沉淀法制备微米四氧化三钴试验研究
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摘要
研究了以氯化钴为钴源,采用碳酸钠、氢氧化钠、碳酸氢铵沉淀体系制备Co_3O_4。以碳酸氢铵为沉淀剂制备前驱体,煅烧后制得四氧化三钴。结果表明,物质的量比是影响前驱体物相的主要因素:碳酸氢铵与氯化钴物质的量比≤3∶1时,前驱体为碱式碳酸钴(Co(CO_3)_(0.5)(OH)·0.11H_2O);碳酸氢铵与氯化钴物质的量比为4.5∶1时,前驱体为碳酸钴(CoCO_3)和复合碱式碳酸钴((NH_4)_2Co_8(CO_3)_6(OH)_6·4H_2O)的混合物。采用该体系,在物质的量比4.5∶1,氯化钴质量浓度13 g/L、反应温度60℃、反应时间10 h条件下,所得Co_3O_4粉体粒度分布均匀且范围窄,D_(50)为9.08μm,形貌为类球形。
Co_3O_4 was prepared by reaction of sodium carbonate,sodium hydroxide and ammonium bicarbonate as precipitant and cobalt chloride.Through particle size analysis,we know that ammonium bicarbonate system is better.Then the precursor was prepared with ammonium bicarbonate as precipitant,the results show that the molar ratio is the main factor affecting the precursor phase.When the molar ratio of ammonium bicarbonate to cobalt chloride is less than 3,the precursor is(Co(CO_3)_(0.5)(OH)·0.11(H_2 O));when the molar ratio of ammonium bicarbonate to cobalt chloride is 4.5,the precursor is mixture of cobalt carbonate(CoCO_3)and cobaltous dihydroxycarbonate((NH_4)_2Co_8(CO_3)_6(OH)_6·4H_2O).The suitable conditions for the system are:mole ratio is 4.5∶1,concentration of cobalt chloride is 13 g/L,reaction temperature is 60 ℃ and reaction time is 10 h.Under these conditions,Co_3O_4 powders with uniform particle size distribution and narrow range can be obtained.D_(50) of particles is 9.08 micron and the morphology is spherical.
Co_3O_4 was prepared by reaction of sodium carbonate,sodium hydroxide and ammonium bicarbonate as precipitant and cobalt chloride.Through particle size analysis,we know that ammonium bicarbonate system is better.Then the precursor was prepared with ammonium bicarbonate as precipitant,the results show that the molar ratio is the main factor affecting the precursor phase.When the molar ratio of ammonium bicarbonate to cobalt chloride is less than 3,the precursor is(Co(CO_3)_(0.5)(OH)·0.11(H_2 O));when the molar ratio of ammonium bicarbonate to cobalt chloride is 4.5,the precursor is mixture of cobalt carbonate(CoCO_3)and cobaltous dihydroxycarbonate((NH_4)_2Co_8(CO_3)_6(OH)_6·4H_2O).The suitable conditions for the system are:mole ratio is 4.5∶1,concentration of cobalt chloride is 13 g/L,reaction temperature is 60 ℃ and reaction time is 10 h.Under these conditions,Co_3O_4 powders with uniform particle size distribution and narrow range can be obtained.D_(50) of particles is 9.08 micron and the morphology is spherical.
引文
[1]乐颂光.钴冶金[M].北京:冶金工业出版社,1987.
[2]WANG F,LU C,QIN Y,et al.Solid state coalescence growth and electrochemical performance of plate-like Co3O4,mesocrystals as anode materials for lithium-ion batteries[J].Journal of Power Sources,2013,235(4):67-73.
[3]王成均,党晓娥,马旭利,等.电池级四氧化三钴生产工艺研究[J].金属功能材料,2014,21(2):36-40.
[4]JANSSON J,PALMQVIST A E C,FRIDELL E,et al.On the catalytic activity of Co3O4,in low-temperature CO oxidation[J].Journal of Catalysis,2002,211(2):387-397.
