锂离子电池安全材料的研究进展

锂离子电池因其清洁、充放电快、高能量密度等优点广泛应用于电动汽车。最近,电动汽车起火、爆炸事故引起人们对锂离子电池安全性的担忧。针对锂离子电池电解液易燃、易爆、易泄漏等安全问题,本文综述了电解液中加入阻燃剂磷酸酯、离子液体、氢氟醚的最新研究进展及其优缺点。电池如果在过充危险状况下会造成热积累,进而引发电池内部一系列危险副反应。本文还总结了氧化还原保护和电聚合保护两种措施来避免电池过度充电的研究进展。由于锂电池发生危险事故前内部会有一个热积累过程以及随着电池内部温度上升隔膜难以保持其力学性能,本文分别从热响应开关正极材料和安全隔膜两部分阐述了近年来锂离子电池内部热积累的应对策略,以期为最终解决锂离子电池的安全问题指明方向。     

锂离子电池中的含氟电极和电解质材料

绿色能源技术和低碳经济的发展对高性能锂离子电池提出了越来越高的要求。锂离子电池的发展主要依赖于电池材料的突破,而含氟材料因其结构稳定性好、安全性高而广泛应用。系统介绍了锂离子电池中涉及的含氟电极和电解质材料,着重对其应用特点和研究现状等进行了总结,并对锂电池相关含氟材料的发展方向进行了展望。     

离子液体和低共熔溶剂绿色回收废旧锂离子电池的研究进展

温和条件下废旧锂离子电池的绿色高效回收具有重大意义，目前利用离子液体和低共熔溶剂回废旧收锂离子电池的综述报道较少。本综述回顾近年离子液体和低共熔溶剂回收废旧锂离子电池，分析离子液体和低共熔溶剂对不同锂离子电池正极材料回收的差异性，介绍绿色溶剂结构、酸碱性、电池组成、温度、时间、质量比等因素对回收的影响，归纳绿色溶剂回收废旧锂离子电池的热力学和动力学规律及其溶解机制，并指出利用离子液体和低共熔溶剂回收废旧锂离子电池目前存在的一些问题及其提出可能的应对策略。     

Tri-(4-methoxythphenyl) phosphate: A new electrolyte additive with both fire-retardancy and overcharge protection for Li-ion batteries

A novel compound, tri-(4-methoxythphenyl) phosphate, was synthesized and investigated as a safety electrolyte additive for lithium-ion batteries. It was found that this additive could lower the flammability of the electrolyte, and thereby enhance the thermal stability of the Li-ion battery. Moreover, this molecule can also be polymerized at 4.35 V (vs. Li/Li⁺) to form a conducting polymer, which can protect the batteries from voltage runaway at overcharge by internal bypassing the overcharging current in the batteries. Thus, it is possible to use this electrolyte additive to provide both overcharge protection and flame retardancy for lithium-ion batteries without much influence on the battery performance.     

废旧三元锂离子电池回收技术研究新进展

随着锂离子电池产业的发展,退役三元锂离子电池带来的环境污染和资源浪费问题日益严重。数量庞大的废旧三元锂电池材料蕴含丰富的锂、镍、钴等有价元素,潜在资源量巨大,回收经济价值高,系统地开展废旧三元锂电池材料的回收及再生技术,将有助于防治废旧电池污染、缓解镍钴锂资源短缺压力,促进我国锂电池产业的良性发展。本文介绍了废旧三元锂离子电池中正极、负极材料、电解液回收的研究现状,主要包括正极材料的预处理、酸浸、碱浸出与材料再生、石墨和铜箔回收、电解液回收,着重介绍现阶段材料的制备方法和工艺,简要比较了各种工艺路线的优缺点,探讨了当前废旧三元锂离子电池回收存在的关键共性问题,并提出绿色环保、短流程、低成本、自动化的废旧三元锂离子电池回收利用发展思路。     

