Effect of safety valve types on the gas venting behavior and thermal runaway hazard severity of large-format prismatic lithium iron phosphate batteries

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.

Three-in-one fire-retardant poly(phosphate)-based fast ion-conductor for all-solid-state lithium batteries

The development of flame retardant or nonflammable electrolytes is the key to improve the safety of lithium batteries,owing to inflammable organic solvents and polymer matrix in common liquid and polymer electrolytes regarded as the main cause of battery fire.Herein,a series of solid-state polyphosphate oligomers(SPPO)as a three-in-one electrolyte that integrated the roles of lithium salt,dissociation matrix,and flame retardant were synthesized.The well-designed SPPO electrolytes showed an optimal ionic conductivity of 5.5×10^(-4)S cm-1at 30℃,an acceptable electrochemical window up to 4.0 V vs.Li/Li+,and lithium ion transference number of 0.547.Stable Li-ion stripping/plating behavior for 500 h of charge-discharge cycles without internal short-circuit in a Li|SPPO|Li cell was confirmed,together with outstanding interface compatibility between the SPPO electrolyte and lithium foil.The optimal Li|SPPO|LiFePO4cell presented good reversible discharge capacity of 149.4 mA h g-1at 0.1 C and Coulombic efficiency of 96.4%after 120 cycles.More importantly,the prepared SPPO cannot be ignited by the lighter fire and show a limited-oxygen-index value as high as 35.5%,indicating splendid nonflammable nature.The SPPO could be a promising candidate as a three-in-one solid-state electrolyte for the improved safety of rechargeable lithium batteries.

Upcycling the spent graphite/LiCoO_(2) batteries for high-voltage graphite/LiCoPO_(4)-co-workable dual-ion batteries

The worldwide proliferation of portable electronics has resulted in a dramatic increase in the number of spent lithium-ion batteries(LIBs).However,traditional recycling methods still have limitations because of such huge amounts of spent LIBs.Therefore,we proposed an ecofriendly and sustainable double recycling strategy to concurrently reuse the cathode(LiCoO_(2))and anode(graphite)materials of spent LIBs and recycled LiCoPO_(4)/graphite(RLCPG)in Li^(+)/PF^(-)_(6) co-de/intercalation dual-ion batteries.The recycle-derived dualion batteries of Li/RLCPG show impressive electrochemical performance,with an appropriate discharge capacity of 86.2 mAh·g^(-1) at25 mA·g^(-1) and 69%capacity retention after 400 cycles.Dual recycling of the cathode and anode from spent LIBs avoids wastage of resources and yields cathode materials with excellent performance,thereby offering an ecofriendly and sustainable way to design novel secondary batteries.

Incorporation of layered tin(Ⅳ) phosphate in graphene framework for high performance lithium-sulfur batteries

To anchor the polysulfide and enhance the conversion kinetics of polysulfide to disulfide/sulfide is critical for improving the performance of lithium-sulfur battery.For this purpose,the graphene-supported tin(Ⅳ) phosphate(Sn(HPO_4)_2·H_2 O,SnP) composites(SnP-G) are employed as the novel sulfur hosts in this work.When compared to the graphene-sulfur and carbon-sulfur composites,the SnP-G-sulfur composites exhibit much better cycling performance at 1.0 C over 800 cycles.Meanwhile,the pouch cell fabricated with the SnP-G-sulfur cathodes also exhibits excellent performance with an initial capacity of1266.6 mAh g^(-1)(S) and capacity retention of 76.9% after 100 cycles at 0.1 C.The adsorption tests,density functional theory(DFT) calculations in combination with physical cha racterizations and electrochemical measurements provide insights into the mechanism of capture-accelerated conversion mechanism of polysulfide at the surface of SnP.DFT calculations indicate that the Li-O bond formed between Li atom(from Li_2 S_n,n=1,2,4,6,8) and O atom(from PO_3-OH in SnP) is the main reason for the strong interactions between Li_2 S_n and SnP.As a result,SnP can effectively restrain the shuttle effect and improving the cycling performance of Li-S cell.In addition,by employing the climbing-image nudged elastic band(ciNEB) methods,the energy barrier for lithium sulfide decomposition(charging reaction) on SnP is proved to decrease significantly compared to that on graphene.It can be concluded that SnP is an effective sulfur hosts acting as dual-functional accelerators for the conversion reactions of polysulfude to sulfide(discharging reaction) as well as polysulfide to sulfur(charging reaction).

