1、The Current Status and Development ofElectrolyte Additives For Lithium IonBatteriesOutlineResearch background12Adjusting solution structureFluoranated additivesS-based electrolyte additivesConclusion3451.Background2017国内锂离子电池电解液市场近200亿元，添加剂市场超15亿元电动汽车的发展将带动锂离子迅速发展和电解液技术的巨大进步,更多新型配方和添加剂投入实际应用高电压、高能量密
2、度锂离子电池、功率型电池、高低温电池、高安全电池等The importance of battery electrolyte纵观电池的发展历史，电解液的革新对电池科学发展的贡献绝不亚于任何一种电极材料，例如锌锰电池自诞生以来经历了三次革命，其中两次革命源于电解液组成的变化，分别是从第二代NH Cl为主的电解液到第三代的4ZnCl 为主的电解液，再到第四代的KOH溶2液为主的碱锰电池，由于电解液组成的变化，电池的反应机理和成流机制也发生了明显的变化。Zn+2MnO+2NH Cl 2MnOOH+Zn(NH)Cl2243 24Zn+8MnO+9H O+ZnCl 8MnOOH+ZnCl 4ZnO5H
3、O22222KOHZn+2MnO+2H O 2MnOOH+Zn(OH)222The development andrevolution of LIB electrolyte 类似地，锂离子电池的电解液技术也已经经历了3次变革，电解质的多样性也为锂离子电池多样化做出了实质性的贡献，人们常根据电解质的类型把锂离子电池分为液体锂离子电池、聚合物锂离子电池和全固态锂离子电池，并用以满足不同的生产和生活实践。当然，由于液体电解质特殊的优势，在未来相当长的一个时期，液体锂离子电池仍将主导锂离子电池市场。PC+DME PC+DMCPC+DECEC+DMC EC+DMC functionalEC+DEC EC
4、+EMC additiveslithiumbatterybased on based on COKEanode)Li metallithium ion battery(1st generationlithium ion battery(2nd generationwith graphiteanode)当然，由于液体电解质特殊的优势，在未来相当长的一个时期，液体锂离子电池仍将主导锂离子电池市场。Confifential MaterialsThe role of electrolytes in lithium ion batteriesElectrolyte is the bridge conne
5、cting cathode and anode,the media for Li transportation,the place where sidereaction occursl Cycle lifel Safetyl Operating temperaturel Shelf lifel Rate capabilityl Reversible capacityl Self-discharge properties1.BackgroundObjective for electrolyte development Performance,calendar-life,and safety ch
6、aracteristics ofLi-ion cells are dictated by the nature and stability ofthe electrolyte and the electrode-electrolyte interfaces.The goal is to develop novel electrolytes with the followingcharacteristics:Wide electrochemical stability window,0 to 5 V Wide temperature stability range,-30 to+80 C Non
7、-reactivity with other cell components Excellent ionic conductivity to enable rapid ion transport Stability for over 5000 deep-discharge cycles Stability over the 10yrs battery life1.BackgroundElectrolyte additives play a crucial role for organicelectrolyte systems1 Adjusting solution structureThe l
8、ine on the right of the negative charges represents the innerHelmholtz plane(IHP).The dashed lines depicts the outerHelmholtz plane(OHP)and the dotted line illustrates the plane ofelectrokinetic charge,or the shear plane(SP).阴离子竞争性溶剂化改变溶剂化结构pure PC solventLiTFSI/PCLiTFSI/PC:NMA(2.5:1)EC:PC(1:1)EC:PC
9、(1:1)+NMA(5%)2.01.61.20.80.40.080006000400020000Li+-PC interactionelectrolyte decomposition7607407207006800100200300400500600700-1Specific capacity/mAh gWave number/cm-13210PC:NMA(2.5:1)DMC:NMA(1:1)PC1000200030004000Wave number/cm-1阳离子竞争性溶剂化对电解液性能的调控Li ionPC moleculecompetation ion1.301.251.201.151.
