CN105720263A - Preparation for raw material Co3O4 of battery - Google Patents

Preparation for raw material Co3O4 of battery Download PDF

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Publication number
CN105720263A
CN105720263A CN201610228907.2A CN201610228907A CN105720263A CN 105720263 A CN105720263 A CN 105720263A CN 201610228907 A CN201610228907 A CN 201610228907A CN 105720263 A CN105720263 A CN 105720263A
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cocl
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裴俊
许博伟
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • 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 provides a preparation method for a raw material Co3O4 of a battery, belonging to the field of chemical synthesis. The preparation method comprises the following steps of complexing a complexing agent citric acid with cheap cost and cobalt ions; obtaining a Co(OH)2 sediment suspension liquid by taking a NaOH solution as a precipitator; dissolving sodium dodecyl sulfate serving as a surfactant and n-butyl alcohol serving as an assistant surfactant in an oily solvent normal hexane; mixing the mixed solution with the above suspension liquid, and forming an upper phase and a lower phase after balancing; separating the product to obtain an upper-phase water-in-oil micro emulsion; adding Na2O2 and dry ice; enabling the upper-phase micro emulsion to be dehydrated and simultaneously enabling the Co(OH)2 to be oxidized to Co2O4 to be precipitated by the Na2O2 under the condition of ultrasonic demulsification; enabling the temperature of the solution to be rapidly reduced and the solution and the NaOH to be combined to generate Na2CO3 crystals with the addition of the dry ice; and finally carrying out centrifugal separation, washing and drying to obtain the target product Co3O4 powder. By the method, a wet process is used for smelting, dust pollution is greatly prevented, moreover, high-temperature calcination is not needed, the production cost is greatly saved, and the generated organic wastewater can be treated by a relatively mature biodegradation method.

