Preparation of hierarchical CoO@NiMo-O(P) composites and its supercapacitive performance
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摘要: 超级电容器具有充放电快、比电容高、循环稳定性好等优点，已成为一种重要的储能器件，其性能主要取决于电极材料的电化学性能。具有高比表面积和环境友好性的复合纳米材料，是超级电容器的理想电极材料。本文首先采用水热法在碳布基底上制备了氢氧化钴纳米线，并以纳米线为基体，在其上二次水热合成镍钼氢氧化物纳米片，再经过低温退火和磷化，最终获得了CoO@NiMo-O(P)分级复合纳米材料。利用SEM、TEM及XPS等技术对样品形貌、结构和元素化合价进行了表征和分析。电化学测试结果表明：该分级复合纳米材料具有良好的电容性能，在1 A/g的电流密度下比电容可达1304.55 F/g，且在10 A/g的电流密度下经过1000次充放电后，比电容保持率高达87%，表现出了良好的循环特性。Abstract: Supercapacitor, which has a series of advantages such as fast charge and discharge, high specific capacitance as well as good cycle stability, has become an important energy storage device, whose performance mainly depends on the electrochemical properties of electrode materials. Composite nanomaterials with high specific surface area and environmental friendliness are ideal electrode materials for supercapacitors. In this paper, nickel-molybdenum nanosheets were grown on the surface of cobalt hydroxide nanowires on the carbon cloth substrate by a two-step hydrothermal method to achieve CoO@NiMo-O(P) composite nanomaterials after low temperature annealing and phosphorlation. The morphology, structure and chemical valence of the samples were characterized and analyzed by SEM, TEM and XPS. The results of electrochemical tests show that the hierarchical CoO@NiMo-O(P) composites has good capacitance performance. The specific capacitance reaches 1304.55 F/g at a low current density of 1 A/g, and a capacity retention of 87% is exhibited after 1000 charge and discharge at a current density of 10 A/g, showing good cycle stability.
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图 1 制备CoO@NiMo-O(P)分级复合材料的流程示意图
Figure 1. Schematic illustration of the synthesis process of the CoO@NiMo-O(P) composites
图 2 生长在碳布上的Co(OH)2纳米线的低倍 (a) 和高倍 (b) SEM图像；(c) Co(OH)2纳米线EDS谱图；((d)、(e)) 在Co(OH)2纳米线上生长NiMo-O(OH)纳米片后的SEM图像；(f) 相应的EDS谱图；((g)、(h)) CoO@NiMoO4纳米复合材料的SEM图像；(i) CoO@NiMo-O(P)复合材料的EDS谱图；((j)、(k)) CoO@NiMo-O(P)的SEM图像；(l) CoO@NiMo-O(P)的EDS谱图
Figure 2. Low (a) and high (b) magnification SEM images of the Co(OH)2 nanowires grown on carbon cloth; (c) EDS spectrum of the Co(OH)2 nanowires; ((d), (e)) SEM images of the NiMo-O(OH) nanoflakes grown on the Co(OH)2 nanowires; (f) EDS spectrum of the nanoflakes; ((g), (h)) SEM images of the CoO@NiMoO4 composites; (i) EDS spectrum of the composites of CoO@NiMo-O(P); ((j), (k)) SEM images of CoO@NiMo-O(P); (l) Corresponding EDS spectrum of CoO@NiMo-O(P)
图 3 CoO@NiMo-O(P)分级复合材料的SEM图像 (a) 及能量色散X射线谱图 ((b)~(f))
Figure 3. SEM image (a) and energy dispersive X-ray spectroscopy (EDS) mapping ((b)-(f)) of CoO@NiMo-O(P) hierarchical composites
图 4 (a) 实验中各步骤所得样品的XRD图谱；((b)、(c)) 最终样品CoO@NiMo-O(P)的TEM图像和相应的SAED图谱
Figure 4. (a) XRD spectra of the materials obtained in the experiment process; ((b), (c)) TEM images of the final product and the corresponding SAED pattern of CoO@NiMo-O(P)
图 5 CoO@NiMo-O(P)复合纳米材料XPS元素测定谱图：(a) 全谱图；(b) Co2p; (c) Ni2p; (d) Mo3d; (e) O1s; (f) P2p
Figure 5. XPS spectra CoO@NiMo-O(P) hierarchical composites: (a) Survey spectrum; (b) Co2p; (c) Ni2p; (d) Mo3d; (e) O1s; (f) P2p
图 6 (a) CoO@NiMo-O(P)、CoO@NiMoO4、NiMo-O(P)、Co-O(P)在30 mV/s扫速下的循环伏安特性；(b) 上述四种材料在1 A/g电流密度下的恒电流充放电性能；(c) CoO@NiMo-O(P) 不同扫速下的循环伏安特性；(d) CoO@NiMo-O(P)在不同电流密度下的恒电流充放电特性；(e) CoO@NiMo-O(P)、NiMo-O(P)和Co-O(P)在10 A/g电流密度下充放电1000次的稳定性；(f) CoO@NiMo-O(P)复合材料稳定性测试前后的阻抗对比图(插图为CoO@NiMo-O(P)与CoO@NiMoO4的阻抗对比图)
Figure 6. (a) CV curves of CoO@NiMo-O(P), CoO@NiMoO4, NiMo-O(P), Co-O(P) at a scan rate of 30 mV/s; (b) GCD curves of the above fore materials at a current density of 1 A/g; (c) CV curves of CoO@NiMo-O(P) composite at different scanning rates; (d) GCD curves of CoO@NiMo-O(P) at different current densities; (e) Cycling performance of CoO@NiMo-O(P), NiMo-O(P) and Co-O(P) electrode at a current density of 10 A/g; (f) Nyquist plots of CoO@NiMo-O(P) before and after 1000 cycles (Inset: Nyquist plots of CoO@NiMoO4 and CoO@NiMo-O(P))
表 1 不同超级电容器电极材料充放电性能对比
Table 1. Comparison of GCD with different electrode materials for supercapacitor
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