中性水系锌离子电池负极缓蚀剂研究进展

doi:10.11902/1005.4537.2023.361

中国腐蚀与防护学报

2024, Vol. 44

Issue (5): 1089-1099 CSTR: 32134.14.1005.4537.2023.361 DOI: 10.11902/1005.4537.2023.361

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中性水系锌离子电池负极缓蚀剂研究进展

吴浩天, 张天遂, 李广芳, 刘宏芳(

)

华中科技大学能源转换与储存材料化学教育部重点实验室材料化学与服役失效湖北省重点实验室化学与化工学院武汉 430074

Corrosion Inhibitor for Zn Anode of Neutral Aqueous Zinc Ion Batteries

WU Haotian, ZHANG Tiansui, LI Guangfang, LIU Hongfang(

)

Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

引用本文:

吴浩天, 张天遂, 李广芳, 刘宏芳. 中性水系锌离子电池负极缓蚀剂研究进展[J]. 中国腐蚀与防护学报, 2024, 44(5): 1089-1099.
Haotian WU, Tiansui ZHANG, Guangfang LI, Hongfang LIU. Corrosion Inhibitor for Zn Anode of Neutral Aqueous Zinc Ion Batteries[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(5): 1089-1099.

全文: PDF(6866 KB) HTML

摘要:

围绕锌负极在中性电解质中腐蚀产生枝晶、钝化、析氢等关键问题，综述了锌负极缓蚀剂防护方法的研究进展，旨在从溶剂化结构调控、静电屏蔽、吸附作用、原位固态电解质界面4种防护机理，揭示不同类型缓蚀剂的性能、稳定性及实际应用的可行性，进而为锌负极保护提供依据，展望缓蚀剂防护方法未来的发展方向。

关键词 ：锌离子电池, 金属锌负极, 腐蚀, 缓蚀剂

Abstract：

Aqueous Zn-ion batteries are considered as possible substitutes for Li-ion batteries because of their low cost, high safety and environment-friendly. However, the hydrogen evolution side reaction, passivation and dendrite of Zn anode in neutral water electrolyte seriously affect the stability and safety of the battery and hinder its application. Zn anode is the key part that affects the capacity, stability and cycle life of battery. Introduction of corrosion inhibitor into electrolyte is a simple and practical method to inhibit the corrosion of Zn electrode. In this review, the mechanisms related with dendrite formation, passivation and hydrogen evolution reaction of Zn anode in neutral electrolyte are introduced first, and then the countermeasures of using corrosion inhibitor to solve these three problems are summarized. The performance, stability and feasibility of practical application of various corrosion inhibitors for the protection of Zn anode are illustrated in terms of perspectives such as the adjustment of solvation structure, electrostatic shield, adsorption, and in-situ solid electrolyte interface etc. Finally, the future development direction of corrosion inhibitor-based protection method for Zn anode is also proposed.

Key words： zinc ion battery zinc anode corrosion inhibitor

收稿日期: 2023-11-16 32134.14.1005.4537.2023.361

ZTFLH:

TQ152

基金资助:国家自然科学基金(52171069)

通讯作者: 刘宏芳，E-mail：liuhf@hust.edu.cn，研究方向为材料物理与化学、腐蚀与防护、纳米功能材料及应用

Corresponding author: LIU Hongfang, E-mail: liuhf@hust.edu.cn

作者简介: 第一联系人：吴浩文，男，1999年生，硕士生

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图1 Zn2+溶剂化过程示意图以及电极与电解质界面间的相互作用[10]

图2 恒电流下Zn沉积过程的连续TEM图像以及4 s时的TEM图像放大后的六边形锌晶面[19]

图3 Zn沉积溶解过程的连续TEM图像[19]

表1 缓蚀剂种类及其作用机理

图4 分子动力学模拟Zn2+在1 mol/L Zn(TFSI)2添加不同LiTFSI浓度(5, 10, 20 mol/L)电解质中的溶剂化结构[21]

