CN113501510A - Method for recycling and regenerating anode material of waste lithium iron phosphate battery - Google Patents
Method for recycling and regenerating anode material of waste lithium iron phosphate battery Download PDFInfo
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- CN113501510A CN113501510A CN202110788560.8A CN202110788560A CN113501510A CN 113501510 A CN113501510 A CN 113501510A CN 202110788560 A CN202110788560 A CN 202110788560A CN 113501510 A CN113501510 A CN 113501510A
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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 65
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- 239000002699 waste material Substances 0.000 title claims abstract description 25
- 239000010405 anode material Substances 0.000 title claims description 11
- 230000001172 regenerating effect Effects 0.000 title description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 62
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 59
- 239000000243 solution Substances 0.000 claims abstract description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 239000000706 filtrate Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000011149 active material Substances 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000002386 leaching Methods 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 239000011268 mixed slurry Substances 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N 3-methyl-2-pentanone Chemical compound CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000005955 Ferric phosphate Substances 0.000 claims description 3
- 229940032958 ferric phosphate Drugs 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 3
- 239000010926 waste battery Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
-
- 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
- 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 recycling a waste lithium iron phosphate battery positive electrode material, which comprises the steps of firstly stripping a current collector of a waste lithium iron phosphate positive plate or leftover material from an active material by utilizing an organic solvent to obtain lithium iron phosphate powder; adding the obtained lithium iron phosphate powder into a mixed solution of a leaching agent and hydrogen peroxide for liquid-phase leaching, and filtering to obtain a lithium-containing filtrate and iron phosphate filter residues; removing impurities from the lithium-containing filtrate, evaporating and concentrating the lithium-containing filtrate, and adding a sodium carbonate solution to precipitate lithium element in the form of lithium carbonate to obtain battery-grade lithium carbonate; and (3) reversely washing the iron phosphate filter residue by using hydrochloric acid, and drying and crushing to obtain the battery-grade iron phosphate. The lithium iron phosphate positive electrode material is prepared by using the battery-grade lithium carbonate and the battery-grade iron phosphate as raw materials. The invention has short process flow and simple reaction system; the method solves the environmental protection problem, generates no iron-containing waste residue and phosphorus-containing wastewater, improves the product purity, reaches the battery-grade iron phosphate and lithium carbonate products, has high resource recovery rate, and is easy to realize industrial production.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery recovery, and particularly relates to a method for recovering and regenerating a waste lithium iron phosphate battery positive electrode material.
Technical Field
The lithium iron phosphate power battery anode material is highly popular in the industries of electric automobiles, energy storage power stations and the like because the raw material is rich in source, nontoxic, excellent in safety, stability and cyclicity and low in price. The service life of the new energy automobile power battery is 5-8 years, and the new energy automobile power battery popularized earliest is about to meet 'retirement tide'. The positive electrode material of the waste battery can bring a plurality of problems without proper disposal, and can generate great harm to the environment and public safety. On the other hand, precious valuable resources are wasted, the retired power battery has obvious resource characteristics, and obvious economic benefits and environmental protection values are achieved for efficient recycling of the retired power battery.
The recovery method of the waste lithium iron phosphate battery mainly comprises two main types, one is to regenerate lithium iron phosphate by using a solid phase method, and the other is to recover precious metal lithium. For example, patent document No. CN 104362408A discloses a method for recycling waste lithium iron phosphate, which comprises baking a pole piece to be recycled at high temperature to decompose and disable an adhesive, separating lithium iron phosphate and a conductive agent from a current collector aluminum foil, baking the lithium iron phosphate and the conductive agent at high temperature, and sieving to obtain the lithium iron phosphate wasteAnd restoring and regenerating the lithium iron phosphate powder again to obtain the lithium iron phosphate anode material. Due to the limitation of the source and the preparation process of the waste battery, the repaired and regenerated lithium iron phosphate cathode material is easily polluted by the external environment, has low purity and poor electrochemical performance stability, and cannot meet the requirements of the current market on battery materials. Chinese patent publication No. CN 103280610 a discloses a method for recovering aluminum, iron and lithium from lithium iron phosphate waste battery positive plates by an acid-base leaching method. The method comprises the steps of removing the positive electrode of the lithium iron phosphate battery, firstly dissolving the positive electrode with alkali, filtering, dissolving filter residues with mixed acid, enabling iron to exist in a ferric phosphate precipitation form, adding impurities such as carbon black and the like and a lithium-containing solution, adding a 95 ℃ saturated sodium carbonate solution into the lithium-containing solution, and precipitating to obtain lithium carbonate. Adding acid to the iron-containing precipitate to leach iron ions, and adding alkali liquor to adjust the pH value to obtain Fe (OH)3. In the recovery methods, the high-efficiency and high-value-added resource recovery of the lithium iron phosphate waste is not well realized, and the method has the advantages of complex process steps, multiple flow steps, high reagent consumption and high cost.
