Co3O4/Co9S8 核壳结构电极准固态超级电容器的制备和性能

doi:10.11901/1005.3093.2024.435

材料研究学报

2025, Vol. 39

Issue (8): 569-582 DOI: 10.11901/1005.3093.2024.435

研究论文

本期目录 | 过刊浏览

Co₃O₄/Co₉S₈ 核壳结构电极准固态超级电容器的制备和性能

杨志儒(

), 侯文涛, 周海, 杨子, 何浩, 金超

江苏大学机械工程学院镇江 212013

Synthesis of High-performance Core-shell Structured Electrodes of Co₃O₄/Co₉S₈ for Quasi-solid-state Supercapacitors

YANG Zhiru(

), HOU Wentao, ZHOU Hai, YANG Zi, HE Hao, JIN Chao

School of Mechanical Engineering, Jiangsu University, Zhenjiang 212013, China

引用本文:

杨志儒, 侯文涛, 周海, 杨子, 何浩, 金超. Co₃O₄/Co₉S₈ 核壳结构电极准固态超级电容器的制备和性能[J]. 材料研究学报, 2025, 39(8): 569-582.
Zhiru YANG, Wentao HOU, Hai ZHOU, Zi YANG, Hao HE, Chao JIN. Synthesis of High-performance Core-shell Structured Electrodes of Co₃O₄/Co₉S₈ for Quasi-solid-state Supercapacitors[J]. Chinese Journal of Materials Research, 2025, 39(8): 569-582.

全文: PDF(22872 KB) HTML

摘要:

用水热法制备一种核壳结构的电极，其核心由Co₃O₄纳米线组成。使用硫代乙酰胺(TAA)对Co₃O₄纳米线进行硫化生成Co₉S₈外壳。其Co₃O₄纳米线核和Co₉S₈外壳相互连接，形成均匀分布在镍泡沫上的纳米棒。硫化时优化TAA的浓度可增多电极的活性位点，制备出电化学性能优异的电极。这种电极在电流密度为2 mA·cm^-2的条件下其面积比电容为3.54 F·cm^-2。电极优异的导电性和高效离子扩散，使其在电流密度为50 mA·cm^-2的条件下充放电循环可达3000次，且循环后仍保持2 F·cm^-2的高比电容和良好的稳定性。用Co₃O₄/Co₉S₈为正极、活性炭为负极组装的不对称超级电容器(ASC)5000次充放电循环后其比电容保持率为100%，表明其具有优异的循环稳定性。用这种Co₃O₄/Co₉S₈电极组装的软包准固态不对称超级电容器具有良好的机械柔韧性和循环稳定性。

关键词 ：复合材料, 核壳材料, 结构稳定性, 不对称超级电容器

Abstract：

The core-shell composite Co₃O₄/Co₉S₈, as electrode material was prepared by a two-step method. Firstly, Co₃O₄ nanowires were grown on Ni-foam by hydrothermal method, and then they were calcined. Secondly, Co₃O₄/Co₉S₈ core-shell composite materials on templates of Co₃O₄ nanowires were obtained via ion exchange reaction and sulfidation in the presence of thioacetamide (TAA). The nanowire core Co₃O₄ and shell Co₉S₈ are interconnected each other as uniformly distributed nanorods on the Ni-foam. Results indicated that by optimizing the TAA concentration during the second step, the electrode gained a higher number of active sites and improved electrochemical performance. At a current density of 2 mA·cm^-2, the electrode exhibited a specific capacitance of 3.54 F·cm^-2. Due to its excellent conductivity and efficient ion diffusion pathways, it achieved up to 3,000 charge-discharge cycles at a current density of 50 mA·cm^-2, while maintaining a high specific capacitance of 2 F·cm^-2 and stability after cycling. Additionally, by utilizing Co₃O₄/Co₉S₈ as the positive electrode and activated carbon as the negative electrode, an asymmetric supercapacitor was assembled. After 5,000 charge-discharge cycles, this device attained a capacitance retention rate of 100%, demonstrating outstanding cycling stability. The soft-pack quasi-solid-state asymmetric supercapacitor assembled with this Co₃O₄/Co₉S₈ electrode exhibits excellent mechanical flexibility and cycling stability.

Key words： composite core-shell material structural stability asymmetrical supercapacitors

收稿日期: 2024-10-25

ZTFLH:

TB332

基金资助:国家自然科学基金(51505194);江苏省自然科学基金(BK20150517);江苏省自然科学基金(BK20190846);江苏大学高级人才科研启动基金(15JDG033)

通讯作者: 杨志儒，副教授，yangzr2030@outlook.com，研究方向为复合材料储能器件、激光功能化表面、极端环境摩擦学

Corresponding author: YANG Zhiru, Tel: 18260632639, E-mail: yangzr2030@outlook.com

作者简介: 杨志儒，男，1981年生，博士

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https://www.cjmr.org/CN/10.11901/1005.3093.2024.435 或 https://www.cjmr.org/CN/Y2025/V39/I8/569

图1 在镍泡沫(NF)上制备Co3O4/Co9S8复合材料的示意图

图2 生长在NF上的Co3O4的SEM图像和添加不同量TAA的Co3O4/Co9S8的SEM图像

表1 试样不同阶段的含量和其元素的百分比

图3 Co3O4/Co9S8的TEM，SAED和HRTEM图像

图4 Co3O4/Co9S8的XRD 谱

图5 Co3O4/Co9S8、Co9S8和Co3O4的Raman光谱以及C 1s、Co 2p和S 2p的X射线光电子光谱

图6 Co3O4和Co3O4/Co9S8复合材料的氮吸附/脱附等温线和孔径分布

表2 添加不同量TAA的Co3O4/Co9S8反应2 h的比电容

图7 Co3O4/Co9S8在三电极系统中的超级电容器性能

图8 Co3O4/Co9S8、Co3O4和Co9S8的Nyquist 图

表3 钴基材料的性能对比

图9 不同放大倍数的Co3O4/Co9S8循环3000次后的SEM图像以及循环前后的Nyquist图

图10 Co3O4/Co9S8 || AC ASC的性能、不同扫描速率的CV曲线及其对应的电容、不同电流速率的恒流放电曲线及其对应的电容以及电流速率为25 mA·cm-2的长期充放电性能

图11 组装QSS-ASC的示意图、不同电流速率的恒流充放电曲线、不同扫描速率的CV曲线及其对应的电容、电流密度为50 mA·cm-2 QSS-ASC处于平展-弯曲状态的长期充放电性能，

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