CN116177510B - Method for preparing battery-grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder - Google Patents
Method for preparing battery-grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder Download PDFInfo
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- CN116177510B CN116177510B CN202211608389.9A CN202211608389A CN116177510B CN 116177510 B CN116177510 B CN 116177510B CN 202211608389 A CN202211608389 A CN 202211608389A CN 116177510 B CN116177510 B CN 116177510B
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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 82
- 238000000034 method Methods 0.000 title claims abstract description 64
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 62
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 61
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 61
- 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 61
- 239000000843 powder Substances 0.000 title claims abstract description 50
- 239000002699 waste material Substances 0.000 title claims abstract description 50
- 238000002386 leaching Methods 0.000 claims abstract description 126
- 239000012535 impurity Substances 0.000 claims abstract description 69
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002893 slag Substances 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- 238000004090 dissolution Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 229940116007 ferrous phosphate Drugs 0.000 claims description 8
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 8
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- 230000033116 oxidation-reduction process Effects 0.000 claims description 5
- 238000011946 reduction process Methods 0.000 claims description 5
- 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 4
- 239000008103 glucose Substances 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 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 53
- 229910052744 lithium Inorganic materials 0.000 abstract description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 27
- 229910000398 iron phosphate Inorganic materials 0.000 abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 17
- 239000010949 copper Substances 0.000 abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052802 copper Inorganic materials 0.000 abstract description 14
- 229910052759 nickel Inorganic materials 0.000 abstract description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 11
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010936 titanium Substances 0.000 abstract description 6
- 229910052719 titanium Inorganic materials 0.000 abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 229910052742 iron Inorganic materials 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 9
- 238000004064 recycling Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 150000004763 sulfides Chemical class 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for preparing battery-grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder. According to the method, waste lithium iron phosphate battery anode powder is used as a raw material, firstly, two-stage leaching is adopted to leach out lithium preferentially, meanwhile, most of copper, aluminum, nickel and other impurities affecting the quality of ferric phosphate are leached out, the pH value of a leaching end point is controlled to enrich the ferric phosphate in leaching residues, then the leaching residues are leached out of ferric phosphate by sulfuric acid, ferric iron is reduced to ferrous iron, the pH value is adjusted to be high, impurities such as aluminum and titanium are removed, sulfide is added to remove impurities deeply, a small amount of precipitation of ferrous iron is carried out to carry out impurity coprecipitation, most of the impurities remain in solution, and therefore, the effective impurity removal of an iron phosphate solution is realized.
Description
Technical Field
The invention relates to a method for recycling waste lithium iron phosphate battery positive electrode powder, in particular to a method for obtaining battery-grade ferric phosphate by removing aluminum and other metal impurities from waste lithium iron phosphate battery positive electrode powder raw materials, and belongs to the technical field of comprehensive recycling of waste lithium iron phosphate batteries.
Background
In China, electric automobiles are popularized and applied from 2009, and over 10 years, power batteries successively enter a large-scale scrapping period, valuable elements in waste lithium batteries are recovered, and considerable economic benefits and investment opportunities are generated while resource waste and environmental pollution are avoided.
The lithium iron phosphate battery is one of automobile power batteries, and the share of the lithium iron phosphate battery in the automobile power battery is continuously increased due to the safety and the relative economy, and the scrapping amount of the lithium iron phosphate battery is increased year by year, so that valuable elements are recovered from the anode powder of the waste lithium iron phosphate battery, and the lithium iron phosphate battery has important significance.
