CN117080605A - Recovery method of waste lithium iron phosphate battery - Google Patents
Recovery method of waste lithium iron phosphate battery Download PDFInfo
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- CN117080605A CN117080605A CN202311140131.5A CN202311140131A CN117080605A CN 117080605 A CN117080605 A CN 117080605A CN 202311140131 A CN202311140131 A CN 202311140131A CN 117080605 A CN117080605 A CN 117080605A
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- lithium
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- iron phosphate
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- 238000000034 method Methods 0.000 title claims abstract description 72
- 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 67
- 239000002699 waste material Substances 0.000 title claims abstract description 48
- 238000011084 recovery Methods 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 97
- 238000004108 freeze drying Methods 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 20
- 238000004064 recycling Methods 0.000 claims abstract description 17
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 88
- 229910052799 carbon Inorganic materials 0.000 claims description 87
- 239000000243 solution Substances 0.000 claims description 47
- 239000003638 chemical reducing agent Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000007599 discharging Methods 0.000 claims description 14
- 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 13
- 239000008103 glucose Substances 0.000 claims description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 9
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 9
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910010710 LiFePO Inorganic materials 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 230000008929 regeneration Effects 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000002386 leaching Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 8
- 239000002893 slag Substances 0.000 description 7
- 239000005955 Ferric phosphate Substances 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- 229930006000 Sucrose Natural products 0.000 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 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 229940032958 ferric phosphate Drugs 0.000 description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 239000005720 sucrose Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- -1 iron-phosphorus ions Chemical class 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000011056 performance test Methods 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
- 239000002244 precipitate Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 provides a recovery method of a waste lithium iron phosphate battery, which comprises the following steps: (1) Pretreating a waste lithium iron phosphate battery to obtain positive active powder; (2) Performing hydrothermal treatment on the positive electrode active powder obtained in the step (1) in a lithium-containing carbon water solution, and then performing freeze drying; (3) Ball milling is carried out on the sample obtained after freeze drying, and then roasting is carried out under the inert atmosphere condition, thus obtaining regenerated LiFePO 4 and/C. The recovery method adopts hydrothermal lithium-liquid phase compensationCarbon coating coupling method for realizing LiFePO regeneration of waste lithium iron phosphate battery 4 And (3) the short-process reconstruction of the (C) can efficiently realize the recycling of the waste lithium iron phosphate battery with low cost and high added value.
Description
Technical Field
The invention belongs to the technical field of resource recycling, relates to a method for recycling battery materials, and particularly relates to a method for recycling waste lithium iron phosphate batteries.
Background
Lithium iron phosphate (LiFePO) 4 ) As the positive electrode material of the lithium ion battery, the lithium ion battery positive electrode material has the advantages of high theoretical specific capacity, stable structure, good cycle performance, high safety, no toxicity, no harm, environmental friendliness and the like, and is considered to be an ideal positive electrode material of the lithium ion battery. However, due to the periodicity of the life of lithium ion batteries, a large amount of lithium iron phosphate batteries are scrapped, and thus, research on how to dispose of the scrapped lithium iron phosphate batteries is needed.
CN111675203a discloses a method for recovering lithium from waste lithium iron phosphate batteries, and a method for recovering lithium and ferric phosphate, wherein the waste lithium iron phosphate batteries are pretreated to obtain positive and negative electrode powder, the positive and negative electrode powder is reacted with water, concentrated sulfuric acid and ammonia water to form lithium-containing solution and iron-phosphorus slag, and the lithium-containing solution and the iron-phosphorus slag are separated by solid-liquid separation to obtain primary leachate and carbon-containing iron-phosphorus slag; the positive and negative electrode powder reacts with primary leaching liquid, concentrated sulfuric acid and ammonia water, and secondary leaching liquid and carbon-containing iron-phosphorus slag are obtained through solid-liquid separation; and mixing the carbon-containing iron-phosphorus slag with hydrogen peroxide and ammonia water for reaction to form ferric phosphate. However, the recovery time of this method is long and the recovery rate is low.
