CN111834683B - Method for recovering lithium cobaltate waste batteries - Google Patents
Method for recovering lithium cobaltate waste batteries Download PDFInfo
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- CN111834683B CN111834683B CN201910302339.XA CN201910302339A CN111834683B CN 111834683 B CN111834683 B CN 111834683B CN 201910302339 A CN201910302339 A CN 201910302339A CN 111834683 B CN111834683 B CN 111834683B
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for recovering waste lithium cobaltate batteries, which is implemented according to the following steps: step 1, performing biomass energy pyrolysis on waste lithium cobaltate batteries to obtain a mixture of cobalt powder and lithium oxide; step 2, crushing and sorting the mixture obtained in the step 1 to obtain plastic, iron materials, aluminum foils, copper foils and anode and cathode powder; step 3, slurrying and washing the anode and cathode powder obtained in the step 2, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder; step 4, reacting the lithium hydroxide solution obtained in the step 3 with hydrochloric acid to obtain lithium chloride; mixing the carbon-containing cobalt powder obtained in the step (3) with sulfuric acid for reaction, and then carrying out concentration and crystallization to obtain a cobalt sulfate crystal, thereby completing the cyclic regeneration of the lithium cobaltate waste battery; the method for recycling the waste lithium cobaltate batteries has the advantages of low cost, short process flow and easy popularization.
Description
Technical Field
The invention belongs to the technical field of battery material waste treatment, and particularly relates to a method for recovering lithium cobaltate waste batteries.
Background
The new energy automobile is the largest green industry in the world, the positive electrode material of the lithium ion battery as the power core accounts for 40% of the cost, a large amount of unqualified products are inevitably generated in the manufacturing process of the power battery, and how to recycle the unqualified battery is one of the problems to be solved at present.
In the prior art, the recovery of unqualified batteries generally comprises the steps of adding a reducing agent to leach cobalt, nickel, manganese and lithium under an acidic condition, then extracting, separating and recovering the cobalt, the nickel and the manganese, and precipitating a lithium solution by using sodium carbonate or sodium phosphate to obtain lithium carbonate or lithium phosphate. The method has the problems that the lithium extraction separation prime number is low, the content of lithium in the recovered cobalt-nickel-manganese product is high, the recovery rate of lithium is low due to the high solubility of lithium carbonate by adopting carbonate precipitation, the usage of lithium phosphate is low by adopting phosphate precipitation, the cost for converting lithium phosphate into lithium carbonate or lithium hydroxide is high, and the like.
Disclosure of Invention
The invention aims to provide a method for recovering lithium cobaltate waste batteries, which solves the problem of high cost of the existing recovery method.
The technical scheme adopted by the invention is that,
a method for recovering waste lithium cobaltate batteries is implemented according to the following steps:
step 1, performing biomass energy pyrolysis on waste lithium cobaltate batteries to obtain a mixture of cobalt powder and lithium oxide;
step 2, crushing and sorting the mixture obtained in the step 1 to obtain plastic, iron materials, aluminum foils, copper foils and anode and cathode powder;
step 3, slurrying and washing the anode and cathode powder obtained in the step 2, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder;
step 4, reacting the lithium hydroxide solution obtained in the step 3 with hydrochloric acid to obtain lithium chloride; and (3) mixing the carbon-containing cobalt powder obtained in the step (3) with sulfuric acid for reaction, and then carrying out concentration and crystallization to obtain a cobalt sulfate crystal, thereby completing the cyclic regeneration of the lithium cobaltate waste battery.
The present invention is also characterized in that,
and (2) before biomass energy pyrolysis is carried out on the waste lithium cobaltate batteries in the step 1, putting the waste lithium cobaltate batteries into saline water to discharge until the voltage is not more than 2V.
In the step 1, biomass energy pyrolysis is performed on the lithium cobaltate waste battery, and the method specifically comprises the following steps: and (3) adding the straws and the waste lithium cobaltate batteries into a rotary kiln for pyrolysis.
The adding amount of the straw is 5-20% of the mass of the waste lithium cobaltate battery.