At present, the method aims at the disposal of wasteThere are many techniques for recovering lithium from the old lithium iron phosphate positive electrode powder, but there are relatively few techniques for recovering iron phosphate, and there are fewer techniques for how to remove impurities from the ferrophosphorus solution to obtain a qualified ferrophosphorus solution for producing battery grade iron phosphate. For example, nonferrous metals (smelting part), such as "iron lithium waste preparation of battery grade lithium carbonate and iron phosphate Process research", zhou Youchi et al; 2019, 04, volume 3) disclose dissolving the phosphorus iron slag after preferential lithium extraction with HC1, and then using Na 2 CO 3 FePO preparation by adjusting pH of ferrophosphorus liquid 4 ·2H 2 O, but there is no mention of how to remove impurities in the ferrophosphorus solution. ("precipitation method for recovering iron and lithium in waste lithium iron phosphate battery", han Xiaoyun et al, guangdong chemical industry, 2017, 4 th edition, volume 44) discloses that the concentration of sulfuric acid is 4mol/L, H 2 O 2 The dosage is 100g/L, the liquid-solid ratio (ml/g) is 10, lithium and iron are leached at the same time under the condition of the reaction temperature of 60 ℃, then the pH value of the leaching solution is adjusted to 3, the ferric phosphate is recovered by precipitation, no targeted impurity removal measures are provided, the quality of the ferric phosphate is not ensured, and the crude ferric phosphate product is obtained. Chinese patent (publication No. CN106450547 a) discloses a method for recovering iron phosphate and lithium carbonate from lithium iron phosphate waste, which proposes adding phosphoric acid into a positive active material for activation ball milling, then adding sulfuric acid for acid washing to obtain insoluble iron phosphate and a washing solution containing lithium, and recovering lithium carbonate from the washing solution. From the process, the iron phosphate product contains carbon powder, aluminum, nickel, copper, calcium, titanium and the like which are not completely dissolved, and is not subjected to impurity removal. Chinese patent (publication No. CN 106684485B) discloses a method for recycling waste lithium iron phosphate anode materials by an acid leaching method, and specifically discloses a method for obtaining a lithium iron phosphate solution by acid leaching, adding an oxidant for oxidation, adjusting the pH value of the solution to be 1.5-4, and reacting at 60-95 ℃ to obtain a ferric phosphate precipitate without impurity removal process. Chinese patent (publication No. CN 111675203B) discloses a method for recovering lithium and ferric phosphate from waste lithium iron phosphate batteries, and specifically discloses a method for preparing battery-grade ferric phosphate by obtaining ferric phosphate slag after preferential leaching of lithium, adding sulfuric acid or phosphoric acid for dissolution to obtain ferric phosphate, adsorbing aluminum by using macroporous strong acid cation exchange resin, and then adjusting the ratio of ferric phosphate in the solution to 1:1. Chinese patent (publication No. CN 106684485A) disclosesThe method uses waste lithium iron phosphate anode materials as raw materials, and comprises the steps of acid leaching, filtering, oxidizing filtrate by adding an oxidant, adding a surfactant, adjusting the pH value of the solution, and reacting at a certain temperature to generate ferric phosphate precipitates and lithium-containing filtrate. Chinese patent (publication No. CN 113772649A) discloses a method for preparing battery grade ferric phosphate from waste lithium iron phosphate black powder, which comprises the steps of selectively leaching valuable metal lithium from waste lithium iron phosphate positive electrode material by using acid and hydrogen peroxide, leaching iron into a solution by sulfuric acid to obtain iron-rich leaching solution, synthesizing hydrated ferric phosphate by adjusting pH, and roasting to obtain ferric orthophosphate, wherein no impurity in the ferrophosphorus solution is proposed. Chinese patent (publication No. CN 113443640A) discloses a method for recycling and preparing lithium carbonate and ferric phosphate from waste lithium iron phosphate black powder, which comprises the following steps: mixing lithium iron phosphate positive and negative waste powder with water to prepare slurry, heating, adding inorganic acid, oxidant and regulator A, reacting, filtering and washing to obtain lithium-containing solution and ferrophosphorus slag; deep impurity removal is carried out on the lithium-containing solution, and the obtained high-concentration lithium solution is used as a raw material to prepare a battery-grade lithium carbonate product; mixing the ferrophosphorus slag with water to prepare slurry, heating, adding inorganic acid, oxidant and regulator B for reaction, filtering and washing to obtain ferrophosphorus solution; after deep impurity removal is carried out on the ferrophosphorus solution, a battery grade ferric phosphate product is prepared, and the process operation and parameters of the deep impurity removal are not given.
