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第 2 期 刘人生，等: 液相沉淀-煅烧法制备大粒径球形四氧化三钴 ·211·

从图 7a~c 可以看出，颗粒无开裂。由图 7d 可 掺杂（掺入 Al、Mg、Zr 等元素）改性，提升钴酸
以看出，煅烧产物出现了大量开裂现象。产生开裂 锂在高电压下的结构稳定性是今后研究的重点。
的原因是，碳酸钴直接进入高温区，分解反应速度
参考文献：
快，产生大量的 CO 2 气体，气体未能及时排出而冲
[1] Xu J J, Xiao T, Tan X Y, et al. A new asymmetric aqueous super
开颗粒。而分段煅烧时物料在低温区有一定的预反 capacitor: Co 3O 4//Co 3O 4@polypyrrole[J]. Journal of Alloys and
应时间，表面形成微孔，进入高温区后 CO 2 能及时 Compounds, 2017, 706: 351-357.
[2] Chen Y C, Hu L. Novel Co 3O 4 porous polyhedrons derived from
释放出来。 metal-organic frame work to ward high performance for
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2.4 XRD 分析 2016, 239: 23-29.
最佳条件下制备的碳酸钴和分段升温时间为 [3] Gao J Z, Zhao Y C, Yang W, et al. Sol-gel preparation and
characterization of Co 3O 4 nanocrystals[J]. Journal of University
60 min 时热分解后所得四氧化三钴的 X 射线衍射图 of Science and Technology Beijing, 2003, 10(1): 54-57.
谱见图 8。由图 8 可知，碳酸钴的衍射峰位置和强 [4] Xu Y Y, Liu Z Y, Chen D, et al. Synthesis and electrochemical
properties of porous α-Co(OH) 2 and Co 3O 4 microspheres[J]. Progress
度均与碳酸钴的 PDF 标准卡片（No. 78—0209）相 in Natural Science: Materials International, 2017, 27: 197-202.
符，没有明显杂质峰。碳酸钴经过高温煅烧后，产 [5] Zhang Weimin (张卫民), Sun Sixiu (孙思修), Yu Haiyun (俞海云),
et al. Synthesis of Co 3O 4 nanopowder with different morphologies by
物衍射峰与四氧化三钴的特征峰（No. 78—1970） hydrothermal treatment followed by decomposition[J]. Chemical
一致。与文献 [18] 相比，本文所得四氧化三钴的 X 射 Journal of Chinese Universities (高等学校化学学报), 2003, 12(24):
2151-2154.
线衍射峰窄而尖，无杂峰，说明热分解产物为纯相 [6] Rajeshkhanna G, Umeshbabu E, Ranga R G. Charge storage,
electrocatalytic and sensing activities of nest-like
四氧化三钴，晶型发育完整。 nanostructured Co 3O 4[J]. Journal of Colloid and Interface Science,

2017, 487: 20-30.
[7] Yu T, Zhu Y W, Xu X J, et al. Controlled growth and field-emission
properties of cobalt oxide nanowalls[J]. Advanced Materials, 2005,
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hollow polyhedrons prepared via cation-exchange metal-organic
framework for superior lithium-ion batteries[J]. Electrochimica Acta,
2016, 222: 1021-1028.
[10] Huang Guoyong (黄国勇), Xu Shengming (徐盛明), Li Linyan(李林
艳),et al. Synthesis and modification of a lamellar Co 3O 4 anode for
lithium-ion batteries[J]. Acta Physico-Chimica Sinica (物理化学学
图 8 碳酸钴前驱体和四氧化三钴的 X 射线衍射图谱 报), 2014, 30(6): 1121-1126.
Fig. 8 XRD patterns of CoCO 3 and Co 3 O 4 [11] Chen S Q, Zhao Y F, Sun B, et al. Microwave-assisted synthesis of
mesoporous Co 3O 4 nanoflakes for applications in Lithium ion
3 结论 batteries and oxygen evolution reactions[J]. ACS Applied Materials
& Interfaces, 2015, 7: 3306-3313.
[12] Huang G Y, Xu S M, Lu S S, et al. Micro-/nanostructured Co 3O 4
（1）大粒径球形碳酸钴最佳合成条件为：晶种 anode with enhanced rate capability for lithium-ion batteries[J]. ACS
Applied Materials & Interfaces, 2014, 6: 7236-7243.
量为 2 kg，温度 42 ℃，搅拌转度 65 r/min，过程 [13] Hou Xiangyu (侯相钰), Feng Jing (冯静), Liu Xiaohan (刘晓寒).
pH 控制在 7.2~7.5，硫酸钴溶液流量 500 mL/h，所 Synthesis and characterizations of self-assembled nano Co 3O 4 by
oxalate-precipitation method[J]. Chinese Journal of Inorganic
得碳酸钴形貌为较规则球形，无小颗粒产生。 Chemistry (无机化学学报), 2010, 26(3): 525-528.
[14] Zhai X M, Xu X M, Zhu X L, et al. Porous layer assembled
（2）大粒径球形碳酸钴的生长机理分为两个过
hierarchical Co 3O 4 as anode materials for lithium-ion batteries[J].
程：在生长初期，小颗粒间通过碰撞和方向调整形 Journal of Materials Science, 2018, 53: 1356-1364.
[15] Yang Youping (杨幼平), Zhang Pingmin (张平民), Liu Rensheng (刘
成带凹缺部位的聚合体；后期通过吸附和再结晶， 人生), et al. Influence of precursor on morphology of Co 3O 4 and
将凹缺处填满，最终生长成完整的球形颗粒。 characterization[J]. Chinese Journal of Nonferrous Metals (中国有色
金属学报), 2011, 21(2): 442-449.
（3）采用分段煅烧，碳酸钴热分解时颗粒不易 [16] Li Xiaoting (李晓婷), Zhang Lexi (张乐喜), Yin Jing (尹静), et al.
开裂。升温时间短，比表面积偏小，D 50 和 TD 偏大。 Effect of calcination temperature on gas-sensing and adsorption
performance of Co 3O 4 nanosheets from solvothermal synthesis[J].
适宜的升温时间为 60 min，所得四氧化三钴 D 50 为 Chinese Journal of Inorganic Chemistry (无机化学学报), 2016,
3
16.521 µm，粒度分布均匀，TD 达 2.26 g/cm 。 32(10): 1739-1746.
[17] Fang Tingting (方婷婷), Wang Qisui (王启岁), Hu Shuwan (胡淑
（4）以硫酸钴为原料，碳酸氢铵为沉淀剂，先 婉), et al. Optimized condition of specific surface area testing of
lithium battery materials[J]. Chinese Journal of Power Sources(电源
合成大粒径球形碳酸钴，再经分段煅烧可制得大粒 技术), 2018, 42(3): 335-338.
径球形四氧化三钴。所得四氧化三钴可用于制备高 [18] Huang Qiuyu (黄秋雨), Dai Yatang (戴亚堂), Zhang Huan (张欢),
et al. Preparation and capacitance performance of Co 3O 4 nanocluster
压实密度钴酸锂；对大粒径四氧化三钴进行进一步 arrays[J]. Fine Chemicals (精细化工), 2016, 33(1): 19-23.