Al掺杂对富锰P2型Na0.67Fe0.30Mn0.70O2储钠性能的调控机理

doi:10.15541/jim20260223

无机材料学报

• 研究论文 • 下一篇

Al掺杂对富锰P2型Na_0.67Fe_0.30Mn_0.70O₂储钠性能的调控机理

谭知涵^1,2, 李堂逸^1,2, 陈炜豪^1,2, 卢涛^1,2, 龙震³, 邱国红^1,2

1.华中农业大学资源与环境学院,武汉 430070;
2.华中农业大学化学学院,新型农业功能材料创制与利用湖北省重点实验室,武汉 430070;
3.天津理工大学功能晶体研究院,天津功能晶体材料重点实验室,天津 300384

收稿日期:2026-05-20 修回日期:2026-08-30
通讯作者: 邱国红,教授. E-mail: qiugh@mail.hzau.edu.cn
作者简介:谭知涵(1998-), 男, 博士研究生. E-mail: tanzh@webmail.hzau.edu.cn
基金资助:
湖北省自然科学基金 (2026AFA021); 湖北省技术创新计划重点研发项目(2025BCB098); 国家自然科学基金 (42477023, 42077133); 湖北省创新计划重大科技项目(2024BCA006)

Regulation Mechanism of Al Doping on Sodium-storage Performance of Mn-rich P2-type Na_0.67Fe_0.30Mn_0.70O₂

TAN Zhihan^1,2, LI Tangyi^1,2, CHEN Weihao^1,2, LU Tao^1,2, LONG Zhen³, QIU Guohong^1,2

1. College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, China;
2. Hubei Key Laboratory of Agricultural Functional Materials, College of Chemistry, Huazhong Agricultural University, Wuhan 430070, China;
3. Institute of Functional Crystals, Tianjin Key Laboratory of Functional Crystal Materials, Tianjin University of Technology, Tianjin 300384, China

Received:2026-05-20 Revised:2026-08-30
Contact: QIU Guohong, professor. E-mail: qiugh@mail.hzau.edu.cn
About author:TAN Zhihan (1998-), male, PhD candidate. E-mail: tanzh@webmail.hzau.edu.cn
Supported by:
Hubei Provincial Natural Science Foundation (2026AFA021); Hubei Province Science and Technology Plan Project (2025BCB098); National Natural Science Foundation of China (42477023, 42077133); Hubei Province Technological Innovation Plan Project (2024BCA006)

摘要/Abstract

摘要： 因钠资源丰富、成本较低等优势,钠离子电池在规模化储能领域具有良好的应用前景。无Li/Co/Ni的层状氧化物正极材料兼具低成本和高容量优势,是推动钠离子电池产业化的重要方向。本研究以富锰P2型层状氧化物Na_0.67Fe_0.30Mn_0.70O₂为研究对象,采用溶胶凝胶法制备了不同Al掺杂量的Na_0.67Fe_0.30-_xMn_0.70Al_xO₂正极材料,并系统考察了Al掺杂对其晶体结构、微观形貌和电化学储钠性能的影响。结果表明,适量掺杂Al未改变材料的P2型层状结构,但使晶胞体积、Na层间距和过渡金属氧层厚度轻微收缩,并减小了材料的颗粒尺寸。其中,Na_0.67Fe_0.26Mn_0.70Al_0.04O₂表现出较优的综合电化学性能,首次放电比容量达到187.6 mAh·g^-1。倍率性能测试后,当电流密度恢复至20 mA·g^-1时,其可逆容量仍可达160.9 mAh·g^-1,明显高于Na_0.67Fe_0.30Mn_0.70O₂(120.0 mAh·g^-1)。进一步分析表明,适量掺杂Al能够降低材料的电荷转移阻抗,促进Na⁺扩散,并缓解充放电过程中的不可逆结构演变。上述结果说明,Al掺杂是提升富锰P2型铁锰基层状氧化物正极储钠性能的有效策略,可为设计低成本高容量的钠离子电池正极材料提供参考。

关键词: 钠离子电池, P2型层状氧化物, 富锰正极, Al掺杂, 电化学性能

Abstract: Owing to abundant sodium resources and low cost, sodium-ion batteries show promising prospects for large-scale energy storage. Developing Li/Co/Ni-free layered oxide cathode materials with low cost and high capacity is an important direction for promoting the industrialization of sodium-ion batteries. In this study, Mn-rich P2-type layered Na_0.67Fe_0.30Mn_0.70O₂ was selected as the parent material, and Na_0.67Fe_0.30-_xMn_0.70Al_xO₂ cathode materials with different Al doping contents were prepared by a Sol-Gel method. The effects of Al doping on crystal structure, microstructure, and electrochemical sodium-storage performance were systematically investigated. Appropriate Al doping does not change the P2-type layered structure, but slightly contracts the unit-cell volume, Na-layer spacing, and transition-metal-oxygen slab thickness, while reducing the particle size. Among them, Na_0.67Fe_0.26Mn_0.70Al_0.04O₂ exhibits better overall electrochemical performance, delivering an initial discharge capacity of 187.6 mAh·g^-1. After rate testing, its reversible capacity recovers to 160.9 mAh·g^-1 when the current density returns to 20 mA·g^-1, which is much higher than that of Na_0.67Fe_0.30Mn_0.70O₂ (120.0 mAh·g^-1). Appropriate Al doping reduces charge-transfer resistance, promotes Na⁺ diffusion, and alleviates irreversible structural evolution during charge-discharge processes. These results demonstrate that Al doping is an effective strategy for improving the sodium-storage performance of Mn-rich P2-type Fe-Mn-based layered oxide cathodes, providing a reference for the design of low-cost and high-capacity cathode materials for sodium-ion batteries.

Key words: sodium-ion battery, P2-type layered oxide, Mn-rich cathode, Al doping, electrochemical performance

谭知涵, 李堂逸, 陈炜豪, 卢涛, 龙震, 邱国红. Al掺杂对富锰P2型Na_0.67Fe_0.30Mn_0.70O₂储钠性能的调控机理[J]. 无机材料学报, DOI: 10.15541/jim20260223.

TAN Zhihan, LI Tangyi, CHEN Weihao, LU Tao, LONG Zhen, QIU Guohong. Regulation Mechanism of Al Doping on Sodium-storage Performance of Mn-rich P2-type Na_0.67Fe_0.30Mn_0.70O₂[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260223.

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Al掺杂对富锰P2型Na_0.67Fe_0.30Mn_0.70O₂储钠性能的调控机理

Regulation Mechanism of Al Doping on Sodium-storage Performance of Mn-rich P2-type Na_0.67Fe_0.30Mn_0.70O₂

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