[5]徐昱,王建平,吴景荣.我国钴矿资源现状及进出口分析[J].矿业研究与开发,2014,34(5):112-115.
[6]周艳晶,李颖,柳群义,等.中国钴需求趋势及供应问题浅析[J].中国矿业,2014,23(12):16-19.
[7]蔡运和,陆益展,沈恒冠,等.四氧化三钴制备方法的研究[J].中国化工贸易,2013(5):173.
[8]郑兴芳,郭成花,张军.四氧化三钴粉末的沉淀法制备及表征[J].光谱实验室,2012,29(3):1838-1841.
[9]LIAN S,WANG E,GAO L,et al.Fabrication of singlecrystalline Co3O4,nanorods via a low-temperature solvothermal process[J].Materials Letters,2007,61(18):3893-3896.
[10]YANG Y P,LIU R S,HUANG K L,et al.Preparation and electrochemical performance of nanosized Co3O4via hydrothermal method[J].Transactions of Nonferrous Metals Society of China,2007,17(6):1334-1338.
[11]陆益展,朱珠,沈恒冠,等.配合剂对四氧化三钴合成的影响研究[J].中国化工贸易,2013(4):206-207.
[12]YANG H,HU Y,ZHANG X,et al.Mechanochemical synthesis of cobalt oxide nanoparticles[J].Materials Letters,2004,58(3):387-389.
[13]WANG G X,CHEN Y,KONSTANTINOV K,et al.Investigation of cobalt oxides as anode materials for Li-ion batteries[J].Journal of Power Sources,2002,109(1):142-147.
[14]李慧颖,王文祥,刘莹,等.草酸盐湿式沉淀-煅烧分解法制备四氧化三钴及其表征[J].粉末冶金工业,2017,27(4):17-21.
[15]PARK J S,CHO J S,KIM J H,et al.Electrochemical properties of micron-sized Co3O4,hollow powders consisting of size controlled hollow nanospheres[J].Journal of Alloys&Compounds,2016,689:554-563.
[16]王晓慧,王子忱,李熙,等.超微粒Co3O4的合成与表征[J].高等学校化学学报,1991,12(11):1421-1424.
[17]丁春桃,莫祥银,王克宇,等.电池级Co3O4的制备与表征[J].应用化学,2008,25(5):543-547.
[18]陈平.超细四氧化三钴的合成与电化学性能研究[D].长沙:湘潭大学,2007.
[19]樊玉川.电池级Co3O4的制备[J].稀有金属,2006,30(3):282-286.
[20]杨幼平,张平民,刘人生,等.前驱体对四氧化三钴形貌的影响与表征[J].中国有色金属学报,2011,21(2):442-449.
[21]POIZOT P,LARUELLE S,GRUGEON S,et al.ChemInform abstract:nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries[J].Nature,2000,407(6803):496-499.
[22]MING B,HAN H.Progress of Lithium ion battery positive pole material[J].Chemical Production&Technology,2012(4):8-9,34-43.
[23]胡雷,刘志宏.四氧化三钴粉末的制备与应用现状[J].粉末冶金材料科学与工程,2008,13(4):195-200.
[24]工业和信息化部.中华人民共和国有色金属行业标准:YS/T 633-2015[S].北京:中国标准出版社,2015.
[25]张克从.近代晶体学基础:下册[M].北京:科学出版社,1987.
[26]张灏,金鑫.用废锂电池制备Co3O4[J].化工环保,2007,27(5):468-472.
[27]李冠军,王同敏.液相法合成碳酸钴的过程控制[J].甘肃冶金,2007,29(4):63-65.
[28]王剑锋.电池级四氧化三钴的实验研究及中试[D].长沙:中南大学,2005.
[2]WANG F,LU C,QIN Y,et al.Solid state coalescence growth and electrochemical performance of plate-like Co3O4,mesocrystals as anode materials for lithium-ion batteries[J].Journal of Power Sources,2013,235(4):67-73.
