甲基九氟丁醚改善NMC811正极高电压电化学性能
PDF下载 (99)赵一博,田浩然,夏 兰*.甲基九氟丁醚改善NMC811正极高电压电化学性能[J].宁波大学学报(理工版),2024,37(6):90-99.DOI:10.20098/j.cnki.1001-5132.2024.0409
ZHAO Yibo,TIAN Haoran,XIA Lan.Methyl 1,1,2,2,3,3,4,4,4-nonafluorobutyl ether (MFE) additive for improving the high voltage electrochemical performances of NMC811 cathode materials[J].Journal of Ningbo University(Natural Science & Engineering Edition),2024,37(6):90-99.DOI:10.20098/j.cnki.1001-5132.2024.0409
| Title: | Methyl 1,1,2,2,3,3,4,4,4-nonafluorobutyl ether (MFE) additive for improving the high voltage electrochemical performances of NMC811 cathode materials |
| 作者: | 赵一博, 田浩然, 夏 兰* |
| Author(s): | ZHAO Yibo, TIAN Haoran, XIA Lan |
| 关键词: | 锂金属电池; 电解液; 添加剂; 高电压; 高镍三元材料; 界面 |
| Keywords: | lithium metal battery; electrolyte; additive; high voltage; high nickel ternary material; interphase |
| 分类号: | O646.21; TM919 |
| DOI: | 10.20098/j.cnki.1001-5132.2024.0409 |
| 文献标识码: | A |
| 摘要: | 锂金属电池能量密度高(>500W·h·kg−1), 在下一代锂离子电池中显示出巨大的应用潜力. 高镍三元正极材料(LiNi0.8Mn0.1Co0.1O2, NMC811)是可选的理想高比能正极材料. 然而, 商用碳酸酯电解液在高电压下会使NMC811正极表面发生不可逆的氧化分解, 引起正极界面膜(CEI)增厚、界面电阻增大等问题, 影响电池的电化学性能. 为此, 研究了甲基九氟丁醚(MFE)高电压正极成膜添加剂对NMC811正极高电压下电化学性能的影响及其正极成膜机理. 结果发现, 在2.7~4.7V区间, MFE在NMC811正极表面参与形成富含LiF和LixPOyFz的界面层, 可以减少LiPF6分解产生HF等物质, 稳定正极表界面结构, 从而实现Li/NMC811锂电池在100周循环后的容量保持率从87.53%提高到91.58%. |
| Abstract: | Lithium metal batteries (LMBs) are regarded as having highly promising application prospects in the next-generation lithium-ion batteries due to their high energy density (>500 W·h·kg−1). High nickel cathode materials LiNi0.8Mn0.1Co0.1O2 (NMC811) are an ideal choice for high energy density cathode materials for LMBs. However, the poor stability against oxidation of the conventional carbonated electrolytes at high voltages results in the parasitic reactions on the surface of NMC811 cathode, which leads to the thickening of the cathode-electrolyte interphase (CEI), consequently affecting the electrochemical performance of the batteries. In this work, methyl 1,1,2,2,3,3,4,4,4-nonafluorobutyl ether (MFE) is selected as a high voltage cathode film-forming additive for Li/NMC811 batteries, and the electrochemical properties and the CEI film-forming mechanism of the NMC811 cells with this MFE additive are both investigated. The results from electrochemical testing methods, including charge-discharge tests, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), as well as X-ray photoelectron spectroscopy (XPS), suggest that MFE participates in the formation of the CEI layer that is rich in LiF and LixPOyFz on the surface of NMC811 at a voltage range of 2.7–4.7 V, which can protect the NMC811 materials from suffering the damage by HF produced from LiPF6 decomposition, resulting in the enhanced capacity retention of Li/NMC811 batteries at high voltage (4.7 V vs. Li+/Li) from 87.53% to 91.58% after 100 cycles. |
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| 备注/Memo: | 收稿日期: 2024−04−07. 宁波大学学报（理工版）网址: http://journallg.nbu.edu.cn/ 基金项目: 国家自然科学基金（22075155）; 浙江省基础公益研究计划项目（LY24B030002）; 宁波市科技项目（22075155, 2024QL036）. 第一作者: 赵一博, 硕士研究生, 主要研究方向: 热能动力与新能源. E-mail: 2111087078@nbu.edu.cn *通信作者: 夏兰, 副教授, 主要研究方向: 二次电池、电解质等. E-mail: xialan@nbu.edu.cn 宁波大学学报（理工版）网址：http://journallg.nbu.edu.cn/ |
