CN116239092A - Repairing and regenerating method for waste lithium iron phosphate anode material - Google Patents
Repairing and regenerating method for waste lithium iron phosphate anode material Download PDFInfo
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- CN116239092A CN116239092A CN202310085872.1A CN202310085872A CN116239092A CN 116239092 A CN116239092 A CN 116239092A CN 202310085872 A CN202310085872 A CN 202310085872A CN 116239092 A CN116239092 A CN 116239092A
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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 94
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 239000010405 anode material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 69
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000011069 regeneration method Methods 0.000 claims abstract description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 10
- 238000005469 granulation Methods 0.000 claims abstract description 10
- 239000004576 sand Substances 0.000 claims description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000000630 rising effect Effects 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 10
- 230000008929 regeneration Effects 0.000 abstract description 8
- 239000011247 coating layer Substances 0.000 abstract description 4
- 239000007774 positive electrode material Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229940116007 ferrous phosphate Drugs 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 4
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/11—Powder tap density
-
- 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
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- 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
- C01P2006/80—Compositional purity
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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 belongs to the technical field of waste material regeneration. The invention provides a repairing and regenerating method of a waste lithium iron phosphate anode material. Pre-oxidizing and sintering the waste lithium iron phosphate anode material to obtain a waste lithium iron phosphate material; sanding the waste lithium iron phosphate material, a lithium source and a carbon source to obtain a mixed material; and granulating and calcining the mixed material in sequence to obtain the regenerated lithium iron phosphate anode material. The method adopts pre-oxidation-granulation to repair and regenerate the waste lithium iron phosphate anode material, and the purity of the recycled material can be improved by pre-oxidation sintering; the size of the material can be adjusted by combining sanding and granulating; the lithium source and the carbon source are added, so that ferrous ions can be reduced, a uniform carbon coating layer can be formed on the surface of the material, and the spherical pure-phase regenerated lithium iron phosphate anode material with uniform particle size is obtained.
Description
Technical Field
The invention relates to the technical field of waste material regeneration, in particular to a method for repairing and regenerating a waste lithium iron phosphate anode material.
Background
Lithium iron phosphate cathode material (LiFePO) 4 ) Due to the advantages of excellent cycle stability, higher safety performance, low cost, environmental friendliness and the like, the method is widely applied to the fields of electric automobiles, energy storage power grids and the like. In recent years, lithium iron phosphate batteries have been stepped into a large-scale retirement stage, and if improperly disposed, not only can the environment be seriously polluted, but also the resource waste can be caused. The development of recycling of the lithium iron phosphate battery has important significance for avoiding the scarce and price fluctuation risks of upstream raw materials, constructing a closed-loop industrial chain and realizing sustainable development of the lithium ion battery industry.
The current recovery treatment mode for the waste lithium iron phosphate battery mainly comprises two process routes of hydrometallurgy and direct regeneration. Hydrometallurgy is to leach lithium, iron and phosphorus elements into solution by adopting alkaline leaching, organic or inorganic acid leaching and other processes, and then adding a precipitant to precipitate the solution step by step to obtain corresponding compounds of the lithium, iron and phosphorus elements. However, the hydrometallurgical process involves complex separation and purification steps and has complex process flow; meanwhile, a large amount of wastewater and other byproducts are generated, which forms a potential threat to the environment and increases the recovery cost. The direct regeneration recovery is to separate the waste lithium iron phosphate from the current collector under the premise of not damaging the structure of the waste lithium iron phosphate, and then to supplement missing elements to directly repair the waste lithium iron phosphate anode material. However, the carbon coating layer, the conductive carbon black and the carbon remained by the decomposition of polyvinylidene fluoride of the waste lithium iron phosphate battery directly cause excessive carbon content and uneven distribution in the regenerated lithium iron phosphate positive electrode material, so that the electrical conductivity of the regenerated lithium iron phosphate positive electrode material is poor, and the electrical property cannot be effectively recovered.
The main reasons for the decline of the electrical properties of the lithium iron phosphate cathode material are lithium loss during cycling, side reactions of the battery and electrolyte decomposition. The lithium iron phosphate positive electrode material with low deterioration degree in the lithium ion battery has basically unchanged particle morphology and crystal structure, and provides possibility for direct regeneration. The method reported in the literature for repairing and regenerating has the ultrasonic-assisted Fenton reaction combined with high-temperature Li + Compensation recovery and regeneration of LiFePO 4 Positive electrode material (Waste Management,2021,136,67-75), but this method requires the addition of a large amount of Fenton reagent during stripping, involves wastewater treatment, and has high regeneration cost. The direct regeneration of the lithium iron phosphate anode material by the one-step hydrothermal method needs to be carried out under the conditions of higher temperature and pressure, and has larger dependence on equipment (ACS Sustainable Chemistry)&Engineering,2020,8,17622-17628). The continuous rest-output current intercalation-lithium process (Journal of Cleaner Production,2021,316,128098) can obtain regenerated lithium iron phosphate positive electrode materials with higher electrochemical performance, but is not beneficial to industrial production.