In summary, there are many techniques for recovering lithium and iron phosphate from waste lithium iron phosphate positive electrode powder, but for recovering iron phosphate, it is basically a crude iron phosphate product, and no method is given for removing impurities in the ferrophosphorus solution to prepare battery grade iron phosphate.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a method for preparing battery grade ferric phosphate by using waste lithium iron phosphate battery positive electrode powder, which takes waste lithium iron phosphate battery positive electrode powder as a raw material, and solves the problem that part of impurities are difficult to reach standards in the preparation process of battery grade ferric phosphate by preferentially leaching lithium and dissolving out most of copper, aluminum, nickel and other impurities affecting the quality of ferric phosphate, dissolving out ferric phosphate and converting ferric iron into ferrous iron, and then sequentially carrying out hydrolysis to remove the impurities such as aluminum, titanium and the like and the impurity removal of vulcanization depth.
In order to achieve the technical aim, the invention provides a method for preparing battery grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder, which comprises the following steps:
1) The method comprises the steps of (1) carrying out oxidation acid leaching on waste lithium iron phosphate battery anode powder, wherein the pH value of a leaching end point is 1.5-2.0, and the oxidation-reduction potential is 400-550 mV, so as to obtain a leaching solution I and ferrophosphorus slag I;
2) Leaching the ferrophosphorus slag I by acid, wherein the pH value of the leaching end point is 0.5-1.0, so as to obtain leaching liquid II and ferrophosphorus slag II;
3) Dissolving the ferrophosphorus slag II by adopting acid, wherein the pH value of the dissolution end point is 0.1-0.7, and obtaining ferric phosphate solution and impurity enriched slag;
4) Reducing the ferric phosphate solution, wherein the potential of a reduction end point is controlled to be-100 mV, so as to obtain a ferrous phosphate solution;
5) And sequentially carrying out water impurity removal and vulcanization impurity removal on the ferrous phosphate solution to obtain the ferrous phosphate solution meeting the preparation requirements of the battery-grade ferric phosphate.
The battery grade ferric phosphate has higher requirements on impurity content: ca (Ca) 2+ 、Mg 2+ 、Al 3+ 、Cu 2+ 、Ni 2+ 、Zn 2+ The mass percentage content of the components is less than or equal to 0.005 percent, K + 、Na + 、Cl - 、SO 4 2- The mass percentage content of the catalyst is less than or equal to 0.01 percent. K (K) + 、Na + 、Cl - 、SO 4 2- Is water-soluble and can be easily removed by washing, ca 2+ 、Mg 2+ 、Al 3+ 、Cu 2+ 、Ni 2+ 、Zn 2+ And the like, must be reduced to a suitable level prior to precipitation of the iron phosphate to produce a acceptable battery grade iron phosphate product. The prior art can not thoroughly separate the waste lithium iron phosphate anode powder, and the grade of lithium is greatly reducedThe lithium iron phosphate anode powder is doped with a large amount of impurities such as aluminum, copper, nickel, manganese, cobalt, niobium, titanium and the like, for example, the composition (mass percentage content) of the waste lithium iron phosphate anode powder is shown in table 1.
