基于正交试验的锂离子电池热失控仿真北大核心CSCD

锂离子电池热失控是由多种因素耦合而导致的结果,得到影响锂离子电池热失控影响因素的重要性程度对于提高电池安全性具有极大意义。对此,针对针刺导致的锂离子电池热失控,利用COMSOL软件仿真分析了不同针刺位置、速度、直径、SOC(state of charge)对锂离子电池单体针刺热失控影响,得到对单体电池热失控影响的重要因素。基于单体针刺热失控仿真结果,以4个锂离子电池单体组成的模组为研究对象,利用单因素仿真试验分析不同钢针直径R、电池SOC以及针刺电池个数N对电池模组热扩散影响;基于此,本文分析了针刺电池个数N、钢针直径R及电池SOC耦合作用热失控的正交试验。结果表明:相对于针刺位置、针刺速度对电池单体热失控影响,电池SOC和针刺直径R对电池单体热失控影响较为显著,且针刺直径R越小,单体电池热失控越剧烈;电池SOC越大,热失控时电池温度分布越不均匀;针刺直径R越大,模组热扩散需要时间越长;当SOC在100%~85%范围内时,模组内各电池单体的热失控最高温度变化较为明显;针刺电池个数N越大,模组热失控越剧烈,但位于模组中间位置的电池热失控最高温度有所降低。针刺电池个数N、SOC、针刺直径R对电池模组热失控温度和扩散时间的影响程度主次顺序为:N>R>SOC*R>SOC*N>N*R>SOC,其中,针刺电池个数N对电池模组热扩散影响最显著,且不同因素间的交互作用不容忽视。本工作为提高电池的安全性及电池设计提供了参考依据。     

锂离子电池热效应模型的研究进展

锂离子电池充放电过程中会产生大量的热,若不及时散热会严重影响到电池的整体性能和寿命,严重时还会引发安全问题。文中阐述锂离子电池热效应模型的研究进展,认为在对锂离子单体进行数值模拟时,应从正极板、负极板和隔膜等简化的均匀发热体过渡到分层、细化、精确的模拟;加大对低温及特殊条件下锂离子电池热行为的探究;电池使用环境的精确仿真模拟将会成为人们今后努力的方向。     

锂离子电池加速循环测试研究北大核心CSCD

以圆型21700 4.8 Ah电池为测试样本,采用零和脉冲法进行加速循环测试研究。以所筛选的10%SOC作为最优的荷电态测试区间,对3种不同正负极材料组成的实验电池进行7天的加速循环测试,以基准电池参数为对比,综合多种参数对电池循环性能优劣进行分析评价。通过对电池加速循环前后的容量保持率分析,即可获得与常规循环测试一致的测评结果:负极二元化电池的放电容量保持率最高,为99.75%,其次是基准方案电池,为99.43%,而正极二元化电池的放电容量保持率最低,为96.33%。此外,通过对电池在加速循环过程中的直流内阻和极化电压增长率的分析,正极二元化电池的增长率远高于其他两种电池。进一步通过对电池瞬时及弛豫阻抗的拆解分析,可知导致正极二元化电池循环较差的原因主要是其正极及负极上均发生了大量的副反应,由于界面膜增厚及沉积物增多导致固相扩散阻抗增大,因此弛豫阻抗增长率达40%。通过对循环后电池进行EIS测试及正负极的物性分析发现,正极二元化电池的扩散阻抗显著较高,且其正极二次颗粒碎裂程度较高,此结果可初步解释正极二元化电池在加速循环中因正极碎裂引发副反应导致固相扩散阻抗增长率较高的现象。该加速循环测试方法以实际循环制式为依据,不引入额外的温度及倍率等应力影响因素,通过对各种测试参数的综合分析,达到定性判断实验电池循环性能优劣的目的,不仅可以大大缩短电池循环测评周期,同时可以为电池循环衰减原因分析提供依据。     