Therefore, the development of a new production process which has a simple process flow and a high recovery rate, can realize the recycling of high value-added resources of phosphorus, iron and lithium elements, has stable quality of the obtained iron phosphate product, and can meet the index requirements of battery-grade products becomes a technical problem to be solved urgently in the field at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for recycling a waste lithium iron phosphate battery positive electrode material.
In order to achieve the purpose, the invention adopts the technical scheme that:
1) soaking a positive plate or leftover material of a waste lithium iron phosphate battery in an organic solvent, dissolving a current collector of the positive plate or leftover material and a binder bonded with an active material to realize stripping of the current collector and the active material, collecting oversize products after screening to obtain an aluminum foil current collector, collecting undersize products to obtain mixed slurry containing the organic solvent and the active material, filtering the mixed slurry to obtain lithium iron phosphate powder and a soak solution, and recycling the organic solvent in the soak solution through reduced pressure distillation;
2) adding the lithium iron phosphate powder obtained in the step 1) into a mixed solution of a leaching agent and hydrogen peroxide for leaching reaction, and then filtering to obtain a lithium-containing filtrate and iron phosphate filter residues;
3) adjusting the lithium-containing filtrate obtained in the step 2) to an alkaline pH value range to remove impurity ions in the lithium-containing filtrate through precipitation reaction, then carrying out solid-liquid separation to obtain an impurity-removed solution, evaporating and concentrating the obtained impurity-removed solution, adding a sodium carbonate solution to carry out reaction crystallization, and filtering and washing to obtain a solid phase, namely battery-grade lithium carbonate;
4) reversely washing the iron phosphate filter residue obtained in the step 2) by using a hydrochloric acid solution with a certain pH value, and then drying and crushing to obtain battery-grade iron phosphate;
5) and 3) preparing the lithium iron phosphate anode material by using the battery-grade lithium carbonate obtained in the step 3) and the battery-grade iron phosphate obtained in the step 4) as raw materials.
Further, the organic solvent in the step 1) is one of acetone, N-dimethylacetamide, methylethylacetone and N-methylpyrrolidone.
Further, in the step 2), a leaching agent is one or more of formic acid, acetic acid, oxalic acid, citric acid and ascorbic acid, the concentration of the leaching agent is 0.05-2 mol/L, and the mass ratio of the lithium iron phosphate powder to the leaching agent is 1 (1-5).
Further, the mass concentration of hydrogen peroxide in the mixed solution in the step 2) is 2-3%.
Further, the alkaline pH value in the step 3) is 10.0-12.0.
Further, the pH value of the hydrochloric acid solution in the step 4) is 1.0-2.0.
Further, the mass ratio of the ferric phosphate filter residue to the hydrochloric acid solution in the step 4) is 1 (2-5), and the reverse washing time is 20-60 min.
Compared with the prior art, the invention has the following beneficial effects:
1) the method can fully realize the recycling of high value-added resources of phosphorus, iron and lithium elements in the waste lithium iron phosphate, prepare battery-grade iron phosphate and lithium carbonate products and synthesize the lithium iron phosphate cathode material.
2) The method has simple process, can fully utilize phosphorus, iron and lithium resources, has high resource recovery rate, does not generate iron-containing waste residues and phosphorus-containing wastewater, and is easy to realize industrial production.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is an XRD characterization of the battery grade iron phosphate obtained in example 1 and a spectrum of iron phosphate standard card 29-0715.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The method for recycling the anode material of the waste lithium iron phosphate battery in the embodiment comprises the following steps:
(1) the method comprises the steps of soaking a positive plate of a waste lithium iron phosphate battery in an N, N-dimethylacetamide solvent, dissolving a current collector of the positive plate and a binder bonded with an active material to realize stripping of the current collector and the active material, collecting oversize products after screening to obtain an aluminum foil current collector, collecting undersize products to obtain mixed slurry containing the N, N-dimethylacetamide solvent and the active material, filtering the mixed slurry to obtain lithium iron phosphate powder and a soak solution, and recycling the N, N-dimethylacetamide solvent in the soak solution through reduced pressure distillation.
