聚偏氟乙烯—六氟丙烯高分子隔膜的制备及其在锂离子电池中的应用

通过非溶剂致相分离工艺制备聚偏氟乙烯—六氟丙烯高分子隔膜,以磷酸铁锂为正极,金属锂为负极,组装锂离子电池.通过制备不同厚度的隔膜,组装出锂离子电池并进行性能测试,对聚偏氟乙烯—六氟丙烯隔膜进行结构和性能优化.经过结构和性能参数对比,得到适用于锂离子电池聚偏氟乙烯—六氟丙烯隔膜的最佳厚度.     

锂离子电池简介

锂离子二次电池于20世纪90年代初由日本SONY公司率先研制成功并实现商品化。所谓锂离子电池是指分别用两个能可逆地嵌入和脱嵌锂离子的化合物作为正负极构成的二次电池。电池在充电时,Li 从正极中脱出,通过电解液和隔膜,嵌入到负极中。反之,电池放电时,Li 由负极中脱嵌,通过电解液和隔膜,重新嵌入到正极中。由于Li 在正负极中有相对固定的空间和位置,因此电池充放电反应的可逆性很好,从而保证了电池的长循环寿命和工作的安全性。锂离子电池具有以下特点:(1)工作电压高。锂离子电池的电压一般在3·6V,是镍镉、镍氢电池工作电压的3倍。(2)…     

锂镍钴锰氧正极材料的热聚合法制备及性能表征①

锂电池发展受锂离子电池正极材料制约,这是因为正极材料与负极材料相比,其功率密度及能量密度均低于负极材料,进而引发钽电池安全隐患。目前在商业锂离子电池中,LiC002正极材料应用最为广泛,具有循环性能好的优点,但由于热稳定性差。且聚毒性特征,难以得到进一步应用。该文拟采用热聚合法合成锂镍钴锰氧材料（LiNi1/3Co1/3Mn1/2O2）,对其制备及表征性能进行研究,以求寻得高能量,高密度、低污染的电极材料。     

氯代磷酸酯作为锂离子电池电解液阻燃添加剂的性能研究

为了提高锂离子电池电解液的热稳定性,使用氯代磷酸酯磷酸三（1-氯2-丙基）酯TCPP和磷酸三（2-氯乙基）酯TCEP作为锂离子电池电解液阻燃添加剂,研究其对锂离子电池电解液热稳定性和电化学性能的影响．循环性能测试、循环伏安法、交流阻抗等电化学分析表明：TCEP和TCPP与正极材料LiNi0.8Co0.2O2有很好的相容性,有良好的电化学稳定性;而对负极石墨材料则有一定的剥离现象发生．微量量热实验表明TCEP和TCPP的加入能提高电解液的热稳定性．     

锂离子电池材料探析

锂离子电池是高效的能量转化和存储设备。锂离子电池材料对其性能有着直接的影响。现阶段,锂离子电池的正极材料主要有层状的钴酸锂（LiCoO2）,氧化镍锂（LiNiO2）,锰酸锂（LiMnO2）和磷酸铁钽（LiFePO4）等;负极材料主要有各种碳材料与一些非碳负极材料,如硅和钛酸锂（Li4Ti5O12）;电解液主要为非水系电解液;隔膜主要为聚烯烃隔膜。锂离子电池不同构成部分的材料,有着一定的发展．应用历程,对其进行探完,具有广泛的应用前景。     

锂离子电池用LiPF_6/PC+FEC电解液的低温性能

研究氟代碳酸乙烯酯(fluoroethylene carbonate,FEC)添加剂对锂离子电池用碳酸丙烯酯(PC)基电解液低温放电性能和常温循环性能的影响,并通过电化学阻抗谱(EIS)、X线光电子能谱(XPS)以及气质联用谱(GC-MS)等对FEC在PC基电解液中的作用机理进行探讨。研究结果表明:往PC电解液中添加质量分数为5%的FEC可以在石墨电极表面形成完整且致密的SEI膜,从而有效阻止PC在负极石墨的共嵌入;电池在低温-20℃及-40℃下0.5C放电容量分别可达到室温容量的98%及87%;FEC形成的SEI膜有效降低了锂离子电池的低温电荷转移阻抗,是提高电池低温性能的主要因素之一;FEC在正极钴酸锂材料表面形成了导电性能优异的SEI膜层,改善了锂离子电池的低温性能和常温循环性能。     