Non-flammable electrolytes based on trimethyl phosphate solvent for lithium-ion batteries

The properties of trimethyl phosphate（TMP）-based nonflammable electrolytes with LiPF6 as solute were investigated using graphite anode and LiCoO2 cathode. The effect of TMP on non-flammability of electrolytes was also evaluated. It is found that the TMP reduction decomposition on graphite electrode at the potential of 1.3V （vs Li/Li+） is suppressed with ethylene carbonate（EC）, dimethyl carbonate（DMC） and ethylmethyl carbonate（EMC） cosolvents and vinylene carbonate（VC） additives. The results show that the non-flammable electrolyte of 1mol/L LiPF6 61%（EC1.5-DMC1.0-EMC1.0）-39% TMP has good electrochemical properties. The discharge capacities of half-cells after 20 cycles are 254.8mA·h/g for Li/graphite and 144.1mA·h/g for Li/LiCoO2. The （graphite/）（LiCoO2） prismatic lithium-ion cell delivers a discharge capacity of 131mA·h/g at first cycle. With an addition of 4%VC to this non-flammable electrolyte, a discharge capacity of 134mA·h/g at first cycle and a capacity ratio of （84.3%） after 50 cycles are obtained for prismatic lithium-ion batteries. Furthermore, a nail penetration test demonstrates that the safety of prismatic lithium-ion batteries is dramatically improved by using TMP-containing （non-）（flammable） electrolytes.

Synthesis and characterization of phosphate-modified LiMn_2O_4 cathode materials for Li-ion battery

LiMn2O4 spinel cathode materials were modified with 2 wt.%Li-M-PO4（M=Co,Ni,Mn） by polyol synthesis method.The phosphate surface-modified LiMn2O4 cathode materials were physically characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM） and energy dispersive X-ray spectroscopy（EDS）.The charge-discharge test showed that the cycling and rate capacities of LiMn2O4 cathode materials were significantly enhanced by stabilizing the electrode surface with phosphate.

Synthesis and electrochemical performance of La-doped Li_3V_(2-x)La_x(PO_4)_3 cathode materials for lithium batteries

La-doped Li3V2-xLax（PO4）3 （ x = 0.01, 0.02, and 0.03） cathode materials for lithium ion batteries were synthesized by the microwave-assisted carbothermal reduction method （MW-CTR）. The structures and properties of the prepared samples were investigated by X-ray diffraction （XRD） and electrochemical measurements. The results showed that all the three Li3V2-xLax（PO4）3 samples had the same monocfinic structures and sharper diffraction peaks of the crystal plane compared with those of the undoped Li3V2（PO4）3. The initial charge/discharge specific capacity, coulomb efficiency, and discharge decay rate of all the three Li3V2-xLax（PO4）3 samples were superior to those of the undoped Li3V2（PO4）3 sample, and the Li3V1.98La0.02（PO4）3 sample exhibited the best features among the three La-doped Li3V2-xLax（PO4）3 samples. Electrochemical impedance spectroscopy （EIS） demonstrated that the Li3V1.98Lao.02（PO4）3 sample had a lower charge transfer resistance and a higher Li ion diffusion coefficient compared with the undoped Li3V2 （PO4）3 sample.

The effect of phosphate additive on the positive electrolyte stability of vanadium redox flow battery

The electrolyte is one of the most important components of vanadium redox flow battery （VRFB）. and its stability and solubility determines the energy density of a VRFB. The performance of current positive elec- trolyte is limited by the low stability of VO2＋ at a higher temperature. Phosphate is proved to be a very effective additive to improve the stability of VO2＋. Even though, the stabilizing mechanism is still not clear, which hinders the further development of VRFBs. In this paper, to clarify the effect of phosphate additive on the positive electrolyte stability, the hydration structures of VO2＋ cations and the reaction mechanisms of precipitation with or without phosphate in the supporting electrolyte of H_2SO_4 solutions were investigated in detail based on calculations of electronic structure. The stable configurations of com- plexes were optimized at the B3LYP/6-311 ＋ G（d,p） level of theory. The zero-point energies and Gibbs free energies for these complexes were further evaluated at the B3LYP/aug-cc-pVTZ level of theory. It shows that a structure of [VO_2（H_2O）_2]＋ surrounded by water molecules in H2S04 solution can be formed at the room temperature. With the temperature rises, [VO_2（H_2O）_2]＋ will lose a proton and form the interme- diate of VO（OH）_3, and the further dehydration among VO（OH）_3 molecules will create the precipitate of V_2O_5. When H_3PO_4 was added into electrolytes, the V-O-P bond-containing neutral compound could be formed through interaction between VO（OH）_3 and H_3PO_4, and the activation energy of forming the V-O-P bond-containing neutral compound is about 7 kcal tool-1 lower than that of the VO（OH）_3 dehydration, which could avoid the precipitation of V_2O_5 and improve the electrolyte stability.

