CN114988381A - Method for preparing iron phosphate by using waste lithium iron phosphate battery - Google Patents
Method for preparing iron phosphate by using waste lithium iron phosphate battery Download PDFInfo
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- CN114988381A CN114988381A CN202210578802.5A CN202210578802A CN114988381A CN 114988381 A CN114988381 A CN 114988381A CN 202210578802 A CN202210578802 A CN 202210578802A CN 114988381 A CN114988381 A CN 114988381A
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- iron phosphate
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- waste lithium
- iron
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 77
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 50
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 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 44
- 238000000034 method Methods 0.000 title claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000012452 mother liquor Substances 0.000 claims abstract description 47
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 45
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 45
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- 238000002386 leaching Methods 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 17
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims description 69
- 239000007788 liquid Substances 0.000 claims description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract description 3
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 46
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- 239000000203 mixture Substances 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 22
- -1 dihydrate ferric phosphate Chemical class 0.000 description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 239000010413 mother solution Substances 0.000 description 13
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001105 regulatory effect Effects 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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- 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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Primary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing iron phosphate by using waste lithium iron phosphate batteries, and belongs to the technical field of waste lithium battery recovery. The method comprises the following steps: firstly, carrying out acid leaching on waste lithium iron phosphate battery powder to obtain a leaching solution and tailings; heating the leachate in a water bath to adjust the pH value and precipitate lithium to obtain crude lithium carbonate; and (3) drying, roasting and acid leaching the tailings to obtain iron phosphate mother liquor, then adding an iron source into the iron phosphate mother liquor for reaction, heating, adding alkali to adjust the pH, then oxidizing and aging to obtain ferric phosphate dihydrate, and finally calcining at high temperature to obtain the anhydrous iron phosphate. The invention effectively solves the problem that a large amount of waste residues generated by the existing wet recovery process of the waste lithium iron phosphate batteries cannot be fully utilized, and the anhydrous iron phosphate prepared by using the waste lithium iron phosphate batteries has high purity, moderate iron-phosphorus ratio and high product quality.
Description
Technical Field
The invention belongs to the technical field of waste lithium battery recovery, and particularly relates to a method for preparing iron phosphate by using waste lithium iron phosphate batteries.
Background
The lithium iron phosphate battery has the advantages of low cost, long cycle life, good safety and the like, and is widely applied to the field of various new energy automobiles. China is a country with large consumption of lithium batteries, and with the rapid development of new energy automobiles in recent years, the demand of lithium iron phosphate batteries is increased rapidly, but the scrap quantity brought by the lithium iron phosphate batteries is increased year by year. If the waste lithium iron phosphate batteries are not properly treated, not only can great resource waste be caused, but also great pollution can be caused to the environment.
At present, the waste lithium iron phosphate batteries are recycled mainly by adopting a wet process to recover valuable metal components, the waste lithium iron phosphate batteries are crushed to a certain particle size, and then the valuable metals in the anode materials of the waste lithium iron phosphate batteries are recovered in the form of lithium carbonate by using acid dissolution. The method can effectively recover lithium element in the lithium iron phosphate cathode material, but can generate a large amount of tailings which can not be continuously utilized, and has the defect of insufficient resource recovery.
In view of the above, a method capable of more fully recycling the waste lithium iron phosphate batteries needs to be developed.
Disclosure of Invention
Aiming at the technical defect that the existing wet recovery process produces a large amount of tailings which cannot be utilized in the background art, the invention aims to provide a method for preparing iron phosphate by utilizing waste lithium iron phosphate batteries, and aims to provide a method capable of more fully recycling the waste lithium iron phosphate batteries, so that the environment is protected and the resource waste is reduced.
The invention is realized by the following technical scheme:
the invention provides a method for preparing iron phosphate by using waste lithium iron phosphate batteries, which comprises the following steps:
1) crushing waste lithium iron phosphate batteries to obtain mixed powder, adding acid into the powder, uniformly mixing and leaching for 1-5 hours at normal temperature, and filtering to obtain leachate and tailings;
2) heating the leachate obtained in the step 1) to 70-95 ℃ in a water bath, adding alkali liquor to adjust the pH to 9-12, and filtering to obtain solid and lithium water mother liquor; heating the lithium water mother liquor in 70-95 ℃ water bath, adding sodium carbonate to adjust the pH value to 9-12, and filtering to obtain white crude lithium carbonate;
3) drying and roasting the tailings obtained in the step 1), adding acid, uniformly mixing for 2-5h at normal temperature, and filtering to obtain carbon powder and iron phosphate mother liquor;
4) adding an iron source into the iron phosphate mother liquor at normal temperature, and reacting for 0.5-2h to obtain a solution A; heating the solution A, adding alkali to adjust the pH value to 2-3, and reacting for 1-2h to obtain a solution B; adding an oxidant into the solution B, and aging for 2-6h to obtain a solution C; and finally, filtering, washing and drying the obtained solution C to obtain ferric phosphate dihydrate, and further calcining at high temperature to obtain the anhydrous ferric phosphate.