TABLE 1 composition of waste lithium iron phosphate Positive electrode powder
The technical scheme of the invention adopts a two-stage leaching method to realize preferential lithium extraction, and simultaneously, impurities such as copper, aluminum, nickel, manganese, zinc and the like which influence the quality of ferric phosphate can be leached out as much as possible while the preferential lithium extraction is realized, the leaching rate of lithium is 95-98%, the leaching rate of copper is 80-90%, the leaching rate of nickel is more than 95%, and the leaching rate of aluminum is 60%. In the two-stage leaching process, the pH and oxidation potential are strictly controlled in one stage of leaching, so that most of lithium leaching is ensured, valuable metals such as copper, aluminum and the like except iron are leached as much as possible, the lithium concentration in the leaching liquid I is high, the leaching liquid I can be directly used for recycling lithium to obtain a lithium carbonate product, and other valuable metals can be recycled by adopting the conventional method. The second stage leaching is mainly carried out by acidity, so that a small amount of lithium and residual valuable metals can be further leached, the purity of the ferrophosphorus slag II is mainly improved, the concentration of the lithium and other valuable metals in the leaching liquid II is lower, the leaching liquid II has higher acidity, and the leaching liquid II can return to the next stage leaching process, thereby realizing the recycling of acid and the further enrichment of various valuable metals. Although the two-stage leaching can leach lithium with high efficiency and dissolve most of copper, aluminum, nickel, manganese, zinc and other impurities, the ferrophosphorus leaching solution still contains copper, aluminum, nickel, manganese, zinc, titanium, niobium, calcium, magnesium and other impurities affecting the quality of ferric phosphate, and the impurities need to be removed to a proper level before ferric phosphate is precipitated. In the impurity removal process, firstly, insoluble impurities are filtered and separated by adopting an acid dissolution means, the hydrolysis pH based on ferric iron is lower, precipitation can occur at about pH=1.5, the precipitation is complete at about pH=3, and the pH at which ferrous iron begins to precipitate is far higher than that of ferric iron, so that ferric iron is reduced and converted into ferrous iron, and a great amount of precipitation loss of generated iron is avoided. And finally, adding sulfides, copper, nickel, cobalt, zinc, manganese and the like to generate water-insoluble sulfides and weak acid for removing, and removing calcium and magnesium to generate phosphates, and removing the phosphates by coprecipitation with a small amount of ferric phosphate or ferrous phosphate, wherein the finally obtained ferrous phosphate solution is high-purity, the concentration of various impurity metal ions is low, and the preparation requirement of battery-grade ferric phosphate is met.
As a preferable scheme, in the oxidation acid leaching process, concentrated sulfuric acid is used as a leaching agent, hydrogen peroxide is used as an oxidant, and the addition amount of the concentrated sulfuric acid is 10-40% of the mass of the anode powder of the waste lithium iron phosphate battery. The hydrogen peroxide is a green oxidant, so that the introduction of impurity ions can be reduced, and the sulfuric acid and the hydrogen peroxide are combined to be used, so that metals such as copper and the like which are difficult to leach out can be leached out.
As a preferable scheme, the conditions of the oxidation acid leaching are as follows: the liquid-solid ratio L/S=3 mL/1 g-4 mL/1g, the leaching temperature is 40-80 ℃ and the leaching time is 20-60 min. Under the preferential oxidation acid leaching condition, by controlling the end point pH and oxidation-reduction potential, efficient selective leaching of lithium and most of copper, aluminum, nickel, manganese, zinc and other impurities can be realized, while ferric phosphate is enriched in a slag phase, and proper heating conditions can accelerate the leaching process, and excessive temperature easily causes iron loss.
As a preferable scheme, in the acid leaching process, concentrated sulfuric acid is used as a leaching agent, and the adding amount of the concentrated sulfuric acid is 5-20% of the mass of the positive electrode powder of the waste lithium iron phosphate battery.
As a preferable scheme, the conditions of the acid leaching are as follows: the liquid-solid ratio L/S=3 mL/1 g-4 mL/1g, the leaching temperature is 40-80 ℃ and the leaching time is 20-60 min. Under the preferable acid leaching condition, the further leaching of valuable metals such as lithium in the ferrophosphorus slag can be realized by controlling the end-point pH value, and the purity of the ferrophosphorus slag is improved.
As a preferable scheme, in the acid dissolution process, concentrated sulfuric acid or concentrated hydrochloric acid is used as a dissolution agent, and the mass of the dissolution agent is 5-15% of that of the waste lithium iron phosphate battery anode powder.
As a preferred embodiment, the acid-soluble conditions are: the liquid-solid ratio L/S=3 mL/1 g-4 mL/1g, the leaching temperature is 40-80 ℃ and the leaching time is 30-60 min. In the acid dissolution, the pH at the dissolution end point is preferably 0.1 to 0.4.
