Journal Article

PUBDB-2025-02172

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Exploring the Mechanism of Surface Cationic Vacancy Induces High Activity of Metastable Lattice Oxygen in Li‐ and Mn‐Rich Cathode Materials

Zhao, T. ; Zhang, J.Extern* ; Wang, K. ; Xiao, Y. (Corresponding author) ; Wang, Q. ; Li, L. ; Tseng, J. ; Chen, M.-C. ; Ma, J.-J.Extern* ; Lu, Y.-R. ; Hirofumi, I. ; Shao, Y.-C.Extern* ; Zhao, X. (Corresponding author) ; Hung, S.-F.Extern*XFEL.EU* ; Su, Y. ; Mu, X. ; Hua, W. (Corresponding author)Extern*

2025
Wiley-VCH Weinheim

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Please use a persistent id in citations: doi:10.1002/ange.202419664

Abstract: Li- and Mn-rich layered oxides exhibit high specific capacity due to the cationic and anionic reaction process during high-voltage cycling (≥4.6 V). However, they face challenges such as low initial coulombic efficiency (~70 %) and poor cycling stability. Here, we propose a combination of H3BO3 treatment and low temperature calcination to construct a shell with cationic vacancy on the surface of Li1.2Ni0.2Mn0.6O2 (LLNMO). The H3BO3 treatment produces cationic vacancy and lattice distortion, forming an oxidized On− (0<n<2) on the surface, accompanied by electrons redistribution. Low temperature calcination eliminates lattice distortion, activates metastable On− and promotes coherent lattice formation. In addition, the cationic vacancy shell reduces the diffusion energy barrier of Li+, allowing more Li+ and oxygen to participate in deeper reactions and increasing the oxidation depth of oxygen. The modified material (LLNMO-H10-200) exhibits an initial coulombic efficiency of up to 88 % and a capacity of 256 mAh g−1. Moreover, similar enhancements were observed with Co-containing lithium-rich materials, with a 280 mAh g−1 discharge capacity and 89 % coulombic efficiency. These findings reveal the correlation between cationic vacancy, metastable oxygen activation and bulk phase activity, offering a novel approach to enhancing the initial coulombic efficiency and cycle stability of Li-rich materials.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)

Experiment(s):

1. PETRA Beamline P02.1 (PETRA III)
2. PETRA Beamline P64 (PETRA III)

Appears in the scientific report 2025

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Database coverage:
; DEAL Wiley ; Ebsco Academic Search ; Nationallizenz ; SCOPUS

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