CN112047320A - Treatment method for low-pollution recycling of lithium iron phosphate material - Google Patents
Treatment method for low-pollution recycling of lithium iron phosphate material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 120
- 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 72
- 238000004064 recycling Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 230000001502 supplementing effect Effects 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005453 pelletization Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000000376 reactant Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 17
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 16
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 16
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 10
- 239000011654 magnesium acetate Substances 0.000 claims description 10
- 235000011285 magnesium acetate Nutrition 0.000 claims description 10
- 229940069446 magnesium acetate Drugs 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 235000015165 citric acid Nutrition 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-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
- 229920002472 Starch Polymers 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 2
- 239000004137 magnesium phosphate Substances 0.000 claims description 2
- 229960002261 magnesium phosphate Drugs 0.000 claims description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 2
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 claims description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 8
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 5
- 229910012453 Li3Fe2(PO4)3 Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000009469 supplementation Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229960004793 sucrose Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a treatment method for recycling a lithium iron phosphate material with low pollution, which comprises the steps of firstly, discharging, disassembling and separating waste lithium iron phosphate batteries to obtain positive and negative pole pieces, using a combination method of hot acid solution soaking, ultrasonic wave loosening and high-pressure water gun stripping to obtain a lithium iron phosphate mixed material, then calcining the lithium iron phosphate mixed material, detecting the contents of elements Fe, Li and P in the lithium iron phosphate mixed material, supplementing an Fe source, an Li source, a P source and a sugar source according to the detection result, simultaneously adding an Mg source, a Ti source and an Mn source for doping, loosening a grain structure of the calcined material by using an acid solution with the weight percentage concentration of 1-5%, adding a proportioned supplementing material to obtain a slurry, finally grinding the slurry, spraying, pelletizing and drying, and calcining again to obtain the lithium iron phosphate material. The method is simple to operate, the waste lithium iron phosphate battery is recycled and utilized as a qualified lithium iron phosphate finished product, the pollution is low, the conversion rate is high, and the performance is good and stable.
Description
Technical Field
The invention relates to the technical field of lithium iron phosphate battery recovery, in particular to a treatment method for low-pollution recovery and reuse of a lithium iron phosphate material.
Background
The electric vehicle industry has developed vigorously, and batteries, one of the core accessories, have been widely researched and paid attention to. The olivine-type lithium iron phosphate has the advantages of low raw material price, high specific energy, good thermal stability, no pollution to the environment and the like, and is widely applied to the aspect of power batteries. According to the requirement of 'notice on carrying out new energy automobile power storage battery recycling and pilot plant work by organizations' (Ministry of industry and communications 'Union letter No. [ 2018 ] 68'), government related departments strengthen experience exchange and cooperation with pilot plant areas and enterprises, promote to form a cross-region and cross-industry cooperation mechanism, and ensure efficient recycling and harmless disposal of the power storage battery. Comprehensively considers the recycling of the lithium iron phosphate anode material for reproduction, and is beneficial to saving resources and protecting environment.
Abnormal materials are inevitably produced in the production of the lithium iron phosphate due to equipment failure or other reasons. Including oxidation during production, unbalanced raw material ratio, overburning and the like. In order to reduce the production loss to the maximum extent, the treatment method for recycling, doping and modifying the lithium iron phosphate material has simple process, and effectively recycles and resynthesizes the lithium iron phosphate material.
At present, lithium batteries are mostly recycled on anode materials with higher values, and the recycling routes are as follows:
direct calcination: for example, CN 200710129898.2, a recycling method of waste lithium iron phosphate power batteries, calcining a positive electrode material at 450-600 ℃ for 2-5 hours, adding an ethanol solution of ferric salt, mixing, calcining at 300-500 ℃ for 2-5 hours, and using nitrogen as a protective gas. The obtained lithium iron phosphate anode material has high cost and unstable material performance.
Dissolving: for example, CN 201010148325.6, a comprehensive recycling method for waste lithium iron phosphate batteries, which is to dissolve lithium iron phosphate with acid, remove copper ions with sodium sulfide, precipitate iron and lithium in the solution with NaOH or ammonia water, add an iron source, a lithium source or a phosphorus source compound to the precipitate to adjust the components of iron, lithium and phosphorus, add a carbon source, ball mill, and calcine in an inert atmosphere to obtain a new lithium iron phosphate positive electrode material. The cost is high, the pollution is large, meanwhile, the product consistency is difficult to ensure, and the industrialized recovery of the lithium iron phosphate can not be met.