[3]王成均,党晓娥,马旭利,等.电池级四氧化三钴生产工艺研究[J].金属功能材料,2014,21(2):36-40.
[4]JANSSON J,PALMQVIST A E C,FRIDELL E,et al.On the catalytic activity of Co3O4,in low-temperature CO oxidation[J].Journal of Catalysis,2002,211(2):387-397.
[5]徐昱,王建平,吴景荣.我国钴矿资源现状及进出口分析[J].矿业研究与开发,2014,34(5):112-115.
[6]周艳晶,李颖,柳群义,等.中国钴需求趋势及供应问题浅析[J].中国矿业,2014,23(12):16-19.
[7]蔡运和,陆益展,沈恒冠,等.四氧化三钴制备方法的研究[J].中国化工贸易,2013(5):173.
[8]郑兴芳,郭成花,张军.四氧化三钴粉末的沉淀法制备及表征[J].光谱实验室,2012,29(3):1838-1841.
[9]LIAN S,WANG E,GAO L,et al.Fabrication of singlecrystalline Co3O4,nanorods via a low-temperature solvothermal process[J].Materials Letters,2007,61(18):3893-3896.
[10]YANG Y P,LIU R S,HUANG K L,et al.Preparation and electrochemical performance of nanosized Co3O4via hydrothermal method[J].Transactions of Nonferrous Metals Society of China,2007,17(6):1334-1338.
[11]陆益展,朱珠,沈恒冠,等.配合剂对四氧化三钴合成的影响研究[J].中国化工贸易,2013(4):206-207.
[12]YANG H,HU Y,ZHANG X,et al.Mechanochemical synthesis of cobalt oxide nanoparticles[J].Materials Letters,2004,58(3):387-389.
[13]WANG G X,CHEN Y,KONSTANTINOV K,et al.Investigation of cobalt oxides as anode materials for Li-ion batteries[J].Journal of Power Sources,2002,109(1):142-147.
[14]李慧颖,王文祥,刘莹,等.草酸盐湿式沉淀-煅烧分解法制备四氧化三钴及其表征[J].粉末冶金工业,2017,27(4):17-21.
[15]PARK J S,CHO J S,KIM J H,et al.Electrochemical properties of micron-sized Co3O4,hollow powders consisting of size controlled hollow nanospheres[J].Journal of Alloys&Compounds,2016,689:554-563.
[16]王晓慧,王子忱,李熙,等.超微粒Co3O4的合成与表征[J].高等学校化学学报,1991,12(11):1421-1424.
[17]丁春桃,莫祥银,王克宇,等.电池级Co3O4的制备与表征[J].应用化学,2008,25(5):543-547.
[18]陈平.超细四氧化三钴的合成与电化学性能研究[D].长沙:湘潭大学,2007.
[19]樊玉川.电池级Co3O4的制备[J].稀有金属,2006,30(3):282-286.
[20]杨幼平,张平民,刘人生,等.前驱体对四氧化三钴形貌的影响与表征[J].中国有色金属学报,2011,21(2):442-449.
[21]POIZOT P,LARUELLE S,GRUGEON S,et al.ChemInform abstract:nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries[J].Nature,2000,407(6803):496-499.
[22]MING B,HAN H.Progress of Lithium ion battery positive pole material[J].Chemical Production&Technology,2012(4):8-9,34-43.
[23]胡雷,刘志宏.四氧化三钴粉末的制备与应用现状[J].粉末冶金材料科学与工程,2008,13(4):195-200.
[24]工业和信息化部.中华人民共和国有色金属行业标准:YS/T 633-2015[S].北京:中国标准出版社,2015.
[25]张克从.近代晶体学基础:下册[M].北京:科学出版社,1987.
[26]张灏,金鑫.用废锂电池制备Co3O4[J].化工环保,2007,27(5):468-472.
[27]李冠军,王同敏.液相法合成碳酸钴的过程控制[J].甘肃冶金,2007,29(4):63-65.
[28]王剑锋.电池级四氧化三钴的实验研究及中试[D].长沙:中南大学,2005.
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