ZnCo2O4-ZnO@C@CoS核壳复合材料的制备及其在超级电容器中的应用

doi:10.15541/jim20230481

无机材料学报 ›› 2024, Vol. 39 ›› Issue (5): 485-493.DOI: 10.15541/jim20230481 CSTR: 32189.14.10.15541/jim20230481

所属专题：【能源环境】超级电容器,锂金属电池,钠离子电池和水系电池(202409)；【能源环境】超级电容器(202409)

ZnCo₂O₄-ZnO@C@CoS核壳复合材料的制备及其在超级电容器中的应用

杨恩东¹(), 李宝乐², 张珂², 谭鲁², 娄永兵²()

1.南通江海储能技术有限公司, 南通 226000
2.东南大学化学化工学院, 南京 210096

收稿日期:2023-10-18 修回日期:2024-01-08 出版日期:2024-05-20 网络出版日期:2024-01-31
通讯作者: 娄永兵, 教授. E-mail: lou@seu.edu.cn
作者简介:杨恩东 (1973-), 男, 高级工程师. E-mail: yangendong.sh@163.com
基金资助:
2020年江苏省科技成果转化专项(BA2020060)

ZnCo₂O₄-ZnO@C@CoS Core-shell Composite: Preparation and Application in Supercapacitors

YANG Endong¹(), LI Baole², ZHANG Ke², TAN Lu², LOU Yongbing²()

1. Nantong Jianghai Energy Storage Technology Co., Ltd., Nantong 226000, China
2. School of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, China

Received:2023-10-18 Revised:2024-01-08 Published:2024-05-20 Online:2024-01-31
Contact: LOU Yongbing, professor. E-mail: lou@seu.edu.cn
About author:YANG Endong (1973-), male, senior engineer. E-mail: yangendong.sh@163.com
Supported by:
Special Fund of Jiangsu Province for Science and Technology Achievements Transformation(BA2020060)

摘要/Abstract

摘要：

超级电容器以其高功率性能、稳定的循环性能和优良的安全性等独特优势, 作为储能器件在新能源汽车和移动电子设备等方面极具前景。然而, 其能量密度相对较低, 限制了实际应用。为提升电化学活性, 本研究通过简便的溶剂热法、煅烧处理和电化学沉积技术, 在碳包覆的ZnCo₂O₄-ZnO微球上沉积了CoS纳米片(ZCO-ZO@C@CoS)。碳层不仅可以促进电子传输, 增强导电性, 还提升了结构的稳定性; CoS纳米片之间形成的开放网络空间促进了离子快速传输。此外, CoS纳米片具备丰富的电活性位点, 实现了快速可逆的氧化还原反应; 核壳结构内部的纳米线、碳层和外层纳米片的共同作用, 有效提升了材料的整体电化学性能。因此, ZCO-ZO@C@CoS在1.5 A·g⁻¹时的比电容达到1944 F·g⁻¹(972.0 C·g⁻¹), 20 A·g⁻¹高电流密度下循环10000次后比容量保持率为75%。由ZCO-ZO@C@CoS(正极)和活性炭(负极)组成的非对称超级电容器器件也表现出优异的比电容、高的倍率性能和优异的循环稳定性, 显示出良好的应用前景。

关键词: 非对称超级电容器, 过渡金属硫化物, CoS纳米片, 分级核壳结构

Abstract:

Supercapacitors, distinguished by their unique advantages, including high power performance, stable cycling behavior, and excellent safety, emerge as highly promising energy storage devices in the fields of new energy vehicles and mobile electronic applications. However, the issue of relatively low energy density continues to constrain their practical applications. To enhance electrochemical activity, CoS nanosheets were deposited onto ZnCo₂O₄-ZnO microspheres coated with carbon (ZCO-ZO@C@CoS) using a facile solvothermal method, calcination treatment, and electrochemical deposition reaction. Carbon layer not only promoted electron transport to enhance electrical conductivity, but also improved the stability of the structure. The open network space formed between CoS nanosheets facilitated rapid ion transport. Additionally, CoS nanosheets possessed abundant electroactive sites, enabling rapid reversible redox reactions. The co-effect of nanowires of the core-shell structure, the carbon layer, and the outer nanosheets effectively enhanced the overall electrochemical performance. Consequently, ZCO-ZO@C@CoS exhibited a specific capacitance of 1944 F·g^-1 (972.0 C·g^-1) at 1.5 A·g^-1, with an initial capacity retention of 75% after 10000 cycles at high current density of 20 A·g^-1. The asymmetric supercapacitor device, comprising ZCO-ZO@C@CoS (positive electrode) and activated carbon (negative electrode), also demonstrated excellent specific capacitance, high-rate performance, and exceptional cycling stability, indicating significant potential for practical applications.

