CN100348502C - Process for preparing high purity cobalto-cobaltic oxide - Google Patents
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- CN100348502C CN100348502C CNB2004100601279A CN200410060127A CN100348502C CN 100348502 C CN100348502 C CN 100348502C CN B2004100601279 A CNB2004100601279 A CN B2004100601279A CN 200410060127 A CN200410060127 A CN 200410060127A CN 100348502 C CN100348502 C CN 100348502C
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Abstract
The present invention relates to a high purity tricobalt tetraoxide manufacture method which comprises the following steps: a cobaltous saline solution and a sodium hydroxide solution react under intense stir with the pH value of 4.5 to 13.5 at the temperature of 50 DEG C to 100 DEG C, a reducing agent is added, and cobaltous hydroxide precipitates are obtained. The quantity ratio of cobalt, sodium hydrate to reducing agent is 1.00: 2.0 to 3.0: 0.01 to 0.1. Filter cakes obtained by the filter and washing of the precipitates are dried and ground at the temperature of 80 DEG C to 125 DEG C, and then put in a calciner with adjustable airflow for roasting at the temperature of 200 DEG C to 950 DEG C and calcination for 0.5 to 14 hours. Through grinding and grading, high purity tricobalt tetraoxide powder is obtained.
Description
Technical field
The present invention relates to a kind of manufacture method of high purity tricobalt tetroxide.For the production of lithium cobalt oxide of lithium-ion secondary battery cathode materials provides critical materials, also be widely used in production such as catalyzer, magneticsubstance, electronic material.Belong to inorganic chemical industry and power material and make the field.
Background technology
Advanced information society, the mobile electronic device fast development, have benefited from the good electro-chemical properties of green lithium-ion secondary cell: specific storage is big, volume is little, operating voltage is high, have extended cycle life, self-discharge is little etc.Be widely used in every field such as mobile phone, mobile computing, space flight, modern biomedical engineering.
The production of lithium ion secondary battery anode material, the most ripe with cobalt acid lithium at present.The electro-chemical properties of cobalt acid lithium is subjected to the influence of the purity of its critical materials tricobalt tetroxide and crystalline structure very big.At present, the suitability for industrialized production of purity height, tap density is big, crystalline structure is good tricobalt tetroxide, still blank at home.This country also needs import high-quality tricobalt tetroxide day after day.
(spy opens flat 11-292548 to Japanese Patent " tricobalt tetroxide and manufacture method thereof ", classification number CO1G
51/
04) the middle synthetic Co (OH) of low temperature that proposes
2, its particle is hexagonal cylindricality sheet, and the particle height is less than 1/3 bottom surface diameter, and degree of crystallinity is poor.Can only become tricobalt tetroxide in 300 ℃ of following roastings, tap density is little.And use a large amount of ammoniacal liquor, 36～72 hours production cycles of liquid-phase precipitation reaction, poor working environment, cost for wastewater treatment height are unsuitable for industrial production.
Chinese invention patent " manufacture method of tricobalt tetroxide " (application number 02112970.3, classification number CO1G and for example
51/
04) the middle proposition: in cobalt salt solution " add the complex-precipitation agent, reaction end pH value is between 7.0～8.0 ".But still have a large amount of cobalt ions not enter precipitation in the reaction mixture this moment.If when having EDTA to exist, the loss of precious metal cobalt is bigger.And the calcination time among the embodiment reaches 14～20 hours, is unsuitable for industrial production.The tricobalt tetroxide " cobalt contents 73.0～74.0% " that this method is produced, wherein the massfraction of cobalt is to contain more cobaltous oxide in 73.55～74.0% the tricobalt tetroxide, and is unsuitable as the raw material of producing cobalt acid lithium.
Summary of the invention
Purpose of the present invention is just in order to solve the defective of above-mentioned prior art, proposes a kind of with short production cyclely, and tap density is big, impurity is few, non-environmental-pollution, is applicable to the manufacture method of the tricobalt tetroxide that cobalt acid lithium is produced.
