CN1648054A - Preparation method of cobaltosic oxide - Google Patents
Preparation method of cobaltosic oxide Download PDFInfo
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- CN1648054A CN1648054A CN 200410047035 CN200410047035A CN1648054A CN 1648054 A CN1648054 A CN 1648054A CN 200410047035 CN200410047035 CN 200410047035 CN 200410047035 A CN200410047035 A CN 200410047035A CN 1648054 A CN1648054 A CN 1648054A
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Abstract
The invention relates to cobaltosic oxide 3O4) The preparation method of (1), which comprises the following steps: preparing cobalt sulfate or cobalt chloride into a cobalt solution, adding one or more of oxalate, carbonate or bicarbonate to generate a precursor precipitate of a cobalt salt compound, and filtering and washing to obtain a precursor with sulfate ions, chloride ions or sodium ions of less than 50 ppm; and granulating, drying, roasting and crushing the precursor to obtain the cobaltosic oxide product with a crystal form of a nodular polyhedron or an octahedron. Or drying and roasting the washed precursor, making the roasted material into blocks or pellets, drying and roasting for the second time, and finally crushing to obtain the cobaltosic oxide product with the crystal form of a nodular polyhedron or an octahedron. The product has large apparent density and tap density, uniform particle size and stable performance; the preparation method has low cost and easily controlled conditions, and is a new method suitable for industrial production of cobaltosic oxide.
Description
Technical field:
The present invention relates to a kind of preparation method of cobalt oxide, belong to the chemical material preparation field.Product is mainly used in the production lithium ion cell anode material lithium cobaltate, also can be used for producing fuel cell material, piezoresistor, magneticsubstance, catalyzer.
Background technology:
Along with the exploitation of electronic products such as mobile phone, digital camera, video camera, notebook computer and the rapid growth of demand, performance requriements to lithium ion battery is also more and more higher, but requires characteristics such as battery has energy density height, voltage height heavy-current discharge, self-discharge is little, memoryless, cycle index is many, the life-span is long.Thereby it is also more and more higher to the requirement of tricobalt tetroxide quality as the cobalt acid lithium of anode material for lithium-ion batteries, not only require foreign matter content low, and specific crystal morphology, big loose density and tap density will be arranged, and it is big that even, the single crystal grain of particle diameter is wanted, and performance will be stablized.
The method for preparing at present tricobalt tetroxide mainly contains: 1. be the feedstock production tricobalt tetroxide with the cobalt metal: adopt the cobalt metal sheet to make raw material, behind the nitric acid dissolve, make precipitation agent with bicarbonate of ammonia, throw out obtains the uniform nano-cobaltic-cobaltous oxide powder of particle diameter (ZL01135170.5) after 300～450 ℃ of roastings; Adopt sour molten cobalt metal to generate cobalt salt, add complexing agent, the presoma with the synthetic cobalt compound of precipitation agent after 300～1000 ℃ of roastings, obtains the tricobalt tetroxide (ZL02112970.3) of spinel structure.This kind preparation method, feed metal cobalt cost is higher, and technology is complicated, produces investment greatly, has problem of environmental pollution.2. Preparation by Uniform Precipitation tricobalt tetroxide: with Xiao Suangu and urea is raw material, sluggish precipitation make the tricobalt tetroxide micro mist that particle diameter is 25nm (" inorganic chemicals industry " 2002, Vol.34, No.1).This method precipitation agent consumption is big, the production cost height; Products obtained therefrom loose density and tap density are little, can not satisfy the demand that big particle diameter cobalt acid lithium is produced.3. three section calcining legal systems are equipped with tricobalt tetroxide: with cobalt oxalate, cobaltous hydroxide or cobaltous carbonate is raw material, becomes class spherical cobaltic-cobaltous oxide (publication number: CN1544340A, Xu Kaihua etc.) through three section calcinings.This preparation method can obtain loose density and the big product of tap density, but the difficult control of processing condition.
Summary of the invention:
The object of the present invention is to provide a kind of production cost low, particle diameter is even, has high loose density and tap density, stable performance, and the processing condition preparation method of cobalt oxide that is easy to control.
