郑洪河-杭州电解液报告.pdf-solarbe文库

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Innovation for Application , Progress with integrity The Current Status and Development of Electrolyte Additives For Lithium Ion Batteries 郑洪河苏州大学能源学院School of Energy, Soochow University, China第九届国际储能大会交流报告 1234 Research background Adjusting solution structureFluoranated additivesS-based electrolyte additives5 ConclusionOutline 2017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、高能量密度锂离子电池、功率型电池、高低温电池、高安全电池等 1. Background 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 NH4Cl为主的电解液到第三代的ZnCl2为主的电解液，再到第四代的 KOH溶液为主的碱锰电池，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。 KOH The importance of battery electrolyteZn2MnO 2 2NH4Cl  2MnOOH ZnNH32Cl2 4Zn8MnO2 9H2OZnCl2 8MnOOHZnCl2·4ZnO·5H2OZn2MnO22H2O 2MnOOHZnOH2 The development and revolution 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。PCDME PCDMCPCDEC ECDMCECDEC ECDMCECEMC functional additiveslithium battery based on Li metal lithium ion battery 1st generationbased on COKE anode lithium ion battery 2nd generationwith graphite anode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。 The role of electrolytes in lithium ion batteries l Reversible capacityl Rate capabilityl Operating temperaturel Safety l Shelf life l Self-discharge propertiesl Cycle lifeElectrolyte is the bridge connecting cathode and anode, the media for Li transportation, the place where side reaction occurs Confifential Materials Performance, calendar-life, and safety characteristics of Li-ion cells are dictated by the nature and stability of the electrolyte and the electrode-electrolyte interfaces. The goal is to develop novel electrolytes with the following characteristics– Wide electrochemical stability window, 0 to 5 V– Wide temperature stability range, -30 to 80 °C– Non-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 lifeObjective for electrolyte development1. Background Electrolyte additives play a crucial role for organic electrolyte systems1. Background 1 Adjusting solution structureThe line on the right of the negative charges represents the inner Helmholtz plane IHP. The dashed lines depicts the outer Helmholtz plane OHP and the dotted line illustrates the plane of electrokinetic charge, or the shear plane SP. 阴离子竞争性溶剂化改变溶剂化结构 760 740 720 700 680020004000 60008000 Intensity pure PC solvent LiTFSI/PC LiTFSI/PCNMA2.51 Wave number/cm-1 Li-PC interaction 1000 2000 3000 400001 23Absorptivity Wave number/cm-1 PCNMA 2.51 DMCNMA11 PC 0 100 200 300 400 500 600 7000.0 0.40.81.21.6 2.0Potential/V Specific capacity/mAh g-1 ECPC11 ECPC11NMA5 electrolyte decomposition 阳离子竞争性溶剂化对电解液性能的调控 Li ion PC molecule competation ion 0 100 200 300 400 500 6000.00.5 1.01.52.0Voltage/ V Capacity/ mAh/g ionic liquidregulation 400 600 800 1000 1200 1400 1600 1800 20000.750.800.850.900.951.00 1.051.101.151.201.251.30Intensity Wave Number/ cm-1 0.05 电解液中纳米团簇结构取向和溶剂化数调整A B 2. Fluoranated additives fluoro solvents is less flammable– Solvent with a F to H ratio 4 appears to have improved thermal properties. In the wick test the electrolyte containing the fluoro solvent didn’t catch fire. Fluoro solvents in conjunction with cyclic carbonates should exhibit improved thermal properties– Low temperature performance may suffer Fluoro-EC may be an alternative Fluoro ether is used as co-solvent to improve oxidation potential in Hatachi. 