CN101503218A - Low temperature synthesizing method for high-density cobaltosic oxide for lithium ionic cell - Google Patents
Low temperature synthesizing method for high-density cobaltosic oxide for lithium ionic cell Download PDFInfo
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- CN101503218A CN101503218A CNA200910064453XA CN200910064453A CN101503218A CN 101503218 A CN101503218 A CN 101503218A CN A200910064453X A CNA200910064453X A CN A200910064453XA CN 200910064453 A CN200910064453 A CN 200910064453A CN 101503218 A CN101503218 A CN 101503218A
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- cobaltosic oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method for high density cobaltosic oxide, relating to cobaltic compound. The invention aims at providing a low temperature preparation method for high density cobaltosic oxide. The method does not need high sintering and any oxidizer to be added. The prepared cobaltosic oxide has high tap density, smaller grain diameter and is suitable for preparing lithium ion cell material with high density and high degree of crystallinity. The invention has the technical proposal that the low temperature preparation method for high density cobaltosic oxide is as follows: (1) solution preparation: solubility cobalt salt is prepared into 0.5-3.0 mol.dm<minus 3> of acqueous solution and 0.5-6.0 mol/dm<3> of sodium hydroxide or potassium hydroxide solution is prepared; (2) chemical reaction: the aqueous alkali is added into a reactor, and then the cobalt salt solution is gradually added into the reactor and reacts to generate cobalt oxide sizing agent by controlling the temperature within the range of 20-80 DEG C, the initial addition of the alkali is controlled so as to ensure the final solution to present alkaline; (3) the generated sizing agent is filtered, the filtration time is controlled to cause the moisture content of the filter cake to be within 60-80%; (4) the filter cake is dehydrated and dried within the temperature of 80-140 DEG C, and then ground, bathed, parched, crashed and shifted to obtain cobaltosic oxide.
Description
Technical field
The invention belongs to the low-temperature synthetic method of a kind of compound of cobalt, particularly a kind of high-density cobaltosic oxide, be used for the anode material for lithium-ion batteries preparation.
Background technology
Lithium ion battery with its specific energy height, have extended cycle life, the operating voltage height, in light weight, volume is little etc., and series of advantages is widely used in mobile communication, notebook computer and portable electronics and instrument.The positive electrode material of lithium ion battery mainly is lithium cobalt oxygen (LiCoO in the market
2Although) LiCoO
2Positive electrode material is subjected to the restriction of factors such as raw material and price, but other positive electrode materials are (as LiNiO
2, LiMn
2O
4, LiNi
1/3Co
1/3Mn
1/3O
2, LiFePO
4Deng) technology of preparing that is that all right is ripe, thermostability and chemical property remain to be improved, and replace LiCoO fully
2Still need than longue haleine.Therefore, update the preparation method, further improve LiCoO
2The performance of product still is of great practical significance.
As everyone knows, for example tap density, size distribution, form, specific surface etc. have great effect to the performance of material to the physical property of battery material.Wherein, high tap density and high-crystallinity are LiCoO
2Most important index.Prepare LiCoO at present
2The presoma major part select Co for use
3O
4, this presoma mainly be with divalent cobalt solution with solvable carbonate or oxalate precipitation, throw out is calcined under 300-900 ℃ high temperature made then, this method is the energy consumption height not only, and the tricobalt tetroxide short texture that makes, density is low, directly has influence on LiCoO
2The raising of tap density, thus the battery volume and capacity ratio reduced.CN1623908A discloses the method for the synthetic tricobalt tetroxide of a kind of low temperature, though this method synthesis temperature is lower, reaction relates to autoclave, and a large amount of oxygenants, and density is low.The method for preparing the cobaltosic oxide nano crystalline substance of CN101348283 and CN1837066 report, though temperature is lower, the particle footpath is tiny, relates to high-pressure hydrothermal reaction kettle and some organic solvents, output is little, severe reaction conditions, and also product density is extremely low.CN1470460A discloses a kind of preparation method of high-density spherical cobaltic-cobaltous oxide, uses a large amount of oxygenants but this method also relates to, and also relates to high-temperature calcination, the tricobalt tetroxide particle diameter 5-30um that obtains, and tap density only has 1.2g/cm
3Though CN1583576, CN101200308, CN10126848, CN101293677 disclosed method density are higher, all relate to high-temperature calcination technology, the energy consumption height.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, the method of the synthetic high-density cobaltosic oxide of a kind of low temperature is provided, this method does not need to add any oxygenant, do not need high-temperature calcination, energy consumption is low, the tricobalt tetroxide of preparation has higher tap density, as preparation high-density lithium cobalt oxide material.Technical scheme of the present invention is that a kind of low temperature preparation method of high-density cobaltosic oxide is characterized in that: include following operation: (1) solution preparation: the solubility cobalt salt is mixed with 0.5-3.0mol.dm
-3The aqueous solution, the solubility cobalt salt is selected from any of nitrate, vitriol and hydrochloride and acetate; Preparation 0.5-6.0mol.dm
-3Sodium hydroxide or potassium hydroxide solution; (2) chemical reaction adds above-mentioned alkaline solution solution in the reactor earlier, adds above-mentioned cobalt salt solution in the reactor gradually again, temperature is controlled at 20-80 ℃, preferred 50-60 ℃, reaction generates the cobalt/cobalt oxide slurry, and the initial add-on of control alkali guarantees that final mother liquor is alkalescence; (3) with the slurry suction filtration that generates, the chien shih cake moisture is at 60-80% during the control suction filtration; (4) filter cake is dehydrated, grinds then washing, oven dry and crushing screening at 80-140 ℃ and obtain the high-density cobaltosic oxide powder.