Disclosure of Invention
The invention aims to solve the technical problem of providing a treatment method for recycling a lithium iron phosphate material with low pollution, so that the waste of resources is avoided, and the cost for preparing the lithium iron phosphate material is reduced.
The technical scheme of the invention is as follows:
a treatment method for low-pollution recycling of a lithium iron phosphate material specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive pole piece, a negative pole piece and a shell;
(2) respectively soaking the positive and negative electrode plates in a hot acid solution or an organic solution at the temperature of 80-100 ℃ and simultaneously ultrasonically loosening the material structure for 40-60min, then spraying and stripping the electrode plate material by using a high-pressure water gun, filtering to obtain leaching filtrate and filter residue, and melting, metallurgically recycling and reusing the stripped copper and aluminum electrode plates;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at the temperature of 450-600 ℃ for 60-90min, thereby removing carbon and other organic components;
(4) after the content of elements Fe, Li and P in the calcined material in the step (3) is detected, a Fe source, a Li source, a P source and a sugar source are supplemented according to the detection result, and an Mg source, a Ti source and a Mn source are added for doping, so that the ion transmission performance and the rate capability of the material are improved; wherein, the mol ratio of Fe, Li and P in the materials after supplementing Fe source, Li source and P source is Li: fe: p is 1-1.1:1:1.02-1.04, and the molar ratio of Fe element in the calcined material and the supplementary Fe source is 0.8-8;
(5) loosening the grain structure of the calcined material in the step (3) for 2-10h by using an acid solution with the weight percentage concentration of 1-5%, and adding the prepared supplementary material in the step (4) to obtain slurry;
(6) grinding the slurry proportioned in the step (5) by using a sand mill until the granularity D50 of the slurry is 0.35-0.5 mu m, then spraying, pelletizing and drying, and calcining the dried material in nitrogen at 700-790 ℃ for 8-12h to obtain the lithium iron phosphate material.
The hot acid solution in the step (2) is one or more than two acid solutions of oxalic acid, acetic acid, malic acid and citric acid, and the weight percentage concentration of the hot acid solution is 1-10%.
The organic solution in the step (2) is one or more than two of ethanol, glycol and alkylphenol polyoxyethylene, and the weight percentage concentration of the organic solution is 1-10%.
The ultrasonic power of the ultrasonic material loosening structure in the step (2) is 400-1000W, and the flow of the high-pressure water gun is 4-10L/min.
In the step (4), the Fe source is one or a mixture of two or more of iron phosphate, iron oxalate and iron oxide, the Li source is one or a mixture of two or more of lithium carbonate, lithium hydroxide and lithium phosphate, and the P source is one or a mixture of two or more of phosphoric acid, ammonium hydrogen phosphate and lithium phosphate.
In the step (4), the carbon source is one or a mixture of more than two of glucose, sucrose and starch, and the supplementary mass of the sugar source is 7-15% of the total mass of reactants after Li, Fe and P are supplemented.
In the step (4), the Mg source is one or a mixture of more than two of magnesium carbonate, magnesium acetate and magnesium phosphate, the Ti source is one or a mixture of more than two of titanium dioxide, titanic acid and butyl titanate, and the Mn source is one or a mixture of more than two of trimanganese tetroxide, manganese acetate and manganese carbonate; the Mg source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented, the Ti source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented, and the Mn source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented.
The acid solution with the weight percentage concentration of 1-5% in the step (5) is one or a mixed solution of more than two of oxalic acid, acetic acid, malic acid and citric acid.
The solid content of the slurry obtained in the step (5) is 30-35%.