火焰检测探头中光电池的加速寿命试验研究

提出一种利用加速寿命试验对火焰检测探头中光电池进行寿命检测的方法。光电池的寿命分布可以用威布尔函数来描述,采用最小二乘法并结合阿伦尼斯加速模型完成对试验数据的统计及分析。该方法能有效地缩短光电池的寿命测试时间,实现了在短时间内对正常应力下火焰检测探头中光电池寿命的科学估计。     

基于VF-DW-DFN的锂离子电池剩余寿命预测北大核心CSCD

锂离子电池作为各类储能系统与设备的重要组成部分,准确预测锂离子电池的剩余使用寿命对于保障电池相关产业和设施的可靠性与安全性起着关键作用。针对锂离子电池剩余寿命预测中存在的非平稳、非线性特性导致单一数据驱动方法的预测精度低、泛化性能差等问题,提出了一种基于变分滤波、数据规整和深度融合网络的数据驱动融合(VF-DW-DFN)方法。首先,利用变分滤波法去除原始电池退化序列中的随机噪声干扰,得到相对平稳的退化特征数据。然后,采用最优嵌入法构造预测滑窗,实现特征数据规整,减少信息损失。其次,设计了一种新型深度融合网络对电池非线性退化数据进行建模,辨识电池数据中的退化模式,实现最终的锂离子电池剩余寿命预测。最后,在钴酸锂锂离子电池数据集上进行了剩余寿命预测实验,实验预测的平均均方根误差为1.41%,平均剩余寿命绝对误差小于2个循环周期。实验结果表明所提出的方法泛化性能好,预测精度高,误差小,能够对锂离子电池的退化过程进行有效建模和准确预测。     

锂离子电池全寿命周期个性化退役与评价方法

锂离子电池(Lithium-ion batteries, LIBs)广泛应用于储能系统(Energy storage system, ESS)、电动汽车(Electric vehicles,EVs)等领域。然而,电池在运行过程中容量会逐渐下降直至退役。传统方法以80%健康状态(State of health, SOH)作为退役标准,未考虑电池实际衰退速率,不仅不能充分利用健康电池,而且难以有效保障非健康电池的安全性。同时,SOH相等但电池老化特性和衰退速度不一定相同。仅以SOH评价无法准确反映电池老化差异。为此,提出一种锂离子电池全寿命周期个性化退役标准和老化评价方法。以容量衰退梯度和SOH为特征,首次定义全新退役指标(Index of decommissioning,IoD),计算IoD在80%SOH下的分布,获取退役阈值,并以此阈值为标准定义电池退役时刻。提出一种全新的健康状态评价指标—电池容量跳水度(Terminal diving rate,TDR),评价电池在使用过程中出现的非线性老化现象。通过在MIT公开数据集上验证,所提方法计算简单、鲁棒性强,能够实现电池个性化退役,更有效...     

Study on accelerated life test method for Zn-Ag reserve battery

本工作通过比较不同存储期锌银电池中AgO的热力学特性、容量特性,研究AgO热稳定性以有效评价该类电池满足或拓展存储期限的可行性。本工作提出从不同恒速升温条件下的DSC曲线峰温和峰温时的反应深度计算/确定AgO分解反应动力学因子E、A的方法。建立数学模型,估算不同温度条件下锌银电池贮存期限并计算不同存储期锌银电池容量年衰减率,与不同温度下加速升温容量衰减率进行比较,最终确定适用于锌银电池加速寿命试验方法。     

Physicochemical properties of lithium iron phosphate‐carbon as lithium polymer battery cathodes

