CN112551501A - Method for recycling and preparing graphene-based lithium iron phosphate from waste batteries - Google Patents
Method for recycling and preparing graphene-based lithium iron phosphate from waste batteries Download PDFInfo
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- CN112551501A CN112551501A CN202011451019.XA CN202011451019A CN112551501A CN 112551501 A CN112551501 A CN 112551501A CN 202011451019 A CN202011451019 A CN 202011451019A CN 112551501 A CN112551501 A CN 112551501A
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- iron phosphate
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000010926 waste battery Substances 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims description 49
- 239000002699 waste material Substances 0.000 claims description 18
- 239000011268 mixed slurry Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- YVIGPQSYEAOLAD-UHFFFAOYSA-L disodium;dodecyl phosphate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOP([O-])([O-])=O YVIGPQSYEAOLAD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000005022 packaging material Substances 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- 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 and preparing graphene-based lithium iron phosphate from waste batteries, which belongs to the technical field of lithium iron phosphate batteries. Compared with the traditional method, the method for recycling and preparing the graphene-based lithium iron phosphate from the waste batteries can effectively recycle the waste batteries, reduce the cost of raw materials and reduce the environmental pressure, and the obtained graphene-based lithium iron phosphate material has good conductivity and excellent rate charge and discharge performance.
Description
Technical Field
The invention belongs to the technical field of lithium iron phosphate batteries, and particularly relates to a method for recovering and preparing graphene-based lithium iron phosphate from waste lithium iron phosphate batteries.
Background
The lithium iron phosphate can be used as the anode material of the lithium ion battery, has the advantages of rich resources and low cost, and the prepared lithium ion battery has stable charge-discharge cycle structure, good safety, no toxicity and environmental friendliness. Lithium iron phosphate batteries are widely used in various fields such as electric vehicles, energy storage power stations, electronic communication and the like due to excellent performance of the lithium iron phosphate batteries. At present, the service life of the lithium iron phosphate battery is 3-5 years, a large number of waste batteries are generated by the widely used lithium iron phosphate battery, the retired lithium iron phosphate batteries need to be safely, environmentally and efficiently recycled, and the recycling has great recycling and economic values. For example, the invention patent of china with the application number of 201510845201.6 discloses a harmless comprehensive recycling method for waste lithium ion power batteries, which comprises the steps of disassembling and sorting lithium battery packs, discharging, crushing and disassembling the batteries, performing heat treatment through a heating furnace to obtain positive and negative plates, pulverizing the positive and negative plates after separation, and repairing the obtained lithium iron phosphate positive plate powder to realize recycling. However, in the existing recovery of lithium phosphate batteries, the lithium iron phosphate batteries are only disassembled and recovered and then repaired into lithium iron phosphate materials, or refined into raw materials such as lithium carbonate, and the deep recovery of waste batteries with high added value is not developed.
Since the advent of graphene as a novel material, graphene has been widely used in various fields such as energy, catalysis, and chemical industry due to its characteristics of high strength, high toughness, high conductivity, and good lubricity. The graphene and the lithium iron phosphate battery are compounded, so that the conductivity of the material can be improved, and the method becomes a hot spot direction for research and development of research institutions and enterprises. For example, the chinese patent application No. 201711064492.0 discloses a graphene-based lithium iron phosphate composite material, which is prepared by mixing a lithium source, a phosphorus source, an iron source, graphite, an intercalation agent and water to prepare a graphene slurry, performing hydrothermal treatment to obtain a hydrogel, and sintering in a reducing atmosphere to obtain the graphene-based lithium iron phosphate composite material, thereby improving the electrochemical properties of the material. And in addition, as the Chinese invention patent with the application number of 201811603003.9, the method discloses a low-cost high-rate graphene-based lithium iron phosphate pole piece and a preparation method thereof, lithium iron phosphate and polyvinylidene fluoride are dry-mixed and then added into wet-mixed graphene conductive slurry, high-speed dispersion is carried out, the obtained positive electrode slurry is coated on an aluminum foil, and the graphene-based lithium iron phosphate positive pole piece is obtained, so that the rate performance of the material is obviously improved. According to the method, the graphene is applied to the preparation of the lithium iron phosphate battery composite, but the waste lithium iron phosphate batteries are not effectively recycled.
Disclosure of Invention
In order to overcome the defects of the prior art, the technical problems to be solved by the invention are as follows: the method for recycling and preparing the graphene-based lithium iron phosphate from the waste lithium iron phosphate batteries is provided.
