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Chinese Journal of Materials Research  2025, Vol. 39 Issue (8): 569-582    DOI: 10.11901/1005.3093.2024.435
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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
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YANG Zhiru, HOU Wentao, ZHOU Hai, YANG Zi, HE Hao, JIN Chao. Synthesis of High-performance Core-shell Structured Electrodes of Co3O4/Co9S8 for Quasi-solid-state Supercapacitors. Chinese Journal of Materials Research, 2025, 39(8): 569-582.

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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     
Received:  25 October 2024     
ZTFLH:  TB332  
Fund: National Natural Science Foundation of China(51505194);Natural Science Foundation of Jiangsu Province(BK20150517);Natural Science Foundation of Jiangsu Province(BK20190846);Senior Talent Start-up Foundation of Jiangsu University(15JDG033)
Corresponding Authors:  YANG Zhiru, Tel: 18260632639, E-mail: yangzr2030@outlook.com
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YANG Zhiru
HOU Wentao
ZHOU Hai
YANG Zi
HE Hao
JIN Chao

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https://www.cjmr.org/EN/10.11901/1005.3093.2024.435     OR     https://www.cjmr.org/EN/Y2025/V39/I8/569

Fig.1  Schematic diagram of the preparation process of the Co3O4/Co9S8 composite material on nickel foam (NF) (I) Hydrothermal synthesis, (II) Calcination, (III) Hydrothermal sulfidation
Fig.2  SEM images of the growth of Co3O4 on nickel foam (NF) (a-c), SEM images of Co3O4/Co9S8 with different amounts of thioacetamide (TAA) added (d-f) 0.01 g, (g-i) 0.1 g, (j-l) 1 g
Co3O4Co3O4/Co9S8
%, mass fraction%, atomic fraction%, mass fraction%, atomic fraction
Co67.6449.5745.5634.30
O11.8131.883.6910.25
S0.310.4119.4426.91
Table 1  Main content percentages and element percentages of samples at different stages
Fig.3  TEM (a, b), SAED (c) and HRTEM (d, e) images of Co3O4/Co9S8
Fig.4  XRD pattern of Co3O4/Co9S8
Fig.5  Raman spectra of Co3O4/Co9S8, Co9S8 and Co3O4 (a), X-ray photoelectron spectra of C 1s (b), Co 2p (c) and S 2p (d)
Fig.6  Nitrogen adsorption/desorption isotherms (a) and pore size distribution curves (b) of Co3O4 and Co3O4/Co9S8 composites
Current densityAreal capacitance / F·cm-2
mA·cm-2Co3O4/Co9S8-ACo3O4/Co9S8-BCo3O4/Co9S8-C
22.873.542.7
52.873.42.62
102.673.42.48
252.383.182.21
501.712.581.67
Table 2  Specific capacitances of Co3O4/Co9S8 with different amounts of TAA added at a reaction time of 2 h
Fig.7  Supercapacitor performance of Co3O4/Co9S8 in a three-electrode system (a) cyclic voltammetry curves at different scan rates, (b) corresponding specific capacitances calculated from (a), (c) galvanostatic discharge curves at different current rates, (d) corresponding specific capacitances calculated from (c), (e) long-term charge-discharge performance at a current rate of 50 mA·cm-2
Fig.8  Nyquist plots of Co3O4/Co9S8, Co3O4 and Co9S8
Active materialSpecific capacitance-current densityLong-cycle performanceReferences
Co3O4/Co9S83.54 F·cm-2-2 mA·cm-2After 3000 cycles, it retains 77.42% of the initial specific capacitanceThis work
CFF1.538 F·cm-2-1.5 mA·cm-2After 10000 cycles, it retains 100% of the initial specific capacitance[34]
CC@Co(OH)2:Mn2+@T352.2 mF·cm-2-5 mA·cm-2After 1000 cycles, it retains 85.5% of the initial specific capacitance[35]
Co-1/NF1.925 F·cm-2-1 mA·cm-2After 10000 cycles, it retains 80.3% of the initial specific capacitance[36]
FSCs1.29 F·cm-2-2 mA·cm-2After 5000 cycles, it retains 80.13% of the initial specific capacitance[37]
Co(OH)22.313 F·cm-2-0.4 mA·cm-2After 7000 cycles, it retains 83% of the initial specific capacitance[38]
Table 3  Performance comparison of cobalt-based materials
Fig.9  SEM images of Co3O4/Co9S8 after 3000 long-term cycles at different magnifications (a-c) and Nyquist plots before and after the cycles (d)
Fig.10  Performance of Co3O4/Co9S8 || AC ASC. CV curves at different scan rates (a) and the corresponding capacitances (b), galvanostatic discharge curves at different current rates (c) and the corresponding capacitances (d), long-term charge-discharge performance at a current rate of 25 mA·cm-2 (e)
Fig.11  Schematic diagram of the assembly of the QSS-ASC (a), galvanostatic charge-discharge curves at different current rates (b), CV curves at different scan rates and the corresponding capacitance calculation results (c) and long-term charge-discharge performance of the QSS-ASC at a current density of 50 mA·cm-2 in the flat-bent state (d)
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