钠离子电池正极材料P2-Nax[Mg0.33Mn0.67]O2的电化学活性研究

doi:10.15541/jim20200534

无机材料学报 ›› 2021, Vol. 36 ›› Issue (6): 623-628.DOI: 10.15541/jim20200534

所属专题：能源材料论文精选(2021)；【虚拟专辑】计算材料

钠离子电池正极材料P2-Na_x[Mg_0.33Mn_0.67]O₂的电化学活性研究

张晓君¹(), 李佳乐¹^,², 邱吴劼²^,³, 杨淼森¹, 刘建军²^,³^,⁴()

1.东北电力大学吉林省生物质清洁转化与高值化利用科技创新中心, 吉林 132012
2.中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050
3.中国科学院大学材料科学与光电工程中心, 北京 100049
4.中国科学院大学杭州高等研究院, 化学与材料科学学院, 杭州 310024

收稿日期:2020-09-14 修回日期:2020-11-13 出版日期:2021-06-20 网络出版日期:2020-12-01
通讯作者: 刘建军, 研究员. E-mail: jliu@mail.sic.ac.cn
作者简介:张晓君(1974-), 女, 博士, 高级实验师. E-mail: zhangxjun1123@126.com
基金资助:
国家自然科学基金(21973107);国家自然科学基金(11804351);吉林省教育厅项目(JJKH20190693KJ)

Electrochemical Activity of Positive Electrode Material of P2-Na_x[Mg_0.33Mn_0.67]O₂ Sodium Ion Battery

ZHANG Xiaojun¹(), LI Jiale¹^,², QIU Wujie²^,³, YANG Miaosen¹, LIU Jianjun²^,³^,⁴()

1. Jilin Province Sci-Tech Center for Clean Conversion and High-valued Utilization of Biomass, Northeast Electric Power University, Jilin 132012, China
2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
3. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
4. School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China

Received:2020-09-14 Revised:2020-11-13 Published:2021-06-20 Online:2020-12-01
Contact: LIU Jianjun, professor. E-mail: jliu@mail.sic.ac.cn
About author:ZHANG Xiaojun(1974-), female, senior experimentalist. E-mail: zhangxjun1123@126.com
Supported by:
National Natural Science Foundation of China(21973107);National Natural Science Foundation of China(51702345);Project of the Education Department of Jinlin Province(JJKH20190693KJ)

摘要/Abstract

摘要：

钠离子电池具有成本低廉、原料分布广泛等优点, 是锂离子电池正极材料的最佳替代材料。在具有层状结构的P2相NaMnO₂正极材料中, 对过渡金属层进行二元固溶可有效提升电极材料的电化学性能。本研究利用库仑模型构建了Mg离子固溶的Na_x[Mg_0.33Mn_0.67]O₂结构模型。通过第一性原理计算发现, 在钠离子含量小于0.67时, Na_x[Mg_0.33Mn_0.67]O₂的放电电压达到3.0 V。电子态密度和电荷布居分析共同表明, Mg的固溶激活了P2相Na_x[Mg_0.33Mn_0.67]O₂中晶格氧的电化学活性, 使体系的电化学反应机制从阴阳离子协同电化学反应转变为可逆阴离子电化学反应。这一机理为钠离子电池电极材料的设计提供了一种全新方法, 也为其它离子电池的优化和探索提供了全新的思路。

关键词: 钠离子电池, 电化学活性, 第一性原理, 碱金属掺杂

Abstract:

With the advantages of low cost and wide distribution of raw materials, sodium-ion batteries are considered to be the best alternative materials for lithium-ion battery cathode materials. In the P2-phase NaMnO₂ with layered structure, binary solid solution of the transition metal layer can effectively improve the electrochemical performance of the electrode material. In this study, the structural model of Na_x[Mg_0.33Mn_0.67]O₂ with Mg ion solid solution was constructed by using the Coulombic model. The first-principles calculations revealed that discharge voltage of Na_x[Mg_0.33Mn_0.67]O₂reached 3.0 V at a sodium ion content of less than 0.67. Electronic density of states and charge population analysis showed that the solid solution of Mg motivated the anionic electrochemical activity of lattice oxygen in the P2-phase Na_x[Mg_0.33Mn_0.67]O₂, which transformed the electrochemical reaction mechanism of the system from cationic and anionic synergic redox reaction to reversible anionic redox reaction. This transformation provides a novel method for the design of electrode materials for Na ion batteries, as well as a new approach for the optimization and exploration of other ion batteries.

Key words: sodium ion battery, electrochemical activity, first principle, alkali metal doping

中图分类号:

O646

张晓君, 李佳乐, 邱吴劼, 杨淼森, 刘建军. 钠离子电池正极材料P2-Na_x[Mg_0.33Mn_0.67]O₂的电化学活性研究[J]. 无机材料学报, 2021, 36(6): 623-628.

ZHANG Xiaojun, LI Jiale, QIU Wujie, YANG Miaosen, LIU Jianjun. Electrochemical Activity of Positive Electrode Material of P2-Na_x[Mg_0.33Mn_0.67]O₂ Sodium Ion Battery[J]. Journal of Inorganic Materials, 2021, 36(6): 623-628.

图/表 6

图1 P2相Na2/3[Mg1/3Mn2/3]O2结构示意图

Fig. 1 Schematic diagram of P2-Na2/3[Mg1/3Mn2/3]O2

图2 P2相Na0.67[Mg0.33Mn0.67]O2模拟与实验XRD对比

Fig. 2 Comparison of calculated and experimental XRD patterns of Na0.67[Mg0.33Mn0.67]O2

图3 P2相(A) NaMnO2和(B) Na0.67[Mg0.33Mn0.67]O2的晶格振动谱

Fig. 3 Phonon dispersion curves of (A) NaMnO2 and (B) Na0.67[Mg0.33Mn0.67]O2

图4 P2-Nax[Mg0.33Mn0.67]O2的(A)计算得出的放电过程中结构变化示意图及其(B)放电电压曲线。

Fig. 4 (A) DFT-calculated structural changes and (B) discharge voltage curve of P2-Nax[Mg0.33Mn0.67]O2 during discharge

图5 (A) 不同Na离子含量下的P2-Nax[Mg0.33Mn0.67]O2和(B) P2-NaxMnO2在放电过程中电子态密度

Fig. 5 Electronic density of states of (A) P2-Nax[Mg0.33Mn0.67]O2 and (B) P2-NaxMnO2 under different Na ion contents during discharge PDOS: projected density of states

图6 (A) 在不同钠离子含量下的P2-Nax[Mg0.33Mn0.67]O2和(B) P2-NaxMnO2电荷分析

Fig. 6 Charge analysis of (A) Nax[Mg0.33Mn0.67]O2 and (B) P2-NaxMnO2 under different sodium ion content

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钠离子电池正极材料P2-Na_x[Mg_0.33Mn_0.67]O₂的电化学活性研究

Electrochemical Activity of Positive Electrode Material of P2-Na_x[Mg_0.33Mn_0.67]O₂ Sodium Ion Battery

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