Description

A kind of preparation of battery raw material Cobalto-cobaltic oxide
Technical field
The preparation method that the invention provides a kind of battery raw material Cobalto-cobaltic oxide, belongs to the field of chemical synthesis.
Background technology
Co3O4Being a kind of black or dark gray powder, apparent density is 0.5 ~ 1.5g/cm3, tap density is 2.0 ~ 3.0g/cm3.O is easily lost more than 900 DEG C2Become CoO, it is easy to by C, CO, H2It is reduced into metal, water insoluble, dissolve in acid.
Co3O4Crystallization belongs to cubic system, has higher hydration heat, lattice paprmeter α=8.11 × 10-10m。Co3O4It is a kind of functional material with property, is the primary raw material preparing anode material of lithium battery cobalt acid lithium.Along with the exploitation of new-energy automobile, the demand of lithium battery is continuously increased, LITHIUM BATTERY Co3O4The demand of powder is also in quick growth.Although people once attempt using cheap LiMn2O4 to replace cobalt acid lithium, but the attenuation of the battery capacity produced and repetition charge-discharge performance and positive and negative pole material all can not show a candle to cobalt acid lithium.
The Co that current domestic contrast is ripe3O4Production technology is mainly with NH4HCO3Or NaOH is precipitant, with CoCl2Liquid reacts and generates basic cobaltous carbonate or cobalt hydroxide precipitation, through filtering, washing, after drying, calcines, obtain Co under 600 ~ 800 DEG C of hot conditionss3O4Powder.This energy consumption in production process is higher, and production cost is relatively big, and production scene dust is big, and room temperature is higher, and the occupational health of workman is produced ill effect.
Summary of the invention
The technical problem that present invention mainly solves: for current conventional calcination method at preparation Co3O4In the process of powder, it is necessary to carrying out under the high temperature conditions, energy consumption is higher, production scene dust is bigger, the problems such as working condition is severe, it is provided that a kind of adopt cheap chelating agent citric acid and cobalt ion complexation, using NaOH solution is that precipitant obtains Co (OH)2Precipitation suspension, then with dodecyl sodium sulfate for surfactant, n-butyl alcohol is cosurfactant, is dissolved in oil-based solvent normal hexane, is sufficiently mixed with above-mentioned suspension, is formed biphase up and down, separate phase water in oil microemulsion, add Na after balance2O2And dry ice, when ultrasonic emulsion breaking, Na2O2Co (OH) is made while making phase microemulsion dehydration2It is oxidized to Co3O4Precipitation, and the addition of dry ice makes solution lower the temperature rapidly and is combined generation Na with NaOH2CO3Crystallization, is finally performing centrifugal separation on, and washing obtains target product Co after drying3O4Powder；The method adopts hydrometallurgy, will not produce a large amount of dust pollution, and not need high-temperature calcination, be greatly saved production cost, and the organic wastewater of generation can use more ripe biological degradation method to process.
In order to solve the problems referred to above, the technical solution adopted in the present invention is:
(1) adding 0.4 ~ 0.6L mass concentration in 5L beaker is 12 ~ 14g/LCoCl2Solution, starts stirring motor, and adjustment mixing speed is 600 ~ 800r/min, under stirring with thermostat water bath by CoCl2Solution heats to 40 ~ 50 DEG C；
(2) weigh citric acid 0.4 ~ 0.6g, after grinding with mortar, add above-mentioned steps 1 gained CoCl2In solution, measure after the NaOH solution that 0.09 ~ 0.11L molar concentration is 0.9 ~ 1.1mol/L is put in thermostat water bath and is preheated to 40 ~ 50 DEG C simultaneously, add the CoCl of above-mentioned steps 12In solution, regulating speed of agitator is that 1500 ~ 3000r/min stirs rapidly 10 ~ 15s；
(3) reducing speed of agitator after stirring rapidly 10 ~ 15s is 600 ~ 800r/min, being sequentially added into 0.15 ~ 0.2L mass concentration is 15 ~ 20% dodecylbenzene sodium sulfonate hexane solutions, 0.1 ~ 0.15L n-butyl alcohol, water-bath keeps constant temperature constant, continue stirring 15 ~ 30min, stand until mixed liquor is formed substantially is layered up and down, separate, obtain upper oil phase；
(4) gained upper oil phase is put in hermetic container, be sequentially added into 2 ~ 4gNa2O2, 2 ~ 3g dry ice, it is placed in ultrasonic container ultrasonic 10 ~ 15min, treats ultrasonic end, use centrifuge isolated by filtration, obtain filtering residue, be Co3O4Wet feed, with deionized water by gained Co3O4Wet feed washs 3 ~ 5 times；
(5) by Co after washing in above-mentioned steps 43O4Wet feed is put in baking oven, and dry 1 ~ 2h under 105 ~ 110 DEG C of conditions, obtaining tap density is 2.2 ~ 2.5g/cm3, laser particle size ranges for 5 ~ 10 μm, and the mass fraction of cobalt is 72.6 ~ 73.6%, and pattern is the Co that class is spherical3O4Powder.
The concrete application process of the present invention: weigh above-mentioned gained Co3O4Powder 8 ~ 10g, with 8 ~ 10gLi2CO3Mix homogeneously, adds 8 ~ 10ml dehydrated alcohol and disperses, after grinding 1 ~ 2h in planetary ball mill, evaporation removes dehydrated alcohol, then with mortar by finely ground for said mixture material, calcining at constant temperature 12 ~ 24h in 700 ~ 800 DEG C of air, then it is down to 40 ~ 50 DEG C with the speed of 50 ~ 60 DEG C/h, obtains LiCoO2Positive electrode sample.
The invention has the beneficial effects as follows:
(1) present invention process short flow, does not have high-temperature calcination in the process of preparation, has saved energy consumption, and have employed cheap citric acid as chelating agent, made production cost be substantially reduced, belonged to environmental protection low-carbon (LC) technique, it is easy to amplify and carry out industrialized production；
(2) present invention process is reasonable, and having wide range of applications of product has wide market prospect, have significant economic benefit.
Detailed description of the invention