The invention has the advantages that:
(1) the lithium iron phosphate mixed material is obtained by a combined method of soaking in a hot acid solution, ultrasonic wave loosening and high-pressure water gun stripping, and has a good combination effect and high efficiency; impurities introduced into the separated material are less, copper impurities and the like are less introduced compared with a mechanical separation mode, and the copper impurities are key control items of the impurities of the positive electrode material; meanwhile, the pollution is reduced, organic matters can be burnt into carbon, the recovery and the reutilization are convenient, and the stripped copper and aluminum pole pieces are also convenient to be melted again, metallurgically recovered and reused;
(2) the method comprises the following steps of calcining the anode filter residue in the air to remove C and other organic impurities in the material, loosening a grain structure of the calcined material by using an acid solution, wherein the grain structure of the material is compacted due to calcination, so that the directly-reproduced lithium iron phosphate material has high internal resistance, such as citric acid and the like, has a certain chelation effect, the grains can be loosened by using a proper amount of the acid solution (but a large amount of the acid solution can damage the structural performance of the material), supplementing raw materials to participate in reaction to play a role in guiding reaction and grain growth, doping Mg to improve ion transmission, doping Mn and Ti to prevent the material from being over-burnt and improve the cycle performance of the material;
(3) the treatment method is simple to operate, the waste lithium iron phosphate battery is recycled and utilized as a qualified lithium iron phosphate finished product, the pollution is low, the conversion rate is high, and the performance is good and stable.
Drawings
FIG. 1 is a processing device for processing positive and negative plates to obtain a lithium iron phosphate mixed material, and the device comprises an ultrasonic emitter 1, an upper high-pressure water gun 2, a lower high-pressure water gun 3, a hot acid solution or an organic solution 4, a positive plate or a negative plate 5, a filtrate discharge port 6 and a transmission roller 7.
Figure 2 is an electrical property diagram of examples 1-3 of the present invention.
FIG. 3 is an XRD pattern of the calcined materials of examples 1-3 of the present invention.
Figure 4 is a finished XRD pattern of examples 1-3 of the present invention.
FIG. 5 is a SEM photograph of a finished product of example 1 of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A treatment method for low-pollution recycling of a lithium iron phosphate material specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive electrode plate, a negative electrode plate and a shell, and directly recycling the shell;
(2) respectively soaking positive and negative electrode plates 5 in 10 wt% citric acid solution 4 at 80 ℃ and simultaneously releasing the material structure by using an ultrasonic emitter 1 to emit 1000W ultrasonic power for 40min, stripping the materials on the positive and negative electrode plates 5 by using upper and lower high-pressure water guns 2 and 3 (with the flow rate of 3L/min), filtering to obtain leaching filtrate and filter residues, allowing the filtrate to flow out from an aluminum liquid discharge port 6 for recycling, and melting, metallurgically recycling the stripped copper and aluminum electrode plates;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at 450 ℃ for 90min, thereby removing carbon and other organic components;
(4) and (3) detecting the contents of elements Fe, Li and P in the calcined material obtained in the step (3), and obtaining the molar ratio of the three elements Fe, Li and P in the calcined material as Li: Fe: 1.0744 and Fe: supplementing iron phosphate, lithium carbonate and glucose according to the detection result, and adding magnesium acetate, titanium dioxide and manganous-manganic oxide for doping, so as to improve the ion transmission performance and rate capability of the material; wherein the molar ratio of Fe, Li and P in the material supplemented with the iron phosphate and the lithium carbonate is Li: fe: p is 1:1:1.02, the molar ratio of Fe in the calcined material to the supplemented iron phosphate is 5, the supplemented mass of glucose is 7% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, magnesium acetate is 0.1% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, titanium dioxide is 5% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, and manganous oxide is 0.2% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate;
(5) loosening the grain structure of the calcined material in the step (3) for 10 hours by using a citric acid solution with the weight percentage concentration of 1%, and then adding the prepared supplementary material in the step (4), wherein pure water is used as a medium to obtain slurry with the solid content of 30%;
(6) and (3) stirring the slurry proportioned in the step (5) for 2h, grinding the slurry by using a sand mill until the granularity D50 of the slurry is 0.35 mu m, spraying, pelletizing and drying, and calcining the dried material in nitrogen at 700 ℃ for 12h to obtain the lithium iron phosphate material.
5) And (3) after the calcined material in the step 4) is subjected to grain structure loosening for 10 hours by using 1 wt% of citric acid solution, adding the prepared raw material, taking pure water as a medium, grinding the slurry to obtain a particle size D500.35 micrometers by using a sand mill, then performing spray drying, and calcining the dried material in nitrogen at 700 ℃ for 12 hours to obtain the lithium iron phosphate anode material.