The pyrolysis temperature in the step 1 is 275-700 ℃.
Step 3, slurrying the anode and cathode powder, specifically: slurrying the anode powder and the cathode powder with pure water according to the proportion of 1: 3-5 for 1-2 h.
In the step 4, the carbon-containing cobalt powder and sulfuric acid are mixed and reacted, and then concentrated and crystallized to obtain a cobalt sulfate crystal, which specifically comprises the following steps:
step 4.1, mixing carbon-containing cobalt powder and sulfuric acid according to a proportional volume ratio for reaction to obtain a cobalt sulfate solution;
and 4.2, heating the cobalt sulfate solution to 80-95 ℃ until the cobalt sulfate solution is concentrated to 30-50% of the original volume to obtain a cobalt sulfate crystal.
The volume ratio of the sulfuric acid to the carbon-containing cobalt powder is 3-10: 1.
The concentration of the sulfuric acid is 10-50%.
The method has the beneficial effects that firstly, biomass energy pyrolysis reduction is carried out on the waste lithium cobaltate batteries to decompose and volatilize the electrolyte, and the lithium cobaltate is reconstructed under the biomass energy pyrolysis atmosphere to generate a mixture of cobalt powder and lithium oxide; and crushing and sorting the mixture to obtain the anode and cathode powder. Slurrying and washing the positive and negative electrode powder to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder, and then introducing hydrochloric acid into the lithium hydroxide solution to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid for reaction, and then carrying out concentration and crystallization to obtain a cobalt sulfate crystal, thereby completing the cyclic regeneration of the lithium cobaltate waste battery. The invention solves the problem of recovering lithium in the waste lithium cobaltate batteries from the source, overcomes the problems of low lithium recovery rate, difficult utilization of lithium phosphate, high conversion cost and the like in the traditional method, and simultaneously realizes the recovery of cobalt in the waste lithium cobaltate batteries; the method for recycling the waste lithium cobaltate batteries has the advantages of low cost, short process flow and easy popularization; in addition, because PVDF as a binder on an electrolyte and a positive electrode and a negative electrode in a waste battery contains a large amount of F elements, the content of F in a lithium hydroxide solution is high, LiF is generated by combining part of lithium and F, and the purity of a lithium hydroxide product is influenced, so that the problem of high content of F in the lithium hydroxide solution is solved by reacting lithium hydroxide solution with hydrochloric acid.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a method for recovering waste lithium cobaltate batteries, which is implemented according to the following steps:
step 1, performing biomass energy pyrolysis on waste lithium cobaltate batteries to obtain a mixture of cobalt powder and lithium oxide;
step 2, crushing and sorting the mixture obtained in the step 1 to obtain plastic, iron materials, aluminum foils, copper foils and anode and cathode powder;
step 3, slurrying and washing the anode and cathode powder obtained in the step 2, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder;
step 4, reacting the lithium hydroxide solution obtained in the step 3 with hydrochloric acid to obtain lithium chloride; and (3) mixing the carbon-containing cobalt powder obtained in the step (3) with sulfuric acid for reaction, and then carrying out concentration and crystallization to obtain a cobalt sulfate crystal, thereby completing the cyclic regeneration of the lithium cobaltate waste battery.
As the PVDF as the binder on the electrolyte and the positive and negative electrodes in the waste battery contains a large amount of F elements, the content of F in the lithium hydroxide solution is high, part of lithium is combined with F to generate LiF, and the purity of the lithium hydroxide product is influenced, so that the problem of high content of F in the lithium hydroxide solution is solved by reacting the lithium hydroxide solution with hydrochloric acid.
And in the step 1, before biomass energy pyrolysis is carried out on the waste lithium cobaltate batteries, the waste lithium cobaltate batteries are placed into saline water to be discharged until the voltage is not more than 2V.
In the step 1, biomass energy pyrolysis is performed on the lithium cobaltate waste battery, and the method specifically comprises the following steps: and (3) adding the straws and the waste lithium cobaltate batteries into a rotary kiln for pyrolysis.
