CN1623908A - Process for low temp synthesis of tricobalt tetraoxide - Google Patents
Process for low temp synthesis of tricobalt tetraoxide Download PDFInfo
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- CN1623908A CN1623908A CN 200310116889 CN200310116889A CN1623908A CN 1623908 A CN1623908 A CN 1623908A CN 200310116889 CN200310116889 CN 200310116889 CN 200310116889 A CN200310116889 A CN 200310116889A CN 1623908 A CN1623908 A CN 1623908A
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Abstract
A low-temp method for synthesizing Co3O4 includes such steps as adding precipitant to the aqueous solution of cobalt sulfate, cobalt oxide, or cobalt nitrate to generate deposit, and oxidizing reaction at 50-100 deg.C under existance of oxidant in the high-pressure reactor or reflux reactor.
Description
Technical field
The present invention is the method for relevant a kind of synthetic tricobalt tetroxide, the low-temperature synthetic method of especially relevant a kind of tricobalt tetroxide.
Background technology
Because the excellent energy density of chargeable lithium cell, make and to be widely used in for example rechargeable energy source of mobile phone and mobile computer of portable electronic device at present, and the positive electrode material of lithium cell is lithium cobalt oxide (lithium cobalt oxides), pioneer's reactant of making lithium cobalt oxide is tricobalt tetroxide, so market is for the also increase gradually of demand of tricobalt tetroxide.
The general traditional way of making tricobalt tetroxide is for being initiator with the rose vitriol, sodium hydroxid, sodium bicarbonate (sodium hydrogen carbonate) or yellow soda ash (sodium carbonate) are precipitation agent, after washing after filtration,, the drying, with greater than get final product behind the temperature roast (calcining) more than 300 ℃ tricobalt tetroxide, patents such as JP5506281, JP2208227, JP2311318, JP4321523, JP922692, JP08096809, JP11292548 for example.The main processing that do not exist together between these patents at coprecipitation mode, as with different precipitation agent oxalic acid (oxalic acid), ammonium oxalate (ammonium oxalate) or ammoniacal liquor (ammonium hydroxide) etc., yet finally still need use the mode of high temperature power consumption, oxidation generates tricobalt tetroxide.
Summary of the invention
A main purpose of the present invention is being synthesized tricobalt tetroxide with the low-temperature oxidation process technique.
The inventive method is after the aqueous solution that precipitation agent is added rose vitriol, cobalt chloride or Xiao Suangu forms throw out, do not add and give reactor that filtration promptly sends into an autoclave or tool reflux and under 50～100 ℃ low temperature and an oxygenant exist, carry out oxidizing reaction, be oxidable synthetic tricobalt tetroxide, just filter then, wash, drying.
Embodiment
The present invention proposes the synthetic method that a kind of low temperature prepares tricobalt tetroxide, and tricobalt tetroxide also can be used for making magneticsubstance, glaze and catalyzer except can be used for making the positive electrode material of lithium cell.
The method of synthetic cobaltosic oxide powder of the present invention comprises the following step:
A) bivalent Co of a water soluble and an alkali metal hydroxide, an alkali metal salt, ammonium hydroxide or ammonium salt are reacted in water and form cobaltous hydroxide;
B) with reaction mixture that step a) obtains and an oxygenant in 50～100 ℃ temperature and reflux or airtight highly compressed condition under react, and form cobaltosic oxide powder;
C) reaction mixture that is obtained solid-liquid separation step b); And
D) washing and drying step c) cobaltosic oxide powder that obtains.
Preferable, step a) comprises reacts rose vitriol, cobalt chloride or Xiao Suangu and sodium hydroxide between pH=10～13.
Preferable, wherein the oxygenant of step b) is oxygen, potassium permanganate, potassium perchlorate or hydrogen peroxide.
Preferable, the oxygenant of step b) is an oxygen, and this oxidizing reaction is to carry out under the temperature of reflux conditions and 90～100 ℃.
Preferable, the oxygenant of step b) is a potassium perchlorate, and this oxidizing reaction is to carry out under the temperature of reflux conditions and 90～100 ℃.
Preferable, the oxygenant of step b) is an oxygen, and this oxidizing reaction be in an autoclave (autoclave) and 90～100 ℃ temperature under carry out.
Preferable, the solid-liquid separation of step c) adopts filtering mode.
The prepared cobaltosic oxide powder of preferable the inventive method be essentially spherical and median size less than 200nm.
