Annealing in Argon Universally Upgrades the Na‐Storage Performance of Mn‐Based Layered Oxide Cathodes by Creating Bulk Oxygen Vacancies

Jin, Junteng; Liu, Yongchang; Zhao, Xudong; Liu, Hui; Deng, Shiqing; Shen, Qiuyu; Hou, Ying; Qi, He; Xing, Xianran; Jiao, Lifang; Chen, Jun

doi:10.1002/anie.202219230

Annealing in Argon Universally Upgrades the Na‐Storage Performance of Mn‐Based Layered Oxide Cathodes by Creating Bulk Oxygen Vacancies

Journal Article · 28 February 2023 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202219230· OSTI ID:2423286

Jin, Junteng ^[1]; ^[2]; Zhao, Xudong ^[3]; ^[1]; ^[1]; Shen, Qiuyu ^[3]; Hou, Ying ^[1]; ^[1]; ^[1]; ^[4]; ^[1]

Beijing Advanced Innovation Center for Materials Genome Engineering Department of Physical Chemistry University of Science and Technology Beijing Beijing 100083 China
Beijing Advanced Innovation Center for Materials Genome Engineering Department of Physical Chemistry University of Science and Technology Beijing Beijing 100083 China; Institute for Advanced Materials and Technology State Key Laboratory for Advanced Metals and Materials University of Science and Technology Beijing Beijing 100083 China
Institute for Advanced Materials and Technology State Key Laboratory for Advanced Metals and Materials University of Science and Technology Beijing Beijing 100083 China
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Nankai University Tianjin 300071 China

Abstract

Manganese‐rich layered oxide cathodes of sodium‐ion batteries (SIBs) are extremely promising for large‐scale energy storage owing to their high capacities and cost effectiveness, while the Jahn–Teller (J–T) distortion and low operating potential of Mn redox largely hinder their practical applications. Herein, we reveal that annealing in argon rather than conventional air is a universal strategy to comprehensively upgrade the Na‐storage performance of Mn‐based oxide cathodes. Bulk oxygen vacancies are introduced via this method, leading to reduced Mn valence, lowered Mn 3d‐orbital energy level, and formation of the new‐concept Mn domains. As a result, the energy density of the model P2‐Na_0.75Mg_0.25Mn_0.75O₂cathode increases by ≈50 % benefiting from the improved specific capacity and operating potential of Mn redox. The Mn domains can disrupt the cooperative J–T distortion, greatly promoting the cycling stability. This exciting finding opens a new avenue towards high‐performance Mn‐based oxide cathodes for SIBs.

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 2423286

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 15 Vol. 62; ISSN 1433-7851

Publisher:: Wiley

Country of Publication:: United States

Language:: English

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