The adding amount of the straw is 5-20% of the mass of the waste lithium cobaltate battery.
The pyrolysis temperature in the step 1 is 275-700 ℃.
Step 3, slurrying the anode and cathode powder, specifically: slurrying the anode powder and the cathode powder with pure water according to the proportion of 1: 3-5 for 1-2 h.
And 4, mixing carbon-containing cobalt powder and sulfuric acid for reaction, and then carrying out concentration crystallization to obtain a cobalt sulfate crystal, wherein the specific steps are as follows: step 4.1, mixing carbon-containing cobalt powder and sulfuric acid according to a proportional volume ratio for reaction to obtain a cobalt sulfate solution; and 4.2, heating the cobalt sulfate solution to 80-95 ℃ until the cobalt sulfate solution is concentrated to 30-50% of the original volume to obtain a cobalt sulfate crystal.
The volume ratio of the sulfuric acid to the carbon-containing cobalt powder is 3-10: 1, and the concentration of the sulfuric acid is 10-50%.
In addition, the method is also suitable for recycling the waste lithium nickel cobalt aluminate batteries and the waste lithium nickel cobalt manganese acid batteries.
Example 1
The embodiment 1 of the invention provides a method for recovering waste lithium cobaltate batteries, which comprises the following specific steps:
putting the waste lithium cobaltate batteries into saline water, discharging until the voltage is 0.05V, adding the straws and the waste lithium cobaltate batteries into a rotary kiln according to the mass ratio of 1:20, and pyrolyzing at the temperature of 400 ℃ to obtain a mixture of cobalt powder and lithium oxide;
crushing and sorting the mixture to obtain plastic, iron material, aluminum foil, copper foil and anode and cathode powder; pulping and washing the anode powder and the cathode powder with pure water according to the proportion of 1:3, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder; reacting lithium hydroxide solution with hydrochloric acid to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid according to the volume ratio of 1:3 for reaction to obtain a cobalt sulfate solution, then heating the cobalt sulfate solution to 80 ℃ until the cobalt sulfate solution is concentrated to 30% of the original volume to obtain a cobalt sulfate crystal, and completing the cyclic regeneration of the waste lithium cobaltate battery.
In the method for recycling waste lithium cobaltate batteries provided by the embodiment, the recovery rate of lithium reaches 95%, and the recovery rate of cobalt reaches 99%.
Example 2
The embodiment 2 of the invention provides a method for recovering waste lithium cobaltate batteries, which comprises the following specific steps:
putting the waste lithium cobaltate batteries into saline water, discharging until the voltage is 0.12V, adding the straws and the waste lithium cobaltate batteries into a rotary kiln according to the mass ratio of 1:10, and pyrolyzing at 500 ℃ to obtain a mixture of cobalt powder and lithium oxide;
crushing and sorting the mixture to obtain plastic, iron material, aluminum foil, copper foil and anode and cathode powder; pulping and washing the anode powder and the cathode powder with pure water according to the proportion of 1:4, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder; reacting lithium hydroxide solution with hydrochloric acid to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid according to a volume ratio of 1:5 for reaction to obtain a cobalt sulfate solution, then heating the cobalt sulfate solution to 90 ℃ until the cobalt sulfate solution is concentrated to 40% of the original volume to obtain a cobalt sulfate crystal, and completing the cyclic regeneration of the waste lithium cobaltate battery.
In the method for recycling the waste lithium cobaltate batteries provided by the embodiment, the recovery rate of lithium reaches 93.9%, and the recovery rate of cobalt reaches 97%.