By the tricobalt tetroxide that the present invention produces, not classified, only cross 100 mesh sieves, the loose density of its powder is greater than 0.7g/cm
3, tap density is greater than 2.0g/cm
3, the massfraction that contains cobalt is 73.0～73.5%.Fig. 1, Fig. 2 are the sem photographs of this cobaltosic oxide powder.The natural particle appearance is polyhedron, mostly is triangular prism shape laminate granular greatly, and hexagonal cylindricality particle etc. is also arranged.Median size 1～4 μ m is suitable for the raw material as the cobalt acid lithium of making laminate structure.
Technical solution of the present invention
1. the manufacture method of the high purity tricobalt tetroxide that the present invention relates to is undertaken by following step:
A. in qualified technical grade Xiao Suangu, cobalt chloride, the rose vitriol crystal any is dissolved in deionized water, is mixed with 0.8～2.0molL
-1Cobalt salt solution, qualified after testing back is standby,
B. qualified technical grade sodium hydroxide is dissolved in deionized water and is mixed with 3～12molL
-1The sodium hydroxide settled solution,
C. a kind of in qualified industrial glucose, V-Brite B, S-WAT, the hydrazine hydrate reduction agent is mixed with 5～40% the aqueous solution,
D. in reaction vessel, add the cobalt salt solution that 1/3 volumetrical front a item is prepared, stir and be heated to 50 ℃～100 ℃, under violent stirring, press n (Co
2+): n (NaOH)=1.0: 2.0～3.0, the aqueous sodium hydroxide solution that the front b item that is preheated to more than 80 ℃ is prepared joins and reacts in the cobalt salt solution, or under heating and violent stirring, cobalt salt solution joined that to fill 1/4 volumetrical pH value be 8～13.5, precipitin reaction takes place in temperature in the reactor of the sodium hydroxide solution more than 50 ℃, add the sodium hydroxide solution that the b item prepared simultaneously and regulate the pH value 8～13.5, during reaction or after precipitin reaction finishes, ratio by amount of substance between cobalt and reductive agent is 1.00: 0.01～0.1 reductive agent aqueous solution that injection front c item is prepared in reactor
E. filter d item gained slurry, be precipitated to filtrate with the deionized water wash more than 60 ℃ and be neutral, no SO
4 2-, Cl
-, NO
3 -During ion, slough hygroscopic water, obtain hydroxide cobalt filter cake,
F. the hydroxide cobalt powder body that e item gained filter cake is made through 80 ℃～125 ℃ dryings, after pulverizing, sieving, the corundum sintering saggar of packing into, send into the calcining furnace of adjustable air flow, 200 ℃～950 ℃ following roastings and calcined 0.5～14 hour, after batch mixing, pulverizing, classification, analyzer room's analytical test is sent in sampling, promptly gets high purity tricobalt tetroxide finished product after every index is qualified.
2. manufacture method of the present invention, middle test from the feedstock analysis test to each operation and check analysis test are all carried out omnidistance quality monitoring by chemical analysis, instrumental analysis.And the finished product tricobalt tetroxide carried out X diffraction analysis and production stereoscan photograph, the calibration of laser particle size analyzer is analyzed the gained data.Qualified product send cobalt acid lithium factory to try out in making cobalt acid lithium, and are the body making battery anode slice with active substance cobalt acid lithium, are assembled into test cell.Test its charging and discharging capacity, efficiency for charge-discharge and cycle performance.After the test passes, formally be used in cobalt acid lithium industrial production.
In the technical process that the present invention formulates, the part details changes slightly, can obtain to be bordering on the tricobalt tetroxide of spheroidal particle, increases its flowability.Ultra-fine Co below the particle diameter 1 μ m that produces during together with classification
3O
4Powder can be used for magneticsubstance, catalyzer, electronic material production.