10、101.051.000.950.900.850.800.752.01.51.00.50.0ionic liquidregulation0.054006008001000 1200 1400 1600 1800 20000100200300400500600Wave Number/cm-1Capacity/(mAh/g)电解液中纳米团簇结构取向和溶剂化数调整AB2.Fluoranated additives fluoro solvents is less flammable Solvent with a F to H ratio 4 appears to have improvedthermal
11、 properties.In the wick test the electrolytecontaining the fluoro solvent didnt catch fire.Fluoro solvents in conjunction with cycliccarbonates should exhibit improved thermalproperties Low temperature performance may suffer Fluoro-EC may be an alternative Fluoro ether:is used as co-solvent to impro
12、ve oxidationpotential in Hatachi.氟代碳酸酯类添加剂的成膜与钝化该添加剂对负极表面膜结构和性能的影响(a)(b)(d)(f)(c)(e)添加剂在整体电池中的作用,发展具有同时优化正极和负极表面的新型添加剂对电池产业的发展具有特别重要的意义,特别是发展高低温电池和长寿命电池非常重要.3.S-based electrolyte additives环状磺酸酯系列OOOOOOS别名：DTD PCS PEGLSTTSSOO外观：白色固体（部分为液体）含量：99.5%（GC）水分：200PPMOOOOOSSOOO已经成为当前成膜添加剂的主流，特别在三元和磷酸铁锂电池中具有重
13、要的意义Honghe Zheng et.al.For example Control electrolyte：EC/DMC/EMC(1:1:1)1.0M LiPF6EC/FEC/DMC/EMC(1:1:3:1)1.0/1.2M LiPF6 Additives：FEC 5%+VC 5%DTD 1%+MMDS 1%PC 5%LiODFB 5%LiTFSI 5%DTD 1%TFPC 5%BS 1%LiBOB1%+MMDS1%LiPOF21%+DTD1%PST 1%DTD 1%+LiTFSI 5%DTD 1%+LiDOFB 5%VC5%+DTD1%+LiTFSI5%BS 1%+LiDOFB 5%PST
14、 1%+LiDOFB 5%Traditional additive combined with different sulfonate additives includingBS,PST,DTD,MMDS etc.Honghe Zheng et.al.140120100801131-1.01.0-LiODFB5%1.0-LiTFSI5%1.0-DTD1%1.0-BS1%601.0-PST1%401.0-DTD1%-LiTFSI5%1.0-DTD1%-LiODFB5%1.0-BS1%-LiODFB5%1.0-PST1%-LiODFB5%1.0-VC5%-DTD1%-LiTFSI5%2000501
15、00Cycle Number150200Honghe Zheng et.al.140120100801131-1.21.2-LiODFB5%1.2-LiTFSI5%1.2-DTD1%1.2-BS1%1.2-PST1%601.2-DTD1%-LiTFSI5%1.2-DTD1%-LiODFB5%1.2-BS1%-LiODFB5%1.2-PST1%-LiODFB5%1.2-VC5%-DTD1%-LiTFSI5%40200050100150200Cycle Number4.Si based electrolyte additive这是一类新的系统，具有新型官能团的硅烷添加剂，在改善硅负极性能方面取得了
16、一些进展硅烷添加剂用于硅负极的研究OSiSiO样品 C-CD-CFE SE0123453116.4 410076.0 94.3012037.9 271475.0 93.9483140.7 3996.4 78.5 95.0393192.1 4061.7 78.5 9592805.7 369375.9 93.8372048.6 2802.8 73.0 94.519硅烷添加剂用于硅负极的研究OSiOSi引入双键希望增强电极表面的成膜性质稳定硅表面硅烷添加剂用于硅负极的研究SamplesD-CC-CF-ES-ES003S0031%2131.51974.229702798.42634.33812.376
17、.1774.9477.994.0492.7396.812%3%4%3212.73204.53752.640754033.6467478.8479.4480.2894.8695.5594.655%2435309979.5494.47硅烷添加剂用于硅负极的研究0%1%2%首效：91.71%二次：96.65%首效：90.19%二次：95.93%首效：91.03%二次：95.76%引入氟希望增强电极表面的成膜性质3%首效：89.80%二次：96.32%4%首效：89.94%二次：95.47%5%首效：89.34%二次：96.22%稳定硅表面硅烷添加剂用于硅负极的研究首次放电 首次充电比容量 比容量（m
18、Ah/g）（mAh/g）首次效率（%）效率（%）第二圈添加剂体积比%电池电池1电池2电池1电池2电池1电池2电池1电池2电池1电池2电池1电池23128.22741.63135.31626.53477.03817.62806.52806.53427.13408.33696.1981.42918.52486.72827.71417.63165.33458.52520.22520.23082.33068.93302.1787.391.7190.7090.1987.1591.0390.5989.8086.7589.9490.0489.3480.2396.6596.2195.9395.2295.769
19、6.0096.3294.7395.4795.8996.2291.560%1%2%3%4%5%这类添加剂在效率和容量方面也没有表现出明显的优势硅电极的长期循环性能有一定提升，但提升效果不显著硅烷添加剂用于硅负极的研究不同浓度首次放电 首次充电 首次效率四氟硅烷基添加剂比容量3318.81974.32653.43166.12051.52445.5比容量2745.61563.92141.32521.11596.81865.2（%）82.7379.2180.7079.6377.8476.270%1%2%3%4%5%硅烷氟代以后不能显著改善硅基负极的性能导致首次效率和可逆容量的下降，循环性能也没有明显改
20、善磺酸酯类添加剂用于硅负极的研究不同电解液添加剂对硅负极性能的影响电解液添加剂的选择对硅负极具有特别重要的意义2019-4-2828磺酸酯类添加剂用于硅负极的研究电解液添加剂对硅碳复合电极的影响.结果非常令人乐观2019-4-28294.4 磷基添加剂5.Conclusions Novel electrolytes need to be developed to meet the cost,calendar life and safety requirements of batteries for EVand HEVapplications.There are a lot of fundamental issues for the etrolytesystems in lithium ion cells.Electrolyte optimization need to be combined with celltechnologies All-solid cells still have a long way to go and thetransition stage is the advanced gel electrolyte
