Controllable preparation and regulation mechanism of ultrafine spherical cobalt powders
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摘要:
以CoCl2·6H2O和NH4HCO3为原料，通过液相沉淀法制备出粒径细小、均匀可控的CoCO3前驱体，再经过煅烧–氢还原法制备出超细类球形钴粉。分析液相沉淀法中搅拌时间和反应温度对CoCO3前驱体粒径及形貌的影响，讨论氢还原过程中还原温度和还原时间对还原产物物相、粒径及形貌的影响。结果表明，在液相沉淀中，随着搅拌时间的延长和反应温度的升高，CoCO3前驱体形核率提高，CoCO3平均粒径D50减小；在搅拌时间45 min、反应温度25 ℃条件下，制备出粒径均匀、球形度高、平均粒径D50为0.96 μm的CoCO3前驱体。在氢还原制备钴粉过程中，随着氢还原时间的延长和温度的升高，钴粉粒径变大；当氢还原温度为400 ℃、时间为45 min时，钴粉分散性好，粒径均匀，平均粒径为0.4 μm。
Abstract:The CoCO3 precursors with fine, uniform, and controllable particle size were prepared by liquid-phase precipitation method, using CoCl2·6H2O and NH4HCO3 as raw materials, and then the ultrafine spherical cobalt powders were prepared by calcination-hydrogen reduction. The influence of stirring time and reaction temperature on the particle size and morphology of CoCO3 precursors in the liquid-phase precipitation method was analyzed, and the effect of reduction temperature and reduction time on the phase, particle size, and microstructure of the reduction products was investigated. The results show that the nucleation rate of CoCO3 precursors increases with the increase of stirring time and reaction temperature, and then the average particle size of CoCO3 decreases. The CoCO3 precursors with uniform particle size, high sphericity, and average particle size of 0.96 μm are prepared, when the stirring time is 45 min and the reaction temperature is 25 ℃. In the hydrogen reduction, the particle size of cobalt powders increases with the increase of hydrogen reduction time and temperature. When the hydrogen reduction temperature is 400 ℃ for 45 min, the cobalt powders show the good dispersion and uniform particle size with the average particle size of 0.4 μm
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图 1 不同搅拌时间制备CoCO3粉末的显微形貌及粒径分布：（a）、（b）15 min；（c）、（d）30 min；（e）、（f）45 min；（g）、（h）60 min
Figure 1. SEM images and particle size distribution of the CoCO3 powders prepared in different stirring times: (a), (b) 15 min; (c), (d) 30 min; (e), (f) 45 min; (g), (h) 60 min
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图 2 不同反应温度制备CoCO3粉末的显微形貌及粒径分布：（a）、（b）15 ℃；（c）、（d）25 ℃；（e）、（f）35 ℃；（g）、（h）45 ℃
Figure 2. SEM images and particle size distribution of the CoCO3 powders prepared at different reaction temperatures: (a), (b) 15 ℃; (c), (d) 30 ℃; (e), (f) 45 ℃; (g), (h) 45 ℃
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图 4 不同搅拌速度制备CoCO3粉体显微形貌和粒径分布：（a）、（b）200 r/min；（c）、（d）250 r/min；（e）、（f）300 r/min；（g）、（h）350 r/min
Figure 4. SEM images and particle size distribution of the CoCO3 powders prepared at different stirring speeds: (a), (b) 200 r/min; (c), (d) 250 r/min; (e), (f) 300 r/min; (g), (h) 350 r/min
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图 5 不同陈化温度制备CoCO3粉体显微形貌和粒径分布分布：（a）、（b）15 ℃；（c）、（d）25 ℃；（e）、（f）35 ℃；（g）、（h）45 ℃
Figure 5. SEM images and particle size distribution of the CoCO3 powders prepared at different aging temperatures: (a), (b) 15 ℃; (c), (d) 25 ℃; (e), (f) 35 ℃; (g), (h) 45 ℃
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图 6 CoCO3微观形貌（a）和X射线衍射图谱（b）
Figure 6. SEM image (a) and XRD patterns (b) of the CoCO3 precursors
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图 7 CoCO3煅烧反应中ΔG随温度变化曲线（a）和CoCO3在空气气氛下煅烧的同步热分析曲线（b）
Figure 7. Curves of ΔG with temperature in CoCO3 calcination reaction (a) and the DSC‒TG curves of CoCO3 calcination in air atmosphere
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图 8 煅烧产物Co3O4微观形貌（a）和X射线衍射图谱（b）
Figure 8. SEM image (a) and XRD pattern (b) of the calcined product Co3O4
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图 9 Co3O4氢还原反应中ΔG随温度变化曲线
Figure 9. Curves of ΔG with temperature in Co3O4 hydrogen reduction reaction
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图 10 Co3O4试样在不同还原温度氢还原30 min的X射线衍射图谱
Figure 10. XRD patterns of Co3O4 samples at different temperatures for hydrogen reduction for 30 min
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图 11 Co3O4试样在不同还原温度氢还原30 min后还原产物的显微形貌：（a）250 ℃；（b）300 ℃；（c）350 ℃；（d）400 ℃
Figure 11. SEM images of the Co3O4 samples reduced by hydrogen for 30 min at different temperatures: (a) 250 ℃; (b) 300 ℃; (c) 350 ℃; (d) 400 ℃
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图 12 Co3O4试样在400 ℃经不同还原时间氢还原的X射线衍射图谱
Figure 12. XRD patterns of the Co3O4 samples by hydrogen reduction at 400 ℃ for different reduction times
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图 13 Co3O4试样在400 ℃经不同还原时间氢还原所得产物微观形貌：（a）15 min；（b）30 min；（c）45 min；（d）60 min；（e）45 min还原Co粉放大图；（f）45 min还原Co粉粒径分布
Figure 13. SEM images of Co3O4 samples by hydrogen reduction at 400 ℃ for different times: (a) 15 min; (b) 30 min; (c) 45 min; (d) 60 min; (e) 45 min reduction cobalt powder magnification; (e) particle size distribution of cobalt powder reduced in 45 min
表 1 实验制备钴粉的化学成分（质量分数）
Table 1 Chemical compositions of the cobalt powders
% Co Ca S K Na Fe O 99.9680 0.0027 ＜ 0.0020 ＜ 0.0010 ＜ 0.0010 0.0019 0.5400 
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