正极自支撑的聚合物电解质的制备

以N,N-二甲基甲酰胺为溶剂,聚偏氟乙烯-六氟丙烯为聚合物基质,采用直接挥发溶剂法制备正极自支撑的聚合物电解质,并以锂为负极制备LiCoO2聚合物电池.用扫描电子显微镜和循环伏安实验对聚合物电解质进行表征,用红外光谱分析了电解质微孔的形成机理,并对聚合物电池的充放电性能和界面阻抗进行测试。结果表明:直接挥发溶剂制得的聚合物电解质孔穴丰富,电化学稳定窗口达5.5 V.采用正极自支撑电解质可改善材料的力学性能,降低电池的界面阻抗;制备的聚合物电池界面性质稳定,循环40次后容量保持率为97.5%,0.5C和1C倍率放电分别能保持0.1C放电容量的97.8%和95.7%.     

钛酸锂作负极锂离子电池体系研究

研究了以Li4Ti5O12为负极,分别以LiCo0.5Ni0.5Mn0.5O2,LiMn2O4或LiFePO4为正极的锂电池体系. 先筛选不同厂家的正负极材料,然后再匹配成电池做循环性能研究. 测试表明,经筛选的LiCo0.5Ni0.5Mn0.5O2,LiMn2O4与LiFePO4三种材料分别与Li4Ti5O12组成电池的初始容量分别为963、931、960 mAh;500次充放电循环后容量保持率分别为96.56%、87.69%、98.1%. 其中LiCo0.5Ni0.5Mn0.5O2体系的初始容量最高,LiFePO4体系的循环性能最好. 3种不同正极材料的钛酸锂锂离子电池在85 ℃环境下搁置4 h,电池形变少于5%.     

2-噻吩甲腈在高电压锂离子电池中的应用

为了改善锂离子电池在高电压下的电化学性能,以2-噻吩甲腈作为一种新型的电解液添加剂,采用线性扫描伏安法(LSV)研究其对1 mol/L Li PF6/EC+EMC(EC与EMC质量分数之比为1:2)电解液电化学窗口的影响。通过扫描电镜(SEM)、X线光电子能谱(XPS)、傅里叶红外光谱(IR)、充放电测试、循环伏安(CV)和交流阻抗(EIS)对含不同电解液的锂离子电池循环前后的正极材料表面及其电化学性能进行表征。研究结果表明:2-噻吩甲腈能优先于电解液溶剂发生氧化分解反应并在正极表面形成致密的导电聚合物膜;添加质量分数为0.1%2-噻吩甲腈的钴酸锂电池在3.0~4.5 V以0.5 C倍率循环100次后容量保持率高达91.99%,在5C倍率下放电比容量为152.8m A·h·g-1;与电解液中未添加2-噻吩甲腈的电池相比,其循环后电荷转移阻抗的增加被抑制,在高电压下表现出较好的循环和倍率性能。     

导电剂对锂离子电池负极材料钛酸锂电化学性能的影响

研究了乙炔黑、碳纤维和两者的混合物这3种导电剂及用量对锂离子电池负极材料钛酸锂大电流充放电性能的影响.结果表明:导电剂的种类对电极的电化学性能影响较大.粒状乙炔黑表面积丰富但不利于导电网络的形成,电极的极化严重;线性导电剂碳纤维具有较好的导电性和较高的长径比,但与活性物质接触面积小;线性导电剂碳纤维与粒状导电剂乙炔黑相配合,在电极中不但能够形成良好的导电网络,还与活性物质具有较大接触面积,减轻了电极的极化,提高了锂离子二次电池的大电流充放电性能.     

导电填料对聚偏氟乙烯导电胶性能的影响

采用涂膜法制备了以碳纳米管(CNTS)、乙炔黑和石墨粉为导电填料的导电胶,研究了它们的电学性能、力学性能和粘结性能.结果显示,聚偏氟乙烯(PVDF)/CNTS导电胶有较好的综合性能.     