Lithium iron phosphate‐carbon (LiFePO₄/multiwalled carbon nanotubes (MWCNTs)) composite cathode materials were prepared by a hydrothermal method. In this study, we used MWCNTs as conductive additive. Poly (vinylidene fluoride‐co‐hexafluoropropylene)‐based solid polymer electrolyte (SPE) was applied. The structural and morphological performance of LiFePO₄/MWCNTs cathode materials was investigated by X‐ray diffraction and scanning electron microscopy/mapping. The electrochemical properties of Li/SPE/LiFePO₄‐MWCNTs coin‐type polymer batteries were analyzed by cyclic voltammetry, ac impedance and galvanostatic charge/discharge tests. Li/SPE/LiFePO₄‐MWCNTs polymer battery with 5 wt % MWCNTs demonstrates the highest discharge capacity and stable cyclability at room temperature. It is indicated that LiFePO₄‐MWCNTs can be used as the cathode materials for lithium polymer batteries. Copyright © 2011 John Wiley & Sons, Ltd.     

A review on recycling technology of spent lithium iron phosphate battery

纯电动客车用电池以磷酸铁锂电池为主,电池寿命结束后将产生大量的废旧电池,如何处理废旧电池是人们关心的重要问题。基于此,本文介绍了国家目前对于废旧电池回收的相关政策以及废旧LiFePO₄电池的主要有价成分。详细介绍了废旧LiFePO₄材料的多种回收、再利用方法,包括化学沉淀法回收、高温固相修复技术、高温固相再生技术、生物浸出技术以及机械活化处理回收技术等;并分别介绍了高温热解处理、有机溶剂萃取回收、超临界CO₂回收的电解液回收处理技术以及负极材料的分选回收技术、石墨修复改性技术。沉淀法回收产物为含锂、铁的工业原料,该类方法易于实现规模化应用,但是会产生大量酸碱废液;高温固相修复、再生方法工艺流程短,除杂将会是该工艺规模化应用的难点。对不同类型的回收材料提出不同回收处理方法,为废旧磷酸铁锂电池的回收提供参考。     

Lithium iron phosphate with high-rate capability synthesized through hydrothermal reaction in glucose solution

Carbon-coated lithium iron phosphate (LiFePO₄/C) was hydrothermally synthesized from commercial LiOH, FeSO₄ and H₃PO₄ as raw materials and glucose as carbon precursor in aqueous solution at 180 °C for 6 h followed by being fired at 750 °C for 6 h. The samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and constant current charge–discharge cycling test. The results show that the synthesized powders are in situ coated with carbon precursor produced from glucose. At ambient temperature (25 ± 2 °C), the specific discharge capacities are 154 mAh g⁻¹ at 0.2 C and 136 mAh g⁻¹ at 5 C rate, and the cycling capacity retention rate reaches 98% over 90 cycles. The excellent electrochemical performance can be correlated with the in situ formation of carbon precursor/carbon, thus leading to the even distribution of carbon and the enhancement of conductibility of individual grains.     

Synthesis and electrochemical performance of lithium iron phosphate/carbon composites based on controlling the secondary morphology of precursors

In this study, dihydrate iron phosphates with primary and secondary morphology were first prepared with ferric sulfate and phosphoric acid as the major raw materials, which were then taken as the precursor to prepare carbon-coated lithium iron phosphate composite material. Results show that structures of synthesized lithium iron phosphate/Carbon materials are the same, however, the morphologies are significantly different, especially the one synthesized with the secondary morphology iron phosphate precursor. Thus, the particle size, specific surface area and carbon coating effect of the material are changed accordingly, which can affect the electrochemical performance of the composite. The lithium iron phosphate/Carbon synthesized with spherical aggregation morphology (secondary morphology) iron phosphate precursor showed the best electrochemical property. At 0.5C and 10C rates, the first specific discharge capacity is 155.6 and 103.8 mA h/g respectively, which is better than that prepared with cabbage shape aggregation morphology (secondary morphology) and near-spherical simplex (primary morphology), increasing 1.38%, 1.37% and 3.58%, 9.05%, respectively. This research result provided new thoughts to further improve the electrochemical property of lithium iron phosphate/Carbon composites.     