Adding 0.4 ~ 0.6L mass concentration in 5L beaker is 12 ~ 14g/LCoCl2Solution, starts stirring motor, and adjustment mixing speed is 600 ~ 800r/min, under stirring with thermostat water bath by CoCl2Solution heats to 40 ~ 50 DEG C；Weigh citric acid 0.4 ~ 0.6g, after grinding with mortar, add above-mentioned steps gained CoCl2In solution, measure after the NaOH solution that 0.09 ~ 0.11L molar concentration is 0.9 ~ 1.1mol/L is put in thermostat water bath and is preheated to 40 ~ 50 DEG C simultaneously, add the CoCl of above-mentioned steps2In solution, regulating speed of agitator is that 1500 ~ 3000r/min stirs rapidly 10 ~ 15s；Reducing speed of agitator after stirring 10 ~ 15s rapidly is 600 ~ 800r/min, being sequentially added into 0.15 ~ 0.2L mass concentration is 15 ~ 20% dodecylbenzene sodium sulfonate hexane solutions, 0.1 ~ 0.15L n-butyl alcohol, water-bath keeps constant temperature constant, continue stirring 15 ~ 30min, stand until mixed liquor is formed substantially is layered up and down, separate, obtain upper oil phase；Gained upper oil phase is put in hermetic container, is sequentially added into 2 ~ 4gNa2O2, 2 ~ 3g dry ice, it is placed in ultrasonic container ultrasonic 10 ~ 15min, treats ultrasonic end, use centrifuge isolated by filtration, obtain filtering residue, be Co3O4Wet feed, with deionized water by gained Co3O4Wet feed washs 3 ~ 5 times；Co after above-mentioned steps is washed3O4Wet feed is put in baking oven, and dry 1 ~ 2h under 105 ~ 110 DEG C of conditions, obtaining tap density is 2.2 ~ 2.5g/cm3, laser particle size ranges for 5 ~ 10 μm, and the mass fraction of cobalt is 72.6 ~ 73.6%, and pattern is the Co that class is spherical3O4Powder.
Example 1
Adding 0.4L mass concentration in 5L beaker is 12g/LCoCl2Solution, starts stirring motor, and adjustment mixing speed is 600r/min, under stirring with thermostat water bath by CoCl2Solution heats to 40 DEG C；Weigh citric acid 0.4g, after grinding with mortar, add above-mentioned steps gained CoCl2In solution, measure after the NaOH solution that 0.09L molar concentration is 0.9mol/L is put in thermostat water bath and is preheated to 40 DEG C simultaneously, add the CoCl of above-mentioned steps2In solution, regulating speed of agitator is that 1500r/min stirs rapidly 10s；Reducing speed of agitator after stirring 10s rapidly is 600r/min, and being sequentially added into 0.15L mass concentration is 15% dodecylbenzene sodium sulfonate hexane solution, 0.1L n-butyl alcohol, water-bath keeps constant temperature constant, continues stirring 15min, stands until mixed liquor is formed substantially is layered up and down, separate, obtain upper oil phase；Gained upper oil phase is put in hermetic container, is sequentially added into 2gNa2O2, 2g dry ice, it is placed in ultrasonic container ultrasonic 10min, treats ultrasonic end, use centrifuge isolated by filtration, obtain filtering residue, be Co3O4Wet feed, with deionized water by gained Co3O4Wet feed washs 3 ~ 5 times；Co after above-mentioned steps is washed3O4Wet feed is put in baking oven, and dry 1h under 105 DEG C of conditions, obtaining tap density is 2.2g/cm3, laser particle size is 5 μm, and the mass fraction of cobalt is 72.6%, and pattern is the Co that class is spherical3O4Powder.
The concrete application process of the present invention: weigh above-mentioned gained Co3O4Powder 8g, with 8gLi2CO3Mix homogeneously, adds 8ml dehydrated alcohol and disperses, after grinding 1h in planetary ball mill, evaporation removes dehydrated alcohol, then with mortar by finely ground for said mixture material, calcining at constant temperature 12h in 700 DEG C of air, then it is down to 40 DEG C with the speed of 50 DEG C/h, obtains LiCoO2Positive electrode sample.
Example 2
Adding 0.5L mass concentration in 5L beaker is 13g/LCoCl2Solution, starts stirring motor, and adjustment mixing speed is 700r/min, under stirring with thermostat water bath by CoCl2Solution heats to 45 DEG C；Weigh citric acid 0.5g, after grinding with mortar, add above-mentioned steps gained CoCl2In solution, measure after the NaOH solution that 0.1L molar concentration is 1mol/L is put in thermostat water bath and is preheated to 45 DEG C simultaneously, add the CoCl of above-mentioned steps2In solution, regulating speed of agitator is that 2250r/min stirs rapidly 12s；Reducing speed of agitator after stirring 12s rapidly is 700r/min, being sequentially added into 0.18L mass concentration is 18% dodecylbenzene sodium sulfonate hexane solution, 0.12L n-butyl alcohol, water-bath keeps constant temperature constant, continue stirring 20min, stand until mixed liquor is formed substantially is layered up and down, separate, obtain upper oil phase；Gained upper oil phase is put in hermetic container, is sequentially added into 3gNa2O2, 2.5g dry ice, it is placed in ultrasonic container ultrasonic 12min, treats ultrasonic end, use centrifuge isolated by filtration, obtain filtering residue, be Co3O4Wet feed, with deionized water by gained Co3O4Wet feed washs 4 times；Co after above-mentioned steps is washed3O4Wet feed is put in baking oven, and dry 1.5h under 108 DEG C of conditions, obtaining tap density is 2.25g/cm3, laser particle size is 6 μm, and the mass fraction of cobalt is 72.8%, and pattern is the Co that class is spherical3O4Powder.
The concrete application process of the present invention: weigh above-mentioned gained Co3O4Powder 9g, with 9gLi2CO3Mix homogeneously, adds 9ml dehydrated alcohol and disperses, after grinding 1.5h in planetary ball mill, evaporation removes dehydrated alcohol, then with mortar by finely ground for said mixture material, calcining at constant temperature 18h in 750 DEG C of air, then it is down to 45 DEG C with the speed of 55 DEG C/h, obtains LiCoO2Positive electrode sample.
Example 3
Adding 0.6L mass concentration in 5L beaker is 14g/LCoCl2Solution, starts stirring motor, and adjustment mixing speed is 800r/min, under stirring with thermostat water bath by CoCl2Solution heats to 50 DEG C；Weigh citric acid 0.6g, after grinding with mortar, add above-mentioned steps gained CoCl2In solution, measure after the NaOH solution that 0.11L molar concentration is 1.1mol/L is put in thermostat water bath and is preheated to 50 DEG C simultaneously, add the CoCl of above-mentioned steps2In solution, regulating speed of agitator is that 3000r/min stirs rapidly 15s；Reducing speed of agitator after stirring 15s rapidly is 800r/min, and being sequentially added into 0.2L mass concentration is 20% dodecylbenzene sodium sulfonate hexane solution, 0.15L n-butyl alcohol, water-bath keeps constant temperature constant, continues stirring 30min, stands until mixed liquor is formed substantially is layered up and down, separate, obtain upper oil phase；Gained upper oil phase is put in hermetic container, is sequentially added into 4gNa2O2, 3g dry ice, it is placed in ultrasonic container ultrasonic 15min, treats ultrasonic end, use centrifuge isolated by filtration, obtain filtering residue, be Co3O4Wet feed, with deionized water by gained Co3O4Wet feed washs 5 times；Co after above-mentioned steps is washed3O4Wet feed is put in baking oven, and dry 2h under 110 DEG C of conditions, obtaining tap density is 2.3g/cm3, laser particle size is 7 μm, and the mass fraction of cobalt is 73.1%, and pattern is the Co that class is spherical3O4Powder.
The concrete application process of the present invention: weigh above-mentioned gained Co3O4Powder 10g, with 10gLi2CO3Mix homogeneously, adds 10ml dehydrated alcohol and disperses, after grinding 2h in planetary ball mill, evaporation removes dehydrated alcohol, then with mortar by finely ground for said mixture material, calcining at constant temperature 24h in 800 DEG C of air, then it is down to 50 DEG C with the speed of 60 DEG C/h, obtains LiCoO2Positive electrode sample.

