Unlocking the Critical Role of Cations Doping in MnO2 Cathode with Enhanced Reaction Kinetics for Aqueous Zinc Ion Batteries

IF 18.5 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Taotao Li, Nan Zhang, Bingchen Liu, Pengfei Wang, Zonglin Liu, Yuange Wang, Dinghao Xu, Hao Tian, Qianyu Zhang, Ting-Feng Yi
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引用次数: 0

Abstract

MnO2-based cathode aqueous rechargeable zinc-ion batteries (ZIBs) have favorable sustainability characteristics and are considered potential candidates for low-cost effective, high-safety energy storage systems. Nevertheless, the development of them has been hampered by unstable electrode structures and ambiguous charge storage mechanisms. Herein, the role of doping Fe3+ and Co2+ into δ-MnO2 cathode materials (FMO, CMO) is comprehensively probed and the working mechanism of Zn//FMO, Zn//CMO batteries are studied using in situ and ex situ characterization, electrochemical analysis, and theoretical calculations. Metal cations can partially replace Mn to form M─O bonds and enhance the structural stability as well as redox activity of MnO2. It is found that Fe doping effectively modulates the interaction between Zn2+/H+ and the MnO2 structure and inhibits the formation of ZnMn2O4 (ZMO) by-products and Co doping confers the fast diffusion ability of Zn2+. The charge storage reactions of FMO and CMO are mainly via H+/Zn2+ intercalation/deintercalation accompanied by OTF-base-like double hydroxide Znx(OTF)y(OH)2x-y-nH2O (Z-LDH) deposition/dissolution. This research enriches the fundamental comprehension of rechargeable ZIBs and reveals the way to modify electrodes for performance enhancement.

Abstract Image

阳离子掺杂在MnO2正极中的关键作用及增强锌离子电池反应动力学
二氧化锰基阴极水可充电锌离子电池(zib)具有良好的可持续性,被认为是低成本、高效、高安全的储能系统的潜在候选者。然而,由于电极结构不稳定和电荷存储机制不明确,阻碍了它们的发展。本文全面探讨了Fe3+和Co2+掺杂在δ-MnO2正极材料(FMO、CMO)中的作用,并通过原位和非原位表征、电化学分析和理论计算研究了Zn//FMO、Zn//CMO电池的工作机理。金属阳离子可以部分取代Mn形成M─O键,增强MnO2的结构稳定性和氧化还原活性。结果表明,Fe掺杂有效调节了Zn2+/H+与MnO2结构的相互作用,抑制了ZnMn2O4 (ZMO)副产物的形成,Co掺杂使Zn2+具有快速扩散的能力。FMO和CMO的电荷储存反应主要是H+/Zn2+的插入/脱嵌反应,并伴有OTF碱类双氢氧化物Znx(OTF)y(OH)2x-y-nH2O (Z-LDH)的沉积/溶解。本研究丰富了对可充电电极的基本理解,并揭示了改进电极以提高性能的方法。
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 Functional Materials
Advanced Functional Materials 工程技术-材料科学:综合
CiteScore
29.50
自引率
4.20%
发文量
2086
审稿时长
2.1 months
期刊介绍: Firmly established as a top-tier materials science journal, Advanced Functional Materials reports breakthrough research in all aspects of materials science, including nanotechnology, chemistry, physics, and biology every week. Advanced Functional Materials is known for its rapid and fair peer review, quality content, and high impact, making it the first choice of the international materials science community.
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