Therefore, research and development of a repair and regeneration method for waste lithium iron phosphate anode materials with energy conservation, environmental protection, low cost and excellent electrochemical performance is necessary.
Disclosure of Invention
The invention aims to provide a repairing and regenerating method for waste lithium iron phosphate anode materials, aiming at the defects of the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a repairing and regenerating method of a waste lithium iron phosphate anode material, which comprises the following steps:
1) Pre-oxidizing and sintering the waste lithium iron phosphate anode material to obtain a waste lithium iron phosphate material;
2) Sanding the waste lithium iron phosphate material, a lithium source and a carbon source to obtain a mixed material;
3) And granulating and calcining the mixed material in sequence to obtain the regenerated lithium iron phosphate anode material.
Preferably, the pre-oxidation sintering temperature in the step 1) is 400-500 ℃, the pre-oxidation sintering time is 1-3 h, the temperature rising rate of the temperature rising to the pre-oxidation sintering temperature is 4-6 ℃/min, and the pre-oxidation sintering is carried out in an air atmosphere.
Preferably, the lithium source in the step 2) is one or more of lithium carbonate, lithium hydroxide and lithium acetate; the molar ratio of lithium ions to ferrous ions in the mixed material is 1.03-1.07:1.
Preferably, the carbon source in the step 2) is one or more of glucose, sucrose and polyethylene glycol; the mass ratio of the carbon source to the waste lithium iron phosphate material is 0.08-0.18: 1.
preferably, the rotational speed of the sand grinding in the step 2) is 1000-2000 r/min, and the sand grinding time is 0.5-2 h.
Preferably, the power of the granulation in the step 3) is 1-5 kW, and the time of the granulation is 10-30 min.
Preferably, the temperature of the calcination in the step 3) is 650-750 ℃, the calcination time is 3-7 h, and the heating rate of heating to the calcination temperature is 8-12 ℃/min.
Preferably, the calcination of step 3) is performed under a nitrogen atmosphere.
The beneficial effects of the invention include the following points:
1) The method adopts pre-oxidation-granulation to repair and regenerate the waste lithium iron phosphate anode material, and the pre-oxidation sintering can fully remove impurity carbon while decomposing the binder, thereby improving the purity of the recycled material; the size of the material can be adjusted by combining sand grinding and granulation; the lithium source and the carbon source are properly added, so that the oxidized ferrous ions can be fully reduced, a uniform carbon coating layer can be formed on the surface of the material, and finally the spherical pure-phase regenerated lithium ferrous phosphate anode material with uniform particle size is obtained, and the spherical pure-phase regenerated lithium ferrous phosphate anode material has higher tap density, stable multiplying power circulation performance and excellent discharge performance at low temperature.
2) The repairing and regenerating method has the advantages of simple flow, high efficiency, no pollution and low process cost.
Drawings
FIG. 1 is a scanning electron microscope image of a waste lithium iron phosphate positive plate obtained by disassembling a retired lithium iron phosphate battery of example 1;
FIG. 2 is a scanning electron microscope image of the waste lithium iron phosphate material obtained after pre-oxidation sintering in example 1;
FIG. 3 is a scanning electron microscope image of the regenerated lithium iron phosphate positive electrode material obtained in example 1.
Detailed Description
The invention provides a repairing and regenerating method of a waste lithium iron phosphate anode material, which comprises the following steps:
1) Pre-oxidizing and sintering the waste lithium iron phosphate anode material to obtain a waste lithium iron phosphate material;
2) Sanding the waste lithium iron phosphate material, a lithium source and a carbon source to obtain a mixed material;
3) And granulating and calcining the mixed material in sequence to obtain the regenerated lithium iron phosphate anode material.
In the invention, the waste lithium iron phosphate positive electrode material in the step 1) is preferably a waste lithium iron phosphate positive electrode plate obtained by disassembling a retired lithium iron phosphate battery or a lithium iron phosphate corner positive electrode plate generated in the process of producing the lithium iron phosphate battery by a battery manufacturer.
In the invention, the pre-oxidation sintering in the step 1) can strip the waste lithium iron phosphate anode material from the current collector and remove impurities generated by electrochemical reaction on the surface of the anode material.