(2) Adding lithium iron phosphate powder into a mixed solution of 0.05mol/L citric acid and 3wt% of hydrogen peroxide, and filtering to obtain a solution containing Li+And filtering the filtrate and iron phosphate filter residues, wherein the mass ratio of the lithium iron phosphate powder to the citric acid is 1: 2.
(3) And (3) adjusting the pH value of the lithium-containing filtrate obtained in the step (2) to 11 to remove impurity ions in the lithium-containing filtrate through a precipitation reaction, then carrying out solid-liquid separation to obtain an impurity-removed solution, evaporating and concentrating the obtained impurity-removed solution, adding a sodium carbonate solution to carry out reaction crystallization, and filtering and washing to obtain a solid phase, namely battery-grade lithium carbonate.
(4) And (3) reversely washing the iron phosphate filter residue obtained in the step (2) for three times by using hydrochloric acid with the pH value of 1.5, wherein the washing time is 30min each time, the mass ratio of the iron phosphate filter residue to the hydrochloric acid washing liquid is 1:3, and drying and crushing the iron phosphate filter residue until the requirement of battery-grade iron phosphate is met to obtain the battery-grade iron phosphate.
(5) And (3) preparing the lithium iron phosphate positive electrode material by using the prepared battery-grade lithium carbonate and battery-grade iron phosphate as raw materials.
Fig. 1 is an XRD characterization of the battery-grade iron phosphate prepared in this example, and the XRD spectrum of the battery-grade iron phosphate prepared in this example is consistent with the spectrum of the standard card 29-0715 of iron phosphate, and the diffraction peak is sharp and the characteristic peak is obvious, which indicates that the battery-grade iron phosphate is pure-phase FePO4And has good crystallinity, belonging to an orthorhombic system. Table 1 shows the product quality of battery grade iron phosphate and the standard requirements of "HG/T4701-. Table 1 shows the product quality of the battery grade iron phosphate obtained in example 1 and the standard requirements "iron phosphate for HG/T4701-.
TABLE 1
| Item | Fe/P（%） | Fe（%） | P（%） | Al（%） | Cu（%） | Ni（%） | Na（%） | Mg（%） |
| HG/T4701-2014 | 0.97~1.02 | 29~30 | 16.2~17.2 | 0.005 | 0.005 | 0.005 | 0.01 | 0.005 |
| The product | 0.999 | 29.90 | 16.65 | 0.0035 | 0.0025 | 0.002 | 0.002 | 0.002 |
Example 2
The method for recycling the anode material of the waste lithium iron phosphate battery in the embodiment comprises the following steps:
(1) placing a positive plate of a waste lithium iron phosphate battery in an acetone solvent for soaking, dissolving a current collector of the positive plate and a binder bonded with an active material to realize stripping of the current collector and the active material, collecting oversize products after screening to obtain an aluminum foil current collector, collecting undersize products to obtain a mixed slurry containing acetone and the active material, filtering the mixed slurry to obtain lithium iron phosphate powder and a soaking solution, and recycling the acetone solvent in the soaking solution through reduced pressure distillation.
(2) Adding lithium iron phosphate powder into a mixed solution of 2mol/L acetic acid and 2wt% hydrogen peroxide, and filtering to obtain a solution containing Li+And filtering the filtrate and iron phosphate filter residues, wherein the mass ratio of the lithium iron phosphate powder to the acetic acid is 1: 5.
(3) And (3) adjusting the pH value of the lithium-containing filtrate obtained in the step (2) to 12, removing impurity ions in the lithium-containing filtrate through a precipitation reaction, then carrying out solid-liquid separation to obtain an impurity-removed solution, evaporating and concentrating the obtained impurity-removed solution, adding a sodium carbonate solution to carry out reaction crystallization, and filtering and washing to obtain a solid phase, namely battery-grade lithium carbonate.
(4) And (3) reversely washing the iron phosphate filter residue obtained in the step (2) for four times by using hydrochloric acid with the pH value of 2.0, wherein the washing time is 60min each time, the mass ratio of the iron phosphate filter residue to the hydrochloric acid washing liquid is 1:2, and drying and crushing the iron phosphate filter residue until the requirement of battery-grade iron phosphate is met to obtain the battery-grade iron phosphate.