Example 2
A treatment method for low-pollution recycling of a lithium iron phosphate material specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive electrode plate, a negative electrode plate and a shell, and directly recycling the shell;
(2) respectively placing the positive and negative electrode plates in 100 ℃ glycol solution with the weight percentage concentration of 1% for soaking, simultaneously using 400W ultrasonic power to release the material structure for 60min, peeling the materials on the positive and negative electrode plates by using a high-pressure water gun (with the flow rate of 10L/min), filtering to obtain leached filtrate and filter residues, recycling the filtrate, and recycling the peeled copper and aluminum electrode plates by melting metallurgy;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at 600 ℃ for 60min, thereby removing carbon and other organic components;
(4) and (3) detecting the contents of elements Fe, Li and P in the calcined material obtained in the step (3), and obtaining the molar ratio of the three elements Fe, Li and P in the calcined material as Li: Fe: 1.0744 and Fe: supplementing iron phosphate, lithium carbonate and glucose according to the detection result, and adding magnesium acetate, titanium dioxide and manganous-manganic oxide for doping, so as to improve the ion transmission performance and rate capability of the material; wherein the molar ratio of Fe, Li and P in the material supplemented with the iron phosphate and the lithium carbonate is Li: fe: p is 1.02:1:1.03, the molar ratio of Fe in the calcined material to the supplemented iron phosphate is 3, the supplemented mass of glucose is 15% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, magnesium acetate is 5% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, titanium dioxide is 0.1% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate, and mangano-manganic oxide is 0.2% of the total mass of the reactants supplemented by the iron phosphate and the lithium carbonate;
(5) loosening the grain structure of the material calcined in the step (3) for 2 hours by using oxalic acid solution with the weight percentage concentration of 5%, and then adding the supplement material proportioned in the step (4), wherein pure water is used as a medium to obtain slurry with the solid content of 35%;
(6) and (3) stirring the slurry proportioned in the step (5) for 2 hours, grinding the slurry by using a sand mill until the granularity D50 of the slurry is 0.5 mu m, spraying, pelletizing and drying, and calcining the dried material in nitrogen at 790 ℃ for 8 hours to obtain the lithium iron phosphate anode material.
Example 3
A treatment method for low-pollution recycling of a lithium iron phosphate material specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive electrode plate, a negative electrode plate and a shell, and directly recycling the shell;
(2) respectively placing the positive and negative electrode plates in 90 ℃ alkylphenol polyoxyethylene ether solution with the weight percentage concentration of 5% for soaking, simultaneously using 900W ultrasonic power to release the material structure for 50min, peeling the materials on the positive and negative electrode plates by using a high-pressure water gun (with the flow rate of 6L/min), filtering to obtain leached filtrate and filter residues, recycling the filtrate, and recycling the peeled copper and aluminum electrode plates by melting metallurgy;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at 500 ℃ for 70min, thereby removing carbon and other organic components;
(4) and (3) detecting the contents of elements Fe, Li and P in the calcined material obtained in the step (3), and obtaining the content of the elements Fe, Li and P in the calcined material, wherein the molar ratio of the three elements Li to Fe is 0.954, and the molar ratio of Fe to P is Fe: supplementing ferric oxalate, lithium phosphate and starch according to a detection result, and adding magnesium acetate, butyl titanate and manganese acetate for doping, so that the ion transmission performance and the rate capability of the material are improved; wherein, the molar ratio of Fe, Li and P in the material supplemented with ferric oxalate and lithium phosphate is Li: fe: p is 1.1:1:1.04, the molar ratio of Fe in the calcined material to the supplemented ferric oxalate is 8, the supplemented mass of starch is 10% of the total mass of the reactants after the ferric oxalate and the lithium phosphate are supplemented, magnesium acetate is 1% of the total mass of the reactants after the ferric oxalate and the lithium phosphate are supplemented, butyl titanate is 0.1% of the total mass of the reactants after the ferric oxalate and the lithium phosphate are supplemented, and manganese acetate is 5% of the total mass of the reactants after the ferric oxalate and the lithium phosphate are supplemented;
(5) loosening the grain structure of the calcined material in the step (3) for 2 hours by using an acetic acid solution with the weight percentage concentration of 2%, and then adding the prepared supplementary material in the step (4), wherein pure water is used as a medium to obtain slurry with the solid content of 32%;
(6) and (3) stirring the slurry proportioned in the step (5) for 2 hours, grinding the slurry by using a sand mill until the granularity D50 of the slurry is 0.45 mu m, spraying, pelletizing and drying, and calcining the dried material in nitrogen at 750 ℃ for 10 hours to obtain the lithium iron phosphate anode material.