In the present invention, the temperature of the pre-oxidation sintering in step 1) is preferably 400 to 500 ℃, more preferably 420 to 480 ℃, and even more preferably 440 to 460 ℃; the time of the pre-oxidation sintering is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and still more preferably 2 hours; the heating rate to the pre-oxidation sintering temperature is preferably 4 to 6 ℃/min, more preferably 4.5 to 5.5 ℃/min, and even more preferably 5 ℃/min; the pre-oxidation sintering is preferably performed under an air atmosphere.
After the pre-oxidation sintering in the step 1) is finished, the material is preferably naturally cooled to room temperature, so that the waste lithium iron phosphate material is obtained.
In the present invention, the lithium source in step 2) is preferably one or more of lithium carbonate, lithium hydroxide and lithium acetate; the molar ratio of lithium ions to ferrous ions in the mixed material is preferably 1.03-1.07:1, and more preferably 1.04-1.06: 1, more preferably 1.05:1.
in the present invention, the carbon source in step 2) is preferably one or more of glucose, sucrose and polyethylene glycol; the mass ratio of the carbon source to the waste lithium iron phosphate material is preferably 0.08-0.18: 1, more preferably 0.1 to 0.16:1, more preferably 0.12 to 0.14:1.
in the present invention, the rotational speed of the sand grinding in the step 2) is preferably 1000 to 2000r/min, more preferably 1200 to 1800r/min, and even more preferably 1400 to 1600r/min; the time for the sanding is preferably 0.5 to 2 hours, more preferably 0.8 to 1.6 hours, and still more preferably 1 to 1.4 hours.
In the invention, the particle size of the waste lithium iron phosphate material in the step 2) is preferably 150-300 meshes, more preferably 200-250 meshes, and even more preferably 220-230 meshes.
In the present invention, the power of the granulation in the step 3) is preferably 1 to 5kW, more preferably 2 to 4kW, and still more preferably 3kW; the granulating time is preferably 10 to 30 minutes, more preferably 15 to 25 minutes, and still more preferably 20 minutes.
In the present invention, the temperature of the calcination in step 3) is preferably 650 to 750 ℃, more preferably 680 to 720 ℃, and even more preferably 700 ℃; the calcination time is preferably 3 to 7 hours, more preferably 4 to 6 hours, and still more preferably 5 hours; the heating rate to the calcination temperature is preferably 8 to 12℃per minute, more preferably 9 to 11℃per minute, and even more preferably 10℃per minute.
In the present invention, the calcination in step 3) is preferably performed under a nitrogen atmosphere.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
And pre-oxidizing and sintering the waste lithium iron phosphate positive plate obtained by disassembling the retired lithium iron phosphate 50Ah soft package monomer battery in a muffle furnace with the temperature of 450 ℃ for 2 hours (the temperature rising rate of the muffle furnace to 450 ℃ is 4 ℃/min), and naturally cooling to room temperature to obtain the waste lithium iron phosphate material.
Mixing 100g of waste lithium iron phosphate material with the particle size of 200 meshes (content of elements Li, fe and P in the waste lithium iron phosphate material is detected by ICP), lithium hydroxide and 16g of sucrose, wherein the molar ratio of lithium ions to ferrous ions in the mixture is 1.03:1, and performing sand grinding on the mixture in a sand mill with the rotating speed of 2000r/min for 0.5h to obtain a mixed material; granulating the mixed material in a granulator with the power of 5kW for 10min, taking out the mixed material, placing the mixed material in a tubular furnace with the temperature of 650 ℃ and filled with nitrogen, and calcining the mixed material for 7h (the heating rate of the tubular furnace to 650 ℃ is 8 ℃/min), thus obtaining the regenerated lithium iron phosphate anode material.
As can be seen from fig. 1 to 3: the spherical pure-phase regenerated lithium iron phosphate anode material with uniform particle size is obtained in the embodiment, and has higher tap density.
Example 2
And pre-oxidizing and sintering the lithium iron phosphate corner positive plate produced by Henan Dunshi new material science and technology Co in the process of producing the lithium iron phosphate battery in a muffle furnace with the temperature of 500 ℃ for 1h (the temperature rising rate of the muffle furnace to 500 ℃ is 5 ℃/min), and naturally cooling to room temperature to obtain the waste lithium iron phosphate material.