Recovery and regeneration of LiFePO_(4)from spent lithium-ion batteries via a novel pretreatment process

The recycling of spent LiFePO_(4)batteries has received extensive attention due to its environmental impact and economic benefit.In the pretreatment process of spent LiFePO_(4)batteries,the separation of active materials and current collectors determines the difficulty of the re-covery process and product quality.In this work,a facile and efficient pretreatment process is first proposed.After only freezing the electrode pieces and immersing them in boiling water,LiFePO_(4)materials were peeled from the Al foil.Then,after roasting under an inert atmosphere and sieving,all the cathode and anode active materials were easily and efficiently separated from the Al and Cu foils.The active materials were subjected to acid leaching,and the leaching solution was further used to prepare FePO_(4)and Li_(2)CO_(3).Finally,the battery-grade FePO_(4)and Li_(2)CO_(3)were used to re-synthesize LiFePO_(4)/C via the carbon thermal reduction method.The discharge capacities of re-synthesized LiFePO_(4)/C cathode were 144.2,139.0,133.2,125.5,and 110.5 mA·h·g−1 at rates of 0.1,0.5,1,2,and 5 C,which satisfies the requirement for middle-end LiFePO_(4)batteries.The whole process is environmental and has great potential for industrial-scale recycling of spent lithium-ion batteries.

Surfactant assisted solvothermal synthesis of LiFePO4 nanorods for lithium-ion batteries

Well-shaped and uniformly dispersed LiFePOnanorods with a length of 400–500 nm and a diameter of about 100 nm, are obtained with participation of a proper amount of anion surfactant sodium dodecyl sulfonate（SDS） without any further heating as a post-treatment. The surfactant acts as a self-assembling supermolecular template, which stimulated the crystallization of LiFePOand directed the nanoparticles growing into nanorods between bilayers of surfactant（BOS）. LiFePOnanorods with the reducing crystal size along the b axis shorten the diffusion distance of Liextraction/insertion, and thus improve the electrochemical properties of LiFePOnanorods. Such prepared LiFePOnanorods exhibited excellent specific capacity and high rate capability with discharge capacity of 151 mAh/g, 122 mAh/g and 95 mAh/g at 0.1C, 1 C and 5 C, respectively. Such excellent performance of LiFePOnanorods is supposed to be ascribed to the fast Lidiffusion velocity from reduced crystal size along the b axis and the well electrochemical conductivity. The structure, morphology and electrochemical performance of the samples were characterized by XRD, FE-SEM, HRTEM, charge/discharge tests, and EIS（electrochemical impedance spectra）.

Elucidation of the sodiation/desodiation mechanism in Ca_(0.5)Ti_(2)(PO_(4))_(3)/C as promising electrode for sodium batteries: New insights into the phase transitions

The structure evolution and electrochemical performance of Na SICON-type Ca_(0.5)Ti_(2)(PO_(4))_(3) for sodium batteries are presented.This phosphate was synthesized by a solid-state method,and the obtained particles were coated with carbon using sucrose.This compound crystallizes in the rhombohedral system with space group R-3.The presence of carbon in the Ca_(0.5)Ti_(2)(PO_(4))_(3)/C composite was confirmed by Raman and Thermogravimetric analysis.The electrochemical performance of Ca_(0.5)Ti_(2)(PO_(4))_(3)/C was investigated in the potential window 1.5–3.0 V vs.sodium metal at different scan rates.The compound is able to initially intercalate/deintercalate 1.6/1.15 Na per formula unit,respectively.In operando synchrotron diffraction was done in the potential window 0.02–3.0 V vs.Na|Na+and revealed the occurrence of several reaction regions upon first discharge.Up to 4 Na+ion per formula unit can be inserted during the first discharge.An intensive refinement of the synchrotron X-ray diffraction(SXRD)patterns of discharged Ca_(0.5)Ti_(2)(PO_(4))_(3) evidenced the existence of five regions depending on the sodium content while the crystal structures of new phases were elucidated for the first time where sodium insertion occurs in the unusual M3 and M’3 sites of the Na SICON structure.