Further, in the step 1) and the step 3), the acid is at least one of sulfuric acid, hydrochloric acid and phosphoric acid, and the concentration is 0.1-0.2 mol/L; the acid-adding solid-liquid ratio is 1 (2-6).
Further, the solid obtained by filtering the leachate in the step 2) mainly contains nickel, magnesium, aluminum and other substances. Firstly, adding acid into lithium iron phosphate battery powder to completely dissolve magnesium, aluminum, lithium and other elements into leachate, then adjusting the pH value of the leachate, generating solids by regulating the pH value of the leachate, filtering and removing the solids of nickel, magnesium, aluminum and other substances in the solution in a chemical precipitation mode, and adding sodium carbonate into lithium water mother liquor obtained by filtering to prepare crude lithium carbonate.
Further, the roasting temperature in the step 3) is 350-600 ℃, and the roasting time is 2-5 h.
Further, the iron source in the step 4) is at least one of iron powder, ferric sulfate, ferric oxide and ferrous sulfate; the adding amount of the iron source is calculated according to the ratio (1-2) of the amount of iron and the amount of phosphorus substances in the feed liquid to 1.
Further, the temperature of the solution A in the step 4) is increased to 50-90 ℃ before the pH is adjusted.
Further, the alkali in the step 4) is at least one of alkali metal hydroxide, alkali metal carbonate solution and ammonia water.
Further, the oxidant in step 4) is at least one of chlorate, peroxide, oxygen and ozone; the adding amount of the oxidant is 1-2 times of the amount of iron substances in the feed liquid.
Further, the temperature of the high-temperature calcination in the step 4) is 500-800 ℃, and the calcination time is 2-5 h.
Firstly, carrying out high-temperature treatment on acid-leaching filtered tailings to remove substances such as a binder and the like, then adding acid and filtering to obtain a ferric phosphate mother solution, adding an iron source into the mother solution, adjusting the pH value to generate ferric phosphate dihydrate complex precipitates, and continuously adding an oxidant and ageing to completely oxidize ferrous ions in the solution into ferric ions; and calcining the finally obtained ferric phosphate dihydrate at high temperature to remove crystal water, thereby obtaining the battery grade pure anhydrous ferric phosphate.
Compared with the prior art, the invention has the beneficial effects that:
firstly, carrying out acid leaching on waste lithium iron phosphate battery powder to obtain a leaching solution and tailings; heating the leachate in a water bath to adjust the pH value and precipitate lithium to obtain crude lithium carbonate; and (3) drying, roasting and acid leaching tailings to obtain iron phosphate mother liquor, adding an iron source into the iron phosphate mother liquor for reaction, heating, adding alkali to adjust the pH value, oxidizing and aging to obtain ferric phosphate dihydrate, and calcining the ferric phosphate dihydrate at high temperature to obtain the anhydrous iron phosphate. The invention effectively solves the problem that a large amount of waste residues generated by the existing wet recovery process of the waste lithium iron phosphate batteries can not be fully utilized, and the anhydrous iron phosphate prepared by using the waste lithium iron phosphate batteries has high purity, proper iron-phosphorus ratio and high product quality.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.16mol/L according to the solid-to-liquid ratio of 1:4.2, uniformly mixing at normal temperature, leaching for 3.5h, and filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4h, adding a sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5h at normal temperature, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath kettle, adding iron powder (the amount ratio of iron to phosphorus in the feed liquid is 1.8:1) at normal temperature, and reacting for 1.4 h; then heating the mixture in a water bath to 65 ℃, adding potassium hydroxide to adjust the pH value of the solution to 2.4, and continuing to react for 1.8 h; adding hydrogen peroxide with the mass being twice that of the iron in the feed liquid into the mixture, and aging the mixture for 4 hours; and filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and calcining the ferric phosphate dihydrate in a high-temperature furnace at 650 ℃ for 4 hours to obtain the pure anhydrous ferric phosphate.