Example 3
The embodiment 3 of the invention provides a method for recovering waste lithium cobaltate batteries, which comprises the following specific steps:
putting the waste lithium cobaltate batteries into saline water, discharging until the voltage is 0.08V, adding the straws and the waste lithium cobaltate batteries into a rotary kiln according to the mass ratio of 3:20, and pyrolyzing at 700 ℃ to obtain a mixture of cobalt powder and lithium oxide;
crushing and sorting the mixture to obtain plastic, iron material, aluminum foil, copper foil and anode and cathode powder; pulping and washing the anode powder and the cathode powder with pure water according to the proportion of 1:5, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder; reacting lithium hydroxide solution with hydrochloric acid to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid according to a volume ratio of 1:10 for reaction to obtain a cobalt sulfate solution, then heating the cobalt sulfate solution to 95 ℃ until the cobalt sulfate solution is concentrated to 48% of the original volume to obtain a cobalt sulfate crystal, and completing the cyclic regeneration of the waste lithium cobaltate battery.
In the method for recycling the waste lithium cobaltate battery provided by the embodiment, the recovery rate of lithium reaches 95.2%, and the recovery rate of cobalt reaches 99.1%.
Example 4
The embodiment 4 of the invention provides a method for recovering waste lithium cobaltate batteries, which comprises the following specific steps:
putting the waste lithium cobaltate batteries into saline water, discharging until the voltage is not more than 2V, adding the straws and the waste lithium cobaltate batteries into a rotary kiln according to the mass ratio of 1:20, and pyrolyzing at 450 ℃ to obtain a mixture of cobalt powder and lithium oxide;
crushing and sorting the mixture to obtain plastic, iron material, aluminum foil, copper foil and anode and cathode powder; pulping and washing the anode powder and the cathode powder with pure water according to the proportion of 1:4.5, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder; reacting lithium hydroxide solution with hydrochloric acid to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid according to the volume ratio of 1:9 for reaction to obtain a cobalt sulfate solution, then heating the cobalt sulfate solution to 94 ℃ until the cobalt sulfate solution is concentrated to 35% of the original volume to obtain a cobalt sulfate crystal, and completing the cyclic regeneration of the waste lithium cobaltate battery.
In the method for recycling the waste lithium cobaltate batteries provided by the embodiment, the recovery rate of lithium reaches 93.4%, and the recovery rate of cobalt reaches 97.9%.
Example 5
The embodiment 5 of the invention provides a method for recovering waste lithium cobaltate batteries, which comprises the following specific steps:
putting the waste lithium cobaltate batteries into saline water, discharging until the voltage is not more than 2V, adding the straws and the waste lithium cobaltate batteries into a rotary kiln according to the mass ratio of 3.3:20, and pyrolyzing at 680 ℃ to obtain a mixture of cobalt powder and lithium oxide;
crushing and sorting the mixture to obtain plastic, iron material, aluminum foil, copper foil and anode and cathode powder; pulping and washing the anode powder and the cathode powder with pure water according to the proportion of 1:3.2, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder; reacting lithium hydroxide solution with hydrochloric acid to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid according to the volume ratio of 1:7 for reaction to obtain a cobalt sulfate solution, then heating the cobalt sulfate solution to 82 ℃ until the cobalt sulfate solution is concentrated to 36% of the original volume to obtain a cobalt sulfate crystal, and completing the cyclic regeneration of the waste lithium cobaltate battery.
In the method for recycling the waste lithium cobaltate batteries provided by the embodiment, the recovery rate of lithium reaches 92.8%, and the recovery rate of cobalt reaches 98.6%.
Example 6
The embodiment 6 of the invention provides a method for recovering waste lithium cobaltate batteries, which comprises the following specific steps:
putting the waste lithium cobaltate batteries into saline water, discharging until the voltage is not more than 2V, adding the straws and the waste lithium cobaltate batteries into a rotary kiln according to the mass ratio of 1:5, and pyrolyzing at the temperature of 420 ℃ to obtain a mixture of cobalt powder and lithium oxide;
crushing and sorting the mixture to obtain plastic, iron material, aluminum foil, copper foil and anode and cathode powder; pulping and washing the anode powder and the cathode powder with pure water according to the proportion of 1:5, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder; reacting lithium hydroxide solution with hydrochloric acid to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid according to the volume ratio of 1:3 for reaction to obtain a cobalt sulfate solution, then heating the cobalt sulfate solution to 80 ℃ until the cobalt sulfate solution is concentrated to 30% of the original volume to obtain a cobalt sulfate crystal, and completing the cyclic regeneration of the waste lithium cobaltate battery.