Technical scheme of the present invention is: adopt rose vitriol or cobalt chloride to make raw material, add oxalate, carbonate or supercarbonate in cobalt liquor, the presoma throw out of the synthetic cobalt salt compound of reaction; Presoma is filtered, washs, and granulation, roasting, fragmentation make loose density and tap density is big, and particle diameter is even, and crystalline form is bulk polyhedron or octahedral tricobalt tetroxide.Maybe will washing granulates after good presoma drying, the roasting again carries out redrying, roasting, last fragmentation obtain loose density and tap density big, particle diameter is even, pattern is the tricobalt tetroxide of bulk polygonal crystal or octahedral crystal.
The preparation method that the present invention adopts the steps include:
1. the preparation of cobalt liquor
With rose vitriol or cobalt chloride is raw material, be made into rose vitriol or the cobalt chloride solution that contains cobalt 30～100g/L with deionized water, in every liter of solution, add hydrogen peroxide 1～10mL, Sodium Fluoride 0.1～0.5g, adjust pH value to 5～6 with sodium hydroxide, the rose vitriol that filtration is purified or the cobalt liquor of cobalt chloride.
2. presoma is synthetic
Under agitation condition, with concentration is to join in the cobalt liquor for preparing among a kind of or several in 0.5～2.0mol/L oxalate, 0.5～2.0mol/L carbonate or the 0.5～2.0mol/L supercarbonate, 40～90 ℃ of temperature, pH=8.5～13, reaction 0.5～4h, the presoma throw out of synthetic cobalt salt compound after filtration, washing, obtains sulphate-containing ion, chlorion or the sodium ion presoma less than 50ppm.
3. granulate and roasting
Presoma is dried to water content 10%～40% under 90～110 ℃, makes bulk or pelletizing shape that particle diameter is 1～10cm, be dried to water content again less than 5%, at 500～1000 ℃ of following roasting 2～6h, broken calcining matter obtains the tricobalt tetroxide product.
Or presoma is dried to water content less than 5% under 90～110 ℃, at 300～500 ℃ of following roasting 1～6h, again the roasting powder is added moisture content 10%～40%, make bulk or pelletizing shape that particle diameter is 1～10cm, be dried to water content again less than 5%, at 500～1000 ℃ of following re-baking 2～6h, broken calcining matter obtains the tricobalt tetroxide product.
The tricobalt tetroxide of the present invention's preparation, cobalt contents 73.0%～74.0%; Loose density is greater than 0.8g/cm
3, tap density is greater than 2.2g/cm
3Show that under 8000 times of scanning electron microscope crystal morphology is bulk polyhedron or octahedron, single crystal diameter is 0.2～6 μ m; It is normal distribution that laser diffractometry records particle size distribution figure, median size D
50Be 2.0～10.0 μ m.
It is low that the present invention has a raw materials cost, and processing condition are easy to control, and the product foreign matter content is low, and loose density and tap density are big, stable performance, have characteristics such as specific crystalline form, are a kind of novel methods that is suitable for the suitability for industrialized production tricobalt tetroxide.
Embodiment:
Example 1. is made into the cobalt sulfate solution 1L that cobalt contents is 80g/L with rose vitriol and deionized water, adds hydrogen peroxide 1mL, Sodium Fluoride 0.1g, and sodium hydroxide makes pH=5, filters the cobalt liquor of the rose vitriol that is purified; Under agitation condition, be that the sodium carbonate solution of 1mol/L joins in the cobalt liquor for preparing 60 ℃ of temperature with concentration, pH=10, reaction times 1h, the throw out of generation cobalt salt compound presoma, after filtration, the washing, make presoma sulphate-containing ion and sodium ion all less than 50ppm; 100 ℃ down dry presomas granulate to moisture 20%, particle diameter 8cm is shaped as the pelletizing shape, is dried to moisturely 2% again under 100 ℃, at 800 ℃ of following roasting 2h, broken calcining matter obtains the tricobalt tetroxide product.Product contains cobalt 73.4%, and loose density is 1.2g/cm
3, tap density is 2.8g/cm
3, showing that under 8000 times of scanning electron microscope crystal morphology is the bulk polyhedron, single crystal diameter is 1～3 μ m, laser diffractometry records median size D
50Be 3.7 μ m.