3. compared with the prior art the manufacture method of a kind of high purity tricobalt tetroxide that the present invention relates to and technical process have the following advantages:
A. by the cobaltosic oxide powder of the inventive method manufacturing, when not classified, its stereoscan photograph Fig. 1, Fig. 2 show: mostly be triangular prism shape laminate structure particle greatly, and particle diameter 1～4 μ m, loose density is greater than 0.7g/cm
3, tap density is greater than 2.0g/cm
3Co
3O
4The massfraction that contains cobalt is 0.730～0.735, and foreign matter content is low, and the impurity calcium that wherein relative content is the highest, the massfraction of sodium are not more than 0.00010.Be suitable for making the good lithium cobalt oxide of lithium-ion secondary battery cathode materials of electro-chemical properties.
B. manufacture method of the present invention, technical process is short, and with short production cycle, equipment is simple.The primary recovery of cobalt is greater than 99%, and raw material sources are wide, and cost is low, non-environmental-pollution.Be suitable for suitability for industrialized production, the cut-throat competition of reply world market.
Embodiment
Enumerate embodiments of the invention below, but the present invention is not limited only to these examples.
Embodiment 1. usefulness deionized waters are mixed with the CoSO that concentration of cobalt ions is 60g/L respectively with qualified technical grade rose vitriol crystal, sodium hydrate solid, glucose powder
4The NaOH settled solution of solution, 335g/L, 30% glucose solution.
In 100L volumetrical reactor, add 40LCoSO
4Solution, violent stirring also is heated to more than 90 ℃, 10.5L has been preheated to NaOH solution joins in the reactor more than 90 ℃, and precipitin reaction takes place.It is even to continue heated and stirred, injects 30L deionized water and 1.2 liters of glucose solutions.Precipitation is through vacuum suction filter and with deionized water wash more than 70 ℃ 4～6 times, and filtrate is neutrality, no SO after testing
4 2-In time, blot.The filtrate concentration of cobalt ions is less than 0.01g/L.Filter cake through 80 ℃～125 ℃ dryings, pulverize, sieving obtains Co (OH)
2Powder.Get 1～2kg powder corundum sintering saggar of packing into, send into the calcining furnace of adjustable air flow, 200 ℃～930 ℃ following roastings and calcined 10 hours.Promptly get cobaltosic oxide powder through slightly pulverizing, cross 100 mesh sieves.Its massfraction that contains cobalt is 73.3%, loose density 1.08g/cm
3, tap density 2.41g/cm
3, median size 2～3 μ m.
Embodiment 2. usefulness deionized waters are mixed with the Co (NO that concentration of cobalt ions is 100g/L respectively with qualified technical grade cobalt nitrate crystals, sodium hydrate solid, glucose powder
3)
2The NaOH settled solution of solution, 400g/L, 30% glucose solution.Fill the above-mentioned Co (NO that has been preheated to more than 90 ℃ respectively in two header tanks
3)
2Solution 250L and NaOH solution 89.5L.To 1m
3Add the 300L deionized water in the volumetrical reactor, under violent stirring, with NaOH solution adjust pH to 13, be heated to boiling in addition.Under violent stirring, with the Co (NO in two header tanks
3)
2Solution, NaOH solution join simultaneously by 3: 1 flow precipitin reaction take place in the reactor, and the 10L glucose solution that reinjects behind reinforced the finishing stops heating, discharging immediately.Precipitation is neutral through press filtration, also with deionized water slurrying washing more than 75 ℃ 4～6 times to filtrate.Filter cake through 100 ℃～120 ℃ dryings, pulverize, sieve, gained Co (OH)
2The powder corundum sintering saggar of packing into is sent into the calcining furnace of adjustable air flow, 250 ℃～930 ℃ following roastings and calcined 10 hours.The massfraction that contains cobalt through slight pulverizing, classification gained tricobalt tetroxide is 73.15%, loose density 0.86g/cm
3, tap density 2.17g/cm
3, median size 2～3 μ m.
