavior. The most used types of PVDF separators are composites, polymer blends, and the combination of both. Among the most common fillers, metal–organic frameworks, ionic liquids, and ceramic particles have been used for the development of PVDF-based composites and polymers such as poly(m-phenylene isophthalamide), poly(acrylonitrile), poly(tetrafluoroethylene), or poly(methyl methacrylate), for the development of polymer blends. Electrospinning is one of the most used processing techniques to improve wettability, thermal stability, and mechanical properties. The wettability of separators has been also improved by using PVDF as a coating on commercial separators.It is shown that PVDF-based battery separators can play an important role in the next generation of high-performance batteries.     

Thermal runaway propagation characteristics of lithium-ion batteries with a non-uniform state of charge distribution

Journal of Solid State Electrochemistry - Alleviating and restraining thermal runaway (TR) of lithium-ion batteries is a critical issue in developing new energy vehicles. The battery state of...     

Rational Design of Cellulose Nanofibrils Separator for Sodium-Ion Batteries

Cellulose nanofibrils (CNF) with high thermal stability and excellent electrolyte wettability attracted tremendous attention as a promising separator for the emerging sodium-ion batteries. The pore structure of the separator plays a vital role in electrochemical performance. CNF separators are assembled using the bottom-up approach in this study, and the pore structure is carefully controlled through film-forming techniques. The acid-treated separators prepared from the solvent exchange and freeze-drying demonstrated an optimal pore structure with a high electrolyte uptake rate (978.8%) and Na⁺ transference number (0.88). Consequently, the obtained separator showed a reversible specific capacity of 320 mAh/g and enhanced cycling performance at high rates compared to the commercial glass fiber separator (290 mAh/g). The results highlight that CNF separators with an optimized pore structure are advisable for sodium-ion batteries.     

A roadmap of battery separator development: Past and future

The battery separator is one of the most essential components that highly affect the electrochemical stability and performance in lithium-ion batteries. In order to keep up with a nationwide trend and needs in the battery society, the role of battery separators starts to change from passive to active. Many efforts have been devoted to developing new types of battery separators by tailoring the separator chemistry. In this article, the overall characteristics of battery separators with different structures and compositions are reviewed. In addition, the research directions and prospects of separator engineering are suggested to provide a solid guideline for developing a safe and reliable battery system.     

静电纺丝技术在新能源电池中应用的研究进展

简要介绍了五种新能源电池和静电纺丝技术,综述了静电纺丝技术用于锂电池的正负极材料和燃料电池电极材料的现状,以及应用静电纺丝技术制备电极隔膜材料。静电纺丝制备纳米纤维具有直径小、比表面积大、孔隙率高等特点,用于正负电极和隔膜材料将大大提高电池的比容量、充放电速率和充放电电流,从而提高电池的蓄电能力、循环性能、离子导电性、力学稳定性和化学稳定性。最后总结了静电纺丝技术产业化需要解决的问题,并展望了在新能源电池中的进一步应用。     

Synthesis and characterization of reversible thermosensitive methylated chitin and its application in zinc-ion battery thermal runaway

Novel water-soluble methylated chitins (MCHs) were synthesized homogeneously in aqueous alkaline solution. The relatively mild reaction conditions resulted in the MCH with high degree of acetylation (DA >0.76). The chemical structure of the obtained MCHs was analyzed and the degree of methylation substitution (DS) and DA were determined by proton NMR in both D₂O and 20% DCl/D₂O. The MCH aqueous solutions (DS = 0.46 ~ 0.71) showed a reversible thermosensitive sol–gel–sol transition upon heating and cooling. The gel transition temperature of these MCHs (in the range of 15–85 °C) increased with increasing DS and decreasing polymer concentration. Thermal runaway has been an important safety issue impeding the development of high-energy-density zinc-ion batteries. A smart thermosensitive reversible electrolyte was prepared based on this MCH for the aqueous zinc-ion battery to prevent thermal runaway. When the temperature of zinc-ion battery rises or even gets out of control, the thermosensitive electrolyte can quickly gel and inhibit the migration of zinc ions, resulting in increase of the internal resistance and realizing intelligent and efficient thermal self-protection. Thus the novel thermosensitive methylated chitin shows promise for safe aqueous zinc-ion batteries.     

Thermo-responsive polymers for thermal regulation in electrochemical energy devices

Thermo-responsive polymers have been widely explored because of their diverse structures and functions in response to temperature stimuli. Great attention has been attracted to exploring and designing such polymers composites, which offer tremendous opportunities to build up a systematic understanding of their structure–function relationships and pave the ways for their extensive applications in electronics, soft robotics, and electrochemical energy storage devices. Here, we review the most recent research of thermal regulation in electrochemical energy storage devices (e.g., batteries, supercapacitors) via thermo-responsive polymers. We summarize how battery components (i.e., electrolytes, separators, electrodes, or current collectors) can be coupled with thermo-responsive polymers based on different operation mechanisms, such as volume expansion, polymerization, phase reversion, and de-doping effects, to effectively prevent catastrophic thermal runaway. Different types of thermo-responsive polymers are evaluated to compare their key features and/or limitations. This review is concluded with perspectives of future design strategies towards more effective thermo-responsive polymers for battery thermal regulation.     

Separator technologies for lithium-ion batteries

Although separators do not participate in the electrochemical reactions in a lithium-ion (Li-ion) battery, they perform the critical functions of physically separating the positive and negative electrodes while permitting the free flow of lithium ions through the liquid electrolyte that fill in their open porous structure. Separators for liquid electrolyte Li-ion batteries can be classified into porous polymeric membranes, nonwoven mats, and composite separators. Porous membranes are most commonly used due to their relatively low processing cost and good mechanical properties. Although not widely used in Li-ion batteries, nonwoven mats have the potential for low cost and thermally stable separators. Recent composite separators have attracted much attention, however, as they offer excellent thermal stability and wettability by the nonaqueous electrolyte. The present paper (1) presents an overview of separator characterization techniques, (2) reviews existing technologies for producing different types of separators, and (3) discusses directions for future investigation. Research into separator fabrication techniques and chemical modifications, coupled with the numerical modeling, should lead to further improvements in the performance and abuse tolerance as well as cost reduction of Li-ion batteries.