As a preferable scheme, at least one of hydrazine hydrate, glucose and formaldehyde is adopted as a reducing agent in the reduction process. The simple substance iron powder is usually selected as the reducing agent, but the iron content in the solution is increased, so that the iron-phosphorus ratio is seriously out of balance, and therefore, a phosphorus source needs to be supplemented, so that the iron-phosphorus ratio is re-balanced, the method is equivalent to that the newly supplemented iron source and the phosphorus source are used for preparing battery grade ferric phosphate in a system containing a large amount of impurities, and the high-purity phosphorus source is relatively expensive, so that the iron is unreasonable as the reducing agent.
As a preferable scheme, the conditions of the hydrolysis impurity removal are as follows: the pH value is regulated to 3.5-5.0, the temperature is 60-90 ℃ and the time is 10-60 min. In the hydrolysis precipitation process by adjusting the pH, niobium, titanium, etc. are preferentially hydrolyzed and removed, and when the pH is further raised to about 4, aluminum is precipitated and removed to form aluminum phosphate.
As a preferable scheme, the conditions for vulcanization impurity removal are as follows: the vulcanizing salt is used as a vulcanizing agent, the temperature is 60-90 ℃, and the time is 10-60 min. Sulfide salts such as sodium sulfide, ammonium sulfide, etc., which do not introduce new impurities.
The invention provides a method for preparing battery-grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder, which comprises the following steps:
1) The method adopts a two-stage countercurrent leaching mode, lithium in the raw materials is leached preferentially, and the one-stage leaching conditions are as follows: the liquid-solid ratio (volume weight ratio) is L/S=3/1-4/1, the dosage of the concentrated sulfuric acid is based on the pH value of the reaction end point of 1.5-2.0, the reaction temperature is 40-80 ℃, and the reaction time is 20-60 min. The oxidant is hydrogen peroxide (commercial industrial hydrogen peroxide), and the addition amount is controlled by controlling the end oxidation reduction potential to be 400-550 mv; two-stage leaching conditions: the liquid-solid ratio L/S=3/1-4/1, the dosage of the concentrated sulfuric acid is based on the pH value of the reaction end point of 0.5-1.0, no oxidant is added, the reaction temperature is 40-80 ℃, and the reaction time is 20-60 min; the leaching rate of lithium is 95-98%, the leaching rate of iron and phosphorus is less than 1%, the leaching rate of copper is 80-90%, the leaching rate of nickel is more than 95%, and the leaching rate of aluminum is 60%.
2) Dissolving phosphorus-containing iron leaching slag by sulfuric acid or hydrochloric acid, wherein the acid consumption is 5-15% of the initial black powder adding amount, the pH value of a reaction end point is 0.1-0.7, the liquid-solid ratio (the ratio of the volume of leaching liquid to the initial black powder adding mass) is L/S=3/1-4/1, no oxidant is added, the reaction temperature is 40-80 ℃, and the reaction time is 30-60 min;
3) Reducing ferric iron into ferrous iron by adding a reducing agent, wherein the reducing agent is hydrazine hydrate, glucose, formaldehyde and the like, and the potential after reduction is controlled to be-100 mv;
4) Adding alkali to adjust the pH value to remove impurities, wherein the alkali is sodium hydroxide solution or ammonia water solution, preferably ammonia water, and the dosage is that the pH value is adjusted to 3.5-5.0, the temperature is 60-90 ℃ and the time is 10-60 min;
5) The sulfide is sodium sulfide or ammonium sulfide, preferably ammonium sulfide, the dosage is 0.1-0.5% of the volume of the ferrophosphorus solution, the temperature is 60-90 ℃ and the time is 10-60 min, and the precipitate is filtered and separated to obtain qualified ferrophosphorus solution for subsequent preparation of battery grade ferric phosphate.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) The method of the invention not only can realize the recovery of lithium, copper, aluminum, nickel and other valuable metals in the positive electrode powder of the waste lithium iron phosphate battery, but also can obtain battery-grade ferric phosphate, thereby realizing the resource utilization of the waste lithium iron phosphate battery.