Example 4
A treatment method for low-pollution recycling of a lithium iron phosphate material specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive electrode plate, a negative electrode plate and a shell, and directly recycling the shell;
(2) respectively placing the positive and negative electrode plates in 90 ℃ alkylphenol polyoxyethylene ether solution with the weight percentage concentration of 2% for soaking, simultaneously using 700W ultrasonic power to release the material structure for 50min, peeling the materials on the positive and negative electrode plates by using a high-pressure water gun (with the flow rate of 5L/min), filtering to obtain leached filtrate and filter residues, recycling the filtrate, and recycling the peeled copper and aluminum electrode plates by melting metallurgy;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at 480 ℃ for 80min, thereby removing carbon and other organic components;
(4) and (3) detecting the contents of elements Fe, Li and P in the calcined material obtained in the step (3), and obtaining the molar ratio of the three elements Fe, Li and P in the calcined material as Li, Fe is 1.024, Fe: supplementing ferric oxalate, lithium phosphate and cane sugar according to a detection result, and adding magnesium acetate, butyl titanate and manganese acetate for doping, so that the ion transmission performance and the rate capability of the material are improved; wherein, the molar ratio of Fe, Li and P in the material supplemented with ferric oxalate and lithium phosphate is Li: fe: p is 1.04:1:1.03, the molar ratio of Fe in the calcined material to the supplemented ferric oxalate is 0.8, the supplemented mass of sucrose is 8% of the total mass of the reactants after the supplementation of ferric oxalate and lithium phosphate, magnesium acetate is 2% of the total mass of the reactants after the supplementation of ferric oxalate and lithium phosphate, butyl titanate is 3% of the total mass of the reactants after the supplementation of ferric oxalate and lithium phosphate, and manganese acetate is 5% of the total mass of the reactants after the supplementation of ferric oxalate and lithium phosphate;
(5) loosening the grain structure of the material calcined in the step (3) for 2 hours by using a malic acid solution with the weight percentage concentration of 2%, and then adding the supplement material proportioned in the step (4), wherein pure water is used as a medium to obtain slurry with the solid content of 32%;
(6) and (3) stirring the slurry proportioned in the step (5) for 2h, grinding the slurry by using a sand mill until the granularity D50 of the slurry is 0.4 mu m, spraying, pelletizing and drying, and calcining the dried material in nitrogen at 770 ℃ for 9h to obtain the lithium iron phosphate anode material.
Preparing the lithium iron phosphate positive electrode material obtained in the embodiment 1-3 into a semi-finished battery according to a mass ratio, wherein the lithium iron phosphate positive electrode material in the semi-finished battery is as follows: SP: PVDF 8:1:1, and the semi-finished cell was subjected to 0.2C, 1C charge/discharge tests, and the test results are shown in fig. 2. And the first charge and discharge efficiency (first charge and discharge efficiency ═ first discharge capacity/first charge capacity) was obtained from the data in fig. 2. The results of the power-off test are shown in Table 1.
TABLE 1
See FIG. 3, calcined material and Li3Fe2(PO4)3The standard spectrum of the material is close to that of the calcined material (450/600/500 ℃) and Li3Fe2(PO4)3If there is a peak not consistent with Li3Fe2(PO4)3、Fe2O3Partial peak coincidence, i.e. a portion of Li3Fe2(PO4)3Not converted, some of the Fe is oxidized to Fe2O3。
Referring to fig. 4, the lithium iron phosphate cathode material prepared in examples 1 to 3 has a standard lithium iron phosphate spectrum, and the lower vertical line in fig. 4 is a standard spectrum peak line.
As shown in fig. 5, it can be seen that the grains on the prepared lithium iron phosphate cathode material in the spheroidal structure are similar to spherical grains, the sizes of the grains are uniformly distributed as a whole, and individual large grains can be seen.
In summary, when the raw materials such as iron phosphate are not added at all, the improvement is not good, but a large amount of raw materials are added, like when the normal raw materials are used for synthesizing the lithium iron phosphate, impurities (calcined materials) are also added, so that the mutual influence is caused, and the electrical property of the material is not as good as that of the pure raw materials by direct synthesis.
