Grotthuss Mechanism for Stable Zinc Anodes: Time‐Resolved pH Buffering in Aqueous Batteries

IF 26 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Advanced Energy Materials Pub Date : 2025-07-21 DOI:10.1002/aenm.202501529

Xuefeng Xu, Shuo San, Zhenjie Lu, Danil Boukhvalov, Liming Dai, Kai Liu, Chenchen Fang, Yaya Wang, Xiaoyuan Zhang, Huiru Duan, Tiannan Su, Rui Gao, Zhuolun Li, Wenyao Zhang, Pan Xiong, Yongsheng Fu, Jingwen Sun, Junwu Zhu

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引用次数: 0

Abstract

In zinc ion batteries, the curtailed lifespan and diminished Coulombic efficiency are primarily ascribed to the hydrogen evolution reaction, surface corrosion, and rampant dendrites, all related to unstable interfacial pH at the anode. To tackle these challenges, hydrogen‐bonded organic frameworks (HOFs) are designed possessing outstanding zincophilic and hydrogen storage capabilities on the surface of Zn, thereby creating a dendrite‐free anode (MACA@Zn). By leveraging the innate and reversible proton‐hopping mechanism of MACA, the interfacial pH at the anode is able to be controlled. In situ scanning electrochemical microscopy has demonstrated a time‐resolved local pH buffering effect. Moreover, the presence of MACA induces preferential growth of the (002) plane, resulting in a uniform and dense Zn deposition layer. Consequently, the Zn//Zn cell with MACA@Zn anode delivers an exceptional cycling stability of ≈2000 h at 5 mA cm−2 and 1 mAh cm−2, with a high cumulative plating capacity of 4950 mAh cm−2. When paired with an α‐MnO2 cathode, the cell retains a specific capacity of 70.4 mAh g−1 after 990 cycles, demonstrating a capacity retention of 44.87%. This research emphasizes the multifunctional protective effects of HOFs on the anode surface and offers critical insights for advancing the development and real‐world implementation of ZIBs.

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稳定锌阳极的Grotthuss机制：水溶液电池中时间溶解pH缓冲

锌离子电池的寿命缩短和库仑效率降低主要是由于析氢反应、表面腐蚀和大量枝晶，这些都与阳极界面pH不稳定有关。为了应对这些挑战，氢键有机框架（hof）被设计成在锌表面具有出色的亲锌和储氢能力，从而创造了一个无枝晶阳极（MACA@Zn）。利用MACA固有的可逆质子跳跃机制，可以控制阳极的界面pH值。原位扫描电化学显微镜已经证明了一种时间分辨的局部pH缓冲效应。此外，MACA的存在诱导（002）平面优先生长，形成均匀致密的Zn沉积层。因此，具有MACA@Zn阳极的Zn//Zn电池在5ma cm - 2和1mah cm - 2下具有≈2000 h的优异循环稳定性，具有4950 mAh cm - 2的高累积镀容量。当与α - MnO2阴极配对时，电池在990次循环后保持70.4 mAh g−1的比容量，显示容量保持率为44.87%。本研究强调了hof在阳极表面的多功能保护作用，并为推进zbs的开发和实际应用提供了重要的见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Advanced Energy Materials CHEMISTRY, PHYSICAL-ENERGY & FUELS

CiteScore

41.90

自引率

4.00%

发文量

889

审稿时长

1.4 months

期刊介绍： Established in 2011, Advanced Energy Materials is an international, interdisciplinary, English-language journal that focuses on materials used in energy harvesting, conversion, and storage. It is regarded as a top-quality journal alongside Advanced Materials, Advanced Functional Materials, and Small. With a 2022 Impact Factor of 27.8, Advanced Energy Materials is considered a prime source for the best energy-related research. The journal covers a wide range of topics in energy-related research, including organic and inorganic photovoltaics, batteries and supercapacitors, fuel cells, hydrogen generation and storage, thermoelectrics, water splitting and photocatalysis, solar fuels and thermosolar power, magnetocalorics, and piezoelectronics. The readership of Advanced Energy Materials includes materials scientists, chemists, physicists, and engineers in both academia and industry. The journal is indexed in various databases and collections, such as Advanced Technologies & Aerospace Database, FIZ Karlsruhe, INSPEC (IET), Science Citation Index Expanded, Technology Collection, and Web of Science, among others.