锂二次电池中的有机和高分子含氟材料

锂离子二次电池兼具高比能和高倍率特性,是目前最为理想的动力与储能电源体系。锂电池的发展主要依赖于电池关键材料的突破,而含氟材料因其结构稳定性好、安全性高而应用广泛。系统介绍了锂二次电池中涉及的溶剂和添加剂、隔膜和粘结剂等含氟材料,着重对其应用特点和研究现状等进行了总结,并对相关领域的发展方向进行了展望。     

低共熔溶剂在废旧锂离子电池正极材料回收中的研究进展

大规模储能与电动汽车市场的发展壮大对锂离子电池的需求水涨船高,由此产生的废旧锂离子电池数量也即将迎来爆发式增长。废旧锂离子电池正极材料蕴含丰富的锂、钴、镍、锰等有价金属元素,回收经济价值高,环境效益显著。低共熔溶剂（DESs）作为一种绿色溶剂,在废旧锂离子电池有价金属元素回收方面显示出巨大的潜力。本文在简要介绍DESs性质及应用的基础上,系统综述了DESs在废旧锂离子电池正极材料回收链中的研究现状,主要包括正极材料的分离、活性物质的浸出以及有价金属的提取,着重介绍了现阶段回收的方法及工艺流程,比较了不同DESs浸出正极活性物质的优缺点,探讨了当前DESs在废旧锂离子电池回收中的共性问题,并展望了未来DESs回收锂离子电池的发展方向。     

基于LiPF6的锂离子电池电解液的发展现状

近年来随着社会的发展和科技的进步,锂离子电池已成为重要的主流动力电池之一。分别从溶剂和添加剂2个方面综述了基于LiPF6的锂离子电池电解液的发展现状,详细介绍了适用于锂离子电池电解液的溶剂和添加剂,应用于锂离子电池电解液的常用有机溶剂有碳酸酯类、醚类和羧酸酯类有机溶剂,添加剂以其作用目的区分,可分为SEI成膜添加剂、导电添加剂、稳定添加剂、控制水分和游离酸添加剂、抗过充添加剂、阻燃添加剂及浸润性添加剂等;展望了锂离子电池电解液的研究方向。     

锂离子电池硅基负极黏结剂的研究新进展

硅具有较高的理论比容量,被认为是极具应用前景的锂离子电池负极材料。然而,硅在充放电过程中会产生巨大的体积变化,导致电极粉化脱落和容量的迅速下降,限制了硅基负极材料的应用。黏结剂是锂离子电池中一个不可或缺的组成部分,对体积变化较大的硅基负极而言,除了满足作为锂离子电池黏结剂的基本要求外,对黏结剂的结构和性能又提出了新的要求,黏结剂的选择对于增强硅基电极结构的稳定性并实现长期循环具有更加重要的意义。总结了近年来硅基负极材料黏结剂的研究进展,重点介绍了用于硅基负极材料的交联类黏结剂、导电类黏结剂和自修复类黏结剂等几种黏结剂的性能特点和应用,为选择和设计更加适合的硅基负极黏结剂提供研究建议。     

Redox shuttle additives for chemical overcharge protection in lithium ion batteries

We disclosed that a few kinds of aromatic compounds having thianthrene derivatives with acetyl or other functional groups were stable up to about 4.2-4.3 V against lithium. These materials, called redox shuttle, have lately been employed as a chemical overcharge protection agent that consumes the excess current during battery overcharge. They oxidized above 4 V and worked as redox shuttle when introduced into the electrolyte of a Carbon/LiCoO₂ prismatic battery within less than one hour rate (1C). We also studied thermal properties of batteries containing the above-mentioned materials with ARC (Accelerating Rate Calorimeter). We ascertained that the current supplied over the full charge was not stored, but instantly and quite completely consumed in an oxidation-reduction reaction.     

