氮杂环咪唑离子液体用于水系锌离子电池负极无枝晶保护

doi:10.19894/j.issn.1000-0518.240029

摘要/Abstract

摘要：

根据可持续发展的需要以及更好地去实现碳达峰、碳中和，水系锌离子电池由于其安全可靠、成本低及离子电导率高等特点逐渐进入人们的视线。相比于传统的锂离子电池，可充电的水系锌离子电池具有很高的安全稳定性，同时，锌金属资源丰富、理论容量（820 mA·h/g）高、氧化还原电位（-0.762 V（vs.SHE））低，这也缓解了金属锂的资源压力。但是，电解质中的活性水会严重腐蚀锌负极，发生析氢反应（HER），并产生羟基硫酸锌（ZHS）等副产物以及引起枝晶生长，从而使电池循环性能大大降低，达不到储能要求。结果表明，通过离子液体添加剂优化水系锌离子电解液，实现了循环过程中无枝晶的锌负极，其中氯化1-氰丁基-3-甲基咪唑（MCBI）添加剂在最佳添加浓度条件下，Zn//Cu半电池200圈库伦效率可达99.37%，Zn//Zn对称电池在小电流密度下可稳定循环1600 h以上，即使在10 mA/cm²、5 mA·h/cm²下也能稳定循环1000 h以上；全电池循环500次后依旧有88.5%的高容量保持率。这项工作解决了水系锌离子电池枝晶问题，并在优化电解质体系方面提供了一个全新的视角。

关键词: 水系锌离子电池, 电解液, 添加剂, 锌阳极, 枝晶, 离子液体

Abstract:

With the development of social industrialization， energy issues have become a hot topic at present. Traditional lithium-ion batteries， due to their poor safety and high cost， cannot meet the current application needs in the energy storage field in the long term. Therefore， the development of suitable new energy has aroused people's deep thinking. Aqueous zinc-ion batteries （AZIBs） have attracted attention from the scientific research community in recent years due to their high safety， cleanliness， and other advantages. However， dendrites are easily grown on the zinc anode， and free water molecules can also corrode the zinc anode， causing side reactions such as hydrogen evolution and passivation， seriously affecting the long-term cycling performance and stability of the battery. This work introduces a new type of ionic liquid additive 1-cyanobutyl-3-methylimidazole chloride （MCBI） to optimize aqueous electrolytes. Before the deposition of zinc ions on the anode surface， MCBI cations will preferentially land on the anode. Due to their special structures of Electron-withdrawing group and nitrogen heterocycles， they will tightly adsorb on the zinc surface in a unique shape of the “Check mark” posture. This provides abundant sites for the deposition of zinc ions， allowing zinc atoms to arrange regularly between MCBI ions， thereby reducing the generation of dendrites. Due to the steric hindrance effect， by-products （Zinc hydroxide sulfate） will also accumulate in an orderly manner around additive ions， forming channels for uniform deposition of zinc ions； The hydrophobic alkyl groups of MCBI cations will repel most of the free water molecules outside the anode， thereby reducing hydrogen evolution reaction （HER）. In this work， under the optimal concentration conditions， the Coulomb efficiency of Zn//Cu asymmetric cell with MCBI additive can reach 99.37% after 200 cycles； Zn//Zn symmetric batteries can stably cycle for more than 1600 h at low current density （0.5 mA/cm²）， and can cycle for more than 1000 h at 10 mA/cm²， 5 mA·h/cm². Finally， VO₂ as the cathode maintains a high-capacity retention rate of 88.5% after 500 cycles in the full battery. This work provides new ideas for the anode modification strategy of aqueous zinc ion batteries.

Key words: Aqueous zinc ion battery, Electrolyte, Additive, Zinc anode, Dendrite, Ionic liquid

中图分类号:

O626

徐磊, 王龙洋, 桃李, 张浩男, 贾鑫旺, 万厚钊, 张军, 王浩. 氮杂环咪唑离子液体用于水系锌离子电池负极无枝晶保护[J]. 应用化学, 2024, 41(7): 998-1009.

Lei XU, Long-Yang WANG, Li TAO, Hao-Nan ZHANG, Xin-Wang JIA, Hou-Zhao WAN, Jun ZHANG, Hao WANG. Long-Term Aqueous Zinc-Ion Batteries without Dendrites Protected by Nitrogen Heterocyclic Imidazole Ionic Liquid[J]. Chinese Journal of Applied Chemistry, 2024, 41(7): 998-1009.

图/表 7

图1 电池组装示意图

Fig.1 Diagram of assembling a battery

图2 锌离子电池的测试与负极表征图像A. Comparison of Zn//Zn symmetric battery cycling performance in electrolyte with or without ionic liquid additives； B. XRD pattern of zinc anode after electroplating/stripping cycle in different solutions； C. SEM image of Zn anode after circulating in pure ZSO electrolyte； D. SEM image of Zn anode after adding 10 mmol/L MCBI； E， F. Deposition of zinc foil in different electrolytes by in-situ optical microscopy

Fig.2 Test and characterization images of zinc-ion batteries

图3 扣式半电池的循环性能A. Coulomb efficiency of Zn//Cu asymmetric batteries under the action of MCBI additive with different concentration； B. Performance curve of Zn//Cu half battery 20th turn galvanizing/stripping under different concentration of MCBI additives

Fig.3 Cycle performance of asymmetric batteries

图4 锌离子电池负极的电化学性能A. LSV performance curves of different concentrations of MCBI additive electrolyt； B. Tafel corrosion polarization curve of MCBI electrolyte； C. CV curves of Zn//Cu batteries in different electrolytes were determined by cyclic voltammetry； D. Electrochemical impedance spectroscopy was used to measure the impedance of pure ZSO and MCBI additives before and after timing current； E. CA curve measured by chronoamperometry； F. Zinc ion transfer number fitting diagram

Fig.4 Electrochemical properties of anode of zinc ion battery

图5 Zn//Zn对称扣式电池的循环性能曲线A. Cyclic performance curve of symmetrical battery under 0.5 mA/cm2，1 mA·h/cm2 condition； B. Cyclic performance curve of symmetrical battery under 10 mA/cm2， 5 mA·h/cm2 condition； C. Rate performance of symmetrical batteries

Fig.5 Cycle performance curve of Zn//Zn symmetric battery

图6 Zn沉积的反应过程示意图以及对应Zn2+迁移和沉积的示意图A-C. Reaction diagram when the electrolyte is 2 mol/L ZnSO4； D-F. Reaction diagram when the electrolyte is 2 mol/L ZnSO4+10 mmol/L MCBI

Fig. 6 Diagram of reaction process of Zn deposition and corresponding Zn2+ migration and deposition

图7 Zn//VO2全电池的测试A. CV image of Zn//VO2 button full battery at 5 mV/s sweep speed in two electrolytes； B. Full battery cycle performance of Zn//VO2 button full battery at 5 A/g current density； C. GCD curves of Zn//VO2 full battery with different cycles in pure ZnSO4 electrolyte； D. GCD curves of Zn//VO2 full battery with different cycles under the action of MCBI additive； E. Rate performance of Zn//VO2 button full battery under two electrolytes； F. Zn//VO2 package full battery cycle performance

Fig.7 Zn//VO2 whole cell test

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