溶剂热法制备磷酸锰锂的优化研究

橄榄石结构的磷酸锰锂(LiMnPO_(4))具有比容量高､热稳定性好和原料来源广泛等特点,与同为橄榄石结构的磷酸铁锂相比具有更高的放电电压。采用溶剂热法制备了高性能的磷酸锰锂正极材料,通过对过程参数进行优化实现材料性能的提升,以柠檬酸为添加剂优化颗粒形貌得到纳米级颗粒,并对碳层包覆进行优化。结果表明,柠檬酸添加量为1 mmol时,椭球状颗粒平均尺寸为42.3 nm;当以蔗糖为碳源且与LiMnPO_(4)质量比为1∶2时得到的碳层包覆颗粒尺寸较小､碳层石墨化程度更高;在最优参数下制备的LiMnPO_(4)材料具有更高的首次放电容量(126.9 mAh/g)及更优的倍率性能。

液氮抑制32650型磷酸铁锂电池组热失控传播特性试验研究

文章从磷酸铁锂电池组热失控危险特性出发,通过试验研究32650型磷酸铁锂电池单体热失控特征及其电池组间热失控传播过程。探究利用液氮喷淋阻断电池组间热失控传播,分析液氮对磷酸铁锂电池的防灭火效能。结果表明:单体锂电池热失控可划分为被动加热、安全阀泄压、自反应、喷射火、明火熄灭等5个阶段,单体电池温度变化曲线呈倒“V”形。液氮可有效阻断电池组间的热失控传播,能够大幅降低喷射火阶段的电池峰值温度。且喷淋时间越长,阻止电池组热失控传播越明显。30 s液氮喷淋条件下,除电池A1外,其他电池未进入安全阀泄压阶段。

退役磷酸铁锂电池负极石墨的预锂化再生

对退役磷酸铁锂(LiFePO_(4))电池的负极石墨进行预锂化,使石墨变为锂碳化合物并进行热处理,从而实现石墨的晶型转变.将预锂化后的LiFePO_(4)电池热处理,回收得到的石墨经不同处理,所得样品分别与导电炭黑和黏结剂等物质进行混合制成新的电极,组装成电池后进行电池的性能测试.结果表明,在电流为0.1C的条件下,预锂化热处理的石墨样品经酸浸后所制成的纽扣电池平均放电比容量为322.3 mAh·g^(-1),远远高于其他对比组,其循环稳定性也强于人造石墨.说明退役电池负极石墨通过预锂化、热处理和酸浸处理后能够得到优质再生石墨.

基于集成聚类的退役锂电池直接分组

针对退役电池筛选分组效率低的问题,提出了一种基于加权表决集成聚类算法的退役锂离子电池直接分组方法。提取充电电压片段特征,对特征进行降维,并使用集成聚类算法直接对特征进行分组,实现退役锂离子电池分组。该方法只需要得到部分恒流充电曲线便可实现退役锂离子电池的按容量分组,提高了筛选效率。搭建了磷酸铁锂电池仿真和实验平台,对所提的电池筛选、分组策略进行仿真和实验分析。从退役电池分组容量精度和分组效率的角度验证了所提策略的正确性和有效性。

磷酸酯基阻燃电解液用于高安全锂硫电池

Li–S电池被认为是最有希望的下一代高能量密度二次电池之一,开发高效阻燃电解液对于提升电池安全性极为重要.本文对高浓度磷酸三乙酯(TEP)和磷酸三(2,2,2-三氟乙基)酯(TFP)电解液在锂–硫化聚丙烯腈(Li–PAN/S)电池中的应用展开了深入研究,以同样的锂盐摩尔比和氟代醚稀释梯度,研究了TEP和TFP基局部高浓度电解液对锂金属负极和硫正极稳定性的影响,详细解析了两种溶剂分子在电池循环过程中的界面反应.研究表明,磷酸酯基高浓度电解液在Li–PAN/S电池中展示了较优异的循环稳定性,通过优化TTE的稀释比例,提升了电池的倍率特性.对比基于TEP和TFP的电解液,发现TEP基电解液具有更好的锂沉积/剥离性能,而TFP基电解液在界面生成更多的有机组分,导致不稳定的界面膜.以TEP212为电解液的锂硫电池能够在1C的倍率下稳定循环200圈以上,放电比容量保持在1080.8 mA·h·g-1.