2) According to the method, lithium is preferentially extracted through two leaching processes, residual acid and oxidation-reduction potential in the two leaching processes are accurately controlled, so that ferrophosphorus enters leaching residues, and lithium and most impurities selectively enter the leaching solution, and the difficulty and the workload of impurity removal in the subsequent iron phosphate preparation process are reduced.
3) The method of the invention reduces and converts ferric iron into ferrous iron, and then carries out water impurity removal and sulfuration impurity removal, thereby avoiding a great deal of precipitation loss of pig iron generated by improving the pH in the impurity removal process.
4) The method of the invention can realize deep impurity removal through acid dissolution, reduction, hydrolysis and vulcanization of the ferrophosphorus slag,Ca 2 + 、Mg 2+ 、Al 3+ 、Cu 2+ 、Ni 2+ 、Zn 2+ the concentration of the plasma metal ions reaches the preparation standard of the battery-grade ferric phosphate.
Drawings
Fig. 1 is a process flow diagram of preparing battery grade iron phosphate from waste lithium iron phosphate battery positive electrode powder.
Detailed Description
In light of the disclosed operating procedures and related parameters, one skilled in the art can achieve the objects of the invention according to the operating principles of the present method, without being limited to the use of the apparatus itself and its manner of use in a particular embodiment. The present invention is described in detail below with reference to examples, which are not intended to limit the scope of the claims.
Example 1
A certain waste lithium iron phosphate positive electrode powder comprises the following components:
TABLE 1 composition of lithium iron phosphate cathode powder (%)
| Composition of the components | Li | Fe | P | Cu | Al | Ni |
| Content% | 2.6 | 22.2 | 11.8 | 5.6 | 0.6 | 0.6 |
Step one: two-stage preferential leaching of lithium
Weighing 500g of the lithium iron phosphate positive electrode powder, adding 1500ml of tap water into a 3000ml three-neck flask, starting stirring, adding 100ml of concentrated sulfuric acid after adding the lithium iron phosphate positive electrode powder, starting the reaction, maintaining the temperature at 60 ℃, reacting for 30min, adding 500ml of 30% hydrogen peroxide, reacting for 60min, detecting the pH value to be 1.5, and filtering to obtain a lithium leaching solution and iron phosphate slag, and recovering lithium from the lithium leaching solution.
Adding 1000ml of tap water into a 3000ml three-neck flask, starting stirring, adding 50ml of concentrated sulfuric acid, maintaining the temperature at 60 ℃, reacting for 60min, detecting the pH value to be 0.5, and filtering and washing to obtain a second-stage leaching solution and a second-stage ferrophosphorus slag, recycling the second-stage leaching solution to be used as a next-stage leaching agent, and removing the second-stage ferrophosphorus slag to leach ferric phosphate later. After two sections of preferential lithium leaching, leaching slag containing phosphorus iron is obtained, and the slag is analyzed to obtain leaching rates of lithium, iron and other key impurities, and the leaching rates are shown in the following table.
TABLE 2 leaching residue composition and related element leaching yield (residue yield 80%)
Step two: iron phosphate leaching from ferrophosphorus slag
1500ml of water is added into a beaker, two sections of ferrophosphorus slag are added and stirred to prepare slurry, 50ml of concentrated sulfuric acid is added, after 60 minutes of reaction, the pH value is detected to be 0.4, and the iron phosphate leaching solution is obtained through filtration. The leaching rate of Fe in the step is 96.5%, and the leaching rate of P is 95.8%.
Step three: reduction of ferrous iron
And adding a reducing agent hydrazine hydrate, reducing ferric iron in the ferric phosphate leaching solution into ferrous iron, monitoring potential change in the reduction process at 60 ℃, stopping adding the hydrazine hydrate when the potential is-80 mV, and ending the reduction process.
Step four: adjusting pH value and removing impurities
Adding ammonia water solution to adjust pH value and remove impurities, monitoring pH value change, adjusting pH value to 3.6 at room temperature (21 ℃), and continuously adjusting pH value to 3.8 to finish adding ammonia water.