Embodiment 3. adds the 1200mL concentration of cobalt ions in the 3000mL large beaker be the CoSO of 75g/L
4Solution, heating in water bath to 62 ℃.The NaOH solution 307mL that will be preheated to 85 ℃, concentration and be 400g/L under violent stirring joins CoSO
4In the solution, reaction generates Co (OH)
2Precipitation.Inject 65 ℃ deionized water 1200mL and 20% SODIUM HYDROSULPHITE sodium solution 80mL.Precipitation is through vacuum suction filter, and with deionized water wash more than 65 ℃ 5～6 times, is neutrality, no SO to filtrate
4 2-Filter cake through 105 ℃～120 ℃ dryings, pulverize, sieve, gained Co (OH)
2The powder corundum sintering saggar of packing into, the thick 3～5cm of the bed of material.Place in the retort furnace that can replenish air, 250 ℃～930 ℃ following roastings and calcined 10 hours.The massfraction that contains cobalt through the gained tricobalt tetroxide of slightly pulverizing, sieve is 73.05%, loose density 0.72g/cm
3, tap density 2.03g/cm
3, median size 2～3 μ m.
Embodiment 4. injects the 1250mL concentration of cobalt ions in 3500mL stainless steel reaction container be the CoCl of 80g/L
2Solution is heated to more than 90 ℃.Under violent stirring, the NaOH solution 480mL that is preheated to more than 90 ℃, concentration is 335g/L is joined CoCl
2In the solution, fully after the reaction, inject 1000mL boiling water and 30% glucose solution 60mL.Leave standstill, use vacuum suction filter behind the supernatant liquid that inclines.Precipitation is with deionized water wash more than 90 ℃ 5～6 times, is neutrality to filtrate.Filter cake through 100 ℃～120 ℃ dryings, pulverize, sieve, the corundum sintering saggar of packing into, the thick 3～5cm of the bed of material.Send in the retort furnace that can replenish air, 250 ℃～930 ℃ roastings and calcined 10 hours.The massfraction that contains cobalt through the gained tricobalt tetroxide of slightly pulverizing, sieve is 73.2%, loose density 0.86g/cm
3, tap density 2.30g/cm
3, median size 2～3 μ m.
Embodiment 5. implantation temperature in 3500mL stainless steel reaction container is 60 ℃ deionized water 700mL, with NaOH solution adjust pH to 13.Install the combined electrode of agitator, thermometer, pH meter, and cover the plastic film that leaves 3 opening for feeds.Heating in water bath, 63 ℃ ± 2 ℃ of constant temperature.Injection contains the aqueous solution of 80% hydrazine hydrate 3mL.Under violent stirring, in reactor, inject the CoCl that concentration of cobalt ions is 60g/L with the 6mL/min flow
2Solution, splashing into concentration simultaneously is the NaOH solution of 372g/L, with the pH value of conditioned reaction mixing solutions 12.7 ± 0.1.After 45 minutes, stop to feed in raw material.Be warming up to more than 90 ℃, reinjecting contains the aqueous solution of 80% hydrazine hydrate 6mL, discharging immediately.Precipitation after filtration, wash to filtrate and be neutral, obtain Co (OH)
2Filter cake.Enlarge charging capacity more than 10 times again, make more filter cakes by same procedure.Filter cake through 100 ℃～120 ℃ dryings, pulverize, sieve, with gained Co (OH)
2The powder corundum sintering saggar of packing into, the thick 3～5cm of the bed of material.Place the retort furnace that can replenish air, 300 ℃～930 ℃ roastings and calcined 10 hours.Through the massfraction of pulverizing, the gained tricobalt tetroxide that sieves contains cobalt is 73.12%, loose density 0.71g/cm
3, tap density 2.01g/cm
3, median size 2～3 μ m.
