Ti和Cu掺杂β-NaMnO2正极材料：钠离子电池的倍率和循环性能

doi:10.15541/jim20240204

无机材料学报 ›› 2024, Vol. 39 ›› Issue (12): 1404-1412.DOI: 10.15541/jim20240204 CSTR: 32189.14.10.15541/jim20240204

所属专题：【能源环境】储能电池(202412)；【材料计算】计算材料(202412)

• 研究快报 • 上一篇

Ti和Cu掺杂β-NaMnO₂正极材料：钠离子电池的倍率和循环性能

周靖渝¹^,²^,³(), 李兴宇², 赵晓琳²^,³, 王有伟²^,³, 宋二红²^,³(), 刘建军¹^,²^,³

1.中国科学院杭州高等研究院, 化学与材料科学学院, 杭州 310024
2.中国科学院上海硅酸盐研究所, 高性能陶瓷和超精密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

收稿日期:2024-04-22 修回日期:2024-06-15 出版日期:2024-07-16 网络出版日期:2024-07-16
通讯作者: 宋二红, 副研究员. E-mail: ehsong@mail.sic.ac.cn
作者简介:周靖渝(1998-), 男, 硕士研究生. E-mail: zhoujingyu211@mails.ucas.ac.cn

Rate and Cycling Performance of Ti and Cu Doped β-NaMnO₂ as Cathode of Sodium-ion Battery

ZHOU Jingyu¹^,²^,³(), LI Xingyu², ZHAO Xiaolin²^,³, WANG Youwei²^,³, SONG Erhong²^,³(), LIU Jianjun¹^,²^,³

1. School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, 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

Received:2024-04-22 Revised:2024-06-15 Published:2024-07-16 Online:2024-07-16
Contact: SONG Erhong, associate professor. E-mail: ehsong@mail.sic.ac.cn
About author:ZHOU Jingyu (1998-), male, Master candidate. E-mail: zhoujingyu211@mails.ucas.ac.cn
Supported by:
National Key R&D Program of China(2022YFB3807700);National Natural Science Foundation of China(22133005);National Natural Science Foundation of China(22103093);Science and Technology Commission of Shanghai Municipality(21ZR1472900);Science and Technology Commission of Shanghai Municipality(22ZR1471600);Science and Technology Commission of Shanghai Municipality(23ZR1472600);Youth Innovation Promotion Association CAS(2022251);Shanghai Super Post-Doctor Incentive Program(2022665);China Postdoctoral Science Foundation(2023M733621);Shanghai Explorer Program (Batch I)(23TS1401500)

摘要/Abstract

摘要：

钠离子电池是一种经济且环境可持续的储能电池。其中, β-NaMnO₂作为前景广阔的钠离子正极材料, 是一种具有波纹形层状结构的锰基氧化物, 因其结构坚固和比容量相对较高而备受关注。然而, β-NaMnO₂存在循环寿命短、倍率性能不佳的问题。为了解决这些问题, 本研究通过第一性原理计算和晶体轨道哈密顿布局(COHP)分析, 在β-NaMnO₂中掺入了可以提高材料结构稳定性的Ti原子和有利于钠离子脱出的Cu原子。β-NaMn_0.8Ti_0.1Cu_0.1O₂的可逆比容量显著增长, 并且具有卓越的倍率性能。在0.2C电流密度(1C=219 mA·g^-1)、1.8~4.0 V电压范围内, 改性材料的初始放电比容量为132 mAh·g^-1。分别在0.2C、0.5C、1C、3C和0.2C的电流密度下进行充放电测试后, 该材料仍能保持110 mAh·g^-1的比容量。掺入Ti减缓了晶体结构的变化, 晶格常数c/a在脱钠过程中仅有微小变化。Mn和Cu分别在3.0 V以下和3.5 V左右发生可逆氧化还原反应, 在放电曲线中, 3.0 V以下的长平台表明Mn是电池容量的主要贡献者。本工作深入研究了改性β-NaMnO₂正极材料的工作机理, 为提高钠离子电池的性能提供了实验依据和理论指导。

关键词: 第一性原理, 钠离子电池, 层状正极材料

Abstract:

Sodium-ion batteries are economical and environmentally sustainable energy storage batteries. Among them, β-NaMnO₂, a promising sodium-ion cathode material, is a manganese-based oxide with a corrugated laminar structure, which has attracted significant attention due to its structural robustness and relatively high specific capacity. However, it has short cycle life and poor rate capability. To address these issues, Ti atoms, known for enhancing structural stability, and Cu atoms, which facilitate desodiation, were doped into β-NaMnO₂by first-principles calculation and crystal orbital Hamilton population (COHP) analysis. β-NaMn_0.8Ti_0.1Cu_0.1O₂ exhibits a notable increase in reversible specific capacity and remarkable rate properties. Operating at a current density of 0.2C (1C = 219 mA·g^-1) and within a voltage range of 1.8-4.0 V, the modified material delivers an initial discharge capacity of 132 mAh·g^-1. After charge/discharge testing at current densities of 0.2C, 0.5C, 1C, 3C, and 0.2C, the material still maintains a capacity of 110 mAh·g^-1. The doping of Ti atoms slows down the changes in the crystal structure, resulting in only minimal variation in the lattice constant c/a during the desodiation process. Mn and Cu engage in reversible redox reactions at voltages below 3.0 V and around 3.5 V, respectively. The extended plateau observed in the discharge curve below 3.0 V signifies that Mn significantly contributes to the overall battery capacity. This study provides insights into modifying β-NaMnO₂ as a cathode material, offering experimental evidence and theoretical guidance for enhancing battery performance in Na-ion batteries.