CN111646447a discloses a method for recovering iron phosphate from iron-phosphorus slag after lithium extraction of lithium iron phosphate batteries. Mixing iron-phosphorus slag after lithium extraction of a lithium iron phosphate battery with water, pulping, reacting with acid, performing solid-liquid separation to obtain leaching solution containing iron-phosphorus ions, adding iron to replace copper and removing aluminum by resin to obtain purifying solution, adding heptahydrate ferric phosphate or phosphoric acid to prepare a phosphorus-iron ratio to obtain a certain P: fe synthetic stock solution, adding hydrogen peroxide and ammonia water, adjusting pH to obtain ferric phosphate precursor precipitate, and performing aftertreatment to obtain a ferric phosphate precursor product. The method has high recovery cost, is not friendly to the environment, and has high impurity content of the obtained ferric phosphate.
The solid phase repair method is a technical route which is considered to have the most cost advantage and meets the low-carbon development requirement in the treatment method of the waste lithium iron phosphate battery. CN114024055a discloses a method for recovering waste lithium iron phosphate battery material in short process, the method comprises discharging, disassembling, stripping the shell, separating to obtain positive plate, carbonizing binder by heating the positive plate under nitrogen protection, vibrating and separating to obtain lithium iron phosphate positive material and aluminum foil, washing the collected lithium iron phosphate positive material with water, oven drying to obtain lithium iron phosphate/carbon powder, adding lithium source, phosphorus source and V into the lithium iron phosphate/carbon powder 2 O 5 And (3) obtaining mixed powder, activating a mechanical liquid phase to obtain mixed slurry, and sequentially drying and calcining the mixed slurry to obtain the regenerated lithium iron phosphate material.
However, the obtained regenerated lithium iron phosphate material has defects in crystal lattices, and has poor cycle performance and rate performance.
In view of the above, it is desirable to provide a method for recovering waste lithium iron phosphate batteries which is simple in regeneration and excellent in electrochemical properties of the obtained lithium iron phosphate material.
Disclosure of Invention
The invention aims to provide a recovery method of waste lithium iron phosphate batteries, which can realize the regeneration of LiFePO of the waste lithium iron phosphate batteries 4 And (3) the short-process reconstruction of the (C) can efficiently realize the recycling of the waste lithium iron phosphate battery with low cost and high added value.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a recovery method of a waste lithium iron phosphate battery, which comprises the following steps:
(1) Pretreating a waste lithium iron phosphate battery to obtain positive active powder;
(2) Performing hydrothermal treatment on the positive electrode active powder obtained in the step (1) in a lithium-containing carbon water solution, and then performing freeze drying;
(3) Ball milling the sample obtained after freeze drying, and then inertRoasting under the atmosphere condition to obtain regenerated LiFePO 4 /C。
The recovery method provided by the invention adopts hydrothermal lithium supplement-liquid phase carbon coating coupling to realize the regeneration of LiFePO of the waste lithium iron phosphate battery 4 And (3) the short-process reconstruction of the (C) can efficiently realize the recycling of the waste lithium iron phosphate battery with low cost and high added value. In addition, the solid-solid conversion can be realized through hydrothermal treatment without adopting acid leaching, alkaline leaching, extraction and other processes in the process of the recovery method, so that the requirements on production equipment and the production cost of the whole recovery process are greatly reduced; in addition, the recycling method provided by the invention does not produce secondary pollution, can give consideration to environmental protection and economic benefits, and is suitable for large-scale industrial production.
Preferably, the lithium source concentration in the lithium-containing aqueous carbon solution of step (2) is from 1g/L to 50g/L.
Preferably, the lithium source in the lithium-containing aqueous carbon solution of step (2) is a soluble salt of lithium, preferably lithium sulfate.
Preferably, the concentration of the carbon source in the lithium-containing aqueous carbon solution of step (2) is 1g/L to 10g/L.
Preferably, the carbon source in the lithium-containing aqueous carbon solution in step (2) is a carbon-containing organic matter, preferably glucose.
Preferably, in step (2), the solid-to-liquid ratio of the positive electrode active powder to the lithium-containing aqueous carbon solution is 10:1 to 200:1, the unit of the solid-to-liquid ratio being g/L.