The carbon removing material contains more hard particles, which is not beneficial to production and processing, the structure of the carbon removing material is considered to be firstly loosened by using the acid solution, the material processing is facilitated, meanwhile, the crystal grain appearance of the carbon removing material can be changed by the acid solution, the desired structural performance of the lithium iron phosphate is facilitated to be obtained, and the carbon removing material can also be used as a partial carbon source and is additionally supplemented with the carbon source. Considering that the carbon material is removed by the pretreatment of citric acid, the carbon material is used as a partial carbon source while the structure is loosened, the more the acid solution is, the poorer the electrical property of the lithium iron phosphate material is, and the lithium iron phosphate material obtained by the experiment after the treatment of the acid solution with the weight percentage concentration of 1-5% has better electrical property and smaller internal resistance.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A treatment method for low-pollution recycling of lithium iron phosphate materials is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) discharging, disassembling and separating the waste lithium iron phosphate battery to obtain a positive pole piece, a negative pole piece and a shell;
(2) respectively soaking the positive and negative electrode plates in a hot acid solution or an organic solution at the temperature of 80-100 ℃ and simultaneously ultrasonically loosening the material structure for 40-60min, then spraying and stripping the electrode plate material by using a high-pressure water gun, filtering to obtain leaching filtrate and filter residue, and melting, metallurgically recycling and reusing the stripped copper and aluminum electrode plates;
(3) calcining the anode filter residue obtained in the step (2), namely the lithium iron phosphate mixed material, in the air at the temperature of 450-600 ℃ for 60-90min, thereby removing carbon and other organic components;
(4) after the content of elements Fe, Li and P in the calcined material in the step (3) is detected, a Fe source, a Li source, a P source and a sugar source are supplemented according to the detection result, and an Mg source, a Ti source and a Mn source are added for doping, so that the ion transmission performance and the rate capability of the material are improved; wherein, the mol ratio of Fe, Li and P in the materials after supplementing Fe source, Li source and P source is Li: fe: p is 1-1.1:1:1.02-1.04, and the molar ratio of Fe element in the calcined material and the supplementary Fe source is 0.8-8;
(5) loosening the grain structure of the calcined material in the step (3) for 2-10h by using an acid solution with the weight percentage concentration of 1-5%, and adding the prepared supplementary material in the step (4) to obtain slurry;
(6) grinding the slurry proportioned in the step (5) by using a sand mill until the granularity D50 of the slurry is 0.35-0.5 mu m, then spraying, pelletizing and drying, and calcining the dried material in nitrogen at 700-790 ℃ for 8-12h to obtain the lithium iron phosphate material.
2. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: the hot acid solution in the step (2) is one or more than two acid solutions of oxalic acid, acetic acid, malic acid and citric acid, and the weight percentage concentration of the hot acid solution is 1-10%.
3. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: the organic solution in the step (2) is one or more than two of ethanol, glycol and alkylphenol polyoxyethylene, and the weight percentage concentration of the organic solution is 1-10%.
4. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: the ultrasonic power of the ultrasonic material loosening structure in the step (2) is 400-1000W, and the flow of the high-pressure water gun is 4-10L/min.
5. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: in the step (4), the Fe source is one or a mixture of two or more of iron phosphate, iron oxalate and iron oxide, the Li source is one or a mixture of two or more of lithium carbonate, lithium hydroxide and lithium phosphate, and the P source is one or a mixture of two or more of phosphoric acid, ammonium hydrogen phosphate and lithium phosphate.
6. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: in the step (4), the carbon source is one or a mixture of more than two of glucose, sucrose and starch, and the supplementary mass of the sugar source is 7-15% of the total mass of reactants after Li, Fe and P are supplemented.
7. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: in the step (4), the Mg source is one or a mixture of more than two of magnesium carbonate, magnesium acetate and magnesium phosphate, the Ti source is one or a mixture of more than two of titanium dioxide, titanic acid and butyl titanate, and the Mn source is one or a mixture of more than two of trimanganese tetroxide, manganese acetate and manganese carbonate; the Mg source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented, the Ti source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented, and the Mn source accounts for 0.1-5% of the total mass of the reactants after Li, Fe and P are supplemented.
8. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: the acid solution with the weight percentage concentration of 1-5% in the step (5) is one or a mixed solution of more than two of oxalic acid, acetic acid, malic acid and citric acid.
9. The processing method for low-pollution recycling of lithium iron phosphate materials according to claim 1, characterized in that: the solid content of the slurry obtained in the step (5) is 30-35%.
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| CN114180546A (en) * | 2021-12-30 | 2022-03-15 | 江西赣锋循环科技有限公司 | Method for preparing anhydrous iron phosphate from titanium-containing lithium iron phosphate waste |
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