(5) And (3) preparing the lithium iron phosphate positive electrode material by using the prepared battery-grade lithium carbonate and battery-grade iron phosphate as raw materials.
Example 3
The method for recycling the anode material of the waste lithium iron phosphate battery in the embodiment comprises the following steps:
(1) the method comprises the steps of soaking leftover materials of waste lithium iron phosphate batteries in an acetone solvent, dissolving a current collector of a positive plate and a binder bonded with an active material to realize stripping of the current collector and the active material, collecting oversize products after screening to obtain an aluminum foil current collector, collecting undersize products to obtain mixed slurry containing acetone and the active material, filtering the mixed slurry to obtain lithium iron phosphate powder and a soak solution, and recycling the acetone solvent in the soak solution through reduced pressure distillation.
(2) Adding lithium iron phosphate powder into a mixed solution of 1 mol/L oxalic acid and 3wt% of hydrogen peroxide, and filtering to obtain a solution containing Li+And filtering the filtrate and iron phosphate filter residues, wherein the mass ratio of the lithium iron phosphate powder to the acetic acid is 1: 1.
(3) And (3) adjusting the pH value of the lithium-containing filtrate obtained in the step (2) to 10 to remove impurity ions in the lithium-containing filtrate through a precipitation reaction, then carrying out solid-liquid separation to obtain an impurity-removed solution, evaporating and concentrating the obtained impurity-removed solution, adding a sodium carbonate solution to carry out reaction crystallization, and filtering and washing to obtain a solid phase, namely battery-grade lithium carbonate.
(4) And (3) reversely washing the iron phosphate filter residue obtained in the step (2) for three times by using hydrochloric acid with the pH value of 1.8, wherein the washing time is 20min each time, the mass ratio of the iron phosphate filter residue to the hydrochloric acid washing liquid is 1:3, and drying and crushing the iron phosphate filter residue until the requirement of battery-grade iron phosphate is met to obtain the battery-grade iron phosphate. And (3) preparing the lithium iron phosphate positive electrode material by using the prepared battery-grade lithium carbonate and battery-grade iron phosphate as raw materials.
Example 4
The method for recycling the anode material of the waste lithium iron phosphate battery in the embodiment comprises the following steps:
(1) the method comprises the steps of soaking leftover materials of waste lithium iron phosphate batteries in an N-methyl pyrrolidone solvent, dissolving a current collector of a positive plate and a binder bonded with an active material to realize stripping of the current collector and the active material, collecting oversize products after screening to obtain an aluminum foil current collector, collecting undersize products to obtain mixed slurry containing the N-methyl pyrrolidone and the active material, filtering the mixed slurry to obtain lithium iron phosphate powder and a soak solution, and recycling the N-methyl pyrrolidone solvent in the soak solution through reduced pressure distillation.
(2) Adding lithium iron phosphate powder into a mixed solution of 0.5mol/L citric acid, 0.5mol/L acetic acid and 2wt% of hydrogen peroxide, and filtering to obtain a solution containing Li+And filtering the filtrate and iron phosphate filter residues, wherein the mass ratio of the lithium iron phosphate powder to the citric acid and the acetic acid is 1:2: 2.
(3) Adjusting the lithium-containing filtrate obtained in the step (2) to an alkaline pH value of 11.5 to remove impurity ions in the lithium-containing filtrate through a precipitation reaction, then performing solid-liquid separation to obtain an impurity-removed solution, evaporating and concentrating the obtained impurity-removed solution, adding a sodium carbonate solution to perform reaction crystallization, and filtering and washing to obtain a solid phase, namely battery-grade lithium carbonate.
(4) And (3) reversely washing the iron phosphate filter residue obtained in the step (2) for three times by using hydrochloric acid with the pH value of 1.2, wherein the washing time is 20min each time, the mass ratio of the iron phosphate filter residue to the hydrochloric acid washing liquid is 1:5, and drying and crushing the iron phosphate filter residue until the requirement of battery-grade iron phosphate is met to obtain the battery-grade iron phosphate.
(5) And (3) preparing the lithium iron phosphate positive electrode material by using the prepared battery-grade lithium carbonate and battery-grade iron phosphate as raw materials.