Preferably, a reducing agent is further disposed in the lithium-containing aqueous carbon solution in step (2).
Preferably, the concentration of the reducing agent in the lithium-containing aqueous carbon solution of step (2) is from 1g/L to 10g/L.
Preferably, the reducing agent in the lithium-containing aqueous carbon solution in step (2) is hydrazine hydrate.
Preferably, the temperature of the hydrothermal treatment of step (2) is from 80 ℃ to 180 ℃.
Preferably, the hydrothermal treatment in step (2) takes 2 to 10 hours.
Preferably, the temperature of the freeze-drying in step (2) is-10 ℃ to 0 ℃ for 2 to 5 hours.
Preferably, the degree of vacuum of the freeze-drying in step (2) is 10Pa to 30Pa.
Preferably, the ball milling in the step (3) is carried out at the end point until the particle size D50 is less than or equal to 5 mu m.
Preferably, the temperature of the firing in step (3) is 500 ℃ to 800 ℃.
Preferably, the roasting time of step (3) is 1 to 24 hours.
Preferably, the pretreatment in step (1) includes sequentially performing discharging, disassembling, crushing, roasting and sieving.
As a preferred technical scheme of the recovery method, the recovery method comprises the following steps:
(1) Pretreating a waste lithium iron phosphate battery to obtain positive active powder; the pretreatment comprises sequentially performing discharging, disassembling, crushing, roasting and screening;
(2) Performing hydrothermal treatment at 80-180 ℃ on the positive electrode active powder obtained in the step (1) in a lithium-containing carbon water solution for 2-10 hours, and then performing freeze drying; the vacuum degree of freeze drying is 10Pa to 30Pa, the temperature is-10 ℃ to 0 ℃ and the time is 2h to 5h;
the concentration of a lithium source in the lithium-containing carbon water solution is 1g/L to 50g/L, and the lithium source is lithium sulfate;
the concentration of a carbon source in the lithium-containing carbon aqueous solution is 1g/L to 10g/L, and the carbon source is glucose;
the lithium-containing carbon aqueous solution is also provided with a reducing agent with the concentration of 1g/L to 10g/L, and the reducing agent is hydrazine hydrate;
the solid-to-liquid ratio of the positive electrode active powder to the lithium-containing carbon aqueous solution is 10:1 to 200:1, and the unit of the solid-to-liquid ratio is g/L;
(3) Ball milling is carried out on the sample obtained after freeze drying until the granularity D50 is less than or equal to 5 mu m, and then roasting is carried out under the inert atmosphere condition, thus obtaining regenerated LiFePO 4 C; the roasting temperature is 500-800 ℃ and the roasting time is 1-24 hours.
Compared with the prior art, the invention has the following beneficial effects:
the recovery method provided by the invention adopts hydrothermal lithium supplement-liquid phase carbon coating coupling to realize wasteLiFePO regeneration method for old lithium iron phosphate battery 4 And (3) the short-process reconstruction of the (C) can efficiently realize the recycling of the waste lithium iron phosphate battery with low cost and high added value. In addition, the solid-solid conversion can be realized through hydrothermal treatment without adopting acid leaching, alkaline leaching, extraction and other processes in the process of the recovery method, so that the requirements on production equipment and the production cost of the whole recovery process are greatly reduced; in addition, the recycling prevention provided by the invention does not generate secondary pollution, can give consideration to environmental protection and economic benefits, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a process flow diagram of a recovery method provided by the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
An embodiment of the present invention provides a method for recycling a waste lithium iron phosphate battery as shown in fig. 1, where the recycling method includes the following steps:
(1) Pretreating a waste lithium iron phosphate battery to obtain positive active powder;
(2) Performing hydrothermal treatment on the positive electrode active powder obtained in the step (1) in a lithium-containing carbon water solution, and then performing freeze drying;
(3) Ball milling is carried out on the sample obtained after freeze drying, and then roasting is carried out under the inert atmosphere condition, thus obtaining regenerated LiFePO 4 /C。
The recovery method provided by the invention adopts hydrothermal lithium supplement-liquid phase carbon coating coupling to realize the regeneration of LiFePO of the waste lithium iron phosphate battery 4 And (3) the short-process reconstruction of the (C) can efficiently realize the recycling of the waste lithium iron phosphate battery with low cost and high added value. In addition, the solid-solid conversion can be realized through hydrothermal treatment without adopting acid leaching, alkaline leaching, extraction and other processes in the process of the recovery method, so that the requirements on production equipment and the production cost of the whole recovery process are greatly reduced; in addition, the recycling prevention provided by the invention does not generate secondaryPollution, environmental protection and economic benefit can be considered, and the method is suitable for large-scale industrial production.