Corrosion inhibitor	Electrolytes	Current density, capacity and cycle time	Ref.
dimethyl sulfoxide	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 2100 h 3 mA·cm^-2, 3 mAh·cm^-2, 200 h	[22]
N-methyl-2-pyrrolidone	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 540 h	[29]
ethylene glycol	ZnSO₄	0.5 mA·cm^-2, 0.5 mAh·cm^-2, 1300 h 5 mA·cm^-2, 0.5 mAh·cm^-2, 800 h	[24]
triethylmethyl ammonium	ZnCl₂	1 mA·cm^-2, 0.5 mAh·cm^-2, 2145 h 5 mA·cm^-2, 2.5 mAh·cm^-2, 500 h	[40]
melamine	ZnSO₄	2 mA·cm^-2, 2 mAh·cm^-2, 3000 h	[42]
monosodium glutamate	ZnSO₄	2 mA·cm^-2, 2 mAh·cm^-2, 2200 h 5 mA·cm^-2, 5 mAh·cm^-2, 1700 h	[43]
glycine	ZnSO₄	1 mA·cm^-2, 0.5 mAh·cm^-2, 2000 h 4 mA·cm^-2, 2 mAh·cm^-2, 600 h	[44]
histidine	ZnSO₄	2 mA·cm^-2, 1 mAh·cm^-2, 4180 h	[45]
L-cysteine	ZnSO₄	1 mA·cm^-2, 0.5 mAh·cm^-2, 2500 h	[46]
SeO₂	ZnSO₄	2 mA·cm^-2, 2 mAh·cm^-2, 2100 h	[55]
sucrose	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 2000 h 2 mA·cm^-2, 2 mAh·cm^-2, 500 h	[57]
sorbitol	ZnSO₄	1 mA·cm^-2, 0.5 mAh·cm^-2, 2000 h	[60]
alkyl polyglucoside	ZnSO₄	1 mA·cm^-2, 0.25 mAh·cm^-2, 4000 h	[61]
silk peptide	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 3000 h	[64]
polyaspartic acid	ZnSO₄	0.5 mA cm^-2, 0.5 mAh·cm^-2, 3200 h	[65]
ovalbumin	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 2200 h	[71]
γ-valerolactone	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 3500 h	[72]
AgNO₃	ZnSO₄	0.5 mA·cm^-2, 0.25 mAh·cm^-2, 1800 h	[73]
KI	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 3000 h	[74]
Ni²⁺	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 900 h	[75]
cholinium cations	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 2000 h	[76]
dioxane	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 2000 h	[77]
sodium tartrate	ZnSO₄	0.5 mA·cm^-2, 0.25 mAh·cm^-2, 1500 h	[78]
tetramethylurea	Zn(OTf)₂	1 mA·cm^-2, 1 mAh·cm^-2, 3000 h	[79]
thiourea	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 1200 h	[80]
tetrahydrofuran	ZnSO₄	0.5 mA·cm^-2, 0.5 mAh·cm^-2, 1300 h 1 mA·cm^-2, 1 mAh·cm^-2, 500 h	[81]
phytic acid	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 1200 h	[82]
penta-potassium triphosphate	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 3800 h	[83]
1-hydroxy ethylidene-1,1-diphosphonic acid	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 1500 h	[84]
taurine	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 3000 h	[85]
tetrabutylammonium 4-toluenesulfonate	Zn(PS)₂	1 mA·cm^-2, 1 mAh·cm^-2, 2000 h	[86]
1-phenylethylamine hydrochloride	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 2082 h	[87]
succinimide	ZnSO₄	20 mA·cm^-2, 10 mAh·cm^-2, 680 h	[88]
hexamethylenetetramine	ZnSO₄	5 mA·cm^-2, 1 mAh·cm^-2, 4000 h	[89]
1-ethyl-3-methylimidazolium chloride	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 500 h	[90]
1-butyl-3-methylimidazolium cation	ZnSO₄	2 mA·cm^-2, 1 mAh·cm^-2, 3162 h 5 mA·cm^-2, 5 mAh·cm^-2, 1410 h 10 mA·cm^-2, 10 mAh·cm^-2, 1000 h	[91]
L-ascorbic acid sodium	ZnSO₄	1 mA·cm^-2, 1 mAh·cm^-2, 1200 h	[92]

表2 不同缓蚀剂的Zn||Zn对称电池循环性能统计对比表

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