氟代碳酸酯类添加剂的成膜与钝化 a bc d e f 该添加剂对负极表面膜结构和性能的影响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. SO O O O SO O O O SO O O O O OS O O 环状磺酸酯系列别名DTD PCS PEGLST TS外观白色固体（部分为液体）含量≥99.5（GC）水分≤200PPM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要的意义3. S-based electrolyte additives For example Control electrolyteEC/DMC/EMC111 1.0M LiPF6 EC/FEC/DMC/EMC1131 1.0/1.2M LiPF6 Additives FEC 5 VC 5 LiODFB 5 DTD 1 MMDS 1 LiTFSI 5 PC 5 DTD 1 TFPC 5 BS 1 LiBOB1MMDS1 PST 1 LiPOF 21DTD1 DTD 1LiTFSI 5 DTD 1LiDOFB 5 VC5DTD1LiTFSI5 BS 1LiDOFB 5 PST 1LiDOFB 5 Honghe Zheng et. al. Traditional additive combined with different sulfonate additives including BS, PST, DTD, MMDS etc. 0 50 100 150 200020 406080 100120140 Specific Ca pacity mA h/g Cycle Number 1131-1.0 1.0-LiODFB5 1.0-LiTFSI5 1.0-DTD1 1.0-BS1 1.0-PST1 1.0-DTD1-LiTFSI5 1.0-DTD1-LiODFB5 1.0-BS1-LiODFB5 1.0-PST1-LiODFB5 1.0-VC5-DTD1-LiTFSI5 PST and BS play a excellent role extending the cycle life Honghe Zheng et. al. 0 50 100 150 200020 406080 100120 140 Specific Ca pacity mA h/g Cycle Number 1131-1.2 1.2-LiODFB5 1.2-LiTFSI5 1.2-DTD1 1.2-BS1 1.2-PST1 1.2-DTD1-LiTFSI5 1.2-DTD1-LiODFB5 1.2-BS1-LiODFB5 1.2-PST1-LiODFB5 1.2-VC5-DTD1-LiTFSI5 PST and BS play a excellent role extending the cycle life Honghe Zheng et. al. 4. 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一些进展 O SiSi O样品C-C D-C FE SE0 3116.4 4100 76.01 94.301 2037.9 2714 75.08 93.942 3140.7 3996.4 78.59 95.033 3192.1 4061.7 78.59 954 2805.7 3693 75.97 93.83 5 2048.6 2802.8 73.09 94.51 硅烷添加剂用于硅负极的研究 Si O O Si 硅烷添加剂用于硅负极的研究引入双键希望增强电极表面的成膜性质稳定硅表面 Samples D-C C-C F-E S-ES003 2131.5 2798.4 76.17 94.04S003 1974.2 2634.3 74.94 92.731 2970 3812.3 77.9 96.812 3212.7 4075 78.84 94.863 3204.5 4033.6 79.44 95.554 3752.6 4674 80.28 94.655 2435 3099 79.54 94.47硅烷添加剂用于硅负极的研究 1 23 4 50首效91.71二次96.65首效90.19二次95.93首效91.03二次95.76首效89.80二次96.32首效89.94二次95.47首效89.34二次96.22硅烷添加剂用于硅负极的研究引入氟希望增强电极表面的成膜性质稳定硅表面添加剂体积比电池首次放电比容量（mAh/g）首次充电比容量（mAh/g）首次效率（）第二圈效率（）0电池1 3128.2 2918.5 91.71 96.65电池2 2741.6 2486.7 90.70 96.211电池1 3135.3 2827.7 90.19 95.93电池2 1626.5 1417.6 87.15 95.222电池1 3477.0 3165.3 91.03 95.76电池2 3817.6 3458.5 90.59 96.003电池1 2806.5 2520.2 89.80 96.32电池2 2806.5 2520.2 86.75 94.734电池1 3427.1 3082.3 89.94 95.47电池2 3408.3 3068.9 90.04 95.89 5电池1 3696.1 3302.1 89.34 96.22电池2 981.4 787.3 80.23 91.56 硅烷添加剂用于硅负极的研究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，但提升效果不显著四氟硅烷基添加剂不同浓度首次放电比容量首次充电比容量首次效率（）0 3318.8 2745.6 82.731 1974.3 1563.9 79.212 2653.4 2141.3 80.703 3166.1 2521.1 79.634 2051.5 1596.8 77.845 2445.5 1865.2 76.27硅烷添加剂用于硅负极的研究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善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 2019-4-28 28 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 2019-4-28 29 磺酸酯类添加剂用于硅负极的研究 4.4 磷基添加剂