无机材料学报

• 研究论文 •    

高稳定性锰基钠离子电池正极材料的双位点掺杂研究

刘德新1, 赵宇泽1, 朱正伟1, 问研良1, 洪明子1, 何伟艳2   

  1. 1.鄂尔多斯实验室,鄂尔多斯 017010;
    2.内蒙古工业大学化工学院,呼和浩特 010051
  • 收稿日期:2025-12-23 修回日期:2026-02-28
  • 通讯作者: 问研良,副教授. E-mail: wenyanliang@163.com; 洪明子, 教授. E-mail: hongmingzi@ordoslab.cn
  • 作者简介:刘德新 (1999-),男,硕士研究生. E-mail: liudexin@ordoslab.cn
  • 基金资助:
    2025年鄂尔多斯实验室工程研究项目(ordoslabpt202501); 自治区科技创新发展专项资金(Ordoslab-kjzc-202504)

Dual-Site Doping for High-stability Manganese-based Cathode Materials in Sodium-ion Batteries

LIU Dexin1, ZHAO Yuze1, ZHU Zhengwei1, WEN Yanliang1, HONG Mingzi1, HE Weiyan2   

  1. 1. Ordos laboratory, Ordos 017010, China;
    2. School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China
  • Received:2025-12-23 Revised:2026-02-28
  • Contact: WEN Yanliang, associate professor. E-mail: wenyanliang@ordoslab.cn; HONG Mingzi, professor. E-mail: hongmingzi@ordoslab.cn
  • About author:LIU Dexin (1999-), male, Master candidate. E-mail: liudexin@ordoslab.cn
  • Supported by:
    2025 Ordos Laboratory Engineering Research Project (ordoslabpt202501); Autonomous Region Science and Technology Innovation Development Special Fund of China (Ordoslab-kjzc-202504)

摘要: 钠离子电池(SIBs)具有环境友好、原料储量丰富、成本低廉等优势,已经成为锂离子电池在储能领域的重要补充甚至替代者,具有广阔的应用前景。然而,锰基SIBs正极材料存在的结构不稳定、循环稳定性差等问题,严重地制约了SIBs的应用。本研究以O3-NaMnO2为基体,探究了K/Cu双位点掺杂对其电化学性能的影响与调控机制。理论计算及实验结果表明,在钠层中引入K+有效地提升了钠离子的扩散速率,同时在过渡金属层中掺杂Cu2+有效抑制了Mn3+的Jahn-Teller畸变,限制了正极材料在充放电过程中发生复杂相变,增强了材料的结构稳定性。K/Cu共掺杂打破了钠离子有序排列所形成的空位结构,激活了阴离子氧化还原反应,从而贡献了额外的比容量,并显著增强了材料的电子导电性。Na0.94K0.06Cu0.05Mn0.95O2在0.2C(1C=226.28 mAh/g)下首次放电比容量达201.16 mAh/g,100次循环后比容量保持率为85.67%,并且在1C和2C大电流循环后,回到0.5C仍可保持170.87 mAh/g的比容量,表现出优异的循环与倍率性能。这种双位点共掺杂策略为高性能SIBs正极材料的设计提供了新思路。

关键词: 钠离子电池, 双位点掺杂, 正极材料, 电化学性能

Abstract: Sodium-ion batteries (SIBs), benefiting from their environmental friendliness, abundant reserves, and low cost, have become the most important supplement even alternative for lithium-ion batteries and hold broad application potential in the field of energy storage. However, manganese-based cathode materials for SIBs face challenges such as structural instability and poor cycling stability, which severely limit their practical application. In this study, O3-NaMnO2 was used as the matrix to investigate the effects and underlying mechanisms of K/Cu dual-site doping on its electrochemical performance. Both theoretical calculations and experimental results demonstrate that the introduction of K into the sodium layer effectively enhances the diffusion rate of sodium ions, while Cu2+ doping in the transition metal layer effectively suppresses the Jahn-Teller distortion of Mn3+, thereby mitigating the complex phase transitions of the cathode material during charging and discharging, and improving its structural stability. K/Cu co-doping disrupts the vacancy structure formed by the ordered arrangement of sodium ions, activates anionic redox reactions, contributes additional specific capacity, and significantly enhances the electronic conductivity of the material. Na0.94K0.06Cu0.05Mn0.95O2 achieves an initial discharge specific capacity of 201.16 mAh/g at 0.2C (1C=226.28 mAh/g), and retains 85.67% of its specific capacity after 100 cycles. After high-current cycling at 1C and 2C, it still delivers 170.87 mAh/g at 0.5C, showing excellent cycling and rate performance. This co-doping strategy offers a new approach for the design of high-performance sodium-ion battery cathode materials.

Key words: sodium-ion battery, dual-site doping, cathode material, electrochemical performance

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