Mixing 100g of waste lithium iron phosphate material with the particle size of 150 meshes (content of Li, fe and P elements in the waste lithium iron phosphate material is detected by ICP), lithium carbonate and 12g of glucose, wherein the molar ratio of lithium ions to ferrous ions in the mixture is 1.05:1, and sanding the mixture in a sand mill with the rotating speed of 1500r/min for 1h to obtain a mixed material; granulating the mixed material in a granulator with the power of 3kW for 20min, taking out the mixed material, placing the mixed material in a tubular furnace with the temperature of 700 ℃ and filled with nitrogen, and calcining the mixed material for 5h (the heating rate of the tubular furnace to 700 ℃ is 10 ℃/min), thus obtaining the regenerated lithium iron phosphate anode material.
Example 3
And pre-oxidizing and sintering the waste lithium iron phosphate positive plate obtained by disassembling the retired lithium iron phosphate 50Ah soft package monomer battery in a muffle furnace with the temperature of 400 ℃ for 3 hours (the temperature rising rate of the muffle furnace to 400 ℃ is 5 ℃/min), and naturally cooling to room temperature to obtain the waste lithium iron phosphate material.
Mixing 100g of waste lithium iron phosphate material with the particle size of 300 meshes (content of Li, fe and P elements in the waste lithium iron phosphate material is detected by ICP), lithium acetate and 8g of polyethylene glycol, wherein the molar ratio of lithium ions to ferrous ions in the mixture is 1.07:1, and performing sand grinding on the mixture in a sand mill with the rotating speed of 2000r/min for 0.5h to obtain a mixed material; granulating the mixed material in a granulator with the power of 1kW for 30min, taking out the mixed material, placing the mixed material in a tube furnace with the temperature of 750 ℃ and filled with nitrogen, and calcining the mixed material for 3h (the heating rate of the tube furnace to 750 ℃ is 12 ℃/min), thus obtaining the regenerated lithium iron phosphate anode material.
Example 4
Pre-oxidizing and sintering a lithium iron phosphate corner positive plate produced by Henan Dunshi new material science and technology Co in a process of producing a lithium iron phosphate battery in a muffle furnace with the temperature of 480 ℃ for 1.2h (the temperature rising rate of the muffle furnace to 480 ℃ is 6 ℃/min), and naturally cooling to room temperature to obtain a waste lithium iron phosphate material.
Mixing 100g of waste lithium iron phosphate material with the particle size of 180 meshes (content of Li, fe and P elements in the waste lithium iron phosphate material is detected by ICP), lithium carbonate, 15g of glucose and 3g of sucrose, wherein the molar ratio of lithium ions to ferrous ions in the mixture is 1.06:1, and sanding the mixture in a sand mill with the rotating speed of 1000r/min for 2 hours to obtain a mixed material; granulating the mixed material in a granulator with the power of 4kW for 25min, taking out the mixed material, placing the mixed material in a tubular furnace with the temperature of 680 ℃ and filled with nitrogen, and calcining the mixed material for 6h (the heating rate of the tubular furnace to 680 ℃ is 9 ℃/min), thus obtaining the regenerated lithium iron phosphate anode material.
Example 5
The lithium carbonate of example 2 was replaced with lithium hydroxide, the temperature of the pre-oxidation sintering was changed to 460 ℃, the time of the pre-oxidation sintering was changed to 1.5h, and the other conditions were the same as those of example 2, to obtain a regenerated lithium iron phosphate positive electrode material.
Example 6
The lithium carbonate in example 2 was replaced with lithium acetate, the rotational speed of the sand mill was changed to 1200r/min, the time of sand milling was changed to 1.5h, and the other conditions were the same as in example 2, to obtain a regenerated lithium iron phosphate positive electrode material.
Example 7
The glucose of example 2 was replaced with sucrose, the temperature of the pre-oxidation sintering was changed to 480 ℃, the power of the granulator was changed to 4kW, and the other conditions were the same as in example 2, to obtain a regenerated lithium iron phosphate cathode material.
Example 8
The glucose of example 2 was replaced with polyethylene glycol, the pre-oxidation sintering time was modified to 1.2h, the granulating time was modified to 25min, and the other conditions were the same as in example 2, to obtain a regenerated lithium iron phosphate cathode material.
Example 9
12g of glucose in example 2 is replaced by 5g of polyethylene glycol and 5g of glucose, the power of a granulator is modified to 4kW, the rotating speed of a sand mill is modified to 1600r/min, and other conditions are the same as in example 2, so that the regenerated lithium iron phosphate anode material is obtained.
Example 10
12g of glucose in example 2 was replaced with 8g of sucrose and 8g of glucose, the calcination temperature was changed to 680 ℃, the calcination time was changed to 4 hours, and the other conditions were the same as in example 2, to obtain a regenerated lithium iron phosphate cathode material.