Example 2
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.16mol/L according to the solid-to-liquid ratio of 1:5.5, uniformly mixing at normal temperature, leaching for 3.5h, and filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4h, adding a sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:5.8, uniformly mixing for 3.5h at normal temperature, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath kettle, adding iron powder (the amount ratio of iron to phosphorus in the feed liquid is 1.8:1) at normal temperature, and reacting for 1.4 h; then heating the mixture in a water bath to 65 ℃, adding potassium hydroxide to adjust the pH value of the solution to 2.4, and continuing to react for 1.8 h; adding hydrogen peroxide with the mass being twice that of the iron in the feed liquid into the mixture, and aging the mixture for 4 hours; and filtering, washing and drying the finally obtained solution to obtain the dihydrate ferric phosphate, and calcining the dihydrate ferric phosphate in a high-temperature furnace at 650 ℃ for 4 hours to obtain the pure anhydrous ferric phosphate.
Example 3
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.20mol/L according to the solid-to-liquid ratio of 1:2, uniformly mixing at normal temperature, leaching for 3.5h, and then filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4h, adding a sulfuric acid aqueous solution with the concentration of 0.14mol/L according to the solid-to-liquid ratio of 1:2.5, uniformly mixing for 3.5h at normal temperature, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath kettle, adding ferric sulfate (the amount ratio of iron to phosphorus in the feed liquid is 1.8:1) at normal temperature, and reacting for 1.4 h; then heating to 65 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing to react for 1.8 h; adding hydrogen peroxide with the mass being twice that of the iron in the feed liquid into the mixture, and aging the mixture for 4 hours; and filtering, washing and drying the finally obtained solution to obtain the dihydrate ferric phosphate, and calcining the dihydrate ferric phosphate in a high-temperature furnace at 650 ℃ for 4 hours to obtain the pure anhydrous ferric phosphate.
Example 4
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.16mol/L according to the solid-to-liquid ratio of 1:4.2, uniformly mixing at normal temperature, leaching for 3.5h, and filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4 hours, adding a sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing at normal temperature for 3.5 hours, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath kettle, adding ferric sulfate (the amount ratio of iron to phosphorus in the feed liquid is 1.2:1) at normal temperature, and reacting for 1.8 h; then heating the mixture in a water bath to 65 ℃, adding potassium hydroxide to adjust the pH value of the solution to 2.4, and continuing to react for 1.8 h; adding hydrogen peroxide with the mass being twice that of the iron in the feed liquid into the mixture, and aging the mixture for 4 hours; and filtering, washing and drying the finally obtained solution to obtain the dihydrate ferric phosphate, and calcining the dihydrate ferric phosphate in a high-temperature furnace at 650 ℃ for 4 hours to obtain the pure anhydrous ferric phosphate.
Example 5
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.16mol/L according to the solid-to-liquid ratio of 1:4.2, uniformly mixing at normal temperature, leaching for 3.5h, and filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4h, adding a sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5h at normal temperature, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath, firstly adding iron oxide (the weight ratio of iron to phosphorus in the feed liquid is 2:1) at normal temperature for reaction for 1.2 h; then heating the mixture in a water bath to 65 ℃, adding potassium hydroxide to adjust the pH value of the solution to 2.4, and continuing to react for 1.8 h; adding sodium chlorate with the mass which is twice of that of the iron in the feed liquid into the feed liquid and aging the mixture for 4 hours; and filtering, washing and drying the finally obtained solution to obtain the dihydrate ferric phosphate, and calcining the dihydrate ferric phosphate in a high-temperature furnace at 650 ℃ for 4 hours to obtain the pure anhydrous ferric phosphate.
Example 6
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.16mol/L according to the solid-to-liquid ratio of 1:4.2, uniformly mixing at normal temperature, leaching for 3.5h, and filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4h, adding a sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5h at normal temperature, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath, firstly adding iron oxide (the quantity ratio of iron to phosphorus in the feed liquid is 1.8:1) at normal temperature for reaction for 1.4 h; then heating the mixture in a water bath to 65 ℃, adding potassium hydroxide to adjust the pH value of the solution to 2.4, and continuing to react for 1.8 h; then adding sodium chlorate with the mass 1.5 times of that of the iron in the feed liquid into the feed liquid and aging the mixture for 3 hours; and filtering, washing and drying the finally obtained solution to obtain the dihydrate ferric phosphate, and calcining the dihydrate ferric phosphate in a high-temperature furnace at 650 ℃ for 4 hours to obtain the pure anhydrous ferric phosphate.