锂电池回收再生石墨增强水泥性能研究

废弃锂离子电池的负极活性材料主要为石墨,现阶段对于废弃锂离子电池中的石墨主要采用填埋等方法进行处理,造成了资源的浪费和环境的污染。现有的研究表明,废弃锂离子电池中的石墨经高温热解及酸浸处理后可以得到纯净的再生石墨,采用再生石墨增强水泥基复合材料的力学性能和电学性能。结果表明：再生石墨的引入可以增强材料的抗压性能和抗折性能,最大增幅分别达到了57.3%和84.4%。此外,再生石墨的加入有效降低了材料的电阻率,减少了极化时间,当再生石墨的掺加量为3%时,养护28 d后材料的电阻率仅为249 Ω·cm。该复合材料还具有典型的压敏特性。所制备的复合材料有望用于混凝土材料结构的实时动态监测。此外,对于废弃锂离子电池的全组分回收利用及功能水泥材料的研发具有重要意义。     

锂离子二次电池5V正极材料的研究进展

综述了近年来有关锂离子二次电池5V高电位正极材料的研究进展,对高电位(>4.5V)正极材料特别是尖晶石类正极材料的放电机理、材料结构和性能之间的关系进行了评述。5V电位可以在非掺杂其它过渡金属离子和掺杂其它过渡金属离子两种条件下产生,与此对应的氧化还原电对种类有所不同;表现出的电化学性能也有所不同。性能优良的材料的得到不但取决于对掺杂元素的正确选择,同样也取决于适宜的合成路线和制备方法与工艺。     

废锂离子电池的热处理：过程污染物迁移和转化

废锂离子电池中不仅富含我国高对外依存度的关键金属，还含有重金属、有机污染物等有毒有害物质，具有资源与环境的双重属性。推进其高效循环利用是保障新能源汽车等战略新兴产业可持续发展的关键。锂离子电池组成结构复杂，有机物成分变化大、种类多，常规的火法和湿法冶金过程容易产生二次环境危害，不利于资源的清洁循环利用。热处理作为保障废锂离子电池中有价金属资源有效回收的重要技术，近年来受到了行业的广泛关注。热处理技术具有二次污染小、设备简单、过程易放大、经济性高等诸多优势。结合热处理技术对废锂离子电池回收中的污染物进行源头治理，既能实现清洁生产，也能强化后续深度处理。本工作立足于行业现状和战略需求，重点讨论了废锂离子电池预处理中的污染物产生、迁移和转化规律，对比总结了热处理在杂质去除和污染防控等方面的技术优势。同时，对废锂离子电池的热处理工艺进行了系统分类，总结了不同热处理条件下的物质转化规律。     

Evaluation of ZnO nanorod arrays with dandelion-like morphology as negative electrodes for lithium-ion batteries

In this study, ZnO nanorod arrays have been evaluated for the negative electrodes of lithium-ion batteries. The ZnO nanorod arrays with dandelion-like morphology were directly grown on copper substrates by a hydrothermal synthesis process at 80 °C. X-ray diffraction, scanning electron microscopy, galvanostatic discharge-charge, and cyclic voltammetry were employed to characterize the structure and electrochemical property of the arrays. The array electrodes showed a stable capacity over 310 mAh g⁻¹ after 40 cycles, and good capacity retention as the anodes of lithium-ion batteries. It was believed that the unique dandelion-like binary-structure played an important role in the electrochemical performance of the array electrodes. The present finding opens the possibility to fabricate micro/nanometer hierarchical ZnO films that might be applied in lithium-ion batteries.     

双极膜分离技术及应用进展

双极膜通过对水解离具有的催化效应,能够使水中的盐重新转变为酸和碱,在环境保护和资源回收等领域发挥着越来越大的作用。本文解析了双极膜的“三明治”结构特点、发展历程及发展趋势、制备工艺技术,阐述了双极膜催化水解离机理的3个模型：第二Wien效应模型、化学反应模型以及中和层模型。探究了双极膜电渗析及与其它化工过程耦合技术在不同领域的应用,其中包括酸碱生产领域、资源分离回收领域以及污染控制领域等。分析了双极膜的具体应用过程中存在的局限性并展望了双极膜在水解制氢、液流电池方面的应用前景。指出双极膜将朝着与传统化工过程、新型液流电池等系统集成化、规模化方向发展,成为多种化工应用领域的重要组件。     

