Citation: Qiang Huang, Yue Wang, Xuejie Wang, Lyubov G. Bulusheva, Tao Liu. La-Ce双掺杂调控电子结构及离子传输增强Na₄Fe₃(PO₄)₂P₂O₇正极的超快储钠性能[J]. Acta Physico-Chimica Sinica, ;2026, 42(11): 100339. doi: 10.1016/j.actphy.2026.100339 shu

La-Ce双掺杂调控电子结构及离子传输增强Na₄Fe₃(PO₄)₂P₂O₇正极的超快储钠性能

1.
Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430078, Hubei Province, China;
2.
Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, Russia

Corresponding author: Tao Liu, liutao54@cug.edu.cn
Received Date: 12 May 2026
Revised Date: 29 May 2026
Accepted Date: 1 June 2026

Na₄Fe₃(PO₄)₂P₂O₇ (NFPP)因其低成本和高理论容量使其成为钠离子电池正极的理想候选材料。然而，合成过程中NaFePO₄存在的电化学惰性且导电性差问题，限制了NFPP的实际应用。本研究提出一种La-Ce双掺杂协同策略，通过调控电子结构与稳定NFPP晶格，同步解决了上述关键难题。第一性原理密度泛函理论(DFT)计算表明，La³⁺和Ce³⁺优先占据NFPP晶格中的Fe位点，通过改变局部热力学环境有效抑制NaFePO₄杂质的成核生长，同时引发电子结构显著变化。具体而言，La/Ce的4f轨道与Fe 3d-O 2p轨道杂化大幅缩小带隙，同时强化Fe-O共价键以增强结构稳定性。Na₄Fe_2.91La_0.03Ce_0.03(PO₄)₂P₂O₇ (La-Ce-NFPP)在20C倍率下展现出92.47 mAh g^-1的高倍率容量，10C循环3000次后容量保持率达93.76%。原位XRD测试证实La-Ce双掺杂将晶胞体积变化率从4.63% (NFPP)降至3.05% (La-Ce-NFPP)，表明掺杂优化了Na⁺扩散路径并缓解了相变过程中的结构应变。此外，La-Ce-NFPP//HC全电池表现出优异的循环稳定性，200次循环后容量保持率达94.9%，展现出巨大的实际应用潜力。
- Sodium-ion batteries,
- Cathode material,
- Na₄Fe₃(PO₄)₂P₂O₇,
- La-Ce dual-doping,
- Electrochemical performance
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

La-Ce双掺杂调控电子结构及离子传输增强Na4Fe3(PO4)2P2O7正极的超快储钠性能

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通讯作者: 陈斌, bchen63@163.com

La-Ce双掺杂调控电子结构及离子传输增强Na₄Fe₃(PO₄)₂P₂O₇正极的超快储钠性能