Comparative example. reaction unit is identical with embodiment 5.Inject deionized water 700mL in 3500mL volumetrical stainless steel reaction container, at 11.8+0.2, heating in water bath is warming up to 60 ℃ and builds plastic film with the ammoniacal liquor adjust pH.Under violent stirring, with concentration of cobalt ions the CoSO of 60g/L with the flow of 6mL/min
4Solution adds in the reactor, adds simultaneously and contains NH
3The ammonia alkali mixing solutions of 34g/L, NaOH120g/L, stops to feed in raw material after 6 hours at 11.8+0.2 with regulation and control pH value.Change and splash into 400g/LNaOH solution adjust pH, be warming up to 95 ℃, add 30% SODIUM HYDROSULPHITE sodium solution 60mL 12.Continue to stir 5 minutes.Precipitate after filtration, filtrate contains cobalt 0.2g/L.Precipitation is neutral with 90 ℃ of deionized water wash to filtrates, no SO
4 2-Filter cake through 100 ℃～120 ℃ dryings, pulverize, sieve, gained Co (OH)
2The powder corundum sintering saggar of packing into is 250 ℃～930 ℃ following roastings and calcined 10 hours.Through the massfraction of pulverizing, the gained cobaltosic oxide powder that sieves contains cobalt is 73.13%, loose density 0.62g/cm
3, tap density 1.72g/cm
3, median size 2.5～3 μ m.
Claims (1)
1. the manufacture method of a high purity tricobalt tetroxide is characterized in that being undertaken by following step:
A. in qualified technical grade Xiao Suangu, cobalt chloride, the rose vitriol crystal any is dissolved in deionized water, is mixed with 0.8～2.0molL
-1Cobalt salt solution, qualified after testing back is standby,
B. qualified technical grade sodium hydroxide is dissolved in deionized water and is mixed with 3～12molL
-1The sodium hydroxide settled solution,
C. a kind of in qualified industrial glucose, V-Brite B, S-WAT, the hydrazine hydrate reduction agent is mixed with 5～40% the aqueous solution,
D. in reaction vessel, add the cobalt salt solution that 1/3 volumetrical front a item is prepared, stir and be heated to 50 ℃～100 ℃, under violent stirring, press n (Co
2+): n (NaOH)=1.0: 2.0～3.0, the aqueous sodium hydroxide solution that the front b item that is preheated to more than 80 ℃ is prepared joins and reacts in the cobalt salt solution, or under heating and violent stirring, cobalt salt solution joined that to fill 1/4 volumetrical pH value be 8～13.5, precipitin reaction takes place in temperature in the reactor of the sodium hydroxide solution more than 50 ℃, add the sodium hydroxide solution that the b item prepared simultaneously and regulate the pH value 8～13.5, during reaction or after precipitin reaction finishes, ratio by amount of substance between cobalt and reductive agent is 1.00: 0.01～0.1 reductive agent aqueous solution that injection front c item is prepared in reactor
E. filter d item gained slurry, be precipitated to filtrate with the deionized water wash more than 60 ℃ and be neutral, no SO
4 2-, Cl
-, NO
3 -During ion, slough hygroscopic water, obtain hydroxide cobalt filter cake,
F. the hydroxide cobalt powder body that e item gained filter cake is made through 80 ℃～125 ℃ dryings, after pulverizing, sieving, the corundum sintering saggar of packing into, send into the calcining furnace of adjustable air flow, 200 ℃～950 ℃ following roastings and calcined 0.5～14 hour, after batch mixing, pulverizing, classification, analyzer room's analytical test is sent in sampling, promptly gets high purity tricobalt tetroxide finished product after every index is qualified.