Example 2. usefulness cobalt contentss are the cobalt chloride solution 1L of 40g/L, add hydrogen peroxide 2mL, Sodium Fluoride 0.2g, and sodium hydroxide makes pH=5.5, filters the cobalt liquor of the cobalt chloride that is purified; Under agitation condition, be that the sodium hydrogen carbonate solution of 1.5mol/L joins in the cobalt liquor for preparing 70 ℃ of temperature with concentration, pH=9, reaction 2h, the throw out of generation cobalt salt compound presoma, after filtration, washing, make presoma contain chlorion and sodium ion all less than 50ppm; The presoma that washing is good is dried to water content 5% under 110 ℃, at 400 ℃ of following roasting 2h, it is the 5cm pelletizing that the roasting powder is made particle diameter, is dried to water content 1%, and at 750 ℃ of following roasting 3h, broken calcining matter obtains the tricobalt tetroxide product.Product contains cobalt 73.6%, and loose density is 1.1g/cm
3, tap density is 2.6g/cm
3, showing that under 8000 times of scanning electron microscope crystal morphology is octahedra, single crystal diameter is 0.5～4 μ m, laser diffractometry records median size D
50Be 3.5 μ m.
Example 3. usefulness cobalt contentss are the cobalt chloride solution 1L of 60g/L, add hydrogen peroxide 3mL, Sodium Fluoride 0.3g, and sodium hydroxide makes pH=6, filters the cobalt liquor of the cobalt chloride that is purified; Under agitation, be that the sodium oxalate solution of 2mol/L joins in the cobalt liquor for preparing with concentration, 80 ℃ of temperature, pH=8.5, reaction 3h generates the throw out of cobalt salt compound presoma, after filtration, washing, makes presoma contain sodium ion less than 50ppm; The presoma that washing is good is dried to water content 3% under 90 ℃, at 500 ℃ of following roasting 1h, it is the 2cm pelletizing that the roasting powder is made particle diameter, is dried to water content 3% under 90 ℃, and again at 700 ℃ of following roasting 4h, broken calcining matter obtains the tricobalt tetroxide product.Product contains cobalt 73.7%, and loose density is 1.0g/cm
3, tap density is 2.5g/cm
3, showing that under 8000 times of scanning electron microscope crystal morphology is the bulk polyhedron, single crystal diameter is 1.5～3.5 μ m, laser diffractometry records median size D
50Be 4.2 μ m.
Claims (2)
1, a kind of preparation method of cobalt oxide, poly-comprising in its step:
(1) preparation of cobalt liquor:
With rose vitriol or cobalt chloride is raw material, be made into rose vitriol or the cobalt chloride solution that contains cobalt 30～100g/L with deionized water, in every liter of solution, add hydrogen peroxide 1～10mL, Sodium Fluoride 0.1～0.5g, adjust pH value to 5～6 with sodium hydroxide, the rose vitriol that filtration is purified or the cobalt liquor of cobalt chloride;
(2) presoma is synthetic:
Under agitation condition, with concentration is to join in the cobalt liquor for preparing among a kind of or several in 0.5～2.0mol/L oxalate, 0.5～2.0mol/L carbonate or the 0.5～2.0mol/L supercarbonate, 40～90 ℃ of temperature, pH=8.5～13, reaction 0.5～4h, generate the presoma throw out of cobalt salt compound, after filtration, washing, obtain sulphate-containing ion, chlorion or sodium ion presoma less than 50ppm;
(3) granulation, roasting
Presoma is dried to water content 10%～40% under 90～110 ℃, makes bulk or pelletizing shape that particle diameter is 1～10cm, be dried to water content again less than 5%, at 500～1000 ℃ of following roasting 2～6h, broken calcining matter obtains the tricobalt tetroxide product.