Key words: asymmetric supercapacitor, transition metal dichalcogenide, CoS nanosheet, hierarchical core-shell structure

中图分类号:

O614

杨恩东, 李宝乐, 张珂, 谭鲁, 娄永兵. ZnCo₂O₄-ZnO@C@CoS核壳复合材料的制备及其在超级电容器中的应用[J]. 无机材料学报, 2024, 39(5): 485-493.

YANG Endong, LI Baole, ZHANG Ke, TAN Lu, LOU Yongbing. ZnCo₂O₄-ZnO@C@CoS Core-shell Composite: Preparation and Application in Supercapacitors[J]. Journal of Inorganic Materials, 2024, 39(5): 485-493.

图/表 8

图1 ZCO-ZO@C@CoS-6的形貌表征

Fig. 1 Morphological characterization of ZCO-ZO@C@CoS-6 (a, b) FESEM images; (c) TEM image; (d) HRTEM image; (e) Corresponding EDS elemental mappings

图2 复合材料的成分及元素价态表征

Fig. 2 Characterization of components and elemental valence states for composites (a) XRD patterns; (b) Total XPS spectrum; (c-f) High-resolution XPS spectra of (c) Zn2p, (d) O1s, (e) Co2p, and (f) S2p

图3 ZCO-ZO微球、ZCO-ZO@C和ZCO-ZO@C@CoS-6复合电极的电化学表征

Fig. 3 Electrochemical characterization of ZCO-ZO microspheres, ZCO-ZO@C and ZCO-ZO@C@CoS-6 composite electrodes (a) CV curves at a scan rate of 5 mV·s-1; (b) GCD curves at a current density of 2 A·g-1; (c) CV curves at various scan rates and (d) GCD curves at different current densities of ZCO-ZO@C@CoS-6 composite electrode; (e) Specific capacities at different current densities; (f) Nyquist plots with inset showing corresponding equivalent circuit Colorful figures are available on website

图4 ZCO-ZO@C@CoS-6电极在20 A·g-1条件下10000次的循环性能

Fig. 4 Cycling performance of ZCO-ZO@C@CoS-6 electrode at 20 A·g-1 for 10000 cycles

图5 ZCO-ZO@C@CoS-3和ZCO-ZO@C@CoS-9复合电极的电化学表征

Fig. 5 Electrochemical characterization of ZCO-ZO@C@CoS-3 and ZCO-ZO@C@CoS-9 composite electrodes (a, c) CV curves at various scan rates and (b, d) GCD curves at different current densities of (a, b) ZCO-ZO@C@CoS-3 and (c, d) ZCO-ZO@C@CoS-9 composite electrodes; (e) Specific capacities at different current densities; (f) Nyquist plots Colorful figures are available on website

图6 ZCO-ZO@C@CoS-6复合电极的定量电容分析

Fig. 6 Quantitative capacitance analysis of ZCO-ZO@C@CoS-6 composite electrode (a) CV curves at low scanning rates; (b) Fitted b; (c) Capacitive and diffusive contributions at 0.2 mV·s-1 (grey: total capacity; green: pseudocapacity); (d) Percentage contributions to charge storage at different scan rates Colorful figures are available on website

图7 ZCO-ZO@C@CoS-6//AC ASC的电化学表征

Fig. 7 Electrochemical characterization of ZCO-ZO@C@CoS-6//AC ASC (a) CV curves of ZCO-ZO@C@CoS-6 and AC electrodes in two-electrode system at a constant scan rate of 5 mV·s-1; (b) CV curves at 10 mV·s-1 for different wide ranges of voltage windows; (c) CV curves at a constant voltage window, (d) GCD curves and (e) calculated specific capacities for the ASC device; (f) Ragone plots of this work in comparison with reported SCs Colorful figures are available on website

图8 ZCO-ZO@C@CoS-6//AC ASC的结构及机理示意图

Fig. 8 Structure and mechanism diagram for ZCO-ZO@C@CoS-6//AC ASC

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ZnCo₂O₄-ZnO@C@CoS核壳复合材料的制备及其在超级电容器中的应用

ZnCo₂O₄-ZnO@C@CoS Core-shell Composite: Preparation and Application in Supercapacitors

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