四氧化三钴负极材料合成方法研究进展

四氧化三钴作为锂离子电池负极材料已被广泛研究。近年来对四氧化三钴电极材料性能的改进一直是锂离子电池研究领域的热点和前沿之一。综述了四氧化三钴作为锂离子电池负极材料的最新研究进展,从结构和充放电机理、合成方法及复合改性等方面进行了讨论,指出了其作为锂离子电池负极材料的发展趋势。     

Degradation pathway of 2,5-di-tert-butyl-1,4-dimethoxybenzene at high potential

2,5-Di-tert-butyl-1,4-dimethoxybenzene is a redox shuttle for overcharge protection of LiFePO₄-based lithium-ion batteries with a working potential lower than 4.2 V versus Li⁺/Li. However, an irreversible decomposition occurs when the working potential is higher than 4.2 V versus Li⁺/Li. 2,3,5,6-Tetrafluoro-1,4-di-tert-butoxybenzene was also investigated as a model molecule to further understand the possible degradation pathway of 2,5-di-tert-butyl-1,4-dimethxybenzene. The experimental results strongly suggest that the irreversible reaction be related to the decomposition of OC bond in alkoxy substitution groups.     

磷酸铁锂正极材料的制备及性能强化研究进展

橄榄石型磷酸铁锂是目前应用十分广泛的锂离子电池正极材料之一,具有成本低、安全性高、环境友好、循环寿命长和工作电压稳定的特点。近年来,随着CTP技术、刀片电池技术等取得的突破性进展,磷酸铁锂的商业化程度得到了大幅提高。但磷酸铁锂存在电子导电性较差和离子扩散系数低的缺陷,严重限制了锂离子电池的电化学容量,因此开展磷酸铁锂制备工艺和性能强化研究对磷酸铁锂的性能提升具有重要意义。对比了磷酸铁锂电池与其他正极材料锂离子电池的性能差异和发展现状,系统总结了磷酸铁锂正极材料制备与强化的改性方法及相关研究进展与挑战,并提出了未来的发展方向与研究思路。     

Advanced surface and microstructural characterization of natural graphite anodes for lithium ion batteries

Natural graphite powders were subjected to a series of thermal treatments to improve the anode irreversible capacity loss and capacity retention during long-term cycling of lithium-ion batteries. A baseline thermal treatment in inert Ar or N₂ atmosphere was compared to cases with a proprietary additive to the furnace gas. This additive substantially altered the surface chemistry of the uncoated natural graphite powders and resulted in significantly improved long-term cycling performance of the lithium ion batteries over the commercial, carbon-coated natural graphite baseline. Different heat-treatment temperatures were investigated ranging from 950 to 2900 °C to achieve the desired long-term cycling performance with a significantly reduced thermal budget. A detailed summary of the characterization data is also presented, which includes X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and temperature-programmed desorption-mass spectroscopy. Characterization data was correlated to the observed capacity fade improvements over the course of long-term cycling at high charge–discharge rates in full lithium-ion cells. It is believed that the long-term performance improvements are a result of forming a more stable solid electrolyte interface (SEI) layer on the anode graphite surfaces, which is directly related to the surface chemistry modifications imparted by the proprietary gas environment during thermal treatment.     

Nanodispersed iron, tin and antimony in vapour grown carbon fibres for lithium batteries: an EPR and electrochemical study

The use of iron-, tin- and antimony-containing carbon fibres as potential candidates for the negatives electrode of advanced lithium-ion batteries is described. Two different types of fibres are used: non-graphitic and partially graphitized carbon. EPR results show that both carbon and dispersed iron participate in redox processes during the electrochemical reaction with Li. Lithium test cells evidence higher capacities for partially graphitized fibres. The addition of dispersed tin or antimony is used to improve the capacity of the non-graphitic fibres by formation of lithium-tin and lithium-antimony compounds. Reversible capacity values close to 300 mA h g⁻¹ are achieved in both partially graphitized and composite electrodes containing Li-alloying elements. The use of nanodispersed transition metals, i.e. iron, in a carbon matrix is proposed here as an alternative to carbon composites containing Li-alloying elements.