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Acta Chimica Sinica >

2025 , Vol. 83 >Issue 4: 369 - 376

DOI: https://doi.org/10.6023/A24120377

Article

Influence Research of Decentralized LiMn6 on Structural Stability and Oxidation Mechanism of Li1.17Ni0.17Fe0.17Mn0.49O2 Layered Cathode Materials

  • Xu Zhang ,
  • Xin Guo ,
  • Jiyang Zhang ,
  • Jihong Liu ,
  • Jiapeng Zhu ,
  • Chaoyang Huang ,
  • Ming Li ,
  • Guixiao Jia ,
  • Shengli An
Expand
  • a School of Materials Science and Engineering, Inner Mongolia University of Science and Technology, Inner Mongolia Key Laboratory of Advanced Ceramic Material and Devices, Key Laboratory of Green Extraction & Efficient Utilization of Light Rare-Earth Resources Inner Mongolia University of Science and Technology, Ministry of Education, Baotou 014010, China
    b School of Rare Earth Industry, Inner Mongolia University of Science and Technology, Baotou 014010, China
    c State Key Laboratory of Public Big Data, Guizhou University, Guiyang 550025, China
* E-mail: ; Tel.: 13015151366

Received date: 2024-12-21

  Online published: 2025-03-06

Supported by

National Natural Science Foundation of China(52262039); Inner Mongolia Autonomous Region Natural Science Foundation Program(2024FX19); Basic research expenses of universities directly under the Inner Mongolia Autonomous Region

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Abstract

Lithium-rich layered oxides (LLOs) are a favorable competitor for the next generation of high-capacity lithium-ion battery cathode materials. However, the doped Co in LLOs materials is not only expensive, but also harmful to the environment. Furthermore, in LLOs cathodes, the aggregation of Li2MnO3 domains and lattice oxygen release lead to severe capacity/voltage degradation, ultimately impeding their commercial viability. Therefore, in this work, we substituted environmentally friendly and cost-effective Fe for Co, and designed two structural models—local distribution (LD) and delocalized distribution (DD) in the Li1.17Ni0.17Fe0.17Mn0.49O2 system. A spin-polarized generalized gradient approximation (GGA) method with the PBE (Perdew-Burke-Ernzerhof) exchange-correlation functional was explored. A 2×2×1 supercell with a total of 96 atoms, namely Li28Fe4Ni4Mn12O48 is selected. We systematically investigated geometrical and electronic structures of DD and LD systems, oxidation processes, oxygen release enthalpy, transition metal ion migration and the role of Fe using density functional theory (DFT) calculations. It was found that the doped Fe activates more interfacial oxygen ions to participate to the charge compensation and disperses oxygen oxidation, thereby sharing the oxidation pressure of oxygen in the Li-O-Li configuration, which would be beneficial for suppressing the release of lattice oxygen. The dispersed LiMn6 in the Li1.17Ni0.17Fe0.17Mn0.49O2 system inhibits the Jahn-Teller distortion caused by Fe and the migration of Mn4+ ions, thus stabilizing the structures. Oxygen in the linear Li-O-Li structure serves as the primary redox center, driving the redox reactions. Additionally, oxygen in Fe-O-Li-based systems also participates in the oxidation process. Specifically, the oxygen in the LiTMO2 phase contributes to the early-stage oxidation, while oxygen at the interface between the LiTMO2 and Li2MnO3 phases plays a role in the later stages of oxidation. This work provides new insights into the design of lithium-rich layered cathode materials without Co and with the high structural stability and the high capacity for lithium-ion batteries.

Key words： disperse LiMn6; Fe doping; Jahn-Teller effect; migration of Mn4+; first principles calculations

Cite this article

Xu Zhang , Xin Guo , Jiyang Zhang , Jihong Liu , Jiapeng Zhu , Chaoyang Huang , Ming Li , Guixiao Jia , Shengli An . Influence Research of Decentralized LiMn6 on Structural Stability and Oxidation Mechanism of Li1.17Ni0.17Fe0.17Mn0.49O2 Layered Cathode Materials[J]. Acta Chimica Sinica, 2025 , 83(4) : 369 -376 . DOI: 10.6023/A24120377

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