Microwave synthesis of ZIF-67 derived nickel-cobalt hydroxide and its electrochemical performance
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摘要: 采用微波辅助加热法，以类沸石二甲基咪唑钴（ZIF-67）为模板和钴源，快速制备了三维中空结构的镍钴氢氧化物（Ni-Co LDH）。通过X射线衍射仪（XRD）、扫描电子显微镜（SEM）、X射线光电子能谱仪（XPS）、透射电子显微镜（TEM）和比表面积及孔径分析仪（BET）探究了微波反应时间对材料形貌、结构的影响；通过循环伏安法（CV）、恒电流充放电（GCD）曲线和电化学阻抗谱（EIS）分析了材料的电化学性能。结果显示，Ni-Co LDH-15 min电极材料的电化学性能最优：在0.5 A /g时，比电容高达2371.0 F/g；电流密度扩大20倍，材料具有较好的倍率性能（78.5%）。以镍钴氢氧化物为正极，活性炭为负极组装成非对称式超级电容器，在功率密度为448.05 W/kg时，能量密度高达19.17 W·h/kg，且循环5000圈后电容保持率高达88.7%，表明镍钴氢氧化物是一种具有优异电化学性能和实际应用潜力的超级电容器电极材料。Abstract: Microwave-assisted heating method was used to rapidly prepare three-dimensional hollow nickel-cobalt hydroxide (Ni-Co LDH) by using zeolite dimethyl imidazolium cobalt (ZIF-67) as template and cobalt source. The effect of microwave reaction time on the morphology and electrochemical properties of the materials was investigated. X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and specific surface and aperture analyzer (BET) were used to investigate the effect of microwave reaction time on the structure and morphology of the samples. The electrochemical properties of Ni-Co LDH electrode materials were analyzed by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). The results showed that the electrochemical properties of Ni-Co LDH-15 min electrode were the best. The specific capacitance was 2371.0 F/g at 0.5 A/g. The Ni-Co LDH-15 min also possessed excellent capacity retention of 78.5% when the current density increased by 20 times. An asymmetric supercapacitor (Ni-Co LDH//AC) was assembled by using Ni-Co LDH as the positive electrode and AC as the negative electrode. The Ni-Co LDH//AC device delivered a high energy density of 19.17 W·h/kg at the power density of 448.05 W/kg. Furthermore, the capacitance retention rate still maintained 88.7% after 5000 cycles. These results showed that Ni-Co LDH was a kind of electrode material for supercapacitor with excellent electrochemical performance and practical application potential.
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图 1 ZIF-67样品（a）和不同微波加热时间制得的镍钴氢氧化物（b）的XRD谱图
Figure 1 XRD pattern of (a) ZIF-67, (b) Ni-Co LDH prepared by different microwave heating time
图 2 （a）ZIF-67，（b）Ni-Co LDH-5 min，（c）Ni-Co LDH-10 min，（d）Ni-Co LDH-15 min，（e）Ni-Co LDH-15 min，（f）Ni-Co LDH-20 min，（g）Ni-Co LDH-20 min，（h）Ni-Co LDH-30 min和（i）Ni-Co LDH-35 min的 SEM照片
Figure 2 SEM images of (a) ZIF-67, (b) Ni-Co LDH-5 min, (c) Ni-Co LDH-10 min, (d) Ni-Co LDH-15 min, (e) Ni-Co LDH-15 min, (f) Ni-Co LDH-20 min, (g) Ni-Co LDH-20 min, (h) Ni-Co LDH-30 min and (i) Ni-Co LDH-35 min
图 3 （a）镍钴氢氧化物的氮气吸附-脱附等温曲线和（b）孔径分布
Figure 3 (a) Nitrogen adsorption/desorption isotherms plots and (b) pore size distribution curves of Ni-Co LDH samples
图 4 镍钴氢氧化物的XPS谱图（a）Ni 2p高分辨谱图，（b）Co 2p高分辨谱图
Figure 4 High-resolution XPS spectrum of (a) Ni 2p, (b) Co 2p for Ni-Co LDH
图 5 镍钴氢氧化物的（a）、（b）TEM照片和（c）EDX mapping照片
Figure 5 (a), (b) TEM images and (c) EDX mapping of Ni-Co LDH
图 6 所有镍钴氢氧化物样品的（a）CV曲线（10 mV/s)，（b）GCD曲线（0.5 A/g），（c）不同电流密度下的比电容关系，（d）EIS谱图，Ni-Co LDH-15 min的（e）CV曲线和（f）GCD曲线
Figure 6 CV curves (10 mV/s), (b) GCD curves (0.5 A/g), (c) specific capacity versus at different current densities, (d) EIS spectra of all Ni-Co LDH samples, (e) CV curves and (f) GCD curves of Ni-Co LDH-15 min
图 7 （a）活性炭和镍钴氢氧化物电极在10 mV/s下的CV曲线，（b）Ni-Co LDH//AC器件在不同扫速下的CV曲线，（c）Ni-Co LDH//AC器件在不同电流密度下的GCD曲线，（d）Ni-Co LDH//AC器件的循环稳定性，（e）Ni-Co LDH//AC器件循环5000圈前后的XRD谱图和SEM照片，（f）Ni-Co LDH//AC器件的拉贡图
Figure 7 (a) CV curves of AC and Ni-Co LDH electrode at 10 mV/s, (b) CV curves of Ni-Co LDH//AC at different scan rates, (c) GCD curves of Ni-Co LDH//AC at different current density, (d) cycling stability of Ni-Co LDH//AC, (e) before and after 5000 cycles of XRD patterns and SEM image, (f) Ragone plot of Ni-Co LDH//AC
表 1 所有镍钴氢氧化物样品的BET比表面积和孔结构
Table 1 BET surface area and pore structure of all the Ni-Co LDH samples
Sample SBET/ (m2·g−1) Dave/nm vt/ (cm3·g−1) Ni-Co LDH-5 min 313 10.14 0.79 Ni-Co LDH-10 min 253 9.28 0.59 Ni-Co LDH-15 min 326 8.87 0.72 Ni-Co LDH-20 min 273 10.06 0.69 Ni-Co LDH-25 min 305 10.90 0.83 Ni-Co LDH-30 min 318 11.94 0.95 Ni-Co LDH-35 min 273 8.79 0.60 
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