Adopt the technology of the present invention route synthetic tricobalt tetroxide to be aspherical particle, particle diameter is little, specific surface area is big, the tap density height, the reactive behavior height, lithium ion cell anode material lithium cobaltate as the presoma preparation has high tap density and high degree of crystallinity, can improve the volume and capacity ratio of material greatly; And the selected prices of raw and semifnished materials of the technology of the present invention are low, do not add any oxygenant and complexing agent, and without high-temperature calcination technology, energy consumption is low.
Description of drawings:
Fig. 1 is the x-ray diffraction pattern of embodiment sample tricobalt tetroxide
Fig. 2 is the x-ray diffraction pattern of cobalt acid lithium
Embodiment:
In conjunction with following example the present invention is elaborated,
Embodiment 1
Take by weighing 42.2g CoSO
4.7H
2O is dissolved in the 100ml deionized water solution, take by weighing 14.0g NaOH and place reaction vessel, add the dissolving of 200ml ionized water, join cobalt salt solution in the sodium hydroxide solution gradually, 50 ℃ of temperature maintenance, the throw out suction filtration is obtained the filter cake of water ratio 65%, filter cake is placed 120 ℃ of blast dry oven dehydration dryings, then through grind washing, dry, pulverize and sieve and obtain the black cobaltosic oxide powder.Tap density 1.85g.cm
-3, particle diameter 0.5-8um is with Li
2CO
3Mix (Co and Li mol ratio 1:1.05), 850 ℃ of sintering 20h obtain LiCoO under air atmosphere
2Sample, its tap density 2.96g.cm
-3, the I of measurement degree of crystallinity
003/I104The diffraction peak intensity ratio is up to 26.8, and specific discharge capacity reaches 150mA.h.g
-1(0.2C multiplying power discharging).
Embodiment 2
Take by weighing 29.1g Co (NO
3)
2.6H
2O is dissolved in the 100ml deionized water solution, take by weighing 10.0g NaOH and place reaction vessel, add the 200ml deionized water dissolving, join cobalt salt solution in the sodium hydroxide solution gradually, 60 ℃ of temperature maintenance obtain the filter cake of water ratio 72% with the throw out suction filtration, and filter cake is placed 130 ℃ of air dry oven dehydration dryings, then through grind washing, dry, pulverize and sieve and obtain black cobaltosic oxide powder, tap density 1.92g.cm
-3, particle diameter 0.5-8um is with Li
2CO
3Mix (Co and Li mol ratio 1: 1.05), 850 ℃ of sintering 20h obtain LiCoO under air atmosphere
2Sample, its tap density 3.02g.cm
-3, I
003/ I
104The diffraction peak intensity ratio is up to 28.5, and specific discharge capacity reaches 152mA.h.g
-1(0.2C multiplying power discharging).
Claims (1)
1, a kind of low temperature synthetic method of high-density cobaltosic oxide for lithium ionic cell is characterized in that: include following operation:
(1) solution preparation: the solubility cobalt salt is mixed with 0.5-3.0mol.dm
-3The aqueous solution, the solubility cobalt salt is selected from any of nitrate, vitriol and hydrochloride and acetate; Preparation 0.5-6.0mol/dm
3Sodium hydroxide or potassium hydroxide solution;
(2) chemical reaction adds above-mentioned alkaline solution solution in the reactor earlier, adds above-mentioned cobalt salt solution in the reactor gradually again, temperature is controlled at 20-80 ℃, preferred 50-60 ℃, reaction generates the cobalt/cobalt oxide slurry, and the initial add-on of control alkali guarantees that final mother liquor is alkalescence;
(3) with the slurry suction filtration that generates, the chien shih cake moisture is at 60-80% during the control suction filtration;
(4) filter cake is dehydrated, grinds then washing, oven dry and crushing screening at 80-140 ℃ and obtain the high-density cobaltosic oxide powder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200910064453XA CN101503218A (en) | 2009-03-24 | 2009-03-24 | Low temperature synthesizing method for high-density cobaltosic oxide for lithium ionic cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200910064453XA CN101503218A (en) | 2009-03-24 | 2009-03-24 | Low temperature synthesizing method for high-density cobaltosic oxide for lithium ionic cell |
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|---|---|
| CN101503218A true CN101503218A (en) | 2009-08-12 |
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ID=40975608
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145200A (en) * | 2013-03-25 | 2013-06-12 | 安徽亚兰德新能源材料股份有限公司 | Method for synthesizing spherical cobaltosic oxide through mixing type oxidation |
| CN108172782A (en) * | 2017-12-13 | 2018-06-15 | 郑州大学 | A kind of preparation method and application with shell-core structure carbon package porous oxidation Asia cobalt nano material |
| 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 |
-
2009
- 2009-03-24 CN CNA200910064453XA patent/CN101503218A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| RONG XU ET AL.: "Mechanistic Investigation on Salt-Mediated Formation of Free-Standing Co3O4 Nanocubes at 95 °C", 《J. PHYS. CHEM. B》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145200A (en) * | 2013-03-25 | 2013-06-12 | 安徽亚兰德新能源材料股份有限公司 | Method for synthesizing spherical cobaltosic oxide through mixing type oxidation |
| CN103145200B (en) * | 2013-03-25 | 2015-08-05 | 安徽亚兰德新能源材料股份有限公司 | A kind of method of hybrid oxidative synthesis spherical cobaltic-cobaltous oxide |
| CN108172782A (en) * | 2017-12-13 | 2018-06-15 | 郑州大学 | A kind of preparation method and application with shell-core structure carbon package porous oxidation Asia cobalt nano material |
| CN108172782B (en) * | 2017-12-13 | 2021-06-04 | 郑州大学 | Preparation method and application of carbon-coated porous cobaltous oxide nano material with shell-core structure |
| 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 |
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Application publication date: 20090812 |