脂肪族冠醚在电池电解液中的应用

doi:10.19799/j.cnki.2095-4239.2022.0211

摘要/Abstract

摘要：

电池中各材料之间的相容性是影响其性能的重要因素之一，在电解液中添加12-冠醚-4、15-冠醚-5、18-冠醚-6等脂肪族冠醚可以通过改善相容性来提升电池性能。本文介绍了冠醚的分子结构及其对应的表界面活性和配位包结能力；综述了历年来脂肪族冠醚在锂电池电解液中的应用研究情况，将其作为电解液添加剂的效果归纳为抑制金属的不规则析出、在电极表面成膜、减少溶剂副反应、增溶电解质、提高离子传导率、提升固态电解质性能等；列举了国内相关发明专利的发表情况；分析了限制脂肪族冠醚在电解液中广泛应用的主要原因是当前主流威廉姆森醚合成工艺的选择性低、副产物多、纯化困难，导致生产成本高昂，而更为理想的环氧乙烷低聚合成工艺，尚需改进以避免使用含氟盐；最后，对脂肪族冠醚在电解液中的应用前景进行了展望。

关键词: 电解液, 相容性, 脂肪族冠醚, 12冠醚-4, 15-冠醚-5, 18-冠醚-6

Abstract:

The compatibility between battery materials affects their performance. The performance of batteries can be improved by adding 12-crown-4, 15-crown-5, 18-crown-6, and other aliphatic-crown ethers to the electrolyte, which improves the compatibility. This article introduced the molecular structure of crown ethers, which determines their surface-interface activities and coordination inclusion capabilities. In addition, it reviews the application history of aliphatic crown ethers in lithium-ion battery electrolytes, summarizes the effects of crown ether on the inhibition of the irregular precipitation of metals, forming films on the electrode surface, reducing solvent side reactions, solubilizing electrolytes, improving ionic conductivity, improving the performance of solid electrolytes, etc. The application of aliphatic crown ethers in electrolytes is limited by the high production costs of the Williamson ether-synthesis process, which has low selectivity, many by-products, and difficult purification. Oligomerization using ethylene oxide is a preferable process for producing aliphatic crown ethers; however, it needs to be improved to avoid the use of fluorine-containing salts. Finally, there are prospects for the application of aliphatic-crown ethers in electrolytes.

Key words: electrolyte, compatibility, aliphatic crown ethers, 12-crown-4, 15-crown-5, 18-crown-6

中图分类号:

TM 911

方黎锋. 脂肪族冠醚在电池电解液中的应用[J]. 储能科学与技术, 2022, 11(10): 3100-3111.

Lifeng FANG. Application of aliphatic-crown ethers in battery electrolytes[J]. Energy Storage Science and Technology, 2022, 11(10): 3100-3111.

图/表 6

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冠醚	孔径直径/nm	金属离子	离子直径/nm
12-冠醚-4	0.11～0.14	Li⁺	0.136
15-冠醚-5	0.17～0.22	Na⁺	0.194
18-冠醚-6	0.26～0.32	K⁺	0.266

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[3]	房茂霖, 张英, 乔琳, 刘淑敏, 曹中琦, 张华民, 马相坤. 铁铬液流电池技术的研究进展[J]. 储能科学与技术, 2022, 11(5): 1358-1367.
[4]	方亮, 张凯, 周丽敏. 铝离子电池电解液的研究进展[J]. 储能科学与技术, 2022, 11(4): 1236-1245.
[5]	王心怡, 李维杰, 韩朝, 刘化鹍, 窦世学. 水系锌离子电池金属负极的挑战与优化策略[J]. 储能科学与技术, 2022, 11(4): 1211-1225.
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[7]	岳博文, 佟佳欢, 刘玉文, 霍锋. 离子液体电解液的模拟计算方法及应用[J]. 储能科学与技术, 2022, 11(3): 897-911.
[8]	周思飞, 李骏, 张道明, 薛浩亮, 王小飞. 基于数理统计方法的锂电池电解液电导率优化设计[J]. 储能科学与技术, 2022, 11(10): 3364-3370.
[9]	胡华坤, 李新丽, 薛文东, 蒋朋, 李勇. 基于CiteSpace的锂离子电池用低温电解液知识图谱分析[J]. 储能科学与技术, 2022, 11(1): 379-396.
[10]	王子璇, 李俊成, 李金东, 易娟, 石霖, 吴旭. 废磷酸铁锂正极材料资源化回收工艺[J]. 储能科学与技术, 2022, 11(1): 45-52.
[11]	姚祯, 王锐, 阳雪, 张琦, 刘庆华, 王保国, 缪平. 锌铁液流电池研究现状及展望[J]. 储能科学与技术, 2022, 11(1): 78-88.
[12]	王青萌, 刘志, 程晓敏, 程千驹, 吕泽安. In元素对Sn-Bi-Zn传热储热合金高温容器相容性的影响[J]. 储能科学与技术, 2022, 11(1): 9-18.
[13]	衡永丽, 谷振一, 郭晋芝, 吴兴隆. Na₃V₂（PO₄）₃@C用作水系锌离子电池正极材料的研究[J]. 储能科学与技术, 2021, 10(3): 938-944.
[14]	池上森, 姜益栋, 王庆荣, 叶子威, 余凯, 马骏, 靳俊, 王军, 王朝阳, 温兆银, 邓永红. 液体电解液改性石榴石型固体电解质与锂负极的界面[J]. 储能科学与技术, 2021, 10(3): 914-924.
[15]	周琳, 杨佯, 胡勇胜. 合金电极失效机制：体积膨胀？电解液分解？[J]. 储能科学与技术, 2021, 10(3): 813-820.