Composite cathode and anode films for rechargeable lithium batteries

Recently the rechargeable Li and Li-ion polymer batteries have improved due to development of Li-ion conductive gel electrolytes and of high energe granting intercalation compounds. In our laboratory the composite cathodic film, the composite carbon anode film and PVC-based electralyte film were successfully prepared by casting procedures. Cycling experiments of the cells with Li or composite carbon anode in contact with PVC-based electrolyte and composite cathode were performed. Relatively good performance of the cell with Li anode, the composite cathode and LiPF₆-EC-DEC electrolyte was achieved in that over 50 cycles were possible with minimal capacity loss upon cycling. The same cell with PVC-based electrolyte was cycled over 20 cycles. Replacing Li anode by composite carbon anode, the cell behaved like the latter. It is found that appropriate amount of carbon content is helpful to improving specific capacity.     

Double carbon decorated lithium titanate as anode material with high rate performance for lithium-ion batteries

Spinel lithium titanate(Li_4Ti_5O_(12)) has the advantages of structural stability, however it suffers the disadvantages of low lithium-ion diffusion coefficient as well as low conductivity. In order to solve issues,we reported a simple method to prepare carbon-coated Li_4Ti_5O_(12)/CNTs(C@Li_4Ti_5O_(12)/CNTs) using stearic acid as surfactant and carbon source to prepare carbon coated nanosized particles. The obtained Li_4Ti_5O_(12) particles of 100 nm in size are coated with the carbon layers pyrolyzed from stearic acid and dispersed in CNTs matrix homogeneously. These results show that the synthesized C@Li_4Ti_5O_(12)/CNTs material used as anode materials for lithium ion batteries, presenting a better high-rate performance(147 m Ahg~(-1)at20 C). The key factors affecting the high-rate properties of the C@Li_4Ti_5O_(12)/CNTs composite may be related to the synergistic effects of the CNTs matrix and the carbon- coating layers with conductivity enhancement. Additionally, the amorphous carbon coating is an effective route to ameliorate the rate capability of Li_4Ti_5O_(12)/CNTs.     

全固态薄膜锂离子二次电池的研究进展

本文综述了全固态薄膜锂离子二次电池的研究进展,主要阐述了薄膜锂电池的结构设计以及正极、负极和固体电解质材料研究现状,并对其今后的发展趋势及研发热点进行了展望。     

Synthesis of urchin-like Sn–ZnO–C composite and its enhanced electrochemical performance for lithium-ion batteries

Urchin-like Sn–ZnO–C composite have been successfully prepared by thermal annealing of ZnSn(OH)6precursor in acetylene/argon gas(1/9;v/v).The phase of the urchin-like Sn–ZnO–C has been characterized by X-ray diffraction(XRD)and Raman spectrum.The images of scanning electron microscopy(SEM)and transmission electron microscope(TEM)demonstrate that the Sn–ZnO–C composite with an average of 3 lm in diameter is composed of many core–shell nanowires and carbon nanotubes emanated from the center.The thermal annealing temperature and time have crucial effects on the formation of urchin-like structure and carbon content of the Sn–ZnO–C composites.As an anode for lithium-ion batteries,the urchin-like Sn–ZnO–C composite delivers a discharge capacity of 1,034.5 mAh/g in initial cycle and 571.9 mAh/g reversible discharge capacity after 25 cycles at a current density of 50 mA/g.The superior energy storage properties highlight the urchin-like Sn–ZnO–C composite as a potential alternative anode material in lithium-ion batteries.     

