Anionic redox reaction triggered by trivalent Al3+ in P3-Na0.65Mn0.5Al0.5O2

Ding-Ren Shi; Tian Wang; Zulipiya Shadike; Lu Ma; Xiao-Qing Yang; Shu-Fen Chu; Zhi-Wei Zhao; Zhang-Quan Peng; Zheng-Wen Fu

doi:10.1039/D1CC00373A

Anionic redox reaction triggered by trivalent Al³⁺ in P3-Na_0.65Mn_0.5Al_0.5O₂†

Ding-Ren Shi,^a Tian Wang,^a Zulipiya Shadike,^b Lu Ma,^c Xiao-Qing Yang,

^b Shu-Fen Chu,^d Zhi-Wei Zhao,

^e Zhang-Quan Peng^f and Zheng-Wen Fu

*^a

Author affiliations

* Corresponding authors

^a Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, P. R. China
E-mail: zwfu@fudan.edu.cn

^b Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973, USA

^c National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, New York 11973, USA

^d Shanghai Key Laboratory of Advanced High-temperature Materials and Precision Forming, State Key Laboratory of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

^e State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

^f Laboratory of Advanced Spectro-electrochemistry and Li-ion Batteries, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Abstract

P3-Na_0.65Mn_0.5Al_0.5O₂ (NMAO) has been synthesized and studied as a cathode for sodium batteries, and shows anionic redox reaction (ARR) and exhibits a first charging capacity of ∼110 mA h g⁻¹. The electrochemical mechanism of NMAO was comprehensively investigated by X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and density functional theory (DFT) calculations. The reversible oxygen redox behaviour is triggered by Al³⁺ through oxygen quasi non-bonding states generated by the relatively ionic interaction of Al and O. Furthermore, the presence of Al³⁺ can suppress oxygen loss in ARR. This work provides new insights into the design and mechanism of anionic redox active cathode materials.

This article is part of the themed collection: Chemical Communications HOT articles

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Article information

DOI: https://doi.org/10.1039/D1CC00373A
Article type: Communication
Submitted: 22 Jan 2021
Accepted: 16 Feb 2021
First published: 17 Feb 2021

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Chem. Commun., 2021,57, 2867-2870

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Anionic redox reaction triggered by trivalent Al³⁺ in P3-Na_0.65Mn_0.5Al_0.5O₂

D. Shi, T. Wang, Z. Shadike, L. Ma, X. Yang, S. Chu, Z. Zhao, Z. Peng and Z. Fu, Chem. Commun., 2021, 57, 2867 DOI: 10.1039/D1CC00373A

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