The processing procedure that the low temperature of finishing according to a preferred embodiment of the present invention is made tricobalt tetroxide comprises: precipitin reaction, oxidizing reaction, filtration, washing, drying and other steps.
This precipitin reaction can use rose vitriol, cobalt chloride or Xiao Suangu to be initiator, adds a precipitation agent for example sodium hydroxide, sodium bicarbonate or yellow soda ash, is between 10～13 in the pH value, and preferable pH value is to carry out between 11～12.
This oxidizing reaction is in the reactor of an autoclave or tool reflux, and at 50～100 ℃, the preferable temperature at 90～100 ℃ is carried out.Earlier oxygen or an oxygenant are directed in when using autoclave and are positioned at this autoclave by the reaction mixture that this precipitin reaction obtained, airtight again autoclave carries out oxidizing reaction, the pressure nature supercharging in this autoclave.When making the reactor of apparatus reflux, then can once add oxygenant or successive and import oxygen in being positioned at this reactor by reaction mixture that this precipitin reaction obtained.
This filtration step can use the vacuum filtration mode to carry out.The filter cake that comprises use deionized water washing filtering gained that this water-washing step is preferable.This drying step is preferable is contained in 100 ℃ of filter cakes after the oven dry washing.Dry so get final product the loose tricobalt tetroxide product of black.
Description of drawings
Fig. 1 is the X-ray diffraction chart (XRD) of the cobaltosic oxide powder of high temperature and low temperature (the present invention) gained.
Fig. 2 is the sweep electron microscope striograph (SEM) of the prepared tricobalt tetroxide of the inventive method.
Embodiment
Embodiment 1:
Get rose vitriol (CoSO
47H
2O, molecular weight 281.11, MECHEMA CHEMICALSINTERNATIONAL CORP., Taiwan) 22.488g adds deionized water and the stirring and dissolving of 100ml.Other gets sodium hydroxide 4.8g and is dissolved in the 100ml deionized water.With two aqueous solution and stir and finished precipitin reaction in 24 hours.Then the reaction mixture that this precipitin reaction obtained is sent in the reactor of a tool reflux and under refluxing, carried out oxidizing reaction with the flow aerating oxygen of 2l/min, wherein with the oil bath type of heating, keep temperature of reaction at 90～100 ℃, 24 hours reaction times.Filter the reaction mixture that this oxidizing reaction is obtained in the vacuum filtration mode, with deionized water washing filter cake, to remove the foreign ion on it.Filter cake after the washing is sent into baking oven in 100 ℃ of oven dry 12 hours the most at last, gets the loose tricobalt tetroxide product of black.
The X-ray diffraction chart of the 1 prepared product of embodiment for this reason shown in Figure 1, its with Fig. 1 in the tricobalt tetroxide of the conventional high-temperature processing procedure gained that illustrates simultaneously have identical characteristic peak position, so embodiment 1 prepared product powder is a tricobalt tetroxide.Fig. 2 is the scanning electron microscope striograph of embodiment 1 prepared product powder, is spherical shape from wherein finding this product particles of powder, and most particle grain size is less than 200nm.
Embodiment 2:
Change the potassium perchlorate (KClO of 7.353g into except the oxygen that this oxidizing reaction is employed
3) outside, all the other all repeat the step of embodiment 1.
Embodiment 3:
Except replacing the reactor of tool reflux with autoclave, all the other all repeat the step of embodiment 1.
Embodiment 2 and 3 obtains the cobaltosic oxide powder identical with embodiment 1.
Claims (8)
1. the method for a synthetic cobaltosic oxide powder comprises the following step:
A) bivalent Co of a water soluble and an alkali metal hydroxide, an alkali metal salt, ammonium hydroxide or ammonium salt are reacted in water and form cobaltous hydroxide;
B) with reaction mixture that step a) obtains and an oxygenant in 50～100 ℃ temperature and reflux or airtight highly compressed condition under react, and form cobaltosic oxide powder;
C) reaction mixture that is obtained solid-liquid separation step b); And
D) washing and drying step c) cobaltosic oxide powder that obtains.
2. the method for claim 1, wherein step a) comprises rose vitriol, cobalt chloride or Xiao Suangu and sodium hydroxide is reacted between pH=10～13.
3. the method for claim 1, wherein the oxygenant of step b) is oxygen, potassium permanganate, potassium perchlorate or hydrogen peroxide.
4. method as claimed in claim 3, oxygenant wherein are oxygen, and the oxidizing reaction of step b) is to carry out under the temperature of reflux conditions and 90～100 ℃.
