CN102134104A - Method for preparing superfine octahedral cobaltosic oxide through cobalt salt precipitated microwave-induced pyrolysis method - Google Patents
Method for preparing superfine octahedral cobaltosic oxide through cobalt salt precipitated microwave-induced pyrolysis method Download PDFInfo
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- CN102134104A CN102134104A CN2011100768402A CN201110076840A CN102134104A CN 102134104 A CN102134104 A CN 102134104A CN 2011100768402 A CN2011100768402 A CN 2011100768402A CN 201110076840 A CN201110076840 A CN 201110076840A CN 102134104 A CN102134104 A CN 102134104A
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Abstract
The invention relates to a method for preparing superfine octahedral cobaltosic oxide through a cobalt salt precipitated microwave-induced pyrolysis method, comprising the following steps of: preparing a base solution of a surface active dispersing agent; carrying out precipitation reaction on a precursor; carrying out solid-liquid separation; washing, and filtering; carrying out microwave-induced pyrolysis, calcining, and the like. Superfine octahedral cobaltosic oxide powder prepared by adopting the method has the apparent density of 0.7-1.1 g/cm<3>, the granular meso-position diameter D50 of 1.05-1.35 micrometers, uniform grain distribution and narrow grain distribution range, is shaped as an octahedral crystal in microcosmic appearance and has high purity; the invention has the advantages of simple process, convenience for operation, low cost and easiness in industrialized production realization; and in addition, a product can be widely used for the fields of batteries, electrons, catalysts, ceramics, and the like.
Description
Technical field
This explanation relates to a kind of preparation method who is applied to the ultra-fine octahedra cobaltosic oxide powder in fields such as battery, electronics, catalyzer, pottery, and specifically a kind of cobalt salt precipitation---microwave induced pyrolysis method prepares the preparation method of ultra-fine octahedra cobaltosic oxide powder.
Background technology
Tricobalt tetroxide is a kind of important inorganic functional powder body material, is widely used in fields such as catalyzer, magneticsubstance, pressure-sensitive ceramic material, anode material for lithium-ion batteries, thermistor, voltage dependent resistor.Because purity, granularity, pattern, the structure of powder have material impact to powder property, therefore in the preparation process of powder, tackle these performance index and carry out strictness control.Preparing in the method for tricobalt tetroxide at present, selection to precipitation agent, feed way, process parameter is considered more, influence product purity and granularity and how to control its granularity and pattern consideration deficiency according to the purposes of the finished product tricobalt tetroxide but to precipitation and pyrolytic process powder agglomeration may take place, the powder of preparation shape spherical in shape, coarse size, size-grade distribution is inhomogeneous, quality fluctuation is bigger.
Summary of the invention
Problem at above-mentioned existence, the objective of the invention is to overcome above shortcoming, providing a kind of cobalt salt to precipitate---microwave induced pyrolysis prepares the method for ultra-fine octahedra cobaltosic oxide powder, its technological line advanced person, processing unit is simple, production cost is low, is suitable for suitability for industrialized production and can be widely used in fields such as battery, electronics, pottery.
For achieving the above object, the present invention takes following design:
Cobalt salt precipitation---microwave induced pyrolysis prepares the ultimate principle of ultra-fine octahedra tricobalt tetroxide method: the cobalt sulfate solution for preparing and ammonium bicarbonate soln and stream are joined at the bottom of the ethanol that is added with an amount of surfactivity dispersion agent in the liquid, by control precipitation process stirring velocity, reaction and digestion time, temperature of reaction, pH value of solution value etc., form insoluble presoma cobaltous dihydroxycarbonate precipitation.The adding of surfactivity dispersion agent can prevent that precipitation process from producing the reunion of powder, because of the precipitating washing difficulty of the reunion of powder and solubility salt impurity are difficult to remove and influence product purity and granularity.With the presoma cobaltous dihydroxycarbonate of preparation after deionized water and absolute ethanol washing are overanxious, add surfactivity dispersion agent PEG6000, place microwave oven, the microwave oven pyrolysis makes all molecules of object produce vibration by launched microwave, vibration processes makes between the object molecule and to take place that friction generates heat and make remaining moisture content waving rapidly, having eliminated ordinary method, to add the time long, produce serious aggregation phenomenon between the ultrafine particulate, after presoma removes remaining moisture content, because the further rising generation thermal dissociation of temperature, by controlled microwave heat-up time and temperature, the final pyrolysis of presoma generates ultra-fine octahedra cobaltosic oxide powder product.Prepare ultra-fine octahedra cobaltosic oxide powder technical process and see Fig. 1.
