无机材料学报 ›› 2026, Vol. 41 ›› Issue (10): 1407-1414.DOI: 10.15541/jim20250512
刘德新1(
), 赵宇泽1, 朱正伟1, 问研良1(
), 洪明子1(
), 何伟艳2
收稿日期:2025-12-23
修回日期:2026-02-28
出版日期:2026-10-20
网络出版日期:2026-04-03
通讯作者:
问研良, 副教授. E-mail: wenyanliang@163.com;作者简介:刘德新(1999-), 男, 硕士研究生. E-mail: liudexin@ordoslab.cn
基金资助:
LIU Dexin1(
), ZHAO Yuze1, ZHU Zhengwei1, WEN Yanliang1(
), HONG Mingzi1(
), HE Weiyan2
Received:2025-12-23
Revised:2026-02-28
Published:2026-10-20
Online:2026-04-03
Contact:
WEN Yanliang, associate professor. E-mail: wenyanliang@163.com;About author:LIU Dexin (1999-), male, Master candidate. E-mail: liudexin@ordoslab.cn
Supported by: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大电流下循环后, 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。
中图分类号:
刘德新, 赵宇泽, 朱正伟, 问研良, 洪明子, 何伟艳. 高稳定性锰基钠离子电池正极材料的双位点掺杂研究[J]. 无机材料学报, 2026, 41(10): 1407-1414.
LIU Dexin, ZHAO Yuze, ZHU Zhengwei, WEN Yanliang, HONG Mingzi, HE Weiyan. Dual-site Doping for High-stability Manganese-based Cathode Materials in Sodium-ion Batteries[J]. Journal of Inorganic Materials, 2026, 41(10): 1407-1414.
| Sample | Element | Mass fraction% | Actual | Theoretical |
|---|---|---|---|---|
| NKCMO-0.05 | Na | 22.32 | 0.97 | 0.95 |
| K | 1.84 | 0.05 | 0.05 | |
| Mn | 47.57 | 0.87 | 0.95 | |
| Cu | 3.43 | 0.06 | 0.05 | |
| NKCMO-0.06 | Na | 22.48 | 0.97 | 0.94 |
| K | 2.42 | 0.06 | 0.06 | |
| Mn | 47.91 | 0.87 | 0.95 | |
| Cu | 3.37 | 0.05 | 0.05 | |
| NKCMO-0.07 | Na | 21.31 | 0.93 | 0.93 |
| K | 2.93 | 0.08 | 0.07 | |
| Mn | 48.68 | 0.89 | 0.95 | |
| Cu | 3.43 | 0.05 | 0.05 |
表1 NKCMO的各元素的含量
Table 1 Elemental contents of NKCMO
| Sample | Element | Mass fraction% | Actual | Theoretical |
|---|---|---|---|---|
| NKCMO-0.05 | Na | 22.32 | 0.97 | 0.95 |
| K | 1.84 | 0.05 | 0.05 | |
| Mn | 47.57 | 0.87 | 0.95 | |
| Cu | 3.43 | 0.06 | 0.05 | |
| NKCMO-0.06 | Na | 22.48 | 0.97 | 0.94 |
| K | 2.42 | 0.06 | 0.06 | |
| Mn | 47.91 | 0.87 | 0.95 | |
| Cu | 3.37 | 0.05 | 0.05 | |
| NKCMO-0.07 | Na | 21.31 | 0.93 | 0.93 |
| K | 2.93 | 0.08 | 0.07 | |
| Mn | 48.68 | 0.89 | 0.95 | |
| Cu | 3.43 | 0.05 | 0.05 |
图3 NKCMO-0.06的K2p (a)和Cu2p (b) XPS谱图; NMO和NKCMO-0.06的Mn2p (c)和O1s (d) XPS谱图
Fig. 3 K2p (a) and Cu2p (b) XPS spectra for NKCMO-0.06; Mn2p (c) and O1s (d) XPS spectra for NMO and NKCMO-0.06
图4 NMO、NKCMO-x的首次充放电曲线(a)和CV曲线(b)
Fig. 4 Initial charge/discharge curves (a) and CV curves (b) of NMO and NKCMO-x Colorful figures are available on website
图5 NMO和NKCMO-x的长循环性能(a)和倍率性能(b); (c) NMO和NKCMO-x的电化学阻抗谱图; (d) NKCMO-0.06循环后的SEM照片
Fig. 5 Long-term cycling performance (a) and rate capability (b) of NMO and NKCMO-x; (c) Electrochemical impedance spectra of NMO and NKCMO-x; (d) SEM image of NKCMO-0.06 after cycling Colorful figures are available on website
图6 NMO (a)、NKMO (b)、NCMO (c)和NKCMO-0.06 (d)的能带结构图; NMO (e)与NKCMO-0.06 (f)偏态密度图
Fig. 6 Band structure diagrams of NMO (a), NKMO (b), NCMO (c), and NKCMO-0.06 (d); Partial density of states diagrams of NMO (e) and NKCMO-0.06 (f) Colorful figures are available on website
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