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浙江大学学报(工学版)
浙江大学学报(工学版)  2022, Vol. 56 Issue (1): 152-160    DOI: 10.3785/j.issn.1008-973X.2022.01.017
能源工程、机械工程     
Z-CoS2-MoS2/rGO的合成及电化学储锂性能
姜孝男(),徐刚,陈卫祥*()
浙江大学 化学系，浙江 杭州 310027
Synthesis of Z-CoS2-MoS2/rGO composite and its electrochemical lithium storage performance
Xiao-nan JIANG(),Gang XU,Wei-xiang CHEN*()
Department of Chemistry, Zhejiang University, Hangzhou 310027, China
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摘要：

为了研发比容量高和循环性能稳定的电化学储锂电极材料，用二甲基咪唑钴(ZIF-67)作为Co源前驱体，通过一步水热法制备Z-CoS2-MoS2/rGO(还原氧化石墨烯)复合材料，研究微观结构和电化学储锂性能. 结果表明，与采用CoCl2作为钴源制得的CoS2-MoS2/rGO相比，Z-CoS2-MoS2/rGO复合材料中CoS2粒子有着更加细小和较均匀的粒径，很好地分散在MoS2和rGO表面，形成了相应的异质结构. 作为电化学储锂电极材料，Z-CoS2-MoS2/rGO的可逆比容量可以达到1 092 mA·h/g，经900次循环后在500 mA/g电流密度下保持了941 mA·h/g的储锂可逆比容量，显示了稳定的充放电循环性能. Z-CoS2-MoS2/rGO优异的电化学储锂性能主要归因于该双金属硫化物复合材料具有较多的电化学储锂电极反应电对以及复合材料中CoS2纳米颗粒、MoS2纳米片和rGO之间均匀的复合及所形成的异质结构.
关键词： 金属硫化物复合材料;  二甲基咪唑钴;  二硫化钴;  二硫化钼;  电化学储锂    
Abstract:

Dimethyl imidazole cobalt (ZIF-67) was employed as the cobalt source precursor to prepare Z-CoS2-MoS2/rGO (reduced graphene oxide) composite material by one-step hydrothermal method in order to develop the electrode materials for electrochemical lithium storage with high specific capacity and stable cycle performance. The microstructure and electrochemical lithium storage performance were analyzed. Results showed that the CoS2 particles in the Z-CoS2-MoS2/rGO composite had a smaller and more uniform particle size compared with CoS2-MoS2/rGO prepared by using CoCl2 as the cobalt source, and dispersed in MoS2 and the surface of rGO, forming the corresponding heterostructure. The reversible specific capacity of Z-CoS2-MoS2/rGO can reach 1 092 mA·h/g as an electrochemical lithium storage electrode material, and maintains 941 mA·h/g at a current density of 500 mA/g after 900 cycles, demonstrating its stable cycle performance. The excellent electrochemical lithium storage performance of Z-CoS2-MoS2/rGO is mainly attributed to the bimetallic sulfide composite that has more redox pairs for electrochemical lithium storage and the heterostructure formed by the uniform composited of CoS2 nanoparticles, MoS2 nanosheets and rGO.
Key words: metal sulfide composite    dimethyl imidazole cobalt    CoS2    MoS2    electrochemical lithium storage
收稿日期: 2021-01-25 出版日期: 2022-01-05
CLC:  TM 911  
基金资助: 国家自然科学基金资助项目(21473156)；浙江省科技计划资助项目(2015C01001)
通讯作者: 陈卫祥     E-mail: dd52143@qq.com;weixiangchen@zju.edu.cn
作者简介: 姜孝男（1997—），男，硕士生，从事锂离子电池的研究. orcid.org/0000-0002-7606-521X. E-mail： dd52143@qq.com
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引用本文:

姜孝男,徐刚,陈卫祥. Z-CoS2-MoS2/rGO的合成及电化学储锂性能[J]. 浙江大学学报(工学版), 2022, 56(1): 152-160.

Xiao-nan JIANG,Gang XU,Wei-xiang CHEN. Synthesis of Z-CoS2-MoS2/rGO composite and its electrochemical lithium storage performance. Journal of ZheJiang University (Engineering Science), 2022, 56(1): 152-160.

链接本文:

https://www.zjujournals.com/eng/CN/10.3785/j.issn.1008-973X.2022.01.017    或    https://www.zjujournals.com/eng/CN/Y2022/V56/I1/152

图 1  不同复合材料样品的XRD图
图 2  不同复合材料的SEM图
样品 nCo∶nMo n(Co+Mo)∶nS
MoS2/rGO - 1∶2.11
CoS2-MoS2/rGO 1∶1.18 1∶2.18
Z-CoS2-MoS2/rGO 1∶1.13 1∶2.20
表 1  MoS2/rGO, CoS2-MoS2/rGO和Z-CoS2-MoS2/rGO 复合材料中Co、Mo和S元素的物质的量比
图 3  MoS2/rGO、CoS2-MoS2/rGO和Z-CoS2-MoS2/rGO复合材料的热重分析曲线
图 4  不同复合材料的TEM/HRTEM图
图 5  Z-CoS2-MoS2/rGO复合材料的XPS图
图 6  电极电化学储锂前3圈的循环伏安曲线(扫描速度为1.0 mV/s)
图 7  不同复合材料电极的前3圈充放电曲线(电流密度为100 mA/g)
图 8  MoS2/rGO、CoS2-MoS2/rGO、Z-CoS2-MoS2/rGO复合电极的循环性能（电流密度为100 mA/g）
图 9  不同复合材料电极的充放电倍率特性和Z-CoS2-MoS2/rGO电极的充放电长循环性能
图 10  不同复合材料极的电化学阻抗图和相应的等效电路(CPE代表恒相位元)
电极材料 Re /Ω Rf /Ω Rct /Ω
MoS2/rGO 10.97 35.27 55.77
CoS2-MoS2/rGO 11.22 43.82 65.58
Z-CoS2-MoS2/rGO 10.74 26.42 36.24
表 2  电化学阻抗拟合得到的电极动力学参数
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