In certain embodiments, the lithium source concentration in the lithium-containing aqueous carbon solution of step (2) is from 1g/L to 50g/L, and may be, for example, 1g/L, 5g/L, 10g/L, 20g/L, 30g/L, 40g/L, or 50g/L, but is not limited to the recited values, as are other non-recited values within the range of values.
In certain embodiments, the lithium source in the lithium-containing aqueous carbon solution of step (2) is a soluble salt of lithium, preferably lithium sulfate.
In certain embodiments, the concentration of the carbon source in the aqueous lithium-containing carbon solution of step (2) is from 1g/L to 10g/L, and may be, for example, 1g/L, 3g/L, 5g/L, 6g/L, 8g/L, or 10g/L, but is not limited to the recited values, as are other non-recited values within the range of values.
In certain embodiments, the carbon source in the lithium-containing aqueous carbon solution of step (2) is a carbon-containing organic matter, including but not limited to any one or a combination of at least two of glucose, starch, sucrose, or an organic acid, typically but not limited to a combination of glucose and starch, a combination of starch and sucrose, a combination of sucrose and an organic acid, a combination of glucose, starch and sucrose, a combination of starch, sucrose and an organic acid, or a combination of glucose, starch, sucrose and an organic acid, preferably glucose.
In certain embodiments, in step (2), the solid-to-liquid ratio of the positive electrode active powder to the lithium-containing aqueous carbon solution is 10:1 to 200:1, and may be, for example, 10:1, 30:1, 50:1, 80:1, 100:1, 120:1, 150:1, 180:1, or 200:1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable, the solid-to-liquid ratio being in g/L.
According to the invention, aiming at the recovered target waste lithium iron phosphate battery, firstly, the lithium deficiency amount in the battery is measured through Inductively Coupled Plasma (ICP), and in the numerical range of 1g/L to 50g/L of lithium source concentration, 1g/L to 10g/L of carbon source concentration and 10:1 to 200:1 of solid-liquid ratio, the proper lithium source concentration, carbon source concentration and solid-liquid ratio can be selected, so that the recovery and repair of lithium iron phosphate in the waste lithium iron phosphate battery are realized.
In certain embodiments, a reducing agent is also disposed in the lithium-containing aqueous carbon solution of step (2).
In certain embodiments, the concentration of the reducing agent in the aqueous lithium-containing carbon solution of step (2) is from 1g/L to 10g/L, and may be, for example, 1g/L, 3g/L, 5g/L, 6g/L, 8g/L, or 10g/L, although not limited to the recited values, other non-recited values within the range of values are equally applicable.
In certain embodiments, the reducing agent in the lithium-containing aqueous carbon solution of step (2) is hydrazine hydrate.
In certain embodiments, the temperature of the hydrothermal treatment of step (2) is from 80 ℃ to 180 ℃, such as 80 ℃, 90 ℃,100 ℃, 120 ℃, 150 ℃, 160 ℃, or 180 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In certain embodiments, the hydrothermal treatment of step (2) is performed for a period of time ranging from 2h to 10h, such as 2h, 4h, 5h, 6h, 8h, or 10h, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In certain embodiments, the freeze-drying of step (2) is at a temperature of-10 ℃ to 0 ℃ for a time of 2 hours to 5 hours.