Example 7
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.16mol/L according to the solid-to-liquid ratio of 1:4.2, uniformly mixing at normal temperature, leaching for 3.5h, and filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4 hours, adding a sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing at normal temperature for 3.5 hours, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath, adding ferrous sulfate (the weight ratio of iron to phosphorus in the feed liquid is 1.8:1) at normal temperature, and reacting for 1.4 h; then heating to 85 ℃ in a water bath, adding potassium hydroxide to adjust the pH of the solution to 2.4, and continuing to react for 1.8 h; adding sodium chlorate with the mass which is twice of that of the iron in the feed liquid into the feed liquid and aging the mixture for 4 hours; and filtering, washing and drying the finally obtained solution to obtain the dihydrate ferric phosphate, and calcining the dihydrate ferric phosphate in a high-temperature furnace at 650 ℃ for 4 hours to obtain the pure anhydrous ferric phosphate.
Example 8
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.16mol/L according to the solid-to-liquid ratio of 1:4.2, uniformly mixing at normal temperature, leaching for 3.5h, and filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4 hours, adding a sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing at normal temperature for 3.5 hours, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath kettle, adding ferrous sulfate (the weight ratio of iron to phosphorus in the feed liquid is 2:1) at normal temperature, and reacting for 1.6 h; then heating the mixture in a water bath to 75 ℃, adding potassium hydroxide to adjust the pH value of the solution to 2.4, and continuing to react for 1.8 h; adding sodium chlorate with the mass twice that of iron in the feed liquid into the feed liquid, and aging for 4 hours; and filtering, washing and drying the finally obtained solution to obtain the dihydrate ferric phosphate, and calcining the dihydrate ferric phosphate in a high-temperature furnace at 650 ℃ for 4 hours to obtain the pure anhydrous ferric phosphate.
The pure anhydrous iron phosphate products prepared in the above examples were tested and the results are shown in table 1.
TABLE 1
Comparative example 1
The preparation process and procedure parameters of example 1 were referenced except that the amount of iron source added was changed.
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.16mol/L according to the solid-to-liquid ratio of 1:4.2, uniformly mixing at normal temperature, leaching for 3.5h, and filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4h, adding a sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5h at normal temperature, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath kettle, adding iron powder (the amount ratio of iron to phosphorus in the feed liquid is 2.5:1) at normal temperature, and reacting for 1.4 h; then heating the mixture in a water bath to 65 ℃, adding potassium hydroxide to adjust the pH value of the solution to 2.4, and continuing to react for 1.8 h; adding hydrogen peroxide with the mass being twice that of the iron in the feed liquid into the mixture, and aging the mixture for 4 hours; and filtering, washing and drying the finally obtained solution to obtain the dihydrate ferric phosphate, and calcining the dihydrate ferric phosphate in a high-temperature furnace at 650 ℃ for 4 hours to obtain the pure anhydrous ferric phosphate.
Comparative example 2
Referring to the preparation method and the step parameters of the example 1, the difference is that the temperature-rising alkali-adding pH-adjusting treatment process of the iron phosphate mother liquor is changed.
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.16mol/L according to the solid-to-liquid ratio of 1:4.2, uniformly mixing at normal temperature, leaching for 3.5h, and filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4 hours, adding a sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing at normal temperature for 3.5 hours, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath kettle, adding iron powder (the amount ratio of iron to phosphorus in the feed liquid is 1.8:1) at normal temperature, and reacting for 1.4 h; then heating the mixture in a water bath to 100 ℃, adding sodium hydroxide to adjust the pH of the solution to 4, and continuing to react for 1.8 h; adding hydrogen peroxide with the mass being twice that of the iron in the feed liquid into the mixture, and aging the mixture for 4 hours; and filtering, washing and drying the finally obtained solution to obtain ferric phosphate dihydrate, and calcining the ferric phosphate dihydrate in a high-temperature furnace at 650 ℃ for 4 hours to obtain the pure anhydrous ferric phosphate.
Comparative example 3
The preparation method and the process parameters of example 1 were referenced, except that the amount of the iron source added and the aging treatment process of the oxidizing agent were changed.
1. Taking 1000g of crushed powder of waste lithium iron phosphate batteries, adding a sulfuric acid aqueous solution with the concentration of 0.16mol/L according to the solid-to-liquid ratio of 1:4.2, uniformly mixing at normal temperature, leaching for 3.5h, and filtering to obtain a leaching solution and tailings.
