Issue 32, 2023

“Mn-locking” effect by anionic coordination manipulation stabilizing Mn-rich phosphate cathodes

Abstract

High-voltage cathodes with high power and stable cyclability are needed for high-performance sodium-ion batteries. However, the low kinetics and inferior capacity retention from structural instability impede the development of Mn-rich phosphate cathodes. Here, we propose light-weight fluorine (F) doping strategy to decrease the energy gap to 0.22 eV from 1.52 eV and trigger a “Mn-locking” effect—to strengthen the adjacent chemical bonding around Mn as confirmed by density functional theory calculations, which ensure the optimized Mn ligand framework, suppressed Mn dissolution, improved structural stability and enhanced electronic conductivity. The combination of in situ and ex situ techniques determine that the F dopant has no influence on the Na+ storage mechanisms. As a result, an outstanding rate performance up to 40C and an improved cycling stability (1000 cycles at 20C) are achieved. This work presents an effective and widely available light-weight anion doping strategy for high-performance polyanionic cathodes.

Graphical abstract: “Mn-locking” effect by anionic coordination manipulation stabilizing Mn-rich phosphate cathodes

Supplementary files

Article information

Article type
Edge Article
Submitted
17 6 2023
Accepted
27 7 2023
First published
27 7 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 8662-8671

“Mn-locking” effect by anionic coordination manipulation stabilizing Mn-rich phosphate cathodes

W. Zhang, Y. Wu, Y. Dai, Z. Xu, L. He, Z. Li, S. Li, R. Chen, X. Gao, W. Zong, F. Guo, J. Zhu, H. Dong, J. Li, C. Ye, S. Li, F. Wu, Z. Zhang, G. He, Y. Lai and I. P. Parkin, Chem. Sci., 2023, 14, 8662 DOI: 10.1039/D3SC03095D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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