A kind of cobalt salt precipitation---microwave induced pyrolysis method prepares the method for ultra-fine octahedra cobaltosic oxide powder, it is characterized in that having following technological process:
(1) preparation cobalt sulfate solution, strength of solution is: 0.5～0.7mol/L, the pH value is controlled between 1.5～5.0.
(2) preparation ammonium bicarbonate soln, strength of solution is: 0.8～1.2mol/L, pH is controlled between 8.0～11.0.
(3) liquid at the bottom of the preparation ethanol, alcohol concn is 20～25%, adds surfactivity dispersion agent polyoxyethylene glycol at the bottom of the ethanol in the liquid, its add-on is 1.0～1.5% of reaction cobalt amount.
(4) mol ratio by bicarbonate of ammonia and rose vitriol is: 2.5～4.0: 1, regulate both add-ons, and stream joins at the bottom of the ethanol in the liquid, keeping the precipitation process pH value of solution is 6.2～6.5, stirring velocity is 200～300 rev/mins, reaction temperature is 50～70 ℃, and digestion time is 0.5～1 hour, and precipitated product is the presoma cobaltous dihydroxycarbonate.
(5) presoma is after deionized water and the filtration of inorganic washing with alcohol, add 1.10～1.35% surfactivity dispersion agent PEG6000, insert then in the microwave oven, microwave heating time is 0.5 hour, through microwave induced pyrolytic reaction, finally obtain the cobaltosic oxide powder product.
The cobaltosic oxide powder product that the present invention prepares, the average meso-position radius D50 of powder particle is 1.10～1.35 μ m, epigranular, narrow distribution range, granule-morphology is octahedra crystalline form, apparent density of powder is 0.7～1.1g/cm3, has reached the requirement of fields such as electronics, battery, pottery to high-quality superfine cobaltosic oxide powder.
The present invention has the following advantages: adopt the cobalt salt precipitation---and the cobaltosic oxide powder granularity of microwave induced pyrolysis method technology preparation is ultra-fine, be evenly distributed and narrow range, and granule-morphology is octahedra crystalline form.The powder agglomeration phenomenon has been eliminated in the adding of surfactivity dispersiveness, has improved product purity, has realized that the powder particle pattern is controlled; Technology is simple, easy to operate simultaneously, can be continuously produced, and the quality of production is stable, and prepared ultra-fine octahedra tricobalt tetroxide can satisfy the requirement of fields such as electronics, battery, pottery to high-quality tricobalt tetroxide.
Description of drawings
Fig. 1 is the ultra-fine octahedra cobaltosic oxide powder technological process of production figure of preparation.
Fig. 2 is ultra-fine octahedra cobaltosic oxide powder granule-morphology figure.
Embodiment
Embodiment 1:
Compound concentration is the cobalt sulfate solution of 0.5mol/L, and pH is controlled between 3.5～4.0; Compound concentration is the ammonium bicarbonate soln of 0.9mol/L, and the pH value is controlled between 8.0～9.0; Compound concentration is a liquid at the bottom of 20% the ethanol, and surfactivity dispersion agent polyoxyethylene glycol add-on is 1.2% of reaction cobalt amount; The mol ratio of control bicarbonate of ammonia and rose vitriol is 3.0: 1, and stream adds at the bottom of the ethanol in the liquid, the pH that keeps precipitation process solution is 6.2～6.5, mixing speed is 250 rev/mins, 60～65 ℃ of temperature of reaction, digestion time 1 hour, precipitated product presoma basic carbonate body is also filtered through 50 ℃ of deionized waters and absolute ethanol washing, the precipitation that washing and filtering is good adds 1.25% surfactivity dispersion agent PEG6000, place in the microwave oven then, microwave heating time is 0.5 hour, through microwave induced pyrolytic reaction, finally obtains the cobaltosic oxide powder product, loose density 0.85g/mcm3, the average meso-position radius D50 of powder particle is 1.25 μ m, the even particle size distribution narrow range, and granule-morphology is octahedra crystalline form (see figure 2).