In order to solve the technical problems, the invention adopts the technical scheme that: the method for recovering and preparing the graphene-based lithium iron phosphate from the waste battery comprises the following steps:
step 3, introducing inert gas into the lithium iron phosphate in a vacuum environment for heat treatment to obtain lithium iron phosphate powder;
step 4, adding a lithium source accounting for 3-10% of the mass of the lithium iron phosphate powder into the lithium iron phosphate powder, and mixing to obtain dry powder;
and 6, evaporating the solvent in the mixed slurry, sintering in an inert atmosphere, and cooling to obtain the graphene-based lithium iron phosphate.
The invention has the beneficial effects that: according to the method for recovering and preparing the graphene-based lithium iron phosphate from the waste batteries, provided by the invention, the lithium iron phosphate is recovered from the waste lithium iron phosphate batteries and then is used together with graphene for preparing the graphene-based lithium iron phosphate material.
Drawings
Fig. 1 is a flowchart illustrating a method for recovering and preparing graphene-based lithium iron phosphate from waste batteries according to an embodiment of the present invention;
fig. 2 is a multiplying power electrochemical performance test chart of a button battery made of graphene-based lithium iron phosphate prepared by the method for recovering and preparing graphene-based lithium iron phosphate from waste batteries according to the embodiment of the invention.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
Referring to fig. 1, the method for recovering and preparing graphene-based lithium iron phosphate from waste batteries includes the following steps:
step 3, introducing inert gas into the lithium iron phosphate obtained in the step 2 in a vacuum environment for heat treatment to obtain lithium iron phosphate powder;
step 4, adding a lithium source accounting for 3-10% of the mass of the lithium iron phosphate powder obtained in the step 3 into the lithium iron phosphate powder obtained in the step 3, and mixing to obtain dry powder;
and 6, evaporating the solvent in the mixed slurry obtained in the step 5, sintering in an inert atmosphere, and cooling to room temperature to obtain the graphene-based lithium iron phosphate.
From the above description, the beneficial effects of the present invention are: according to the method for recycling and preparing the graphene-based lithium iron phosphate from the waste batteries, the lithium iron phosphate is recycled from the waste lithium iron phosphate batteries, the problem of lithium loss in the recycled lithium iron phosphate material is solved by adding a lithium source, and the lithium iron phosphate and the graphene are jointly used for preparing the graphene-based lithium iron phosphate material.
Further, the step 1 disassembly is carried out under the protection of nitrogen.
Further, in the step 1, the waste lithium iron phosphate battery is discharged to below 2.0V.
As can be seen from the above description, the discharge is usually performed to 0.5V or less, and the discharge is performed only to 2.0V or less by performing the dismantling under the nitrogen protection condition.
Further, the temperature of the heat treatment in the step 3 is 400-600 ℃, and the time is 5-10 h.
Further, the inert gas in the step 3 is argon or nitrogen.
Further, the lithium source is lithium carbonate, lithium hydroxide or lithium phosphate.
Further, the dispersing agent is carboxymethyl cellulose, polyacrylate or sodium dodecyl phosphate.
Further, the stirring speed in the step 5 is 50-500 r/min.
Further, in the step 6, the temperature of the mixed slurry obtained in the step 5 is raised to 200 ℃, the temperature is kept for 3-10 hours, and the evaporated solvent is collected.
Further, the sintering temperature in the step 6 is 700 ℃, and the time is 2-5 h.
Example 1:
the method for recovering and preparing the graphene-based lithium iron phosphate from the waste battery comprises the following steps:
step 3, putting the lithium iron phosphate obtained in the step 2 into a vacuum tube furnace, introducing argon, heating to 400 ℃ in an argon atmosphere, and preserving heat for 10 hours to obtain lithium iron phosphate powder;
step 4, adding lithium carbonate with the mass of 10% of the lithium iron phosphate powder obtained in the step 3 into the lithium iron phosphate powder obtained in the step 3, and mixing to obtain dry powder;
and 6, heating the mixed slurry obtained in the step 5 to 200 ℃, preserving heat for 5 hours, collecting the evaporated solvent, sintering at 700 ℃ for 4 hours in an argon atmosphere, and cooling to room temperature to obtain the graphene-based lithium iron phosphate.
The obtained graphene-based lithium iron phosphate material in example 1 is assembled into a button battery, and the rate performance of the button battery is tested in comparison with the rate performance of a button battery with the same specification made of common lithium iron phosphate, and the result is shown in fig. 2, so that the graphene-based lithium iron phosphate material prepared by the invention can be seen in that after being used for preparing the battery, the battery is charged and discharged under a large rate (5C and 10C currents), the capacity is higher, and the rate performance of the material is remarkably improved.
