Co-S合金的水热法制备及电化学性能研究

doi:10.3724/SP.J.1077.2014.13514

无机材料学报 ›› 2014, Vol. 29 ›› Issue (7): 747-752.DOI: 10.3724/SP.J.1077.2014.13514 CSTR: 32189.14.SP.J.1077.2014.13514

Co-S合金的水热法制备及电化学性能研究

胡丽娜, 赵相玉, 李佳佳, 杨猛, 马立群, 张丽艳

(南京工业大学材料科学与工程学院, 南京210009)

收稿日期:2013-10-09 修回日期:2013-11-21 出版日期:2014-07-20 网络出版日期:2014-06-20
作者简介:胡丽娜(1986-), 女, 硕士研究生. E-mail: hlna_nina@163.com
基金资助:
国家自然科学基金(51201089);江苏省2012年度“六大人才高峰”项目(2012-XCL-034);中国博士后科学基金(2012M-5-21064);江苏高校优势学科建设工程(PAPD)

Hydrothermal Preparation and Electrochemical Properties of Co-S alloys

HU Li-Na, ZHAO Xiang-Yu, LI Jia-Jia, YANG-Meng, MA Li-Qun, ZHANG Li-Yan

(College of Materials Science and Engineering, Nanjing University of Technology, Nanjing 210009, China)

Received:2013-10-09 Revised:2013-11-21 Published:2014-07-20 Online:2014-06-20
About author:HU Li-Na. E-mail: hlna_nina@163.com
Supported by:
National Natural Science Foundation of China(51201089);2012 Annual Jiangsu Province "Six Top Talents" Project (2012- XCL-034);China Postdoctoral Science Foundation(2012M521064);Priority Academic Program Development of Jiangsu Higher Education Institution(PAPD)

摘要/Abstract

摘要：

采用水热法合成Co-S合金, 并对工艺参数进行了优化。通过XRD、SEM分析了合金的表面形貌及物相的变化; 用恒电流充放电测试、循环伏安以及交流阻抗对合金进行了电化学性能表征。结果表明: 反应溶液填充度为70%, 160℃保温12 h制得的Co-S合金含有Co与Co₉S₈两相, 颗粒结晶度好, 呈厚约50 nm的交叉薄片状。在150 mA/g的充放电电流下, Co-S合金最大放电容量可达536 mAh/g, 循环50次的容量保持率为77.4%。Co-S合金电极充放电时主要发生Co与Co(OH)₂之间的氧化还原反应, 部分Co的不可逆脱溶, 导致活性物质减少, 电极容量衰减。

关键词: 水热合成法, Co-S合金, 工艺参数, 电化学性能

Abstract:

The Co-S alloys were prepared by a hydrothermal method and the process parameters were optimized. The surface morphology and phase structure of Co-S alloys were characterized by SEM and XRD. The electrochemical properties of Co-S alloys were investigated by galvanostatic charge and discharge tests, cyclic voltammetry and AC impedance. The results indicated that the as-prepared Co-S alloy, which was synthesized using a 70% packing volume of the reaction solution at 160℃ for 12 h, showed good crystallinity. This alloy consisted of metallic Co and Co₉S₈phases with a cross-linked lamellar morphology of about 50 nm in thickness. It possessed a maximum discharge capacity of 536 mAh/g at charge and discharge current density of 150 mA/g and a good cycling stability with capacity retention rate of 77.4% after 50 cycles. The redox reactions between Co and Co(OH)₂ were the main reaction during charge and discharge. Partial dissolution of Co reduced the active material and led to capacity decay.

Key words: hydrothermal method, Co-S alloy, process parameters, electrochemical properties

中图分类号:

TQ174

胡丽娜, 赵相玉, 李佳佳, 杨猛, 马立群, 张丽艳. Co-S合金的水热法制备及电化学性能研究[J]. 无机材料学报, 2014, 29(7): 747-752.

HU Li-Na, ZHAO Xiang-Yu, LI Jia-Jia, YANG-Meng, MA Li-Qun, ZHANG Li-Yan. Hydrothermal Preparation and Electrochemical Properties of Co-S alloys[J]. Journal of Inorganic Materials, 2014, 29(7): 747-752.

图/表 9

图1 160℃、不同填充度下制得Co-S合金的容量循环图

Fig. 1 Cycling stability of the Co-S alloys prepared with different packing volumes after heat-treatment at 160℃ for 12 h

图2 填充度为70%、不同温度下制得Co-S合金的循环容量图

Fig. 2 Cycling stability of the Co-S alloys prepared with 70% packing volumes after heat-treatment at different temperatures for 12 h

图3 填充度为70%、160℃保温不同时间制备Co-S合金的循环容量图

Fig. 3 Cycling stability of the Co-S alloys prepared with 70% packing volumes after heat-treatment at 160℃ for different time

图4 填充度为70%、160℃保温不同时间制得Co-S合金的XRD图谱

Fig. 4 XRD patterns of the Co-S alloys prepared with 70% packing volumes after heat-treatment at 160℃ for different time

图5 填充度为70%、不同温度保温12 h制得Co-S合金的SEM照片

Fig. 5 SEM images of the Co-S alloys prepared with 70% packing volumes after heat-treatment at different temperatures for 12 h (a) 150℃; (b) 160℃; (c) 170℃

图6 Co-S合金电极在150 mA/g电流密度下充放电曲线

Fig. 6 Charge and discharge curves of the Co-S electrodes at current density of 150 mA/g

图7 Co-S合金电极的循环伏安曲线

Fig. 7 Cyclic voltammetry curves of Co-S electrodes

图8 不同循环充放电状态Co-S合金电极的XRD图谱

Fig. 8 XRD patterns of the Co-S electrodes after charge and discharge

图9 Co-S合金电极不同放电深度的交流阻抗图谱

Fig. 9 EIS spectra of the Co-S electrodes (a) Nyquist plots; (b) Bode-phase plots

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Co-S合金的水热法制备及电化学性能研究

Hydrothermal Preparation and Electrochemical Properties of Co-S alloys

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