The freeze-drying temperature in step (2) is-10 ℃ to 0 ℃, and can be, for example, -10 ℃, -8 ℃, -5 ℃, -3 ℃ or 0 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The time of the freeze-drying in the step (2) is 2h to 5h, for example, may be 2h, 3h, 4h or 5h, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In certain embodiments, the degree of vacuum of the freeze-drying in step (2) is 10Pa to 30Pa, for example, 10Pa, 15Pa, 20Pa, 25Pa, or 30Pa, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In certain embodiments, the end point of the ball milling in step (3) is ball milling to a particle size D50. Ltoreq.5. Mu.m, which may be, for example, 1. Mu.m, 2. Mu.m, 3. Mu.m, 4. Mu.m, or 5. Mu.m, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In certain embodiments, the firing in step (3) is at a temperature of 500 ℃ to 800 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In certain embodiments, the firing in step (3) is for a period of time ranging from 1h to 24h, such as 1h, 3h, 5h, 8h, 10h, 12h, 15h, 18h, 20h, 21h, or 24h, although not limited to the recited values, other non-recited values within the range of values are equally applicable.
The inert atmosphere of the present invention may be used with gases including nitrogen and/or argon.
In certain embodiments, the pretreatment of step (1) comprises sequentially performing discharging, dismantling, crushing, roasting, and sieving.
The discharging, disassembling, crushing, roasting and sieving in the pretreatment of the present invention are conventional pretreatment processes in the art, so long as the positive electrode active powder can be obtained, and the present invention is not particularly limited herein.
As a preferred technical scheme of the recovery method, the recovery method comprises the following steps:
(1) Pretreating a waste lithium iron phosphate battery to obtain positive active powder; the pretreatment comprises sequentially performing discharging, disassembling, crushing, roasting and screening;
(2) Performing hydrothermal treatment at 80-180 ℃ on the positive electrode active powder obtained in the step (1) in a lithium-containing carbon water solution for 2-10 hours, and then performing freeze drying; the vacuum degree of freeze drying is 10Pa to 30Pa, the temperature is-10 ℃ to 0 ℃ and the time is 2h to 5h;
the concentration of a lithium source in the lithium-containing carbon water solution is 1g/L to 50g/L, and the lithium source is lithium sulfate;
the concentration of a carbon source in the lithium-containing carbon aqueous solution is 1g/L to 10g/L, and the carbon source is glucose;
the lithium-containing carbon aqueous solution is also provided with a reducing agent with the concentration of 1g/L to 10g/L, and the reducing agent is hydrazine hydrate;
the solid-to-liquid ratio of the positive electrode active powder to the lithium-containing carbon aqueous solution is 10:1 to 200:1, and the unit of the solid-to-liquid ratio is g/L;
(3) Ball milling is carried out on the sample obtained after freeze drying until the grain diameter D50 is less than or equal to 5 mu m, and then roasting is carried out under the inert atmosphere condition, thus obtaining regenerated LiFePO 4 C; the roasting temperature is 500-800 ℃ and the roasting time is 1-24 hours.
In order to clearly illustrate the technical scheme of the invention, in the waste lithium iron phosphate battery treated in the specific embodiment, the chemical formula of the positive electrode active material is Li 0.6 FePO 4 Wherein the amount of lithium deficiency is determined by inductively coupled plasma emission spectroscopy.
Example 1
The embodiment provides a recovery method of a waste lithium iron phosphate battery, which comprises the following steps:
(1) Pretreating a waste lithium iron phosphate battery to obtain positive active powder; the pretreatment comprises sequentially performing discharging, disassembling, crushing, roasting and screening;
(2) Performing hydrothermal treatment at 140 ℃ on the positive electrode active powder obtained in the step (1) in a lithium-containing carbon water solution for 5 hours, and then performing freeze drying; the vacuum degree of freeze drying is 20Pa, the temperature is-5 ℃ and the time is 3 hours;
the concentration of a lithium source in the lithium-containing carbon water solution is 25g/L, and the lithium source is lithium sulfate;
the concentration of a carbon source in the lithium-containing carbon aqueous solution is 5g/L, and the carbon source is glucose;
the lithium-containing carbon aqueous solution is also provided with a reducing agent with the concentration of 5g/L, and the reducing agent is hydrazine hydrate;
the solid-to-liquid ratio of the positive electrode active powder to the lithium-containing carbon aqueous solution is 100:1, and the unit of the solid-to-liquid ratio is g/L;
(3) Ball milling is carried out on the sample obtained after freeze drying until the particle diameter D50 is 5 mu m, and then roasting is carried out under the condition of nitrogen atmosphere, thus obtaining regenerated LiFePO 4 C; the roasting temperature is 600 ℃ and the roasting time is 10 hours.
