聚阴离子COFs基复合膜稳定水系锌离子电池负极的研究

doi:10.19799/j.cnki.2095-4239.2024.1132

摘要/Abstract

摘要：

水系锌离子电池(AZIBs)因其低成本、无毒性及高理论容量等优势，被视为大规模和长期储能领域的理想之选。然而，锌负极不可控地枝晶生长、表面腐蚀和析氢反应等问题，严重限制了AZIBs的实际应用。本工作提出了一种通过聚阴离子共价有机骨架(COFs)纳米片涂覆PP隔膜制备复合隔膜设计，旨在稳定锌负极。所制备的COFs材料具有独特的纳米孔径和丰富的阴离子基团，能够有效筛选离子，抑制SO₄^2-的迁移，并均匀化Zn²⁺通量，诱导Zn²⁺在(002)晶面的择优取向，从而实现了Zn²⁺的均匀沉积。因此，使用复合隔膜可实现高锌离子的迁移数(0.68)和较高的电导率(13.8 mS/cm)。基于该隔膜组装的对称电池在1 mA /cm²、1 mAh/cm²条件下，展现出超过600 h的循环稳定性，表现出高度可逆的电镀/剥离行为。此外，使用NaV₃O₈·1.5H₂O作为正极材料的全电池，表现出高的初始容量(261.5 mAh/g)且可稳定循环超过900圈。该研究为水系电池的隔膜设计提供了新思路，为高容量、无枝晶和规模化应用的水系锌离子电池的实现奠定了基础。

关键词: 水系锌离子电池, 聚阴离子COFs, 锌枝晶, 电化学性能

Abstract:

Aqueous zinc-ion batteries (AZIBs) have emerged as promising candidates for large-scale and long-term energy storage because of their low cost, nontoxicity, and high theoretical capacity. However, issues such as uncontrolled Zinc (Zn) dendrite growth, surface corrosion, and hydrogen evolution at the Zn anode hinder their practical applications. In this study, a composite separator was developed by coating polypropylene (PP) separators with polyanionic covalent organic frameworks (COFs) nanosheets to stabilize the Zn anode. The prepared COF material, featuring unique nanopores and abundant anionic groups, exhibits ion-sieving properties that inhibit the migration of SO₄^2- ions while homogenizing the Zn²⁺ flux. This unique architecture induces a preferential orientation of Zn²⁺ deposition on the (002) plane. As a result, cells using the COF-PP separator achieved a high zinc-ion transference number (0.68) and high ionic conductivity (13.8 mS/cm). The Zn/Zn symmetric cell using COF-PP separators demonstrated cycling stability, exhibiting highly reversible plating/stripping behavior that exceeded 600 h at 1 mA/cm²/1 mAh/cm². Furthermore, when paired with a NaV₃O₈·1.5H₂O cathode, the full cell achieved an impressive initial capacity of 261.5 mAh/g while retaining remarkable stability over 900 cycles. This study provides a novel approach for the development of separators for aqueous batteries, enabling the realization of high-capacity, dendrite-free, and scaleable aqueous zinc-ion batteries.

Key words: aqueous zinc-ion batteries, polyanionic COFs, Zn dendrites, electrochemical performance

中图分类号:

TM 912

冷杨, 黄硕, 桂凯旋, 闫文其, 刘琪. 聚阴离子COFs基复合膜稳定水系锌离子电池负极的研究[J]. 储能科学与技术, 2025, 14(5): 1900-1909.

Yang LENG, Shuo HUANG, Kaixuan GUI, Wenqi YAN, Qi LIU. Study on polyanionic COFs-based composite separators for stabilizing aqueous zinc-ion battery anodes[J]. Energy Storage Science and Technology, 2025, 14(5): 1900-1909.

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