The regenerated lithium iron phosphate positive electrode materials obtained in examples 1 to 10 were assembled into batteries, and electrochemical properties thereof were measured, and the results are shown in table 1.
The assembling method comprises the following steps: mixing 8g of regenerated lithium iron phosphate positive electrode material, 1g of conductive carbon black, 1g of polyvinylidene fluoride and 20 mLN-methyl pyrrolidone, and grinding for 0.5h in a sand mill with the rotating speed of 600r/min to obtain slurry; uniformly coating the slurry on an aluminum foil (coating thickness is 200 μm) by using a coating machine, drying the aluminum foil in a blast drying oven at a temperature of 60 ℃ for 5 hours, transferring the aluminum foil to a vacuum drying oven at a temperature of 110 ℃ and a vacuum degree of 0.08bar for 15 hours, pressing the aluminum foil into a sheet in a sheet press at a pressure of 8MPa for 10 seconds, and cutting the sheet into a sheet (positive sheet) with a diameter of 12mm by using a sheet cutting machine; celgard 2400 is selected as the diaphragm, and the electrolyte is 1mol/LLiPF 6 (DMC: ec=1:1), assembled in the order of button cells, and sealed to obtain a 2032 type button cell.
The electrochemical properties include: the electron conductivity of the regenerated lithium iron phosphate positive electrode material, the diffusion rate of lithium ions, the initial discharge capacity at 25 ℃ and 0.5C multiplying power and the discharge capacity after 100 times of circulation, and the initial discharge capacity at-20 ℃ and 0.5C multiplying power and the discharge capacity after 100 times of circulation.
Table 1 electrochemical properties of the regenerated lithium iron phosphate cathode materials of examples 1 to 10 assembled into batteries
As can be seen from table 1: the regenerated lithium iron phosphate positive electrode material obtained by the invention has stable multiplying power cycle performance and can maintain excellent discharge performance at low temperature (-20 ℃).
The method adopts pre-oxidation-granulation to repair and regenerate the waste lithium iron phosphate anode material, and the pre-oxidation sintering can fully remove impurity carbon while decomposing the binder, thereby improving the purity of the recycled material; the size of the material can be adjusted by combining sand grinding and granulation; the lithium source and the carbon source are properly added, so that the oxidized ferrous ions can be fully reduced, a uniform carbon coating layer can be formed on the surface of the material, and finally, the spherical pure-phase regenerated lithium ferrous phosphate anode material with uniform particle size is obtained, and the spherical pure-phase regenerated lithium ferrous phosphate anode material has higher tap density, stable multiplying power circulation performance and excellent discharge performance at low temperature; the repairing and regenerating method has the advantages of simple flow, high efficiency, no pollution and low process cost.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A repairing and regenerating method of waste lithium iron phosphate anode materials is characterized by comprising the following steps:
1) Pre-oxidizing and sintering the waste lithium iron phosphate anode material to obtain a waste lithium iron phosphate material;
2) Sanding the waste lithium iron phosphate material, a lithium source and a carbon source to obtain a mixed material;
3) And granulating and calcining the mixed material in sequence to obtain the regenerated lithium iron phosphate anode material.
2. The repair and regeneration method according to claim 1, wherein the pre-oxidation sintering temperature in step 1) is 400-500 ℃, the pre-oxidation sintering time is 1-3 h, the temperature rising rate from the temperature rising to the pre-oxidation sintering temperature is 4-6 ℃/min, and the pre-oxidation sintering is performed in an air atmosphere.
3. The repair regeneration method according to claim 1 or 2, wherein the lithium source of step 2) is one or more of lithium carbonate, lithium hydroxide and lithium acetate; the molar ratio of lithium ions to ferrous ions in the mixed material is 1.03-1.07:1.
4. The repair and regeneration method according to claim 3, wherein the carbon source in step 2) is one or more of glucose, sucrose and polyethylene glycol; the mass ratio of the carbon source to the waste lithium iron phosphate material is 0.08-0.18: 1.
5. the repairing and regenerating method according to claim 4, wherein the rotational speed of the sand grinding in the step 2) is 1000-2000 r/min, and the sand grinding time is 0.5-2 h.
6. The repair and regeneration method according to claim 5, wherein the power of the granulation in the step 3) is 1-5 kW, and the time of the granulation is 10-30 min.
7. The repair and regeneration method according to claim 5 or 6, wherein the calcination temperature in step 3) is 650-750 ℃, the calcination time is 3-7 hours, and the heating rate to the calcination temperature is 8-12 ℃/min.
8. The repair regeneration method according to claim 7, wherein the calcination of step 3) is performed under a nitrogen atmosphere.
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