2. Heating the leachate to 85 ℃ in a water bath, adding alkali to adjust the pH value to 11, and filtering to obtain a solid and a lithium water mother solution; and (3) heating the lithium water mother liquor in a water bath at 85 ℃, adding sodium carbonate to adjust the pH to 10.5, and filtering to obtain white crude lithium carbonate solid.
3. And (3) drying the tailings, roasting at 520 ℃ for 4h, adding a sulfuric acid aqueous solution with the concentration of 0.12mol/L according to the solid-to-liquid ratio of 1:3.5, uniformly mixing for 3.5h at normal temperature, and filtering to obtain carbon powder and iron phosphate mother liquor.
4. Putting the obtained iron phosphate mother liquor into a water bath kettle, adding iron powder (the amount ratio of iron to phosphorus in the feed liquid is 2.5:1) at normal temperature, and reacting for 1.4 h; then heating the mixture in a water bath to 65 ℃, adding potassium hydroxide to adjust the pH value of the solution to 2.4, and continuing to react for 1.8 h; adding hydrogen peroxide with the mass of 3.5 times of that of the iron in the feed liquid into the mixture, and aging for 4 hours; and filtering, washing and drying the finally obtained solution to obtain the dihydrate ferric phosphate, and calcining the dihydrate ferric phosphate in a high-temperature furnace at 750 ℃ for 5 hours to obtain the pure anhydrous ferric phosphate.
The results of examination of the anhydrous iron phosphate products prepared in the above comparative examples are shown in table 1.
TABLE 2
The embodiments described above merely represent some preferred embodiments of the present invention, which are described in more detail and detail, but are not intended to limit the present invention. It should be understood that various changes and modifications can be made by those skilled in the art, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the invention should be included in the scope of the invention.
Claims (8)
1. A method for preparing iron phosphate by using waste lithium iron phosphate batteries is characterized by comprising the following steps:
1) crushing waste lithium iron phosphate batteries to obtain mixed powder, adding acid into the powder, uniformly mixing and leaching for 1-5 hours at normal temperature, and filtering to obtain leachate and tailings;
2) heating the leachate obtained in the step 1) to 70-95 ℃ in a water bath, adding alkali liquor to adjust the pH to 9-12, and filtering to obtain solid and lithium water mother liquor; heating the lithium water mother liquor in 70-95 ℃ water bath, adding sodium carbonate to adjust the pH value to 9-12, and filtering to obtain white crude lithium carbonate;
3) drying and roasting the tailings obtained in the step 1), adding acid, uniformly mixing for 2-5h at normal temperature, and filtering to obtain carbon powder and iron phosphate mother liquor;
4) adding an iron source into the ferric phosphate mother liquor at normal temperature, and reacting for 0.5-2h to obtain a solution A; heating the solution A, adding alkali to adjust the pH value to 2-3, and reacting for 1-2h to obtain a solution B; adding an oxidant into the solution B, and aging for 2-6h to obtain a solution C; and finally, filtering, washing and drying the obtained solution C to obtain ferric phosphate dihydrate, and further calcining at high temperature to obtain the anhydrous ferric phosphate.
2. The method for preparing iron phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the acid in the step 1) and the step 3) is at least one of sulfuric acid, hydrochloric acid and phosphoric acid, and the concentration of the acid is 0.1-0.2 mol/L; the acid-solid-liquid ratio is 1 (2-6).
3. The method for preparing iron phosphate by using the waste lithium iron phosphate batteries as claimed in claim 1, wherein the roasting temperature in the step 3) is 350-600 ℃, and the roasting time is 2-5 h.
4. The method for preparing iron phosphate by using the waste lithium iron phosphate batteries according to claim 1, wherein the iron source in the step 4) is at least one of iron powder, ferric sulfate, ferric oxide and ferrous sulfate; the adding amount of the iron source is calculated according to the ratio (1-2) of the amount of iron and the amount of phosphorus substances in the feed liquid to 1.
5. The method for preparing iron phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the temperature of the solution A in the step 4) is raised to 50-90 ℃ before the pH is adjusted.
6. The method for preparing iron phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the alkali in the step 4) is at least one of alkali metal hydroxide, alkali metal carbonate solution and ammonia water.
7. The method for preparing iron phosphate by using waste lithium iron phosphate batteries according to claim 1, wherein the oxidant in step 4) is at least one of chlorate, peroxide, oxygen and ozone; the adding amount of the oxidant is 1-2 times of the amount of iron substances in the feed liquid.