Example 2
The embodiment provides a recovery method of a waste lithium iron phosphate battery, which comprises the following steps:
(1) Pretreating a waste lithium iron phosphate battery to obtain positive active powder; the pretreatment comprises sequentially performing discharging, disassembling, crushing, roasting and screening;
(2) Performing hydrothermal treatment at 80 ℃ on the positive electrode active powder obtained in the step (1) in a lithium-containing carbon water solution for 10 hours, and then performing freeze drying; the vacuum degree of freeze drying is 10Pa, the temperature is-10 ℃ and the time is 2 hours;
the concentration of a lithium source in the lithium-containing carbon water solution is 1g/L, and the lithium source is lithium sulfate;
the concentration of a carbon source in the lithium-containing carbon aqueous solution is 1g/L, and the carbon source is glucose;
the lithium-containing carbon aqueous solution is also provided with a reducing agent with the concentration of 1g/L, and the reducing agent is hydrazine hydrate;
the solid-to-liquid ratio of the positive electrode active powder to the lithium-containing carbon aqueous solution is 10:1, and the unit of the solid-to-liquid ratio is g/L;
(3) Ball milling is carried out on the sample obtained after freeze drying until the particle diameter D50 is 5 mu m, and then roasting is carried out under the condition of nitrogen atmosphere, thus obtaining regenerated LiFePO 4 C; the roasting temperature is 500 ℃ and the roasting time is 24 hours.
Example 3
The embodiment provides a recovery method of a waste lithium iron phosphate battery, which comprises the following steps:
(1) Pretreating a waste lithium iron phosphate battery to obtain positive active powder; the pretreatment comprises sequentially performing discharging, disassembling, crushing, roasting and screening;
(2) Carrying out hydrothermal treatment at 180 ℃ on the positive electrode active powder obtained in the step (1) in a lithium-containing carbon water solution for 2 hours, and then carrying out freeze drying; the vacuum degree of freeze drying is 30Pa, the temperature is 0 ℃ and the time is 5 hours;
the concentration of a lithium source in the lithium-containing carbon water solution is 50g/L, and the lithium source is lithium sulfate;
the concentration of a carbon source in the lithium-containing carbon aqueous solution is 10g/L, and the carbon source is glucose;
the lithium-containing carbon aqueous solution is also provided with a reducing agent with the concentration of 10g/L, and the reducing agent is hydrazine hydrate;
the solid-to-liquid ratio of the positive electrode active powder to the lithium-containing carbon aqueous solution is 200:1, and the unit of the solid-to-liquid ratio is g/L;
(3) Ball milling is carried out on the sample obtained after freeze drying until the particle diameter D50 is 5 mu m, and then roasting is carried out under the condition of nitrogen atmosphere, thus obtaining regenerated LiFePO 4 C; the roasting temperature is 800 ℃ and the roasting time is 1h.
Example 4
The present example provided a method for recovering a waste lithium iron phosphate battery, the remainder being the same as example 1, except that the carbon source concentration in the aqueous lithium-containing carbon solution was 0.5 g/L.
Example 5
The present example provided a method for recovering a waste lithium iron phosphate battery, the remainder being the same as example 1 except that the carbon source concentration in the lithium-containing aqueous carbon solution was 11 g/L.
Example 6
The present example provided a method for recovering waste lithium iron phosphate batteries, which was the same as in example 1 except that the carbon source was sodium acetate.
Example 7
The present example provided a method for recovering a waste lithium iron phosphate battery, the remainder being the same as example 1, except that the concentration of the reducing agent in the aqueous solution containing lithium and carbon was 0.5 g/L.
Example 8
The present example provided a method for recovering waste lithium iron phosphate batteries, which was the same as in example 1 except that the concentration of the reducing agent in the aqueous solution containing lithium and carbon was 11 g/L.
