磷酸三乙酯与亚磷酸三乙酯电解液添加剂在富锂层状氧化物正极中的性能对比
李浩祥,周浩岚,吴立祺,王 甫,夏 兰.磷酸三乙酯与亚磷酸三乙酯电解液添加剂在富锂层状氧化物正极中的性能对比[J].宁波大学学报(理工版),2026,39(3):92-103.DOI:10.20098/j.cnki.1001-5132.2025.1209
LI Haoxiang,ZHOU Haolan,WU Liqi,WANG Fu,XIA Lan.Performance comparison
of triethyl phosphate and triethyl phosphite electrolyte additives in lithium-rich
layered oxide cathodes
[J].Journal of Ningbo University(Natural Science & Engineering Edition),2026,39(3):92-103.DOI:10.20098/j.cnki.1001-5132.2025.1209
| Title: | Performance comparison
of triethyl phosphate and triethyl phosphite electrolyte additives in lithium-rich
layered oxide cathodes |
| 作者: | 李浩祥, 周浩岚, 吴立祺, 王 甫, 夏 兰 |
| Author(s): | LI Haoxiang, ZHOU Haolan, WU Liqi, WANG Fu, XIA Lan |
| 关键词: | 锂离子电池; 电解液; 富锂锰基层状氧化物正极; 添加剂; 磷酸三乙酯; 亚磷酸三乙酯 |
| Keywords: | lithium-ion batteries; electrolyte; lithium-rich layered oxide cathodes; additive; triethyl phosphate; triethyl phosphite |
| 分类号: | O646.21；TM919 |
| DOI: | 10.20098/j.cnki.1001-5132.2025.1209 |
| 文献标识码: | A |
| 摘要: | 富锂锰基层状氧化物（Lithium-rich layered oxide，LLO）正极材料在高电压（2.0~4.8V）循环过程中易发生界面失效，严重限制了其能量密度和循环寿命。本文系统对比了两种典型含磷酯电解液添加剂—–磷五价的磷酸三乙酯（TEP）与磷三价的亚磷酸三乙酯（TEPI）对LLO界面稳定性的调控作用。结果表明，TEP在高电压下优先发生可控氧化，在正极表面原位形成富含LiF致密的正极电解质界面膜（CEI），有效提高了富锂电池的电化学循环与倍率性能。该体系在0.2C下经300次循环后容量保持率为92%，显示出较好的循环稳定性。相比之下，TEPI氧化路径分散，形成有机组分为主、疏松多孔的CEI，界面钝化作用有限，导致循环中后期阻抗显著升高，并在第260圈出现电压平台异常下降，电池性能迅速衰退。 |
| Abstract: | Lithium-rich layered oxide (LLO) cathode materials suffer from severe interfacial degradation during high-voltage cycling (2.0–4.8V), which critically limits their achievable energy density and long-term cycling life span stability. In this study, the interfacial regulation effects of two representative phosphorus-containing electrolyte additives are compared systematically, including those of triethyl phosphate (TEP, pentavalent phosphorus) and those of triethyl phosphite (TEPI, trivalent phosphorus). The results demonstrate that TEP undergoes preferential and well-controlled oxidation at high voltages, forming an in situ LiF-rich and compact cathode-electrolyte interphase (CEI) on the LLO surface, which markedly enhances both cycling and rate performance, yielding a capacity retention of 92% after 300 cycles at 0.2C. In contrast, TEPI follows a more dispersed oxidation pathway, generating an organic-rich, porous, and loosely structured CEI with insufficient passivation capability, leading to a pronounced increase in interfacial impedance during mid-to-late cycling and an abnormal drop in the voltage plateau at around the 260th cycle, ultimately resulting in rapid cell degradation. |
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| 备注/Memo: | 收稿日期：2025-12-15 宁波大学学报（理工版）网址：http://journallg.nbu.edu.cn/ 基金项目：浙江省基础公益研究计划（LY24B030002）；宁波市科技项目（2024QL036，2024QL015） 第一作者：李浩祥，硕士研究生，主要研究方向为热能动力与新能源。E-mail: 2311120063@nbu.edu.cn *通信作者：夏 兰，教授，主要研究方向为电化学储能电池。E-mail: xialan@nbu.edu.cn 宁波大学学报（理工版）网址：http://journallg.nbu.edu.cn/ |