Example 2:
the method for recovering and preparing the graphene-based lithium iron phosphate from the waste battery comprises the following steps:
step 3, putting the lithium iron phosphate obtained in the step 2 into a vacuum tube furnace, introducing nitrogen, heating to 500 ℃ in the nitrogen atmosphere, and preserving heat for 8 hours to obtain lithium iron phosphate powder;
step 4, adding lithium hydroxide which accounts for 7% of the mass of the lithium iron phosphate powder obtained in the step 3 into the lithium iron phosphate powder obtained in the step 3, and mixing to obtain dry powder;
and 6, heating the mixed slurry obtained in the step 5 to 200 ℃, preserving heat for 10 hours, collecting the evaporated solvent, sintering at 700 ℃ for 5 hours in a nitrogen atmosphere, and cooling to room temperature to obtain the graphene-based lithium iron phosphate.
Example 3:
the method for recovering and preparing the graphene-based lithium iron phosphate from the waste battery comprises the following steps:
step 3, putting the lithium iron phosphate obtained in the step 2 into a vacuum tube furnace, introducing argon, heating to 600 ℃ in an argon atmosphere, and preserving heat for 5 hours to obtain lithium iron phosphate powder;
step 4, adding lithium phosphate with the mass of 3% of the lithium iron phosphate powder obtained in the step 3 into the lithium iron phosphate powder obtained in the step 3, and mixing to obtain dry powder;
and 6, heating the mixed slurry obtained in the step 5 to 200 ℃, preserving heat for 3 hours, collecting the evaporated solvent, sintering at 700 ℃ for 2 hours in an argon atmosphere, and cooling to room temperature to obtain the graphene-based lithium iron phosphate.
In summary, according to the method for recovering and preparing graphene-based lithium iron phosphate from waste batteries, provided by the invention, lithium iron phosphate is recovered from waste lithium iron phosphate batteries, a lithium source is added to supplement the problem of lithium loss in the recovered lithium iron phosphate material, and the lithium iron phosphate is used together with graphene for preparing the graphene-based lithium iron phosphate material.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (9)
1. The method for recycling and preparing the graphene-based lithium iron phosphate from the waste battery is characterized by comprising the following steps of:
step 1, discharging waste lithium iron phosphate batteries, crushing and disassembling to obtain a positive plate and a negative plate;
step 2, respectively crushing and winnowing the positive plate and the negative plate, obtaining aluminum powder and lithium iron phosphate from the positive plate, and obtaining copper powder and graphite powder from the negative plate;
step 3, introducing inert gas into the lithium iron phosphate in a vacuum environment for heat treatment to obtain lithium iron phosphate powder;
step 4, adding a lithium source accounting for 3-10% of the mass of the lithium iron phosphate powder into the lithium iron phosphate powder, and mixing to obtain dry powder;
step 5, adding the dry powder, a dispersing agent accounting for 1-5% of the mass of the dry powder and graphene powder accounting for 1-3% of the mass of the dry powder into N-methyl pyrrolidone, and uniformly stirring to obtain mixed slurry;
and 6, evaporating the solvent in the mixed slurry, sintering in an inert atmosphere, and cooling to obtain the graphene-based lithium iron phosphate.
2. The method for recycling and preparing graphene-based lithium iron phosphate from waste batteries according to claim 1, wherein in the step 1, the waste lithium iron phosphate batteries are discharged to a voltage of less than 2.0V.
3. The method for recovering and preparing graphene-based lithium iron phosphate from waste batteries according to claim 1, wherein the temperature of the heat treatment in the step 3 is 400-600 ℃, and the time is 5-10 h.
4. The method for recycling and preparing graphene-based lithium iron phosphate from waste batteries according to claim 1, wherein the inert gas in the step 3 is argon or nitrogen.
5. The method for recycling and preparing graphene-based lithium iron phosphate from waste batteries according to claim 1, wherein the lithium source is lithium carbonate, lithium hydroxide or lithium phosphate.
6. The method for recycling and preparing graphene-based lithium iron phosphate from waste batteries according to claim 1, wherein the dispersing agent is carboxymethyl cellulose, polyacrylate or sodium dodecyl phosphate.
7. The method for recycling and preparing graphene-based lithium iron phosphate from waste batteries according to claim 1, wherein the stirring speed in the step 5 is 50-500 r/min.
8. The method for recycling and preparing graphene-based lithium iron phosphate from waste batteries according to claim 1, wherein in the step 6, the mixed slurry is heated to 200 ℃ and is kept warm for 3-10h, and the evaporated solvent is collected.
9. The method for recycling and preparing graphene-based lithium iron phosphate from waste batteries according to claim 1, wherein the sintering temperature in the step 6 is 700 ℃ and the sintering time is 2-5 hours.
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