Degradation of α-MnO2 in Zn-air battery gas-diffusion electrodes: An investigation based on chemical-state mapping

IF 5.5 3区 材料科学 Q1 ELECTROCHEMISTRY
Benedetto Bozzini , Alessandro Alleva , Valentina Bonanni , Regina Ciancio , George Kourousias , Francesco Guzzi , Piu Rajak , Alessandra Gianoncelli
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Abstract

Rechargeable zinc-air batteries (RZABs) could enable cheap and safe high energy density electrochemical energy storage, but durability issues impair their real-life implementation, both Zn anodes and oxygen gas-diffusion electrodes (GDEs) exhibiting cyclability issues. This study focusses on the electrochemical operation and durability of GDEs based on α-MnO2 nanowires and Ni-core / NiO shell nanoparticles (Ni@NiO) nanoparticles (NPs) as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts. Specifically, we concentrated on chemical-state mapping with sub-micrometre resolution of electrocatalyst clusters extracted from GDEs operated under well-characterized electrochemical conditions closely representative of real-life conditions. This approach is enabled by synchrotron-based Scanning Transmission X-ray Spectro-Microscopy (STXSM), complemented by high-resolution Transmission Electron Microscopy (TEM) to assess the correlated morphological and structural changes of electrocatalyst units. Specifically, this work analyses the performance of monofunctional and bifunctional GDEs aged electrochemically under ORR or ORR/OER cycling conditions in 6 M KOH electrolyte without and with Zn2+ addition. In brief, GDE activity was found to correlate with the spatial correlation Mn(III) and Mn(IV), the species that favour the 4-electron ORR mechanism. Instead, degradation is accompanied by the formation of Mn(II)- and Mn(IV)-rich islands of dead electrocatalyst, Mn(III)/Mn(IV) uncorrelation, resulting from cathodic an anodic stress due to high anodic polarization in monofunctional GDEs or to the formation of inactive Zn2+-containing phases. Ni@NiO NPs reduce anodic stress stabilizing Mn(III)/Mn(IV) correlation.

Abstract Image

Abstract Image

基于化学态映射的zn -空气电池气体扩散电极α-MnO2降解研究
可充电锌空气电池(RZABs)可实现廉价、安全的高能量密度电化学储能,但耐久性问题影响了其在现实生活中的应用,锌阳极和氧气气体扩散电极(GDEs)都表现出循环性问题。本研究的重点是以α-MnO2纳米线和镍核/镍氧化物壳纳米颗粒(Ni@NiO)为基础的GDEs的电化学操作和耐久性,作为氧还原反应(ORR)和氧进化反应(OER)的电催化剂。具体来说,我们集中研究了从 GDEs 中提取的电催化剂团簇的亚微米级分辨率的化学状态图谱,GDEs 是在与实际生活条件密切相关的表征良好的电化学条件下运行的。这种方法通过同步辐射扫描透射 X 射线分光显微镜 (STXSM) 以及高分辨率透射电子显微镜 (TEM) 来实现,以评估电催化剂单元的相关形态和结构变化。具体来说,这项研究分析了单功能和双功能 GDE 在 6 M KOH 电解液中不添加和添加 Zn2+ 的 ORR 或 ORR/OER 循环条件下的电化学老化性能。简而言之,研究发现 GDE 的活性与 Mn(III)和 Mn(IV)的空间相关性有关,Mn(III)和 Mn(IV)是有利于 4 电子 ORR 机制的物种。相反,降解伴随着富含 Mn(II)- 和 Mn(IV)- 的死电催化剂岛的形成、Mn(III)/Mn(IV) 的非相关性,这是由于单功能 GDE 的高阳极极化或含 Zn2+ 的非活性相的形成所导致的阴阳极应力造成的。Ni@NiO NPs 可降低阳极应力,稳定锰(III)/锰(IV)的相关性。
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来源期刊
Electrochimica Acta
Electrochimica Acta 工程技术-电化学
CiteScore
11.30
自引率
6.10%
发文量
1634
审稿时长
41 days
期刊介绍: Electrochimica Acta is an international journal. It is intended for the publication of both original work and reviews in the field of electrochemistry. Electrochemistry should be interpreted to mean any of the research fields covered by the Divisions of the International Society of Electrochemistry listed below, as well as emerging scientific domains covered by ISE New Topics Committee.
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