Claims (1)

1. the preparation method of a battery raw material Cobalto-cobaltic oxide, it is characterised in that concrete preparation process is:
(1) adding 0.4 ~ 0.6L mass concentration in 5L beaker is 12 ~ 14g/LCoCl2Solution, starts stirring motor, and adjustment mixing speed is 600 ~ 800r/min, under stirring with thermostat water bath by CoCl2Solution heats to 40 ~ 50 DEG C；
(2) weigh citric acid 0.4 ~ 0.6g, after grinding with mortar, add above-mentioned steps 1 gained CoCl2In solution, measure after the NaOH solution that 0.09 ~ 0.11L molar concentration is 0.9 ~ 1.1mol/L is put in thermostat water bath and is preheated to 40 ~ 50 DEG C simultaneously, add the CoCl of above-mentioned steps 12In solution, regulating speed of agitator is that 1500 ~ 3000r/min stirs rapidly 10 ~ 15s；
(3) reducing speed of agitator after stirring rapidly 10 ~ 15s is 600 ~ 800r/min, being sequentially added into 0.15 ~ 0.2L mass concentration is 15 ~ 20% dodecylbenzene sodium sulfonate hexane solutions, 0.1 ~ 0.15L n-butyl alcohol, water-bath keeps constant temperature constant, after continuing stirring 15 ~ 30min, stand until mixed liquor is formed substantially is layered up and down, separate, obtain upper oil phase；
(4) gained upper oil phase is put in hermetic container, be sequentially added into 2 ~ 4gNa2O2, 2 ~ 3g dry ice, it is placed in ultrasonic container ultrasonic 10 ~ 15min, treats ultrasonic end, use centrifuge isolated by filtration, obtain filtering residue, be Co3O4Wet feed, with deionized water by gained Co3O4Wet feed washs 3 ~ 5 times；
(5) by Co after washing in above-mentioned steps 43O4Wet feed is put in baking oven, and dry 1 ~ 2h under 105 ~ 110 DEG C of conditions, obtaining tap density is 2.2 ~ 2.5g/cm3, laser particle size ranges for 5 ~ 10 μm, and the mass fraction of cobalt is 72.6 ~ 73.6%, and pattern is the Co that class is spherical3O4Powder.
CN201610228907.2A 2016-04-14 2016-04-14 Preparation for raw material Co3O4 of battery Withdrawn CN105720263A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106517262A (en) * 2016-10-21 2017-03-22 吴迪 Preparation method of spherical nanometer magnesia
CN111048776A (en) * 2019-12-18 2020-04-21 深圳大学 Morphology-adjustable cubic cobaltosic oxide, preparation method thereof and lithium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106517262A (en) * 2016-10-21 2017-03-22 吴迪 Preparation method of spherical nanometer magnesia
CN111048776A (en) * 2019-12-18 2020-04-21 深圳大学 Morphology-adjustable cubic cobaltosic oxide, preparation method thereof and lithium ion battery

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