Key words: first-principles, sodium-ion battery, layered cathode material

中图分类号:

TQ174

周靖渝, 李兴宇, 赵晓琳, 王有伟, 宋二红, 刘建军. Ti和Cu掺杂β-NaMnO₂正极材料：钠离子电池的倍率和循环性能[J]. 无机材料学报, 2024, 39(12): 1404-1412.

ZHOU Jingyu, LI Xingyu, ZHAO Xiaolin, WANG Youwei, SONG Erhong, LIU Jianjun. Rate and Cycling Performance of Ti and Cu Doped β-NaMnO₂ as Cathode of Sodium-ion Battery[J]. Journal of Inorganic Materials, 2024, 39(12): 1404-1412.

图/表 14

Fig. 1 Screening of doped atoms in β-NaMnO2 (a) Schematic crystal structure of β-NaMnO2 doped by 3d transition metal atoms; (b) -ICOHP of Na-O and TM-O (TM=Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn); (c) -COHP of Na-O and Cu-O in Cu doped β-NaMnO2; (d) -COHP of Na-O and Ti-O in Ti doped β-NaMnO2. Colorful figures are available on website

Fig. 2 Structure and morphology of β-MTC811 (a) Crystal structure modeling of β-MTC811 that obtained by calculation; (b) Comparison of calculated and experimental XRD patterns of β-MTC811; (c) SEM image of β-MTC811; (d) EDS mappings of β-MTC811; (e) TEM image of β-MTC811; (f) Enlarged image of zig-zag layered structure in (e)

Fig. 3 Electrochemical performance of β-MTC811 cathode (a-c) Charge/discharge curves of (a) β-MTC811, (b) β-MTC721 and (c) β-MTC712 at 0.2C; (d) Cycling performance, (e) rate performance and (f) dQ/dV curves of β-MTC811 Colorful figures are available on website

Fig. 4 Electrochemical reaction mechanisms (a) Mn2p and (b) Cu2p XPS spectra of β-MTC811 in different charging and discharging states. Colorful figures are available on website

Fig. 5 First-principles calculations of β-MTC811 cathode (a) Schematic diagram of desodiation process; (b) Lattice constant c/a during desodiation; (c) Calculated and fitted voltage plateaus, and experimental voltage curve; (d) Bader charge of Mn and Cu; (e-g) pDOS of Mn3d and Cu3d during different desodiation processes Colorful figures are available on website

Fig. S1 -COHP of Na-O (O from Na-O-TM) (TM=Co, Cu, V, Cr, Ni, Fe, Mn, Zn, Ti) in doped β-NaMnO2

Fig. S2 -COHP of TM-O (TM=Mn, Zn, Ti, V, Cr, Fe, Co, Ni, Cu) in doped β-NaMnO2

Fig. S3 XRD patterns of β-MTC811, β-MTC721 and β-MTC712

Fig. S4 Crystal-structure modelings of (a, b) β-MTC712 and (c, d) β-MTC721

Fig. S5 Electrochemical performance of (a-c) β-MTC721 and (d-f) β-MTC712 cathodes (a, d) Cycling performance during 50 cycles; (b, e) rate performance; (c, f) dQ/dV curves

Fig. S6 CV curves of β-MTC811

Table S1 Bond lengths of Na-O (in Na-O-TM) and TM-O

Element	Na-O/Å	TM-O/Å
Ti	2.37641	1.95505
V	2.32810	1.98783
Cr	2.36871	1.98479
Mn	2.33621	1.97821
Fe	2.34627	2.00070
Co	2.36626	1.94259
Ni	2.35691	1.91536
Cu	2.39119	1.98934
Zn	2.36493	2.08207

Table S2 ICP-OES results of β-MTC811, β-MT712 and β-MTC721

Sample	Measured atomic ration
Sample	Mn	Ti	Cu
β-MTC811	0.8	0.09	0.1
β-MTC712	0.7	0.08	0.2
β-MTC721	0.7	0.19	0.1

Table S3 Parameters for button cell batteries

Material	Cathodes’ mass loading/mg	Electrolyte amount/μL	Radius/mm
β-MTC811	4.192	160	14
β-MTC721	4.360	160	14
β-MTC712	5.696	160	14

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Ti和Cu掺杂β-NaMnO₂正极材料：钠离子电池的倍率和循环性能

Rate and Cycling Performance of Ti and Cu Doped β-NaMnO₂ as Cathode of Sodium-ion Battery

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