可充电锌离子电池电解质的研究进展

doi:10.19799/j.cnki.2095-4239.2022.0040

摘要/Abstract

摘要：

锌离子电池以其低价、安全、高可用性、生态友好、易于制备等特点而受到了广泛的研究。作为连通锌离子电池其他部分的纽带，电解质与电化学性能的发挥有着重要关系。为了进一步具备应用的可能性，增强电解质对电池电化学性能的释放具有深刻的意义。尽管在电解质方面已经进行了诸多探索并取得了很多优秀的成果，然而对于锌离子电池电解质的一些问题仍然需要引起足够的关注。本文首先阐述了锌离子电池的一般原理。然后分别从水溶液电解质、有机溶液电解质、凝胶电解质、全固态电解质等四个方面回顾了锌离子电池各种电解质的研究进展。其中，水溶液电解质部分重点介绍了对应电解质存在的溶剂化问题、相关的改性策略及添加剂对电极稳定性的提升机理。有机溶液电解质部分阐述了电池电化学性能的提升。凝胶电解质部分说明了相关电解质的形成原理和其在柔性储能领域的应用。全固态电解质部分则对相应电解质的无液特性和本质导电优势进行了简要说明。最后，对各种电解质的发展近况进行了总结，并对未来可能进行的研究方向进行了展望。

关键词: 锌离子电池, 电解质, 水溶液, 有机溶液, 凝胶, 全固态

Abstract:

Owing to their low cost, safety, high availability, ecological friendliness, and easy preparation, zinc-ion batteries have been extensively investigated. Linking with the other parts of zinc-ion batteries, the electrolyte is strongly related to making the most beneficial electrochemical performance. To further enhance the possibility of application, it has key importance to enhance the release of electrochemical performance of the batteries. Although there has been a lot of research performed and several batteries' remarkable findings have been attained, some challenges of electrolytes in zinc ion batteries still require to be paid enough attention. In this review, the general principle of zinc-ion batteries is introduced first and then the recent advances in a wide range of electrolytes for zinc-ion batteries involving aqueous, organic, gel, and all-solid-state electrolytes are explained. The solvation problem, corresponding modification strategies, and mechanism of improving electrode stability by additives are introduced in the aqueous electrolytes part. The enhancement of electrochemical performance of the batteries is explained in the organic electrolytes part. The formation principle of related electrolytes and their application in flexible energy storage is explained in the gel part. In the all-solid-state part, the benefit of liquid-free and intrinsic conductivity are briefly illustrated. Furthermore, the electrolytes' research progress in zinc-ion batteries is summarized and the prospects research directions of those are proposed.

Key words: zinc-ion battery, electrolyte, aqueous, organic, gel, all-solid-state

中图分类号:

TM 912

裴英伟, 张红, 王星辉. 可充电锌离子电池电解质的研究进展[J]. 储能科学与技术, 2022, 11(7): 2075-2082.

Yingwei PEI, Hong ZHANG, Xinghui WANG. Recent advances in the electrolytes of rechargeable zinc-ion batteries[J]. Energy Storage Science and Technology, 2022, 11(7): 2075-2082.

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分类	电解质	正极	离子电导率 /(mS/cm)	电化学稳定电势窗	成本	参考文献
水溶液	2 mol/L ZnSO₄+0.2 mol/L MnSO₄	(Akhtenskite)MnO₂@CFP	—	1.0～1.8 V	低	[8]
	0.5 mol/L Zn(CH₃COO)₂	Na₃V₂(PO₄)₃/C	—	0.8～1.7 V	低	[11]
	3 mol/L Zn(CF₃SO₃)₂	(Spinel)ZnMn₂O₄/carbon	3470	0.8～1.9 V	高	[12]
	0.3 mol/L Zn(TFSI)₂	Fe₅V₁₅O₃₉(OH)₉∙9H₂O	—	0.4～1.6 V	高	[13]
	20 mol/kg LiTFSI+1 mol/kg Zn(TFSI)₂	LiMn₂O₄	—	0.8～2.1 V	高	[14]
	21 mol/L LiTFSI + 1 mol/L Zn(CF₃SO₃)₂	VOPO₄	—	0.8～2.1 V	高	[15]
	30 mmol/L ZnCl 1 mol/L ZnCl	Ca_0.20V₂O₅∙0.80H₂O	12.7 101	0.25～2.0 V 0.25～1.3 V	高低	[17]
	2 mol/L ZnSO₄(原)+50%体积的甲醇	聚苯胺(PANI)	16.8 (原56.9)	0.6～1.6 V	低低	[19]
	1 mol/L ZnSO₄(原)+10 mmol/L葡萄糖	MnO₂	45.3～45.7 (原43.5～43.8)	1.0～1.9 V	低低	[20]
	3 mol/L Zn(CF₃SO₃)₂+0.1 mol/L Mn(CF₃SO₃)₂	β-MnO₂	6000	0.8～1.9 V	高	[21]
	1 mol/L ZnSO₄+1 mol/L Na₂SO₄	NaV₃O₈∙1.5H₂O	—	0.3～1.25 V	低	[22]
有机溶液	0.5 mol/L AN-Zn(TFSI)₂	双层水合V₂O₅	—	0.3～1.5 V	高	[23]
	0.5 mol/L Zn(OTf)₂/TMP-DMC(体积比=1∶1)	VS₂	4.90	0.3～1.0 V	高	[24]
	0.5 mol/L ZnTFMS/DMF	PQ-MCT	18.9	0.1～1.7 V	较高	[25]
*	0.5 mol/L Zn(CF₃SO₃)₂-TEP∶H₂O(体积比=7∶3)	KCuHCf	6.48	1.3～2.0 V	较高	[27]
凝胶	约0.44 mol/L ZnSO₄/CMC(CMC∶水=3:80)	ZnHCF	—	1.0～2.1 V	较低	[30]
	2 mol/L ZnSO₄+0.1 mol/L MnSO₄/gum(gum∶水=1∶5)	MnO₂	14.6	1.0～1.8 V	较低	[31]
	3 mol/L LiCl+ 2 mol/L ZnCl₂+0.4 mol/L MnSO₄/ PVA(PVA∶水=1∶10)	MnO₂@PEDOT	—	1.0～1.8 V	偏低	[32]
	1 mol/L ZnSO₄/gelatin(gelatin∶水=1∶4)	NaV₃O₈∙1.5H₂O	—	0.3～1.25 V	较低	[22]
	2 mol/L ZnSO₄+0.1 mol/L MnSO₄/PAM(AM∶水=1∶10)	MnO₂	17.3	0.8～1.85 V	较低	[36]
全固态	4 mol/L Zn(BF₄)₂+2 mmol/L Al(OTf)₃/poly(1,3-dioxolane)	CoHCF	19.6	0.5～2.05 V	较高	[38]

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