In the method for recycling the waste lithium cobaltate batteries provided by the embodiment, the recovery rate of lithium reaches 96%, and the recovery rate of cobalt reaches 99.5%.
Example 7
Embodiment 7 of the present invention provides a method for recovering a lithium cobaltate waste battery, which specifically comprises:
putting the waste lithium cobaltate batteries into saline water, discharging until the voltage is not more than 2V, adding the straws and the waste lithium cobaltate batteries into a rotary kiln according to the mass ratio of 1:11, and pyrolyzing at 700 ℃ to obtain a mixture of cobalt powder and lithium oxide;
crushing and sorting the mixture to obtain plastic, iron material, aluminum foil, copper foil and anode and cathode powder; pulping and washing the anode powder and the cathode powder with pure water according to the proportion of 1:3, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder; reacting lithium hydroxide solution with hydrochloric acid to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid according to the volume ratio of 1:3 for reaction to obtain a cobalt sulfate solution, then heating the cobalt sulfate solution to 80 ℃ until the cobalt sulfate solution is concentrated to 40% of the original volume to obtain a cobalt sulfate crystal, and completing the cyclic regeneration of the waste lithium cobaltate battery.
In the method for recycling waste lithium cobaltate batteries provided by the embodiment, the recovery rate of lithium reaches 94%, and the recovery rate of cobalt reaches 99%.
Example 8
The embodiment 8 of the invention provides a method for recovering waste lithium cobaltate batteries, which comprises the following specific steps:
putting the waste lithium cobaltate batteries into saline water, discharging until the voltage is not more than 2V, adding the straws and the waste lithium cobaltate batteries into a rotary kiln according to the mass ratio of 3:20, and pyrolyzing at 500 ℃ to obtain a mixture of cobalt powder and lithium oxide;
crushing and sorting the mixture to obtain plastic, iron material, aluminum foil, copper foil and anode and cathode powder; pulping and washing the anode powder and the cathode powder with pure water according to the proportion of 1:4, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder; reacting lithium hydroxide solution with hydrochloric acid to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid according to the volume ratio of 1:5 for reaction to obtain a cobalt sulfate solution, then heating the cobalt sulfate solution to 90 ℃ until the cobalt sulfate solution is concentrated to 42% of the original volume to obtain a cobalt sulfate crystal, and completing the cyclic regeneration of the waste lithium cobaltate battery.
According to the method for recycling the waste lithium cobaltate batteries, the recovery rate of lithium reaches 93%, and the recovery rate of cobalt reaches 96%.
Example 9
Embodiment 9 of the present invention provides a method for recovering a lithium cobaltate waste battery, which specifically comprises:
putting the waste lithium cobaltate batteries into saline water, discharging until the voltage is not more than 2V, adding the straws and the waste lithium cobaltate batteries into a rotary kiln according to the mass ratio of 3:20, and pyrolyzing at 550 ℃ to obtain a mixture of cobalt powder and lithium oxide;
crushing and sorting the mixture to obtain plastic, iron material, aluminum foil, copper foil and anode and cathode powder; pulping and washing the anode powder and the cathode powder with pure water according to the proportion of 1:3.5, and filtering and separating to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder; reacting lithium hydroxide solution with hydrochloric acid to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid according to the volume ratio of 1:6 for reaction to obtain a cobalt sulfate solution, then heating the cobalt sulfate solution to 86 ℃ until the cobalt sulfate solution is concentrated to 32% of the original volume to obtain a cobalt sulfate crystal, and completing the cyclic regeneration of the waste lithium cobaltate battery.
In the method for recycling the waste lithium cobaltate batteries provided by the embodiment, the recovery rate of lithium reaches 95.5%, and the recovery rate of cobalt reaches 98%.