基于磷酸铁锂电池变电站直流系统BMS的研究与应用

磷酸铁锂电池管理单元（BMS）是文中研究的重点,如何把握电池内部状态的变化规律以及外部因素对电池容量的影响、建立合理有效的电池模型和SOC算法、实现SOC在线估计并减少估算误差,是电池安全管理最基本、最重要的方面。电池管理单元（BMS）与变电站直流系统监控器通过CAN通信,能有效的保证磷酸铁锂电池组及整个直流系统安全可靠的工作。     

Investigation on the root cause of the decreased performances in the overcharged lithium iron phosphate battery

The overcharge of the lithium iron phosphate (LiFePO₄) batteries usually leads to the sharp capacity fading and safety issues, especially under low temperature environment. Thus, investigating their root cause originated from the electrode materials is critical for the safety performance optimization and market promotion of the LiFePO₄ batteries. In this work, the electrochemical/thermal behaviors of 18650 LiFePO₄ batteries are investigated after overcharge under room and low temperature of 25°C and ?20°C, respectively. The results demonstrate a decreased electrochemical performance and faster heating rate of the overcharged battery, particularly under harsh working environments such as high discharge rate and low temperature. Coupling with the analyses of the internal resistance, the crystal structure, and microstructure of the electrodes, the root cause is attributed to the damage of the crystal structure and microstructure, which reduce the electron/Li⁺ migrating capability and electrolyte diffusion/transfer efficiency.     

Combustibility and hazard of lithium iron phosphate power battery components in different aging states

选用四种衰退状态,容量保持率（capacity retention ratio,CRR）分别为100%、85%、75%及65%的磷酸铁锂动力电池为研究对象,采用锥形量热仪（CONE）对电池关键组件（含电解液的正极片、负极片及隔膜）的燃烧性和生烟性进行了研究,并运用层次分析法（analytic hierarchy process,AHP）综合评价了不同衰退状态电池组件的火灾危险性。结果表明,随着电池容量保持率的下降,电池组件中负极的有效燃烧热值有所下降,并且电池组件的CO₂产率和总生烟量逐渐降低;容量保持率100%~85%的电池组件的归一化危险性指数要明显大于75%~65%的电池组件。     

A review on lithium iron phosphate cathode materials

目前全球高动力锂离子电池系统的发展主要集中在锂锰电池,锂钴镍锰电池以及锂铁电池,其中磷酸亚铁锂材料具有高电容量,高放电功率,极佳的长循环寿命以及良好的热稳定性与高温性能等优点,已成为动力锂离子电池首选的高安全性正极材料.然而,磷酸亚铁锂材料在工业化量产时,必须解决电池芯加工性差及材料一致性不佳等问题,作者曾结合多项新颖观念与技术于磷酸亚铁锂材料制做过程,在粉体表面涂布碳层,在晶体内部掺杂金属,分别改善材料电导率与锂离子扩散速度以及有效地控制碳含量,粉体比表面积,碳层均匀性,粒径大小与分布,制备出高质量磷酸亚铁锂产品.该文将回顾并探讨上述研发工作的一些重要结果.     

Improving electrochemical properties of lithium iron phosphate by addition of vanadium

The poor conductivity, resulting from the low lithium-ion diffusion rate and low electronic conductivity in the LiFePO₄ phase, has posed a bottleneck for commercial applications. Well-crystallized LiFePO₄-based powders with vanadium addition were synthesized with solution method. The synthesized powders are coated with carbon. The powder containing the well-mixed LiFePO₄ and Li₃V₂(PO₄)₃ phases (LFVP) with narrow distributed particle size ranging between 0.5 and 2.5 μm exhibits improved electrochemical performance. The small particle size and the presence of the electronically conductive mixed phases can be the reasons why the cells containing LFVP exhibit the high discharge capacity of about 100 mAh g⁻¹ at 10 C, whereas the samples with single phase, such as LiFePO₄ and Li₃V₂(PO₄)₃, have the discharge capacity less than 80 Ah g⁻¹ at the same rate.