Step five: deep impurity removal of sulfides
And (3) heating the slurry solution obtained in the step (4) to 80 ℃, adding ammonium sulfide, ensuring the concentration of the ammonium sulfide to be 1.5g/L, reacting for 30min, filtering and separating precipitate to obtain ferrophosphorus liquid after impurity removal, and removing the ferrophosphorus liquid to prepare battery-grade ferric phosphate subsequently.
The final impurity removal results are shown in Table 4
Example 2
The raw materials used were the same as in example 1.
Step one: two-stage preferential leaching of lithium
Weighing 500g of lithium iron phosphate positive electrode powder, adding 1500ml of the second-stage leaching solution obtained in the first step in the embodiment into a 3000ml three-neck flask, starting stirring, adding 80ml of concentrated sulfuric acid after adding the lithium iron phosphate positive electrode powder, maintaining the temperature at 60 ℃, reacting for 30min, adding 480ml of 30% hydrogen peroxide, reacting for 60min, detecting the pH value to be 1.6, and filtering to obtain a lithium leaching solution and ferrophosphorus slag, and removing the subsequent recovery lithium from the lithium leaching solution.
Adding 1000ml of tap water into a 3000ml three-neck flask, starting stirring, adding 45ml of concentrated sulfuric acid after adding the ferrophosphorus slag, maintaining the temperature at 60 ℃, reacting for 60min, wherein the pH value is 0.6, the potential is 480mV, filtering and washing to obtain a second-stage leaching solution and ferrophosphorus slag, recycling the second-stage leaching solution as a next-stage leaching agent, and removing the second-stage ferrophosphorus slag for subsequent leaching of ferric phosphate.
Step two: iron phosphate leaching from ferrophosphorus slag
1200ml of water is added into a beaker, two sections of ferrophosphorus slag are added, stirring is carried out to prepare slurry, 65ml of concentrated sulfuric acid is added, after reaction is carried out for 60min, the pH value is detected to be 0.3, and the iron phosphate leaching solution is obtained by filtering.
Step three: reduction of ferrous iron
And adding glucose as a reducing agent, reducing ferric iron in the ferric phosphate leaching solution into ferrous iron, monitoring potential change in the reduction process at 60 ℃, and stopping adding hydrazine hydrate when the potential is-20 mV, so that the reduction is finished.
Step four: adjusting pH value and removing impurities
Adding ammonia water to adjust the pH value, when the pH value is adjusted to 3.6, turbidity appears, continuously adjusting the pH value to 4.0, and ending the addition of the ammonia water.
Step five: deep impurity removal of sulfides
Heating the slurry solution in the step 4 to 90 ℃, adding ammonium sulfide, ensuring the concentration of the ammonium sulfide to be 1.0g/L, slowly stirring for 60min, filtering and separating precipitate to obtain qualified ferrophosphorus liquid for impurity removal, and then preparing the battery grade ferric phosphate.
The final impurity removal results are shown in Table 4
Example 3
The raw materials used were the same as in example 1.
Step one: single stage preferential leaching of lithium
Weighing 500g of lithium iron phosphate positive electrode powder, adding 1500ml of the second-stage leaching solution obtained in the first step in the embodiment into a 3000ml three-neck flask, starting stirring, adding 80ml of concentrated sulfuric acid after adding the lithium iron phosphate positive electrode powder, maintaining the temperature at 60 ℃, reacting for 30min, adding 480ml of 30% hydrogen peroxide, reacting for 60min, detecting the pH value to be 1.6, detecting the potential to be 510mv, filtering to obtain a lithium leaching solution and ferrophosphorus slag, and removing the lithium from the lithium leaching solution to be recovered later.
TABLE 3 leaching residue composition and leaching yield (residue yield 83%)
As can be seen from the comparative examples, by adopting a single stage of preferential leaching of lithium, the leaching rate of lithium and the leaching rate of related impurities are obviously reduced.
The subsequent steps of comparative example 1 are the same as those of the example, and a description thereof will not be repeated. The final impurity removal results are shown in Table 4. In the comparative example 1, single-stage preferential lithium leaching is adopted, the leaching rate of lithium and the leaching rate of related impurities are reduced, and the subsequent impurity removal of the ferric phosphate solution is affected to a certain extent.