5. method as claimed in claim 3, oxygenant wherein are potassium perchlorate, and the oxidizing reaction of step b) is to carry out under the temperature of reflux conditions and 90～100 ℃.
6. method as claimed in claim 3, oxygenant wherein are oxygen, and the oxidizing reaction of step b) be in an autoclave and 90～100 ℃ temperature under carry out.
7. the method for claim 1, wherein the solid-liquid separation of step c) is for filtering.
8. as each described method of claim 1 to 7, wherein this cobaltosic oxide powder be spherical and median size less than 200nm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310116889 CN1623908A (en) | 2003-12-02 | 2003-12-02 | Process for low temp synthesis of tricobalt tetraoxide |
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| CN 200310116889 CN1623908A (en) | 2003-12-02 | 2003-12-02 | Process for low temp synthesis of tricobalt tetraoxide |
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| CN1623908A true CN1623908A (en) | 2005-06-08 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408483C (en) * | 2006-11-23 | 2008-08-06 | 南京大学 | Process for preparing nanometer cobalt oxide |
| CN101723472B (en) * | 2008-10-28 | 2011-11-16 | 比亚迪股份有限公司 | Method for preparing tricobalt tetroxide from cathode material of lithium cobalt battery |
| CN102336444A (en) * | 2010-07-16 | 2012-02-01 | 同济大学 | Method for preparing nanoscale disk-like cobaltosic oxide |
| CN103359795A (en) * | 2012-04-06 | 2013-10-23 | 协鑫动力新材料（盐城）有限公司 | Cobalt-covered lithium ion cell anode material precursor as well as preparation method and application |
| CN107768646A (en) * | 2017-10-23 | 2018-03-06 | 兰州金川新材料科技股份有限公司 | A kind of cobaltosic oxide preparation method of doped chemical gradient distribution |
| CN109628949A (en) * | 2019-01-31 | 2019-04-16 | 鲍君杰 | A kind of method that electrolysis method prepares cobaltosic oxide |
| CN110228825A (en) * | 2019-06-12 | 2019-09-13 | 南昌大学 | It is a kind of for the cobaltosic oxide nano piece of removing arsenic in water, preparation method and application |
| CN111620386A (en) * | 2020-05-22 | 2020-09-04 | 兰州理工大学 | Method for preparing cobaltosic oxide powder through Fenton-like catalytic reaction |
| CN112408499A (en) * | 2020-11-09 | 2021-02-26 | 格林美（江苏）钴业股份有限公司 | Method for synthesizing cobaltosic oxide by adopting high-pressure reaction |
-
2003
- 2003-12-02 CN CN 200310116889 patent/CN1623908A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408483C (en) * | 2006-11-23 | 2008-08-06 | 南京大学 | Process for preparing nanometer cobalt oxide |
| CN101723472B (en) * | 2008-10-28 | 2011-11-16 | 比亚迪股份有限公司 | Method for preparing tricobalt tetroxide from cathode material of lithium cobalt battery |
| CN102336444A (en) * | 2010-07-16 | 2012-02-01 | 同济大学 | Method for preparing nanoscale disk-like cobaltosic oxide |
| CN102336444B (en) * | 2010-07-16 | 2013-07-24 | 同济大学 | Method for preparing nanoscale disk-like cobaltosic oxide |
| CN103359795A (en) * | 2012-04-06 | 2013-10-23 | 协鑫动力新材料（盐城）有限公司 | Cobalt-covered lithium ion cell anode material precursor as well as preparation method and application |
| CN107768646A (en) * | 2017-10-23 | 2018-03-06 | 兰州金川新材料科技股份有限公司 | A kind of cobaltosic oxide preparation method of doped chemical gradient distribution |
| CN109628949A (en) * | 2019-01-31 | 2019-04-16 | 鲍君杰 | A kind of method that electrolysis method prepares cobaltosic oxide |
| CN110228825A (en) * | 2019-06-12 | 2019-09-13 | 南昌大学 | It is a kind of for the cobaltosic oxide nano piece of removing arsenic in water, preparation method and application |
| CN111620386A (en) * | 2020-05-22 | 2020-09-04 | 兰州理工大学 | Method for preparing cobaltosic oxide powder through Fenton-like catalytic reaction |
| CN112408499A (en) * | 2020-11-09 | 2021-02-26 | 格林美（江苏）钴业股份有限公司 | Method for synthesizing cobaltosic oxide by adopting high-pressure reaction |
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