Design and fabrication of hydrangea viburnum-like cobalt sulfide@nitrogen-rich carbon for high-performance supercapacitors
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摘要: 本文采用简单的溶剂热法制备了一种独特的具有大量电化学活性位点的绣球荚蒾状硫化钴(HVCS)。接着通过原位聚合将聚苯胺(PANI)组装到HVCS表面，最后将聚苯胺进一步碳化，得到绣球荚蒾状硫化钴@富氮炭复合材料(HVCS@NC)。得益于独特的微观结构设计和两组分电化学性能优势的互补，电化学分析表明制备所得HVCS@NC纳米复合电极具有理想的超级电容器电化学性能。该材料在电流密度为1 A·g−1时展现出622 F·g−1的比电容值，以HVCS@NC和活性炭(AC)分别作正极和负极组装的不对称超级电容器，在功率密度为1912.3 W·kg−1时能量密度达19.9 W·h·kg−1。研究表明：将导电高分子PANI定位组装在具有特殊微观形貌结构硫化钴表面并碳化的工艺可以获得高性能硫化物基超级电容器电极材料，聚苯胺的可塑性及碳化处理后富含氮元素的特性对于改善过渡金属硫化物的电化学性能具有很大优势，这种结构设计策略可以潜在地扩展并应用到其他过渡金属硫化物基超级电容器电极材料的电化学性能提升。Abstract: A unique hydrangea viburnum-like cobalt sulfide (HVCS) with multiple electrochemically active sites was successfully fabricated by a simple solvent thermal method. Polyaniline (PANI) was assembled onto the surface of HVCS through in situ polymerization and finally PANI were further carbonized to obtain hydrangea viburnum-like cobalt sulfide@nitrogen-rich carbon composite (HVCS@NC). Benefiting from the unique microstructure design and synergistic effect produced through the complementary properties of the two components, the fabricated HVCS@NC electrode demonstrates ideal electrochemical performance for supercapacitors through electrochemical analysis. The material exhibits an outstanding capacitive performance of 622 F·g−1 at a current density of 1 A·g−1 and the assembled asymmetric supercapacitor with HVCS@NC and active carbon (AC) as positive and negative electrodes, respectively, achieves a high specific energy of 19.9 W·h·kg−1 at a specific power of 1912.3 W·kg−1. All results show that high-performance supercapacitor electrode materials can be obtained by assembling conductive polymers on the surface of novel cobalt sulfide with special microscopic morphology and structure and then carbonizing. The plasticity and nitrogen-rich properties after carbonization of polyaniline have great advantages for improving the electrochemical performance of transition metal sulfide. This structural design strategy can be potentially extended to the improvement of electrochemical properties of other transition metal sulfide based electrode materials.
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图 1 绣球荚蒾状硫化钴@富氮炭复合材料(HVCS@NC)构造示意图
An—Aniline; APS—Ammonium persulfate; PANI—Polyaniline
Figure 1. Schematic of the hydrangea viburnum-like cobalt sulfide@nitrogen-rich carbon composite (HVCS@NC) fabrication
图 2 HVCS ((a)、(b))、HVCS@PANI ((c)、(d))和HVCS@NC ((e)、(f))在不同放大倍数下的SEM图像
Figure 2. SEM images of HVCS ((a), (b)), HVCS@PANI ((c), (d)) and HVCS@NC ((e), (f)) at different magnifications
图 3 HVCS@NC在不同放大倍数下的TEM图像与元素面扫描图
Figure 3. TEM images of HVCS@NC at different magnifications and elements mapping
图 4 HVCS ((a)~(c))、HVCS@PANI ((d)~(g))和HVCS@NC ((h)~(l))的EDS面谱
Figure 4. EDS mapping of HVCS ((a)-(c)), HVCS@PANI ((d)-(g)) and HVCS@NC ((h)-(l))
图 5 HVCS氮气吸脱附曲线 (a)和HVCS孔径分布曲线(b)
Figure 5. N2 adsorption-desorption isotherm loop of HVCS (a) and pore size distribution curve of HVCS (b)
图 6 HVCS、HVCS@PANI和HVCS@NC的FTIR图谱(a)及HVCS的XRD图谱(b)
Figure 6. FTIR spectra of HVCS, HVCS@PANI and HVCS@NC (a) and XRD pattern of HVCS (b)
图 7 Co2p (a)和S2p (b)的高分辨XPS图谱
Sat.—Satellite peak
Figure 7. High-resolution XPS spectra of Co2p (a) and S2p (b)
图 8 HVCS@NC在不同扫描速率下的CV曲线 (a)、2 A·g−1下的GCD曲线(b)、HVCS@NC在不同电流密度下的GCD曲线(c)、不同电流密度下HVCS@NC的比电容值(d)、20 A·g−1循环稳定性测试(e)、HVCS@NC在20 A·g−1循环稳定性测试(f)和阻抗对比(g)
Figure 8. CV curves of HVCS@NC at different scan rates (a), GCD curves at 2 A·g−1 (b), GCD curves of HVCS@NC at different current densities (c), specific capacitance of HVCS@NC at different current densities (d), cycling stability performance at 20 A·g−1 (e), cycling stability performance of HVCS@NC at 20 A·g−1 (f) and Nyquist plots of HVCS and HVCS@NC (g)
图 9 HVCS@NC//活性炭(AC)在不同扫描速率下的CV曲线(a)、HVCS@NC//AC在不同电流密度下的GCD曲线(b)、HVCS@NC//AC在不同电流密度下的比电容值(c)、HVCS@NC//AC 的Ragone 图(d)和HVCS@NC//AC 在10.5 A·g−1下的循环稳定性能(e)
Figure 9. CV curves of HVCS@NC//activated carbon (AC) at different scan rates (a), GCD curves of HVCS@NC//AC at different current densities (b), specific capacitance of HVCS@NC//AC at different current densities (c), Ragone plot of HVCS@NC//AC (d) and cycling stability of HVCS@NC//AC at 10.5 A·g−1 (e)
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