Application prospects of high-voltage cathode materials in all-solid-state lithium-ion batteries

All-solid-state lithium-ion batteries are lithiumion batteries with solid-state electrolytes instead of liquid electrolytes.They are hopeful in solving the safety problems of lithium-ion batteries,once their large capacity and long life are achieved,they will have broad application prospects in the field of electric vehicles and large-scale energy storage.The working potential window of solid electrolytes is wider than that of liquid electrolytes,so high-voltage cathode materials could be used in all-solidstate lithium-ion batteries to get higher energy density and larger capacity by elevating the working voltage of the batteries.The spinel LiNi0.5Mn1.5O4material,layered Li–Ni–Co–Mn–O cathode materials and lithium-rich cathode materials can be expected to be applied to all-solid-state lithium-ion batteries as cathode materials due to their highvoltage platforms.In this review,the electrochemical properties and structures of spinel LiNi0.5Mn1.5O4material,layered Li–Ni–Co–Mn–O cathode materials and lithiumrich cathode materials are introduced.More attentions are paid on recent research progress of conductivity and interface stability of these materials,in order to improve their compatibility with solid electrolytes as cathode materials in all-solid-state lithium-ion batteries and fully improve the properties of all-solid-state batteries.Finally,the existing problems of their application in all-solid-state lithium-ion batteries are summarized,the main research directions are put forward and their application prospects in all-solid-state lithium-ion batteries are discussed.     

锂离子电池热失控研究综述与文献计量分析

近年来,随着电动汽车行业的大力发展,锂离子电池作为电动交通工具储存和转化电能的重要载体大量涌入市场,但在使用过程中存在过充放电、局部过热以及外部挤压碰撞等滥用情况,可能会导致其性能下降,甚至引发热失控等安全问题。为此,对当前中外锂离子电池热失控的研究进展进行了综述总结,并通过VOSviewer可视化软件对发文量、期刊分布和关键词等进行分析。结果表明:当前锂离子电池的热失控是限制其发展的关键因素,目前主要从电池正极材料改性、电解液中添加阻燃剂、电池热管理设计三方面来提升锂离子电池的安全性。     

Recovery and regeneration of LiFePO4 from spent lithium-ion batteries via a novel pretreatment process

The recycling of spent LiFePO4 batteries has received extensive attention due to its environmental impact and economic benefit. In the pretreatment process of spent LiFePO4 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, LiFePO4 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 FePO4 and Li2CO3. Finally, the battery-grade FePO4 and Li2CO3 were used to re-synthesize LiFePO4/C via the carbon thermal reduction method. The discharge capacities of re-synthesized LiFePO4/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 LiFePO4 batteries. The whole process is environmental and has great potential for industrial-scale recycling of spent lithium-ion batteries.     

磷酸铁锂正极材料的研究现状

磷酸铁锂正极材料具有比容量大、安全性高、性价比高以及循环寿命长等优点,被认为是最具应用前景的锂离子电池正极材料之一。论述了橄榄石型磷酸铁锂的晶体结构特征以及充放电反应机制,综述了近年来采用葡萄糖、活性碳和石墨烯等不同的碳源进行碳包覆, 硫离子、镁离子、镍离子、氟离子、钒离子、钠离子和银离子等不同金属离子和非金属离子进行离子掺杂以及蒸发诱导自组装法、碳热还原法和喷雾干燥法等不同合成方法进行材料纳米化等改性方式对锂离子电池磷酸铁锂正极材料的影响。最后简要分析了目前改性方法仍存在的问题,并对其前景进行了展望。     

碳纳米管作导电剂对LiFePO4锂离子电池性能的影响

考察添加碳纳米管作导电剂对LiFePO4锂离子电池性能的影响.采用液态锂离子电池工艺制备063048型LiFePO4锂离子电池,利用XRD,SEM及充放电方法对电池电极的结构、表面形貌和电化学性能进行表征和测试.研究结果表明:添加碳纳米管作导电剂的极片压实密度与未添加的相比提高了5%,同时也形成了良好的导电网络,电池内阻较小,电池首次放电容量达到131.8 mA·h/g,而未添加碳纳米管的首次放电容量为124.6 mA.h/g;添加碳纳米管作导电剂电池的循环性能较好,120次循环后容量几乎没有衰减,而未添加碳纳米管的电池经120次循环后容量保持率为94.1%.添加碳纳米管作导电剂电池的倍率性能优异,其6C的放电容量是0.5C的81.8%(其中,C为电流倍率),未添加碳纳米管的电池6C的放电容量是0.5C的75%.添加碳纳米管作导电剂的电池,电极界面阻抗比未添加碳纳米管的电池的界面阻抗小.