钾离子电池低温电解质的研究进展

doi:10.19799/j.cnki.2095-4239.2024.0426

储能科学与技术 ›› 2024, Vol. 13 ›› Issue (7): 2308-2316.doi: 10.19799/j.cnki.2095-4239.2024.0426

钾离子电池低温电解质的研究进展

赵飞¹^,²(), 陈英华¹^,², 马征¹, 李茜¹(), 明军¹^,²()

^1.中国科学院长春应用化学研究所，稀土资源利用国家重点实验室，吉林长春 130022
^2.中国科学技术大学，安徽合肥 230026

收稿日期:2024-05-13 修回日期:2024-06-07 出版日期:2024-07-28 发布日期:2024-07-23
通讯作者: 李茜,明军 E-mail:zhaojunhua@ciac.ac.cn;qianli@ciac.ac.cn;jun.ming@ciac.ac.cn
作者简介:赵飞（1998—），男，博士研究生，研究方向为锂离子电池低温电解质设计及界面解析，E-mail：zhaojunhua@ciac.ac.cn；
基金资助:
国家自然科学基金委员会青年科学基金项目(22109155);国家自然科学基金委员会优秀青年科学基金项目(22122904);吉林省自然科学基金项目(YDZJ202101ZYTS022)

Advances in low-temperature electrolytes for potassium-ion batteries

Fei ZHAO¹^,²(), Yinghua CHEN¹^,², Zheng MA¹, Qian LI¹(), Jun MING¹^,²()

^1.State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin, China
^2.University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2024-05-13 Revised:2024-06-07 Online:2024-07-28 Published:2024-07-23
Contact: Qian LI, Jun MING E-mail:zhaojunhua@ciac.ac.cn;qianli@ciac.ac.cn;jun.ming@ciac.ac.cn

摘要/Abstract

摘要：

钾离子电池因其能量密度高、廉价易得等特点，已成为有潜力的储能设备，尤其钾离子更小的斯托克斯半径，使超低温钾离子电池成为可能。然而，传统电解质会使钾离子电池在低温下生长枝晶，导致电池失效并造成安全隐患。因此，改善电解质的低温特性对提高钾离子电池低温性能至关重要。本文综述了近些年钾离子电池低温电解质的研究进展，其大致可分为三类，即非水系电解液、水系电解液和固态电解质。其中，非水系电解液大多含弱溶剂化醚类溶剂和添加剂，提高界面去溶剂化过程的同时使电极表面形成良好的界面膜，以提高电池的低温性能；水系电解液通过引入特定的添加剂分子降低电解液凝固点的同时破坏H₂O分子间氢键网络，实现电池低温性能；固态电解质以准固态电解质为主，使聚合物骨架孔道中保留少量液态电解液以提高电解质体相离子传输，并降低电解质与电极界面接触阻抗，最终提高电池的低温性能。

关键词: 钾离子电池, 低温性能, 非水系电解液, 水系电解液, 固态电解质

Abstract:

Potassium-ion batteries (PIBs) have emerged as a potential energy storage device due to their high energy density and low cost. In particular, the smaller Stokes radius of K⁺ enables ultra-low temperature potassium-ion batteries. However, conventional electrolytes can cause PIBs to grow dendrites at low temperatures, leading to battery failure and safety hazards. Therefore, improving the low-temperature properties of the electrolyte is crucial to improving the low-temperature performance of PIBs. This study reviews the progress made in recent years related to low-temperature electrolytes for PIBs, which can be roughly divided into three categories, namely non-aqueous electrolytes, aqueous electrolytes, and solid electrolytes. Non-aqueous electrolytes mostly contain weakly solvating ether solvents and additives, which enhance the interfacial desolvation process and form a good solid electrolyte interface film on the electrode surface to improve the low-temperature performance of PIBs. The aqueous electrolyte helps PIBs to achieve good low-temperature performance by introducing specific additive molecules to lower the electrolyte freezing point and destroy the network of hydrogen bonds between the H₂O molecules. The quasi-solid-state electrolyte, which retains a small amount of liquid electrolyte in the channels of the polymer skeleton, improves the electrolyte bulk ion transport and reduces the contact resistance between the electrolyte and the electrode interface, which ultimately improves the low-temperature performance of PIBs.

Key words: potassium ion battery, low-temperature performance, non-aqueous electrolyte, aqueous electrolyte, solid-state electrolyte

中图分类号:

TM 911

赵飞, 陈英华, 马征, 李茜, 明军. 钾离子电池低温电解质的研究进展[J]. 储能科学与技术, 2024, 13(7): 2308-2316.

Fei ZHAO, Yinghua CHEN, Zheng MA, Qian LI, Jun MING. Advances in low-temperature electrolytes for potassium-ion batteries[J]. Energy Storage Science and Technology, 2024, 13(7): 2308-2316.

图/表 7

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电解质组分	温度	电池体系	电流密度/(mA/g)	比容量/(mAh/g)	循环圈数	容量保持率	功率密度/ (Wh/kg)
1 mol/L KFSI in THF^[27]	0 ℃	碳纳米纤维\|\|石墨	50	200	—	—	—
0.91 mol/L KFSI in DEECl^[28]	-5 ℃	普鲁士蓝\|\|石墨	20	65.5	80	—	—
1 mol/L KFSI in MTHF^[29]	-20 ℃	预钾化的3, 4, 9, 10-苝-四羧酸-二酐\|\|石墨	—	>100	100	94.38%	197
0.4 mol/L KPF₆ in DME+2 vol.% PDMS^[33]	-40 ℃	预钾化的3, 4, 9, 10-苝-四羧酸-二酐\|\|无负极Cu	26	82.8	50	82%	152
1 mol/L KPF₆ in DME+20 mmol/L LiNO₃^[34]	-40 ℃	3, 4, 9, 10-苝-四羧酸-二酐\|\|硬碳	65	89	100	79%	157
4 mol/L KFSI in PC^[39]	0 ℃	普鲁士白\|\|石墨	200	>60	1000	92.1%	—
2 mol/L KCF₃SO₃ in H₂O+HBCD^[42]	-20 ℃	六氰基铁酸铜\|\|3, 4, 9, 10-苝四甲酰二亚胺-乙烯二胺共聚物	—	>80	60	约100%	—
10 mol/kg KCF₃COO in H₂O^[43]	-35 ℃	K_1.55Fe[Fe-(CN)₆]_0.95·1.03H₂O\|\|3,4,9,10-苝四羧酸二酰亚胺	—	>90	1000	87.5%	41.9
KFSI-L^[14]	-40 ℃	PHA@RP@BNC\|\|PTCDA	100	>60	200	93.6%	—
全氟磺酸树脂聚合物电解质+PC/EC混合溶液^[15]	-15 ℃	3, 4, 9, 10-苝-四羧酸-二酐\|\|石墨	100	90.7	200	99.74%	—

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钾离子电池低温电解质的研究进展

Advances in low-temperature electrolytes for potassium-ion batteries

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