Effect of Fluorinated Linear Carbonate on the Performance of High-voltage LiNi0.5Co0.2Mn0.3O2/Artificial Graphite Pouch Cells
HU Shiguang1,2, GUO Pengkai2, QIAN Yunxian2, ZHANG Guangzhao3, WANG Jun3, DENG Yonghong3,*, WANG Chaoyang1,*
1 Research Institute of Materials Science, South China University of Technology, Guangzhou 510640, China 2 Shenzhen Capchem Technology Co., Ltd., Shenzhen 518118, Guangdong, China 3 Department of Materials Science and Engineering, School of Innovation and Entrepreneurship, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China
摘要 LiNi0.5Co0.2Mn0.3O2正极材料因能量密度高、循环稳定性好及安全性高而被认为是最有前途的高能量密度锂离子电池正极材料之一。然而,传统的常规碳酸酯基电解液的耐氧化性较差,导致LiNi0.5Co0.2Mn0.3O2正极材料在高电压条件下的容量快速衰减。在氟代碳酸乙烯酯(FEC)的基础上,研究了氟代线性碳酸酯(如二(2,2,2-三氟乙基)碳酸酯(TFEC)及甲基(2,2,2-三氟乙基)碳酸酯(MTFEC))替代碳酸二乙酯(DEC)在高电压下的循环稳定性。电化学测试结果表明,TFEC、MTFEC替代DEC后,4.5 V LiNi0.5Co0.2Mn0.3O2/人造石墨软包电池45 ℃循环700圈后容量保持率分别从45.5%提高到72.5%、81.6%。线性扫描伏安法(LSV)、扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、拉曼光谱(Raman)及电感耦合等离子原子发射光谱(ICP-OES)研究表明,与DEC相比,TFEC及MTFEC具有更优异的高电压耐氧化性,能够明显抑制电解液在高电压正极表面的氧化分解,有效保护正负极材料界面稳定性及抑制正极材料过渡金属离子溶出对负极固体电解质界面(SEI)膜的破坏。氟代线性碳酸酯作为电解液溶剂在高电压锂离子电池领域具有广阔的应用前景。
Abstract: LiNi0.5Co0.2Mn0.3O2 cathode material is considered as one of the most promising cathode materials for high energy density lithium ion battery due to its high energy density, good cycling stability and high safety. However, LiNi0.5Co0.2Mn0.3O2 cathode material suffers from rapid capacity decay under high-voltage conditions due to the poor oxidation resistance of conventional carbonate-based electrolytes. Based on fluoroethylene carbonate (FEC), the cycle stability of fluorinated linear carbonates such as bis(2,2,2-trifluoroethyl) carbonate (TFEC) and methyl (2,2,2-trifluoroethyl) carbonate (MTFEC) replacing diethyl carbonate (DEC) were studied under high voltage. Electrochemical test results showed that the capacity retention of 4.5 V LiNi0.5Co0.2Mn0.3O2/artificial graphite pouch cells increased from 45.5% to 72.5% and 81.6% after 700 cycles at 45 ℃ after TFEC and MTFEC replaced DEC. Linear sweep voltammetry (LSV), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Raman spectroscopy (Raman) and inductively coupled plasma atomic emission spectroscopy (ICP-OES) studies proved that TFEC and MTFEC had better oxidation resistance at high voltage than DEC. They could obviously inhibit the oxidation decomposition of electrolyte on the surface of the high-voltage cathode, effectively protect the interface stability of cathode and anode materials, and mitigate the damage of solid electrolyte interphase (SEI) film caused by the dissolution of transition metal ions from cathode materials. Fluorinated linear carbonates as electrolyte solvents are of great promise in the application of high-voltage lithium ion batteries.
胡时光, 郭鹏凯, 钱韫娴, 张光照, 王军, 邓永红, 王朝阳. 氟代线性碳酸酯对高电压LiNi0.5Co0.2Mn0.3O2/人造石墨软包电池性能的影响[J]. 材料导报, 2023, 37(8): 22050331-7.
HU Shiguang, GUO Pengkai, QIAN Yunxian, ZHANG Guangzhao, WANG Jun, DENG Yonghong, WANG Chaoyang. Effect of Fluorinated Linear Carbonate on the Performance of High-voltage LiNi0.5Co0.2Mn0.3O2/Artificial Graphite Pouch Cells. Materials Reports, 2023, 37(8): 22050331-7.
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2023, Vol. 37 