Embodiment 2:
Compound concentration is the cobalt sulfate solution of 0.6mol/L, and pH is controlled between 4.0～4.5; Compound concentration is the ammonium bicarbonate soln of 1.1mol/L, and the pH value is controlled between 9.5～10.5; Compound concentration is a liquid at the bottom of 25% the ethanol, and surfactivity dispersion agent polyoxyethylene glycol add-on is 1.2% of reaction cobalt amount; The mol ratio of control bicarbonate of ammonia and rose vitriol is 3.5: 1, and stream adds at the bottom of the ethanol in the liquid, the pH that keeps precipitation process solution is 6.2～6.5, mixing speed is 300 rev/mins, 55～60 ℃ of temperature of reaction, digestion time 1 hour, precipitated product presoma basic carbonate body is also filtered through 50 ℃ of deionized waters and absolute ethanol washing, the precipitation that washing and filtering is good adds 1.35% surfactivity dispersion agent PEG6000, place in the microwave oven then, microwave heating time is 0.5 hour, through microwave induced pyrolytic reaction, finally obtains the cobaltosic oxide powder product, loose density 0.75g/mcm3, the average meso-position radius D50 of powder particle is 1.10 μ m, the even particle size distribution narrow range, and granule-morphology is octahedra crystalline form.
Claims (7)
1. cobalt salt precipitation---microwave induced pyrolysis method prepares the method for ultra-fine octahedral cobaltosic oxide powder, it is characterized in that: may further comprise the steps (1) cobalt sulfate solution, ammonium bicarbonate soln, contain the preparation of liquid at the bottom of the surfactivity dispersion agent ethanol; (2) with cobalt sulfate solution, ammonium bicarbonate soln by a certain percentage and stream join and contain at the bottom of the surfactivity dispersion agent ethanol in the liquid, control precipitation process stirring velocity, reaction and digestion time, temperature of reaction, pH value of solution value, preparation presoma cobaltous dihydroxycarbonate precipitation; (3) with the presoma filtration and through deionized water, absolute ethanol washing, add an amount of surfactivity dispersion agent PEG6000 after the filtration again, then through microwave induced pyrogenically prepared ultra-fine octahedra cobaltosic oxide powder.
2. preparation method according to claim 1 is characterized in that: the concentration of cobalt sulfate solution is: 0.4～0.8mol/L, the pH value is controlled between 1.5～5.0.
3. preparation method according to claim 1 is characterized in that: the concentration of ammonium bicarbonate soln is: 0.8～1.2mol/L, the pH value is controlled between 8.0～11.0.
4. preparation method according to claim 1 is characterized in that: the ethanol bottom liquid concentration is 20～25%, and the dispersed add-on of surfactivity is 0.1～1.5% of reaction cobalt amount.
5. preparation method according to claim 1 is characterized in that: the surfactivity dispersion agent that is added is a polyoxyethylene glycol.
6. preparation method according to claim 1, it is characterized in that: the mol ratio of control bicarbonate of ammonia and rose vitriol is 2.5～4.0: 1, and stream joins at the bottom of the ethanol in the liquid simultaneously, keeping the precipitation process pH value of solution is 6.2～6.5, stir speed (S.S.) is 200～300 rev/mins, temperature of reaction is 50～70 ℃, and digestion time 0.5～1 hour, precipitated product are the presoma cobaltous dihydroxycarbonate.
7. preparation method according to claim 1, it is characterized in that: presoma filters after deionized water and absolute ethanol washing filtration, add 1.25% surfactivity dispersion agent PEG6000, insert in the microwave oven then, microwave heating time is 0.5 hour, through microwave induced pyrolytic reaction, obtain the tricobalt tetroxide product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395846A (en) * | 2013-08-05 | 2013-11-20 | 青岛科技大学 | Preparation method and application of octahedron-shaped cobaltosic oxide anode material for lithium ion battery |
| CN104098146A (en) * | 2014-07-14 | 2014-10-15 | 北京工业大学 | Molten salt preparation method and application of octahedral Co3O4 nano material |
| 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 |
| CN114162878A (en) * | 2021-12-15 | 2022-03-11 | 先导薄膜材料（广东）有限公司 | Co3O4Method for preparing powder |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395846A (en) * | 2013-08-05 | 2013-11-20 | 青岛科技大学 | Preparation method and application of octahedron-shaped cobaltosic oxide anode material for lithium ion battery |
| CN104098146A (en) * | 2014-07-14 | 2014-10-15 | 北京工业大学 | Molten salt preparation method and application of octahedral Co3O4 nano material |
| CN104098146B (en) * | 2014-07-14 | 2015-12-02 | 北京工业大学 | A kind of octahedra shape Co 3o 4the melting salt preparation method of nano material and application |
| 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 |
| CN114162878A (en) * | 2021-12-15 | 2022-03-11 | 先导薄膜材料（广东）有限公司 | Co3O4Method for preparing powder |
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Application publication date: 20110727 |