Enhancing Structural Stability and Electrochemical Performance of Ultra-high Ni-rich Co-free Cathode via MgHPO4 Dual-functional Modification

doi:10.1007/s40242-025-4246-2

高等学校化学研究 ›› 2025, Vol. 41 ›› Issue (2): 333-342.doi: 10.1007/s40242-025-4246-2

Enhancing Structural Stability and Electrochemical Performance of Ultra-high Ni-rich Co-free Cathode via MgHPO₄ Dual-functional Modification

LIN Huahui¹, SHEN Yu², WEI Li¹, SONG Ran¹, WU Fan¹, WEI Peng¹, YANG Zhenzhong², REN Yurong¹, QU Ke², DING Zhengping¹

1. Changzhou Key Laboratory of Intelligent Manufacturing and Advanced Technology for Power Battery, Jiangsu Province Engineering Research Center of Intelligent Manufacturing Technology for the New Energy Vehicle Power Battery, School of Materials Science and Engineering, Changzhou University, Changzhou 213164, P. R. China;
2. Key Laboratory of Polar Materials and Devices (MOE), Shanghai Center of Brain-inspired Intelligent Materials and Devices, Department of Electronics, East China Normal University, Shanghai 200241, P. R. China

收稿日期:2024-02-19 接受日期:2025-02-17 出版日期:2025-04-01 发布日期:2025-03-31
通讯作者: QU Ke,kqu@chem.ecnu.edu.cn;DING Zhengping,zhengpingding@cczu.edu.cn E-mail:kqu@chem.ecnu.edu.cn;zhengpingding@cczu.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (Nos. 52203291, U22A20420, 52202235).

Enhancing Structural Stability and Electrochemical Performance of Ultra-high Ni-rich Co-free Cathode via MgHPO₄ Dual-functional Modification

LIN Huahui¹, SHEN Yu², WEI Li¹, SONG Ran¹, WU Fan¹, WEI Peng¹, YANG Zhenzhong², REN Yurong¹, QU Ke², DING Zhengping¹

1. Changzhou Key Laboratory of Intelligent Manufacturing and Advanced Technology for Power Battery, Jiangsu Province Engineering Research Center of Intelligent Manufacturing Technology for the New Energy Vehicle Power Battery, School of Materials Science and Engineering, Changzhou University, Changzhou 213164, P. R. China;
2. Key Laboratory of Polar Materials and Devices (MOE), Shanghai Center of Brain-inspired Intelligent Materials and Devices, Department of Electronics, East China Normal University, Shanghai 200241, P. R. China

Received:2024-02-19 Accepted:2025-02-17 Online:2025-04-01 Published:2025-03-31
Contact: QU Ke,kqu@chem.ecnu.edu.cn;DING Zhengping,zhengpingding@cczu.edu.cn E-mail:kqu@chem.ecnu.edu.cn;zhengpingding@cczu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (Nos. 52203291, U22A20420, 52202235).

摘要/Abstract

摘要： Ultra-high nickel layered cathodes (Ni≥95%) have emerged as prospective candidates for next-generation lithium-ion batteries (LIBs) due to their exceptional specific capacity and costeffectiveness. However, the commercial application of these cathodes has been hindered by several challenges, including structural instability during cycling, high sensitivity to air, and slow Li⁺ migration. In this research, a one-step modification strategy was developed to simultaneously achieve Mg doping and Li₃PO₄ layer coating for the ultra-high nickel cathodes. Characterization results demonstrated that Mg doping not only alleviates lattice strain changes during the H2-H3 phase transition (H2: the second hexagonal phase; H3: the third hexagonal phase) but also serves as a structural anchor, preventing Ni²⁺ migration and occupation within the Li layer. The Li₃PO₄ surface coating layer acts as an electrochemical shield, protecting against interfacial side reactions and enhancing the Li+ diffusion rate. As a result, the LiNi_0.95Mn_0.05O₂ cathode, with both internal and external modifications, demonstrates significant improvement in cycling stability (85.7% capacity retention after 100 cycles) and Li⁺ transport performance (130.6 mA·h·g^-1 at 10 C, 1 C=189.6 mA·h·g^-1), providing a solid foundation for the further development and application of ultra-high nickel cathodes.

关键词: Lithium-ion battery, Ni-rich Co-free cathode, MgHPO₄, Surface modification

Abstract: Ultra-high nickel layered cathodes (Ni≥95%) have emerged as prospective candidates for next-generation lithium-ion batteries (LIBs) due to their exceptional specific capacity and costeffectiveness. However, the commercial application of these cathodes has been hindered by several challenges, including structural instability during cycling, high sensitivity to air, and slow Li⁺ migration. In this research, a one-step modification strategy was developed to simultaneously achieve Mg doping and Li₃PO₄ layer coating for the ultra-high nickel cathodes. Characterization results demonstrated that Mg doping not only alleviates lattice strain changes during the H2-H3 phase transition (H2: the second hexagonal phase; H3: the third hexagonal phase) but also serves as a structural anchor, preventing Ni²⁺ migration and occupation within the Li layer. The Li₃PO₄ surface coating layer acts as an electrochemical shield, protecting against interfacial side reactions and enhancing the Li+ diffusion rate. As a result, the LiNi_0.95Mn_0.05O₂ cathode, with both internal and external modifications, demonstrates significant improvement in cycling stability (85.7% capacity retention after 100 cycles) and Li⁺ transport performance (130.6 mA·h·g^-1 at 10 C, 1 C=189.6 mA·h·g^-1), providing a solid foundation for the further development and application of ultra-high nickel cathodes.

Key words: Lithium-ion battery, Ni-rich Co-free cathode, MgHPO₄, Surface modification

LIN Huahui, SHEN Yu, WEI Li, SONG Ran, WU Fan, WEI Peng, YANG Zhenzhong, REN Yurong, QU Ke, DING Zhengping. Enhancing Structural Stability and Electrochemical Performance of Ultra-high Ni-rich Co-free Cathode via MgHPO₄ Dual-functional Modification[J]. 高等学校化学研究, 2025, 41(2): 333-342.

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Enhancing Structural Stability and Electrochemical Performance of Ultra-high Ni-rich Co-free Cathode via MgHPO₄ Dual-functional Modification

Enhancing Structural Stability and Electrochemical Performance of Ultra-high Ni-rich Co-free Cathode via MgHPO₄ Dual-functional Modification

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