l锂离子电池和电解液ll锂离子电池电解液的组成和设计 锂离子电池电解液的功能和种类l电解液的指标分析和使用l东莞杉杉电解液的技术特色和产品格局Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.锂离子电池电解液基础知识介绍 与 发展中的东莞杉杉1 锂离子电池和电解液电解液在电池中的作用就是锂离子在电极之间的传输媒介，在电池工作过程中，电解 液保证锂离子传输的连续进 行，是电池的重要组成部分。Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.1.1 锂离子电池高的电化学操作窗口需求Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.1.1 锂离子电池长的循环寿命300次1000次Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.1.1 锂离子电池表面化学的典型实例SEIGenerated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.1.2 几个重要的概念（1）Nonaqueous（【化学】非水的）aprotic（非质子）（2）Passivation（钝化）the inert component（惰性组分）（3）The redoxpotential（氧化还原电势 ）electrochemical stability（电化学稳定性）Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.1.3 锂离子电池对电 解液的基本要求（1）要求是离子的良好导体和电子绝缘 体，保证锂 离子迁移和控制自放电； （2）要求有宽电 化学窗口，保证在工作电压 下正极和负极表面电解液不发生分解； （3）良好的热稳 定性，使用温度范围尽可能宽； （4）要求良好的化学稳定性，和隔膜、活性物质、 集流体、包装物不发生化学反应； （5）安全、低毒，对环 境友好；Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.ll锂离子电池中电解液的作用就是Li+从一个电极传输 到另一个电极的传输 媒介。工作过 程中，电解液保证Li+传输 的连续稳 定地进行，是电池的重要组成部分。电解液的主要组成部分如下： 有机溶剂：EC/DMC/DEC/EMC/PC/锂 盐: LiPF6 添 加 剂: VC/BP/ES/PS contaminate：N2/CO2/O2/HF/H2OGenerated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.2 锂离子电池电解液的基本组成和设计（3） 化学稳定性好，不和电池其他部件发生反应； （4）液体范围宽，沸点要高，溶点要低；碳酸酯（5）安全，无毒，经济； 电解质盐 （1）可溶解能力强，容易溶解在溶剂中 （2） 电化学稳定性好 （3） 对电池其他组成化学稳定性好 （4） 无毒，热稳定性好 六氟磷 酸锂Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.2.1 理想的锂离子电池电解液的有机溶剂/电解质的要求有机溶剂： （1）介电常数高，溶解锂盐能力强； （2）流体的粘度低，有利于离子迁移；2.2 电解液中有机溶剂的基本组成环状碳酸酯和链状碳酸酯介电常数要高，粘度低有利于提高离子电导 率矛盾：介电常数高的溶剂极性自然大，因此粘度高热稳 定性好，使用温度宽Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.Ionic conductivity ： Thermal stability：LiAsF6 LiPF6 LiTf LiClO4 LiBF4 LiIm LiAsF6 LiTf LiBF4 LiClO4 LiTf LiPF6Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.2.3 锂电电 解液中的锂盐 性能比较Average ion mobility： LiBF4 LiClO4 LiPF6 LiAsF6 LiTf LiIm Dissociation constant： LiTf LiBF4 LiClO4 LiPF6 LiAsF6 LiIm2.4 锂电电 解液中的各种添加剂一Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.2.4 锂电电 解液中的各种添加剂二Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.粘度.250200150.00 .2.0 040 .600 .8.0100.1.0 20140. 配比D E C / DM C D M C / EM CD E C / EM CP C / D ECP C / E MC M P C / EM CP C / M PC 100050000Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.2.5 电解液的配方设计 ：需要实现对 多孔复合电极的润湿和渗透三元体系粘度曲线图(EC:35%;V:100r/min)lPassivation Phenomena in ElectrochemistryThe kinetics of the simplest solid electrolyte interphase (SEI) electrode should include three stages: charge transfer across the solution-film interface, ion migration through the surface films, and charge transfer in the film-metal interface. It is reasonable to assume that the ion migration is the rate- determining step.SEIELECTRODEGenerated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.2.5 电解液的配方设计 ：SEI膜的稳定性控制l lll溶点和沸点的问题 SEI的高温稳定性问题 和低温传导 能力 锂盐 的稳定性控制 低温条件下的粘度的问题Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.2.5 电解液的配方设计 ：电解液的高低温性能的控制lllllEthers（醚） These include diethyl ether; members of the glyme family, namely,polyethers of the type (e.g., dimethoxyethene for n=l), cyclic ethers such as tetrahydrofuran (THF) and 2- methyl tetrahydrofuran; and cyclic acetals such as 1-3 dioxolane. Esters（酯） These include methyl formate, methyl and ethyl acetate, and GBL Alkyl carbonates These include cyclic compounds such as butylene, propylene, and ethylene carbonates (BC, PC, EC), and linear compounds such as dimethyl, diethyl carbonates, ethyl-methyl carbonate, etc. (DMC, DEC, EMC). Inorganic Solvents The most common inorganic solvents used in batteries were (thionylchloride), and (sulfuryl chloride). The former solvent was used in both secondary and primary Li battery systems, while the latter could only be used in primary Li batteries 34. Miscellaneous Solvents such as acetonitrile, nitromethane, N,N-dimethyl formamide, dimethyl sulfoxide, sulfolane, and methyl chloride are also often used in nonaqueous electrochemical studies.Generated by Foxit PDF Creator Foxit Software http:/www.foxitsoftware.com For evaluation only.2.5 电解液的配方设计 ：电化学窗口问题 （3.64.2V）The nonaqueous solvents that are commonly used in electrochemistrycan be classified as follows 33:2.5 电解液的配方设计 ：电化学窗口问题 和纯度和杂质 有关Generated by Foxit PD