Comparative example 1
This comparative example provides a method for recovering a spent lithium iron phosphate battery, which is the same as example 1 except that the carbon source concentration in the aqueous lithium-containing carbon solution is 0g/L.
Comparative example 2
This comparative example provides a method for recycling waste lithium iron phosphate batteries, which is the same as example 1 except that freeze drying is changed to normal pressure drying at 80 ℃.
Performance testing
Regenerated LiFePO recovered in examples and comparative examples 4 And (2) respectively smearing the anode plate/C with conductive carbon black SP and 5wt% polyvinylidene fluoride solution on aluminum foil according to a mass ratio of 8:1:1, wherein a metal sodium sheet is used as a negative electrode, a Celgard2400 type diaphragm is adopted as the diaphragm, and the electrolyte is NaPF with the concentration of 1mol/L 6 (the solvent is ethylene carbonate and diethyl carbonate, the volume ratio is 1:1), and after the battery is kept stand for 12 hours, the first discharge capacity, the capacity retention rate for 100 times of circulation and the rate performance test are carried out on a blue electric battery tester Land CT 2001A.
The test method of the first discharge capacity is as follows: constant current and constant voltage charge to 4V at 0.1C multiplying power, and then discharge to 2V at 0.1C multiplying power;
the capacity retention test method for 100 cycles is as follows: charging to 4V with constant current and constant voltage at 0.1C rate, discharging to 2V at 0.1C rate, and recording discharge capacity after 100 circles of circulation, wherein the ratio of the discharge capacity of 100 circles to the first discharge capacity is the capacity retention rate of 100 times of circulation;
the test method of the cycle rate performance is as follows: standing the assembled battery for 6-12h, and then testing the cycle rate performance in the range of 2.5-4.2V by adopting a BTS-5V-10mA battery charge-discharge tester: carrying out charge and discharge for three times in a voltage interval of 2.5V to 4.2V at 25 ℃ with a 0.1C multiplying power to obtain a discharge capacity C0 of the last circle; then, charging the battery to 4.2V in a charging mode of 0.1C, and discharging the battery to 2.5V in a discharging mode of 0.5C to obtain the discharge capacity C2 of the last circle; the ratio of C2/C0 is the rate capability.
The results obtained are shown in Table 1.
TABLE 1
As can be seen from comparison of examples 4, 5 and 1, a part of Fe in the waste lithium iron phosphate battery is oxidized from Fe (II) to Fe (III), so that Li lattice loss can not be intercalated, the concentration of carbon source is low, fe is insufficiently reduced, the intercalation of lithium ions is affected, and finally the performance of the lithium iron phosphate material is affected; in addition, the low concentration of the carbon source can lead to incomplete carbon coating on the surface of the generated product, influence the conductivity of the prepared lithium iron phosphate and further influence the electrochemical performance.
When the concentration of the carbon source is too high, the recovery cost is increased, excessive redundant carbon inclusion is generated, the tap density of the obtained lithium iron phosphate product is reduced, and the electrochemical performance is adversely affected.
As can be seen from comparison of examples 7, 8 and 1, partial Fe in the waste lithium iron phosphate battery is oxidized from Fe (II) to Fe (III), if the concentration of the reducing agent is too low, trivalent iron can not be sufficiently reduced, and the electrochemical performance of the finally obtained lithium iron phosphate is affected; when the concentration of the reducing agent is too high, the recovery cost is increased.
In conclusion, the recovery method provided by the invention adopts hydrothermal lithium-liquid phase carbon coating coupling to realize the regeneration of LiFePO of the waste lithium iron phosphate battery 4 And (3) the short-process reconstruction of the (C) can efficiently realize the recycling of the waste lithium iron phosphate battery with low cost and high added value. In addition, the solid-solid conversion can be realized through hydrothermal treatment without adopting acid leaching, alkaline leaching, extraction and other processes in the process of the recovery method, so that the requirements on production equipment and the production cost of the whole recovery process are greatly reduced; in addition, the recycling prevention provided by the invention does not generate secondary pollution, can give consideration to environmental protection and economic benefits, and is suitable for large-scale industrial production.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. The recovery method of the waste lithium iron phosphate battery is characterized by comprising the following steps of:
(1) Pretreating a waste lithium iron phosphate battery to obtain positive active powder;
(2) Performing hydrothermal treatment on the positive electrode active powder obtained in the step (1) in a lithium-containing carbon water solution, and then performing freeze drying;
(3) Ball milling is carried out on the sample obtained after freeze drying, and then roasting is carried out under the inert atmosphere condition, thus obtaining regenerated LiFePO 4 /C。
2. The recovery method according to claim 1, wherein the lithium source concentration in the lithium-containing aqueous carbon solution of step (2) is 1g/L to 50g/L;
preferably, the lithium source in the lithium-containing aqueous carbon solution of step (2) is a soluble salt of lithium, preferably lithium sulfate.