The impurity conditions after final impurity removal of examples 1 and 2 and comparative example are shown in table 4 below.
TABLE 4 impurity conditions after impurity removal of ferrophosphorus leachate
Remarks: comparative example 1 is a single stage preferential leaching of lithium.
Claims (10)
1. A method for preparing battery grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder is characterized by comprising the following steps: the method comprises the following steps:
1) The method comprises the steps of (1) carrying out oxidation acid leaching on waste lithium iron phosphate battery anode powder, wherein the pH value of a leaching end point is 1.5-2.0, and the oxidation-reduction potential is 400-550 mV, so as to obtain a leaching solution I and ferrophosphorus slag I;
2) Leaching the ferrophosphorus slag I by acid, wherein the pH value of the leaching end point is 0.5-1.0, so as to obtain leaching liquid II and ferrophosphorus slag II;
3) Dissolving the ferrophosphorus slag II by adopting acid, wherein the pH value of the dissolution end point is 0.1-0.7, and obtaining ferric phosphate solution and impurity enriched slag;
4) Reducing the ferric phosphate solution, wherein the potential of a reduction end point is controlled to be-100 mV, so as to obtain a ferrous phosphate solution;
5) And sequentially carrying out water impurity removal and vulcanization impurity removal on the ferrous phosphate solution to obtain the ferrous phosphate solution meeting the preparation requirements of the battery-grade ferric phosphate.
2. The method for preparing battery grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder, which is characterized in that: in the oxidation acid leaching process, concentrated sulfuric acid is used as a leaching agent, hydrogen peroxide is used as an oxidant, and the addition amount of the concentrated sulfuric acid is 10-40% of the mass of the positive electrode powder of the waste lithium iron phosphate battery.
3. The method for preparing battery grade ferric phosphate by using waste lithium iron phosphate battery anode powder according to claim 1 or 2, which is characterized in that: the conditions of the oxidation acid leaching are as follows: the liquid-solid ratio L/S=3 mL/1 g-4 mL/1g, the leaching temperature is 40-80 ℃ and the leaching time is 20-60 min.
4. The method for preparing battery grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder, which is characterized in that: in the acid leaching process, concentrated sulfuric acid is used as a leaching agent, and the adding amount of the concentrated sulfuric acid is 5-20% of the mass of the positive electrode powder of the waste lithium iron phosphate battery.
5. The method for preparing battery grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder according to claim 1 or 4, which is characterized by comprising the following steps: the conditions of the acid leaching are as follows: the liquid-solid ratio L/S=3 mL/1 g-4 mL/1g, the leaching temperature is 40-80 ℃ and the leaching time is 20-60 min.
6. The method for preparing battery grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder, which is characterized in that: in the acid dissolution process, concentrated sulfuric acid or concentrated hydrochloric acid is used as a dissolution agent, and the mass of the dissolution agent is 5-15% of that of the waste lithium iron phosphate battery anode powder.
7. The method for preparing battery grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder according to claim 1 or 6, which is characterized in that: the conditions of acid dissolution are as follows: the liquid-solid ratio L/S=3 mL/1 g-4 mL/1g, the leaching temperature is 40-80 ℃ and the leaching time is 30-60 min.
8. The method for preparing battery grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder, which is characterized in that: in the reduction process, at least one of hydrazine hydrate, glucose and formaldehyde is adopted as a reducing agent.
9. The method for preparing battery grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder, which is characterized in that: the conditions for hydrolysis and impurity removal are as follows: the pH value is regulated to 3.5-5.0, the temperature is 60-90 ℃ and the time is 10-60 min.
10. The method for preparing battery grade ferric phosphate by utilizing waste lithium iron phosphate battery anode powder, which is characterized in that: the conditions for vulcanization and impurity removal are as follows: the vulcanizing salt is used as a vulcanizing agent, the temperature is 60-90 ℃, and the time is 10-60 min.
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