8. The method for preparing iron phosphate by using waste lithium iron phosphate batteries as claimed in claim 1, wherein the high-temperature calcination temperature in the step 4) is 500-800 ℃, and the calcination time is 2-5 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115448279A (en) * | 2022-10-25 | 2022-12-09 | 四川长虹格润环保科技股份有限公司 | Method for preparing battery-grade iron phosphate material by recycling phosphorus-iron slag after lithium extraction |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108899601A (en) * | 2018-06-11 | 2018-11-27 | 衢州华友钴新材料有限公司 | A method of recycling lithium from LiFePO4 |
| US20190161357A1 (en) * | 2016-08-26 | 2019-05-30 | Hunan Jinyuan New Materials Co., Ltd. | Method for preparing lithium carbonate from lithium iron phosphate battery scraps and lithium carbonate thereof |
| CN111009660A (en) * | 2019-11-26 | 2020-04-14 | 宁夏百川新材料有限公司 | Method for preparing lithium iron phosphate positive electrode material from waste lithium iron phosphate battery |
| CN113061723A (en) * | 2021-03-04 | 2021-07-02 | 长沙友合金属材料有限公司 | Method for recovering lithium from waste lithium iron phosphate batteries and preparing iron phosphate |
| CN113501510A (en) * | 2021-07-13 | 2021-10-15 | 郑州中科新兴产业技术研究院 | Method for recycling and regenerating anode material of waste lithium iron phosphate battery |
| CN113772649A (en) * | 2021-10-26 | 2021-12-10 | 中南大学 | Method for preparing battery-grade iron phosphate by recycling waste lithium iron phosphate positive electrode powder |
| CN113896211A (en) * | 2021-10-26 | 2022-01-07 | 湖北金泉新材料有限公司 | Resource treatment method for waste lithium iron phosphate batteries |
| CN113912032A (en) * | 2021-09-16 | 2022-01-11 | 湖北锂宝新材料科技发展有限公司 | Method for recovering and preparing battery-grade lithium carbonate and iron phosphate from waste lithium iron phosphate battery positive electrode powder |
-
2022
- 2022-05-25 CN CN202210578802.5A patent/CN114988381B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190161357A1 (en) * | 2016-08-26 | 2019-05-30 | Hunan Jinyuan New Materials Co., Ltd. | Method for preparing lithium carbonate from lithium iron phosphate battery scraps and lithium carbonate thereof |
| CN108899601A (en) * | 2018-06-11 | 2018-11-27 | 衢州华友钴新材料有限公司 | A method of recycling lithium from LiFePO4 |
| CN111009660A (en) * | 2019-11-26 | 2020-04-14 | 宁夏百川新材料有限公司 | Method for preparing lithium iron phosphate positive electrode material from waste lithium iron phosphate battery |
| CN113061723A (en) * | 2021-03-04 | 2021-07-02 | 长沙友合金属材料有限公司 | Method for recovering lithium from waste lithium iron phosphate batteries and preparing iron phosphate |
| CN113501510A (en) * | 2021-07-13 | 2021-10-15 | 郑州中科新兴产业技术研究院 | Method for recycling and regenerating anode material of waste lithium iron phosphate battery |
| CN113912032A (en) * | 2021-09-16 | 2022-01-11 | 湖北锂宝新材料科技发展有限公司 | Method for recovering and preparing battery-grade lithium carbonate and iron phosphate from waste lithium iron phosphate battery positive electrode powder |
| CN113772649A (en) * | 2021-10-26 | 2021-12-10 | 中南大学 | Method for preparing battery-grade iron phosphate by recycling waste lithium iron phosphate positive electrode powder |
| CN113896211A (en) * | 2021-10-26 | 2022-01-07 | 湖北金泉新材料有限公司 | Resource treatment method for waste lithium iron phosphate batteries |
Non-Patent Citations (2)
| Title |
|---|
| 周有池;文小强;郭春平;刘雯雯;: "铁锂废料制备电池级碳酸锂和磷酸铁工艺研究", 有色金属(冶炼部分), no. 04 * |
| 纪川: "废动力锂电池资源化技术实验研究", 中国优秀硕士学位论文全文数据库 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115448279A (en) * | 2022-10-25 | 2022-12-09 | 四川长虹格润环保科技股份有限公司 | Method for preparing battery-grade iron phosphate material by recycling phosphorus-iron slag after lithium extraction |
| CN115448279B (en) * | 2022-10-25 | 2024-03-26 | 四川长虹格润环保科技股份有限公司 | Method for preparing battery grade ferric phosphate material by recycling lithium-extracted ferrophosphorus slag |
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