3. The recovery method according to claim 1 or 2, wherein the carbon source concentration in the lithium-containing aqueous carbon solution of step (2) is 1g/L to 10g/L;
preferably, the carbon source in the lithium-containing aqueous carbon solution in step (2) is a carbon-containing organic matter, preferably glucose.
4. A recovery method according to any one of claims 1 to 3, wherein in step (2), the solid-to-liquid ratio of the positive electrode active powder to the lithium-containing aqueous carbon solution is 10:1 to 200:1, the unit of the solid-to-liquid ratio being g/L.
5. The method according to any one of claims 1 to 4, wherein a reducing agent is further provided in the aqueous lithium-containing carbon solution of step (2);
preferably, the concentration of the reducing agent in the lithium-containing aqueous carbon solution of step (2) is 1g/L to 10g/L;
preferably, the reducing agent in the lithium-containing aqueous carbon solution in step (2) is hydrazine hydrate.
6. The recovery method according to any one of claims 1 to 5, wherein the temperature of the hydrothermal treatment of step (2) is 80 ℃ to 180 ℃;
preferably, the time of the hydrothermal treatment in the step (2) is 2 to 10 hours;
preferably, the temperature of the freeze drying in the step (2) is-10 ℃ to 0 ℃ and the time is 2 to 5 hours;
preferably, the degree of vacuum of the freeze-drying in step (2) is 10Pa to 30Pa.
7. The recovery method according to any one of claims 1 to 6, wherein the ball milling in the step (3) is ended at a particle size d50.ltoreq.5 μm.
8. The recovery method according to any one of claims 1 to 7, wherein the roasting temperature of step (3) is 500 ℃ to 800 ℃;
preferably, the roasting time of step (3) is 1 to 24 hours.
9. The recycling method according to any one of claims 1 to 8, wherein the pretreatment of step (1) comprises sequentially performing discharging, disassembling, crushing, firing, and sieving.
10. The recovery method according to any one of claims 1 to 9, characterized in that it comprises the steps of:
(1) Pretreating a waste lithium iron phosphate battery to obtain positive active powder; the pretreatment comprises sequentially performing discharging, disassembling, crushing, roasting and screening;
(2) Performing hydrothermal treatment at 80-180 ℃ on the positive electrode active powder obtained in the step (1) in a lithium-containing carbon water solution for 2-10 hours, and then performing freeze drying; the vacuum degree of freeze drying is 10Pa to 30Pa, the temperature is-10 ℃ to 0 ℃ and the time is 2h to 5h;
the concentration of a lithium source in the lithium-containing carbon water solution is 1g/L to 50g/L, and the lithium source is lithium sulfate;
the concentration of a carbon source in the lithium-containing carbon aqueous solution is 1g/L to 10g/L, and the carbon source is glucose;
the lithium-containing carbon aqueous solution is also provided with a reducing agent with the concentration of 1g/L to 10g/L, and the reducing agent is hydrazine hydrate;
the solid-to-liquid ratio of the positive electrode active powder to the lithium-containing carbon aqueous solution is 10:1 to 200:1, and the unit of the solid-to-liquid ratio is g/L;
(3) Ball milling is carried out on the sample obtained after freeze drying until the granularity D50 is less than or equal to 5 mu m, and then roasting is carried out under the inert atmosphere condition, thus obtaining regenerated LiFePO 4 C; the roasting temperature is 500-800 ℃ and the roasting time is 1-24 hours.
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