钠离子电池中空结构CoSe2/C负极材料的制备及储钠性能研究

doi:10.15541/jim20220224

无机材料学报 ›› 2022, Vol. 37 ›› Issue (12): 1344-1350.DOI: 10.15541/jim20220224

钠离子电池中空结构CoSe₂/C负极材料的制备及储钠性能研究

王晶¹(), 徐守冬¹(), 卢中华¹, 赵壮壮¹, 陈良², 张鼎², 郭春丽³

1.太原理工大学化学工程与技术学院, 太原 030024
2.太原理工大学化学学院, 太原 030024
3.太原理工大学材料科学与工程学院, 太原 030024

收稿日期:2022-04-16 修回日期:2022-05-26 出版日期:2022-12-20 网络出版日期:2022-06-16
通讯作者: 徐守冬, 副教授. E-mail: xushoudong@tyut.edu.cn
作者简介:王晶(1994-), 女, 硕士研究生. E-mail: 513570705@qq.com
基金资助:
国家自然科学基金(21606158);国家自然科学基金(21978193);国家自然科学基金(21706171);国家自然科学基金(U1910210);山西省回国留学人员科研资助项目(2022-049);山西省回国留学人员科研资助项目(2020-048)

Hollow-structured CoSe₂/C Anode Materials: Preparation and Sodium Storage Properties for Sodium-ion Batteries

WANG Jing¹(), XU Shoudong¹(), LU Zhonghua¹, ZHAO Zhuangzhuang¹, CHEN Liang², ZHANG Ding², GUO Chunli³

1. College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China
2. College of Chemistry, Taiyuan University of Technology, Taiyuan 030024, China
3. College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China

Received:2022-04-16 Revised:2022-05-26 Published:2022-12-20 Online:2022-06-16
Contact: XU Shoudong, associate professor. E-mail: xushoudong@tyut.edu.cn
About author:WANG Jing (1994-), female, Master candidate. E-mail: 513570705@qq.com
Supported by:
National Natural Science Foundation of China(21606158);National Natural Science Foundation of China(21978193);National Natural Science Foundation of China(21706171);National Natural Science Foundation of China(U1910210);Shanxi Scholarship Council of China(2022-049);Shanxi Scholarship Council of China(2020-048)

摘要/Abstract

摘要：

过渡金属硒化物具有较高的理论比容量和良好的导电能力, 是钠离子电池潜在的负极材料, 但其在电化学过程中会发生较大体积变化, 循环寿命不佳, 发展受到了限制。为缓解上述问题, 本研究以金属有机框架材料ZIF-67为前驱体, 用单宁酸(Tannic acid, TA)将ZIF-67刻蚀为空心结构, 再通过碳化、硒化制备出以碳为骨架的纳米中空CoSe₂材料(H-CoSe₂/C), 相较于未经刻蚀处理的CoSe₂材料(CoSe₂/C), H-CoSe₂/C表现出更好的储钠性能, 特别是循环稳定性得到显著提高。50 mA·g^-1电流密度下, 经过350次循环, 可逆比容量保持在383.4 mAh·g^-1, 容量保持率为83.6%; 在500 mA·g^-1电流密度下, 经过350次循环后容量保持率仍能达到72.2%。本研究表明, 中空结构能够提供足够的空间以缓解材料在电化学过程中的体积变化, 进而提高电极材料的循环性能。

关键词: 钠离子电池, 负极材料, 金属有机框架材料, CoSe₂, 空心结构

Abstract:

Transition metal selenides (TMSs) with the merits of their versatile material species, ample abundance and high theoretical specific capacity have been regarded as attractive anode materials for sodium-ion batteries (SIBs). However, the large volume changes during the electrochemical reactions which result in limited cycle performance hinder their commercialization. Herein, the hollow structure composed of CoSe₂ and carbon skeleton (denoted as H-CoSe₂/C), derived from the metal organic framework material ZIF-67 using tannic acid as the etching agent, was used as the anode for SIBs. Owing to the unique hollow structure which can alleviate the volume change of the material, H-CoSe₂/C exhibited excellent sodium ions storage performances in terms of cycling stability. Compared with the solid counterpart, the reversible specific capacity of the H-CoSe₂/C electrode remains 383.4 mAh·g^-1 after 350 cycles at a current density of 50 mA·g^-1 with the capacity retention of 83.6%. Even at 500 mA·g^-1, the capacity retention can still reach 72.2% after 350 cycles. This work manifests that hollow structure can provide enough space to alleviate the problem of volume changes for TMSs during the sodiation/desodiation process, thus the cycle performances can be improved.

Key words: sodium-ion battery, anode material, metal organic framework, CoSe₂, hollow structure

中图分类号:

TQ174

王晶, 徐守冬, 卢中华, 赵壮壮, 陈良, 张鼎, 郭春丽. 钠离子电池中空结构CoSe₂/C负极材料的制备及储钠性能研究[J]. 无机材料学报, 2022, 37(12): 1344-1350.