Firstly, carrying out biomass energy pyrolysis reduction on waste lithium cobaltate batteries to decompose and volatilize electrolytes, and reconstructing lithium cobaltate in a biomass energy pyrolysis atmosphere to generate a mixture of cobalt powder and lithium oxide; and crushing and sorting the mixture to obtain the anode and cathode powder. Slurrying and washing the positive and negative electrode powder to obtain a carbon-hydrogen lithium oxide solution and carbon-containing cobalt powder, and then introducing hydrochloric acid into the lithium hydroxide solution to obtain lithium chloride; mixing carbon-containing cobalt powder and sulfuric acid for reaction, and then carrying out concentration and crystallization to obtain a cobalt sulfate crystal, thereby completing the cyclic regeneration of the lithium cobaltate waste battery. The invention solves the problem of recovering lithium in the waste lithium cobaltate batteries from the source, overcomes the problems of low lithium recovery rate, difficult utilization of lithium phosphate, high conversion cost and the like in the traditional method, and simultaneously realizes the recovery of cobalt in the waste lithium cobaltate batteries; the method for recycling the waste lithium cobaltate batteries has the advantages of low cost, short process flow and easy popularization.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. The method for recycling the lithium cobaltate waste battery is characterized by comprising the following steps of:
step 1, performing biomass energy pyrolysis on waste lithium cobaltate batteries to obtain a mixture of cobalt powder and lithium oxide;
step 2, crushing and sorting the mixture obtained in the step 1 to obtain plastic, iron materials, aluminum foils, copper foils and anode and cathode powder;
step 3, slurrying and washing the anode and cathode powder obtained in the step 2, and filtering and separating to obtain a lithium hydroxide solution and carbon-containing cobalt powder;
step 4, reacting the lithium hydroxide solution obtained in the step 3 with hydrochloric acid to obtain lithium chloride; mixing the carbon-containing cobalt powder obtained in the step (3) with sulfuric acid for reaction, and then carrying out concentration and crystallization to obtain a cobalt sulfate crystal, thereby completing the cyclic regeneration of the lithium cobaltate waste battery;
in the step 1, biomass energy pyrolysis is performed on the lithium cobaltate waste battery, and the method specifically comprises the following steps: and (3) adding the straws and the waste lithium cobaltate batteries into a rotary kiln for pyrolysis.
2. The method for recycling the waste lithium cobaltate battery according to claim 1, wherein the waste lithium cobaltate battery is discharged to a voltage of not more than 2V in saline before the waste lithium cobaltate battery is subjected to biomass pyrolysis in the step 1.
3. The method for recycling the lithium cobaltate waste batteries according to claim 2, wherein the adding amount of the straw is 5-20% of the mass of the lithium cobaltate waste batteries.
4. The method for recycling the lithium cobaltate waste battery according to claim 3, wherein the temperature of pyrolysis in the step 1 is 275-700 ℃.
5. The method for recycling lithium cobaltate waste batteries according to claim 1, wherein the step 3 is to slurry the positive and negative electrode powders, specifically: slurrying the anode powder and the cathode powder with pure water according to the proportion of 1: 3-5 for 1-2 h.
6. The method for recycling the lithium cobaltate waste battery according to claim 1, wherein in the step 4, the carbon-containing cobalt powder is mixed with sulfuric acid for reaction, and then concentration and crystallization are performed to obtain a cobalt sulfate crystal, specifically:
step 4.1, mixing carbon-containing cobalt powder and sulfuric acid according to a certain volume ratio for reaction to obtain a cobalt sulfate solution;
and 4.2, heating the cobalt sulfate solution to 80-95 ℃ until the cobalt sulfate solution is concentrated to 30-50% of the original volume to obtain a cobalt sulfate crystal.
7. The method for recycling the lithium cobaltate waste battery according to claim 6, wherein the volume ratio of the sulfuric acid to the carbon-containing cobalt powder is 3-10: 1.
8. The method according to claim 7, wherein the sulfuric acid concentration is 10 to 50%.
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| KR101497041B1 (en) * | 2013-04-24 | 2015-03-02 | 타운마이닝캄파니(주) | Method for recovering valuable metals from cathodic active material of used lithium battery |
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