气凝胶灭火剂抑制锂离子储能电池热失控特性研究

通过对比试验探究了气凝胶灭火剂对锂离子储能电池热失控的抑制效果。研究满荷电状态下的100 Ah磷酸铁锂储能电池热失控演变过程特征参数,识别出3个灾害演变特征拐点作为灭火剂施加的指导节点。在相同节点分别施加灭火参数一致的气凝胶灭火剂与细水雾开展灭火对比测试。结果表明:触发明火前施加灭火剂均可有效阻断电池内部放热副反应,两者表现出相似的冷却效能;电池起火后,气凝胶灭火剂展现出更为出色的明火抑制效果,其接触电池表面形成的致密泡沫可有效阻隔氧气,实现快速灭火;对于已经触发热失控的情形,气凝胶灭火剂凭借预热覆盖效果,显著缩短电池射流火持续时间,可大幅降低电池火灾危害。

不同放电功率下的储能用磷酸铁锂电池热失控特性实验研究

以某款52 Ah储能用方形磷酸铁锂电池单体为对象,采用400 W的外部热源、20.8~166.4 W(1~8 h)的恒功率放电以匹配电池工作状态下的热滥用条件,测量电池热失控过程中的表面温度和电压,记录热失控实验现象和关键时间点,对比研究不同放电功率对热滥用诱发热失控进程的影响。结果表明,放电操作会加速热失控的进程,且放电功率越大,热失控越早发生,从不放电到166.4 W恒功率放电,安全阀打开时间缩短了23.4%,热失控触发时间缩短了5.6%;与此同时,四组放电工况由于放出部分能量,最终热失控的严重程度有所降低,放电工况下的热失控最高温度和最大温升速率比不放电工况最高分别下降了9.0%和53.3%;另外,放电操作会造成热失控过程中电压更大的波动,后续电压下降的时间窗口前移至开阀时间附近,这将更有利于利用电压变化对热失控进行预警。总体而言,放电操作在加速热失控进程的同时,降低了热失控最终的严重程度。本工作可对电化学储能电站的日常安全运营和电池管理系统设计提供参考。

高温固相修复再生磷酸铁锂正极材料研究进展

磷酸铁锂电池作为广泛应用的锂离子电池之一,其关键电极材料的高效回收循环利用在资源、环境、经济等方面具有重要的战略意义。高温固相修复技术能够实现磷酸铁锂正极材料短流程、低成本、高效率、绿色环保的循环利用,获得了广泛的关注和研究。针对高温固相修复再生磷酸铁锂正极材料,介绍了此类材料的电化学性能失效机理,从锂补充、缺陷修复和强化锂的迁移等方面对磷酸铁锂正极材料的修复机理进行了分析;阐述了焙烧温度、保温时间、补锂量等修复再生工艺参数对高温固相法修复磷酸铁锂正极材料的影响;分析了表面包覆和离子掺杂对提升磷酸铁锂正极材料电化学性能的影响和机理;并对高温固相修复法修复磷酸铁锂正极材料的可控制备、杂质控制和材料改性等方面的未来前景进行了展望。

退役磷酸铁锂电池梯次利用生命周期评价与碳减排情景分析

以磷酸铁锂电池为研究对象,综合考虑梯次利用比例、使用周期及电池容量等因素,设定不同梯次利用场景,采用生命周期评价方法量化退役动力电池在梯次利用及后续报废处置阶段的环境影响,并对不同梯次利用率情景下的碳减排量进行分析.结果表明,与直接再生利用相比,储能、通信基站、低速电源三种梯次利用场景均表现为环境效益.其中,储能场景环境效益最大,其在气候变化、化石能源消耗、人体毒性-非致癌、陆地生态毒性指标等环境影响指标上均表现出相对优势.基于电池退役量和梯次利用去向,进一步计算出2023年全年磷酸铁锂电池梯次利用的碳减排量为1.05×10^(8) kg CO_(2)eq.当梯次利用率保持当前水平或以10%增长时,至2030年其全年碳减排量可达1.55×10^(9)kg CO_(2)eq.和5.98×10^(9)kg CO_(2)eq.,梯次利用具有良好的减污降碳环境表现.