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857277B (en) * | 2010-06-13 | 2012-04-04 | 浙江亿利泰钴镍材料有限公司 | Preparation method of cobalt oxide for lithium battery and product prepared by the same |
| CN102390873A (en) * | 2011-08-17 | 2012-03-28 | 金川集团有限公司 | Method for removing sulfate radicals in cobalt hydroxide |
| CN102534247A (en) * | 2012-01-09 | 2012-07-04 | 湖南邦普循环科技有限公司 | Method for leaching valuable metal |
| CN102849804B (en) * | 2012-09-21 | 2014-11-05 | 中国科学院过程工程研究所 | Cobaltosic oxide columnar structure material and preparation method thereof |
| CN103754959B (en) * | 2013-12-31 | 2016-05-04 | 常州博杰新能源材料有限公司 | A kind of preparation method of large granular spherical cobaltosic oxide |
| CN104098145B (en) * | 2014-06-27 | 2016-05-04 | 江苏华东锂电技术研究院有限公司 | The preparation method of cobaltosic oxide |
| CN105329954B (en) * | 2014-08-11 | 2017-09-19 | 荆门市格林美新材料有限公司 | Big particle diameter cobalt hydroxide and preparation method thereof |
| CN106277073B (en) * | 2015-05-20 | 2018-09-21 | 中国科学院大连化学物理研究所 | A kind of hexagonal plate Co3O4 nanometer material and preparation method thereof |
| CN105923659B (en) * | 2016-05-30 | 2017-11-10 | 衢州华友钴新材料有限公司 | A kind of preparation method of LITHIUM BATTERY superfine sheet cobalt hydroxide |
| CN108671922A (en) * | 2018-04-24 | 2018-10-19 | 武汉理工大学 | A kind of Co dendrite electrocatalyst materials and preparation method thereof by nanometer sheet directional assembly |
| CN110002513B (en) * | 2019-04-23 | 2021-06-08 | 金川集团股份有限公司 | Preparation method of cobaltosic oxide |
| CN110756190B (en) * | 2019-10-27 | 2021-07-20 | 华南理工大学 | Cobaltosic oxide nanotube catalyst, and preparation method and application thereof |
| CN115108591B (en) * | 2022-08-31 | 2024-05-03 | 金川集团镍钴有限公司 | Preparation method of low-sulfur cobaltosic oxide |
| CN115676908A (en) * | 2022-11-18 | 2023-02-03 | 贵州雅友新材料有限公司 | Preparation method and application of porous flaky cobaltosic oxide |
| CN116768283A (en) * | 2023-06-02 | 2023-09-19 | 西安交通大学 | Sub-nanometer thickness porous cobaltosic oxide sheet exposing specific crystal face and preparation method and application thereof |
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| JPH11292548A (en) * | 1998-04-13 | 1999-10-26 | Ishihara Sangyo Kaisha Ltd | Tricobalt tetroxide and its production |
| CN1344682A (en) * | 2001-11-13 | 2002-04-17 | 山东大学 | Prepn of nano-cobaltosic oxide powder |
| CN1376638A (en) * | 2002-04-22 | 2002-10-30 | 戴振华 | Process for preparing Co3O4 |
| CN1470460A (en) * | 2003-07-08 | 2004-01-28 | 中信国安盟固利电源技术有限公司 | High-purity spherical cobalto-cobaltic oxide, and its preparing method and use |
-
2004
- 2004-06-27 CN CNB2004100601279A patent/CN100348502C/en not_active Expired - Fee Related
Patent Citations (4)
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|---|---|---|---|---|
| JPH11292548A (en) * | 1998-04-13 | 1999-10-26 | Ishihara Sangyo Kaisha Ltd | Tricobalt tetroxide and its production |
| CN1344682A (en) * | 2001-11-13 | 2002-04-17 | 山东大学 | Prepn of nano-cobaltosic oxide powder |
| CN1376638A (en) * | 2002-04-22 | 2002-10-30 | 戴振华 | Process for preparing Co3O4 |
| CN1470460A (en) * | 2003-07-08 | 2004-01-28 | 中信国安盟固利电源技术有限公司 | High-purity spherical cobalto-cobaltic oxide, and its preparing method and use |
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