基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑

doi:10.3866/PKU.WHXB202309003

物理化学学报 >> 2025, Vol. 41 >> Issue (1): 100003.doi: 10.3866/PKU.WHXB202309003

所属专题：能源化学

基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑

李尚华¹^,², 李玛琳¹^,*(), 迟茜文¹^,², 尹心¹, 罗招娣¹, 于吉红¹^,²^,*()

¹ 吉林大学化学学院, 无机合成与制备化学国家重点实验室, 长春 130012
² 吉林大学未来科学国际合作联合实验室, 长春 130012

收稿日期:2023-09-01 修回日期:2023-09-25 录用日期:2023-10-09 发布日期:2023-12-20
通讯作者: Email: jihong@jlu.edu.cn (于吉红)malinl@jlu.edu.cn (李玛琳)
基金资助:
国家自然科学基金(22288101); 国家自然科学基金(21920102005); 国家自然科学基金(21835002); 国家自然科学基金(22109050); “111计划”(B17020)

High-Stable Aqueous Zinc Metal Anodes Enabled by an Oriented ZnQ Zeolite Protective Layer with Facile Ion Migration Kinetics

Shanghua Li¹^,², Malin Li¹^,*(), Xiwen Chi¹^,², Xin Yin¹, Zhaodi Luo¹, Jihong Yu¹^,²^,*()

¹ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China
² International Center of Future Science, Jilin University, Changchun 130012, China

Received:2023-09-01 Revised:2023-09-25 Accepted:2023-10-09 Published:2023-12-20
Contact: Email: jihong@jlu.edu.cn (Jihong Yu)malinl@jlu.edu.cn (Malin Li)
Supported by:
the National Natural Science Foundation of China(22288101); the National Natural Science Foundation of China(21920102005); the National Natural Science Foundation of China(21835002); the National Natural Science Foundation of China(22109050); the 111 Project(B17020)

1. 附件.pdf(2718KB)

摘要/Abstract

摘要：

水系锌离子电池以其安全可靠、成本低、容量大、环境友好等优点被认为是最有前途的储能体系之一。然而，锌金属负极在水系电解液中通常面临严重的副反应和枝晶生长问题。在锌负极表面构建具有高离子迁移动力学的保护层是构筑高稳定、长寿命锌负极的有效策略。本文中，我们在锌负极表面制备了ZnQ分子筛(BPH拓扑)取向保护层，实现了高离子迁移动力学的稳定锌负极(ZnQ@Zn)的构筑。具有三维有序孔道的ZnQ分子筛在锌箔表面定向排列，为锌离子提供了良好的传导通路，分子筛孔道中的水分子有助于调控锌离子的配位环境，从而提高锌离子的迁移动力学。因此，ZnQ@Zn对称电池在1 mA∙cm⁻²的电流密度下展现出27 mV的超低过电势以及超过1100 h的循环寿命。此外，ZnQ@Zn//NaV₃O₈·1.5H₂O全电池在8 A∙g⁻¹的电流密度下循环1800次后，容量保持率高达96%，展现出优异的循环性能。本研究为构筑高迁移动力学锌负极保护层提供了新思路，并拓展了分子筛材料在储能领域中的应用。

关键词: 水系锌离子电池, 锌金属负极, 保护层, ZnQ分子筛, 离子迁移动力学

Abstract:

Aqueous zinc ion batteries (ZIBs) are regarded as one of the most promising energy storage systems due to their reliable safety, low cost, high volumetric capacity, and environmental friendliness. However, the utilization of Zn metal anode in aqueous electrolyte commonly encounters complex water-induced side reactions and uncontrollable dendrite growth issues. Constructing a protective layer on the surface of Zn anode is an effective strategy to alleviate side reactions and dendrite growth, achieving the stable operation of ZIBs with prolonged cycling life. However, the utilization of protective layers will increase interfacial resistance and result in high polarization in most cases. Thus, developing a desirable artificial protective layer with high ion migration kinetics is a significant task, enabling a fast Zn²⁺ ion flux for homogeneous deposition with low polarization. Considering that porous aluminosilicate zeolite with a low Si/Al ratio can accommodate abundant framework-associated cations as charge carriers for conduction, herein, we prepared an oriented protective layer on the Zn anode using Zn-ion-exchanged Q zeolite with BPH topology (ZnQ@Zn), achieving a stable Zn anode with high ion migration kinetics. The ZnQ zeolite plates parallelly lay on the surface of Zn foil with the c axis normal to the substrate plane. The three-dimensional ordered channels and the oriented arrangement of ZnQ zeolite plates provide facile ion migration pathways for Zn²⁺ ions, and the coordination of framework-associated Zn²⁺ ions with water in zeolite channels also enables fast ion conduction kinetics and high corrosion resistance. Therefore, ZnQ@Zn exhibits enhanced ion conduction kinetics with reduced energy barriers for desolvation, charge transfer, and diffusion processes, resulting in a uniform ion flux to suppress dendrite growth. Consequently, the ZnQ@Zn symmetric cell displays an ultra-low voltage hysteresis of 27 mV with a long lifespan of over 1100 h at 1 mA∙cm⁻² and 1 mAh∙cm⁻². Moreover, the ZnQ@Zn//NaV₃O₈·1.5H₂O full cell delivers a superior long-term cycling performance with a high capacity retention of 96% after 1800 cycles at 8 A∙g⁻¹. This work provides a new sight for constructing protective layers with fast ion migration kinetics to achieve high-stable Zn anodes, and extends the application of zeolite-based ion-conductive materials in energy storage devices.

Key words: Aqueous zinc ion battery, Zn metal anode, Protective layer, ZnQ zeolite, Ion migration kinetics

李尚华, 李玛琳, 迟茜文, 尹心, 罗招娣, 于吉红. 基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑[J]. 物理化学学报, 2025, 41(1), 100003. doi: 10.3866/PKU.WHXB202309003

Shanghua Li, Malin Li, Xiwen Chi, Xin Yin, Zhaodi Luo, Jihong Yu. High-Stable Aqueous Zinc Metal Anodes Enabled by an Oriented ZnQ Zeolite Protective Layer with Facile Ion Migration Kinetics[J]. Acta Phys. -Chim. Sin. 2025, 41(1), 100003. doi: 10.3866/PKU.WHXB202309003

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202309003

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I1/100003

图/表 5

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基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑

High-Stable Aqueous Zinc Metal Anodes Enabled by an Oriented ZnQ Zeolite Protective Layer with Facile Ion Migration Kinetics

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