Example 5
The method for recycling the anode material of the waste lithium iron phosphate battery in the embodiment comprises the following steps:
(1) the leftover materials of the waste lithium iron phosphate batteries are placed in a methyl ethyl acetone solvent for soaking, so that a current collector of a positive plate is dissolved with a binder bonded with an active material, stripping of the current collector and the active material is realized, oversize products are collected after screening to obtain an aluminum foil current collector, undersize products are collected to obtain mixed slurry containing methyl ethyl acetone and the active material, the mixed slurry is filtered to obtain lithium iron phosphate powder and a soak solution, and the methyl ethyl acetone solvent in the soak solution is recycled through reduced pressure distillation.
(2) Adding lithium iron phosphate powder into a mixed solution of 1.5mol/L citric acid and 2wt% hydrogen peroxide, and filtering to obtain a solution containing Li+And filtering the filtrate and iron phosphate filter residues, wherein the mass ratio of the lithium iron phosphate powder to the citric acid and the acetic acid is 1: 4.
(3) And (3) adjusting the pH value of the lithium-containing filtrate obtained in the step (2) to 12, removing impurity ions in the lithium-containing filtrate through a precipitation reaction, then carrying out solid-liquid separation to obtain an impurity-removed solution, evaporating and concentrating the obtained impurity-removed solution, adding a sodium carbonate solution to carry out reaction crystallization, and filtering and washing to obtain a solid phase, namely battery-grade lithium carbonate.
(4) And (3) reversely washing the iron phosphate filter residue obtained in the step (2) for three times by using hydrochloric acid with the pH value of 1.4, wherein the washing time is 50min each time, the mass ratio of the iron phosphate filter residue to the hydrochloric acid washing liquid is 1:2, and drying and crushing the iron phosphate filter residue until the requirement of battery-grade iron phosphate is met to obtain the battery-grade iron phosphate.
(5) And (3) preparing the lithium iron phosphate positive electrode material by using the prepared battery-grade lithium carbonate and battery-grade iron phosphate as raw materials.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A method for recycling a waste lithium iron phosphate battery positive electrode material is characterized by comprising the following steps:
1) soaking a positive plate or leftover material of a waste lithium iron phosphate battery in an organic solvent, dissolving a current collector of the positive plate or leftover material and a binder bonded with an active material to realize stripping of the current collector and the active material, collecting oversize products after screening to obtain an aluminum foil current collector, collecting undersize products to obtain mixed slurry containing the organic solvent and the active material, filtering the mixed slurry to obtain lithium iron phosphate powder and a soak solution, and recycling the organic solvent in the soak solution through reduced pressure distillation;
2) adding the lithium iron phosphate powder obtained in the step 1) into a mixed solution of a leaching agent and hydrogen peroxide for leaching reaction, and then filtering to obtain a lithium-containing filtrate and iron phosphate filter residues;
3) adjusting the lithium-containing filtrate obtained in the step 2) to be alkaline so as to remove impurity ions in the lithium-containing filtrate through precipitation reaction, then carrying out solid-liquid separation to obtain impurity-removed liquid, evaporating and concentrating the obtained impurity-removed liquid, adding a sodium carbonate solution to carry out reaction crystallization, and filtering and washing to obtain a solid phase, namely battery-grade lithium carbonate;
4) reversely washing the iron phosphate filter residue obtained in the step 2) by using a hydrochloric acid solution, and then drying and crushing to obtain battery-grade iron phosphate;
5) and 3) preparing the lithium iron phosphate anode material by using the battery-grade lithium carbonate obtained in the step 3) and the battery-grade iron phosphate obtained in the step 4) as raw materials.
2. The recycling method according to claim 1, characterized in that: the organic solvent in the step 1) is one of acetone, N-dimethylacetamide, methyl ethyl acetone and N-methylpyrrolidone.
3. The recycling method according to claim 1, characterized in that: in the step 2), the leaching agent is one or more of formic acid, acetic acid, oxalic acid, citric acid and ascorbic acid, the concentration of the leaching agent is 0.05-2 mol/L, and the mass ratio of the lithium iron phosphate powder to the leaching agent is 1 (1-5).
4. The recycling method according to claim 1, characterized in that: the mass concentration of hydrogen peroxide in the mixed solution in the step 2) is 2-3%.
5. The recycling method according to claim 1, characterized in that: the alkaline pH value in the step 3) is 10.0-12.0.
6. The recycling method according to claim 1, characterized in that: the pH value of the hydrochloric acid solution in the step 4) is 1.0-2.0.
7. The recycling method according to claim 1, characterized in that: the mass ratio of the ferric phosphate filter residue to the hydrochloric acid solution in the step 4) is 1 (2-5), and the reverse washing time is 20-60 min.
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