WANG Jing, XU Shoudong, LU Zhonghua, ZHAO Zhuangzhuang, CHEN Liang, ZHANG Ding, GUO Chunli. Hollow-structured CoSe₂/C Anode Materials: Preparation and Sodium Storage Properties for Sodium-ion Batteries[J]. Journal of Inorganic Materials, 2022, 37(12): 1344-1350.

图/表 13

图1 H-CoSe2/C和CoSe2/C的制备示意图

Fig. 1 Schematic illustrations of preparation of H-CoSe2/C and CoSe2/C

图2 H-CoSe2/C的(a) SEM、(b) TEM、(c) HRTEM照片及(d) Co、Se和C的EDS元素分布图

Fig. 2 (a) SEM, (b) TEM, (c) HRTEM images and (d) EDS elemental mappings of Co, Se, and C of H-CoSe2/C

图3 (a) ZIF-67, TA-Co和H-Co/C, (b) H-CoSe2/C和CoSe2/C的XRD图谱; (c) H-CoSe2/C和CoSe2/C的拉曼光谱图; H-CoSe2/C的(d) C1s、(e) Co2p和(f) Se3d XPS分谱图

Fig. 3 XRD patterns of (a) ZIF-67, TA-Co and H-Co/C, (b) H-CoSe2/C and CoSe2/C, (c) Raman spectra of H-CoSe2/C and CoSe2/C, (d) C1s, (e) Co2p, and (f) Se3d XPS spectra of H-CoSe2/C

图4 (a) H-CoSe2/C在0.1 mV·s-1扫速下的CV曲线, 以及(b) H-CoSe2/C和CoSe2/C的循环性能(50 mA·g-1)

Fig. 4 (a) CV curves of H-CoSe2/C at scan rate of 0.1 mV·s-1, and (b) cycle performance of H-CoSe2/C and CoSe2/C (50 mA·g-1)

图5 (a, c) H-CoSe2/C和(b, d) CoSe2/C电极(a, b)循环1周和(c, d) 350周后的SEM照片

Fig. 5 SEM images of (a, c) H-CoSe2/C and (b, d) CoSe2/C after (a, b) 1 and (c, d) 350 cycles

图6 H-CoSe2/C电极(a)在不同扫描速率下的CV曲线, (b)氧化还原峰的lgi与lgv的关系(i: 峰值电流, v: 扫描速率), (c)在不同扫描率下赝电容贡献百分比的柱状图, (d)在扫描速率1.5 V·s-1下的电容贡献率

Fig. 6 (a) CV curves at different scan rates, (b) corresponding lgi versus lgv plots at each redox peak (i: peak current, v: scan rate), (c) histogram of pseudo capacitive contribution at different scan rates, and (d) capacitive contribution at scan rate of 1.5 V·s-1 of H-CoSe2/C electrode Colorful figures are available on website

图7 Na0.44MnO2/H-CoSe2/C全电池的(a)工作原理示意图, (b)充放电曲线和(c)在500 mA·g-1下的循环性能

Fig. 7 (a) Schematic diagram of the working mechanism, (b) charge-discharge curves and (c) cycle performance at 500 mA·g-1 of Na0.44MnO2/H-CoSe2/C full cell Colorful figures are available on website

图S1 (a) ZIF-67, (b) TA-Co, (c) H-Co/C和(d) H-CoSe2/C材料的SEM照片

Fig. S1 SEM images of (a) ZIF-67, (b) TA-Co, (c) H-Co/C, and (d) H-CoSe2/C samples

图S2 (a) ZIF-67, (b) TA-Co, (c) H-Co/C和(d) H-CoSe2/C材料的TEM照片

Fig. S2 TEM images of (a) ZIF-67, (b) TA-Co, (c) H-Co/C, and (d)H-CoSe2/C samples

图S3 CoSe2/C的(a) SEM和(b) TEM照片

Fig. S3 (a) SEM and (b) TEM images of CoSe2/C

图S4 (a) H-CoSe2/C电极在50 mA·g-1下的充放电曲线; (b) H-CoSe2/C和CoSe2/C电极的倍率性能; (c) H-CoSe2/C和CoSe2/C电极在500 mA·g-1下的循环性能

Fig. S4 (a) Charge-discharge curves of H-CoSe2/C electrode at 50 mA·g-1; (b) Rate performances of H-CoSe2/C and CoSe2/C; (c) Cycle performance of H-CoSe2/C and CoSe2/C at 500 mA·g-1

图S5 H-CoSe2/C和CoSe2/C在(a) 循环1周、(b) 120周和 (c) 350周后的EIS图谱和(d) R2柱状图, 插图为等效电路

Fig. S5 EIS spectra of H-CoSe2/C and CoSe2/C after (a) 1 cycle, (b) 120 cycles, and (c) 350 cycles and (d) corresponding histogram of R2 with inset showing equivalent circuit model

图S6 Na0.44MnO2正极材料在500 mA·g-1下的(a)充放电曲线和(b)循环性能

Fig. S6 (a) Charge-discharge curves and (b) cycle performance of Na0.44MnO2 cathode at 500 mA·g-1

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钠离子电池中空结构CoSe₂/C负极材料的制备及储钠性能研究

Hollow-structured CoSe₂/C Anode Materials: Preparation and Sodium Storage Properties for Sodium-ion Batteries

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