2, preparation method of cobalt oxide according to claim 1, behind the presoma that makes the cobalt salt compound, granulation, roasting can also be that presoma is dried to water content less than 5% under 90～110 ℃, at 300～500 ℃ of following roasting 1～6h, again the roasting powder is added moisture content 10%～40%, make bulk or pelletizing shape that particle diameter is 1～10cm, be dried to water content again less than 5%, at 500～1000 ℃ of following re-baking 2～6h, broken calcining matter obtains the tricobalt tetroxide product.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293677B (en) * | 2007-04-28 | 2010-08-11 | 北京有色金属研究总院 | Method for preparing cobaltic-cobaltous oxide powder with octahedron shape |
| CN102134104A (en) * | 2011-03-29 | 2011-07-27 | 长沙拓智金属材料科技有限责任公司 | Method for preparing superfine octahedral cobaltosic oxide through cobalt salt precipitated microwave-induced pyrolysis method |
| CN101607885B (en) * | 2008-11-20 | 2012-07-18 | 厦门钨业股份有限公司 | Method for industrially producing cobaltous oxalate with low apparent density |
| CN102583584A (en) * | 2012-03-27 | 2012-07-18 | 湖南雅城新材料发展有限公司 | Preparation method of spherical cobaltosic oxide |
| CN103241781A (en) * | 2013-04-19 | 2013-08-14 | 浙江大学 | Method for preparing porous Co3O4 powder |
| CN104003454B (en) * | 2014-05-22 | 2015-11-18 | 中国科学院化学研究所 | Porous oxidation cobalt nanowire and preparation method thereof and application |
| CN105271440A (en) * | 2015-09-29 | 2016-01-27 | 曲阜师范大学 | Structured octahedral nanometer cobaltosic oxide, and preparation method and application thereof |
| CN113233516A (en) * | 2021-05-28 | 2021-08-10 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
| CN113716618A (en) * | 2021-09-01 | 2021-11-30 | 荆门市格林美新材料有限公司 | Preparation method of cobaltosic oxide with octahedral morphology |
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2004
- 2004-12-10 CN CN 200410047035 patent/CN1288092C/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293677B (en) * | 2007-04-28 | 2010-08-11 | 北京有色金属研究总院 | Method for preparing cobaltic-cobaltous oxide powder with octahedron shape |
| CN101607885B (en) * | 2008-11-20 | 2012-07-18 | 厦门钨业股份有限公司 | Method for industrially producing cobaltous oxalate with low apparent density |
| CN102134104A (en) * | 2011-03-29 | 2011-07-27 | 长沙拓智金属材料科技有限责任公司 | Method for preparing superfine octahedral cobaltosic oxide through cobalt salt precipitated microwave-induced pyrolysis method |
| CN102583584A (en) * | 2012-03-27 | 2012-07-18 | 湖南雅城新材料发展有限公司 | Preparation method of spherical cobaltosic oxide |
| CN103241781A (en) * | 2013-04-19 | 2013-08-14 | 浙江大学 | Method for preparing porous Co3O4 powder |
| CN103241781B (en) * | 2013-04-19 | 2014-09-03 | 浙江大学 | Method for preparing porous Co3O4 powder |
| CN104003454B (en) * | 2014-05-22 | 2015-11-18 | 中国科学院化学研究所 | Porous oxidation cobalt nanowire and preparation method thereof and application |
| CN105271440A (en) * | 2015-09-29 | 2016-01-27 | 曲阜师范大学 | Structured octahedral nanometer cobaltosic oxide, and preparation method and application thereof |
| CN105271440B (en) * | 2015-09-29 | 2017-03-08 | 曲阜师范大学 | A kind of preparation method of nano-cobaltic-cobaltous oxide |
| CN113233516A (en) * | 2021-05-28 | 2021-08-10 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
| CN113716618A (en) * | 2021-09-01 | 2021-11-30 | 荆门市格林美新材料有限公司 | Preparation method of cobaltosic oxide with octahedral morphology |
| CN113716618B (en) * | 2021-09-01 | 2023-08-01 | 荆门市格林美新材料有限公司 | Preparation method of cobaltosic oxide with octahedral morphology |
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Assignee: Kingray New Materials Science and Technology Co., Ltd. Assignor: Changsha Inst. of Mining &. Metallurgy Contract fulfillment period: 2007.11.12 to 2024.12.9 contract change Contract record no.: 2008430000020 Denomination of invention: Process for preparing tricobalt tetroxide Co3O4 Granted publication date: 20061206 License type: Exclusive license Record date: 20081113 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.11.12 TO 2024.12.9; CHANGE OF CONTRACT Name of requester: KINGRAY NEW MATERIAL SCIENCE + TECHNOLOGY CO., LTD Effective date: 20081113 |