Morphology control and electrochemical properties of three-dimensional hierarchical NiCo2O4 structure
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摘要: 形貌结构的调控对材料的电化学性能具有重要影响。本文采用溶剂热法结合煅烧在不同溶剂比及温度下合成不同形貌结构的钴酸镍，利用XRD及SEM和TEM等对样品的物相组成及形貌结构进行了表征，并对其电化学性能进行了分析。结果表明：当水与乙醇体积比为1∶1时，样品为中空的海胆状NiCo2O4，随着水比例的增加，形貌逐渐转变为规则的中心放射状的针状形貌，且有第二相物质的存在。在水与乙醇体积比为1∶1时，随着温度的增加，形貌主要由毛绒球向花状、海胆状、中心放射状的针状过渡，而样品均为纯NiCo2O4。90℃合成的样品具有较好的电化学性能，在1 A·g−1电流密度下，比电容高达1287.5 F·g−1，当扫速从20~100 mV·s−1变化时，电容保持率达到59.4%，循环1500圈，比电容保持率高达80.1%，此外，在整个电化学反应过程中扩散控制过程起主导作用。Abstract: The control of the morphology and structure has an important influence on the electrochemical properties of materials. In this work, NiCo2O4 samples with different morphologies and structures were synthesized by solvothermal method combined with calcination at different solvent ratios and temperatures. The phase composition and morphology of the samples were characterized by XRD, SEM and TEM et al, and the electrochemical performance was further studied. The results show that the sample is hollow sea urchin-like NiCo2O4, when the volume ratio of water to ethanol is 1∶1. With the increase of the content of water, the morphology gradually changes to regular central radial needle-like morphology, and there is a second phase substance. Under the condition of the volume ratio of water to ethanol is 1∶1, with the increase of temperature, the morphology mainly changes from fluffy ball to a flower-like, sea urchin-like, and center-radiating needle, while the phases of samples are pure NiCo2O4. The sample synthesized at 90℃ exhibits better electrochemical performance. The specific capacitance is up to 1287.5 F·g−1 at a current density of 1 A·g−1. The specific capacitance retention rate reaches 59.4% with the scan rate changes from 20-100 mV·s−1, and the specific capacitance retention rate is up to 80.1% after 1500 cycles. In addition, the whole electrochemical reaction is dominated by the diffusion-controlled process.
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图 1 不同溶剂比例合成NiCo2O4的XRD图谱
Figure 1. XRD patterns of the obtained NiCo2O4 with different solvent ratios
图 2 不同溶剂比例合成NiCo2O4的SEM图像
Figure 2. SEM images of the obtained NiCo2O4 with different solvent ratios
图 3 不同溶剂比例合成NiCo2O4的XPS图谱
Figure 3. XPS spectra of the obtained NiCo2O4 with different solvent ratios
Vo—Vacancy defect oxygen; Sat1, Sat2—Satellite peak 1 and satellite peak 2
图 4 不同温度下合成NiCo2O4的XRD图谱
Figure 4. XRD patterns of the obtained NiCo2O4 at different synthesis temperature
图 5 不同温度下合成NiCo2O4样品的SEM图像：((a), (b)) 90℃；((c), (d)) 110℃；((e), (f)) 130℃；((g), (h)) 150℃；(i) 90℃样品的元素面扫图
Figure 5. SEM images of the obtained NiCo2O4 samples at different synthesis temperature: ((a), (b)) 90℃; ((c), (d)) 110℃; ((e), (f)) 130℃; ((g), (h)) 150℃; (i) Elemental mapping images of sample obtained at 90℃
图 6 不同温度下合成NiCo2O4的TEM图像
Figure 6. TEM images of the obtained NiCo2O4 at different synthesis temperature
图 7 不同温度下合成NiCo2O4的机制示意图
Figure 7. Mechanism schematic diagram of the obtained NiCo2O4 at different synthesis temperature
图 8 不同温度合成的NiCo2O4的CV曲线((a)~(d))；(e) 100 mV·s−1扫速下的CV曲线对比图；(f) 扫速与比电容关系图
Figure 8. ((a)-(d)) CV curves of the obtained NiCo2O4 at different synthesis temperature; (e) CV curves at 100 mV·s−1; (f) Relationship between scan rate and specific capacity
图 9 (a) 不同温度合成的NiCo2O4的N2吸脱附曲线(插图为孔径分布图)；(b) 90℃的NiCo2O4的结构优势示意图
Figure 9. (a) Nitrogen adsorption-desorption isotherm of the obtained NiCo2O4 at different synthesis temperature (Inset of pore size distribution ); (b) Schematic illustration of the structural advantages of NiCo2O4 at 90℃
dV/dD—Pore volume
图 10 ((a)~(d)) 不同温度合成的NiCo2O4的GCD曲线；(e) 1 A·g−1电流密度下GCD曲线对比图；(f) 与图10(e)对应的电容值，插图为90℃的NiCo2O4电流密度与比电容关系图
Figure 10. ((a)-(d)) GCD curves of the obtained NiCo2O4 at different synthesis temperature; (e) GCD curves at 1 A·g−1; (f) Corresponding specific capacity of Fig. 10(e) (Inset of the relationship between current density and specific capacity of NiCo2O4 at 90℃)
图 11 不同温度合成的NiCo2O4的EIS曲线
Figure 11. EIS curves of the obtained NiCo2O4 at different synthesis temperature
Rs—Equivalent series resistance; Rct—Charge-transfer resistance; Cd—Double electric layer capacitance; w—Warburg’s resistance
图 13 90℃的NiCo2O4电极的阴极峰电流与扫速的对数关系图(a)和不同扫速下电容和扩散控制的相对贡献(b)
Figure 13. Relationship between logarithm cathode peak current and logarithm scan rates (a) and relative contributions of capacitive and diffusion-controlled processes at different scanning rates (b) of NiCo2O4 at 90℃
b—Constants obtained from the slope of the fitting linear curve of lg(scan rate) against lg(peak current)
表 1 不同溶剂比例合成NiCo2O4的表面原子比
Table 1. Surface atomic ratios of the obtained NiCo2O4 with different solvent ratios
Sample Ni2p3/2/at% Co2p3/2/at% Ni2+/Ni3+
(Atomic ratio)Co3+/Co2+
(Atomic ratio)Ni/Co
(Atomic ratio)Ni2+ Ni3+ Co3+ Co2+ 5 mL water 77.1 22.9 72.2 27.8 3.37 2.60 0.37 20 mL water 69.8 30.2 80.1 19.9 2.31 4.02 0.60 35 mL water 65.3 34.7 75.1 24.9 1.88 3.01 0.71 
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