CN112811404A - Recycling method of waste lithium iron phosphate anode powder - Google Patents
Recycling method of waste lithium iron phosphate anode powder Download PDFInfo
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- CN112811404A CN112811404A CN202011640432.0A CN202011640432A CN112811404A CN 112811404 A CN112811404 A CN 112811404A CN 202011640432 A CN202011640432 A CN 202011640432A CN 112811404 A CN112811404 A CN 112811404A
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- Prior art keywords
- iron phosphate
- phosphorus
- lithium iron
- inorganic acid
- filtering
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 123
- 239000002699 waste material Substances 0.000 title claims abstract description 70
- 239000000843 powder Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000001914 filtration Methods 0.000 claims abstract description 50
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 49
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 48
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 47
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011574 phosphorus Substances 0.000 claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 claims abstract description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000706 filtrate Substances 0.000 claims abstract description 38
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000004537 pulping Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008139 complexing agent Substances 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- -1 hydrogen ions Chemical class 0.000 claims description 7
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 2
- PHEDXBVPIONUQT-RGYGYFBISA-N phorbol 13-acetate 12-myristate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(CO)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C PHEDXBVPIONUQT-RGYGYFBISA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000012065 filter cake Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 22
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910001448 ferrous ion Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001447 ferric ion Inorganic materials 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 238000013386 optimize process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
Abstract
The invention relates to a recycling method of waste lithium iron phosphate anode powder, which comprises the following steps: s1, mixing the lithium iron phosphate positive electrode powder with a first inorganic acid, a metal complexing agent and water for aluminum removal treatment, and filtering to obtain a lithium iron phosphate material after aluminum removal; s2, mixing and pulping the aluminum-removed lithium iron phosphate material and a second inorganic acid, adding hydrogen peroxide for oxidation reaction, and filtering to obtain iron-phosphorus-containing filter residues; s3, mixing the iron and phosphorus-containing filter residue with a third inorganic acid, pulping, dissolving, and filtering to remove graphite to obtain iron and phosphorus-containing filtrate; and S4, adjusting the pH value of the filtrate containing the iron and the phosphorus by alkali for reaction, separating out a precipitate, and filtering to obtain filter residue to obtain the iron phosphate. The recycling method can prepare the iron phosphate with higher purity and less impurities by using the waste lithium iron phosphate anode powder as a raw material, and has high yield.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a recycling method of waste lithium iron phosphate anode powder.
Background
The lithium iron phosphate battery has the advantages of high working voltage, high energy density, long cycle life, good safety performance, small self-discharge rate and no memory effect, so that the market share of the lithium iron phosphate battery is increased year by year. In the next 10 years, lithium iron phosphate batteries replace nickel cobalt lithium manganate ternary batteries (NMC) batteries to become main fixed electric energy storage tools. Although the cycle life of the lithium iron phosphate battery is long, the battery capacity is greatly reduced after the lithium iron phosphate battery is normally used for 5 to 8 years, so that the lithium iron phosphate battery cannot be normally used and is discarded. The method is limited to the existing battery material recovery technology, and at present, only about 4% of lithium is recovered by each recovery enterprise, but the main components of iron and phosphorus in the lithium iron phosphate battery positive electrode powder cannot be recycled due to high aluminum impurity content, so that the environmental burden is increased, and the popularization and application of the lithium iron phosphate battery are also restricted.
Therefore, how to effectively utilize the main components of iron and phosphorus in the lithium iron phosphate battery positive electrode powder becomes a problem which is urgently to be solved in the whole industry.
Disclosure of Invention
Based on this, there is a need for a method for recycling waste lithium iron phosphate positive electrode powder, which can prepare iron phosphate with high purity and less impurities from the waste lithium iron phosphate positive electrode powder as a raw material, and has high yield.
A recycling method of waste lithium iron phosphate anode powder comprises the following steps:
s1, mixing the lithium iron phosphate positive electrode powder with a first inorganic acid, a metal complexing agent and water for aluminum removal treatment, and filtering to obtain a lithium iron phosphate material after aluminum removal;
s2, mixing and pulping the aluminum-removed lithium iron phosphate material and a second inorganic acid, adding hydrogen peroxide for oxidation reaction, and filtering to obtain iron-phosphorus-containing filter residues;
s3, mixing the iron and phosphorus-containing filter residue with a third inorganic acid, pulping, dissolving, and filtering to remove graphite to obtain iron and phosphorus-containing filtrate; and
and S4, adjusting the pH value of the filtrate containing the iron and the phosphorus by using alkali for reaction, separating out a precipitate, and filtering to obtain filter residue to obtain the iron phosphate.
In some embodiments, in step S1, the mass ratio of the waste lithium iron phosphate positive electrode powder to the water is 1 (2-5); and/or
The adding amount of the first inorganic acid and the metal complexing agent is based on the molar ratio of the lithium iron phosphate in the waste lithium iron phosphate anode powder to the first inorganic acid (100-500): 1, and the molar ratio of the lithium iron phosphate in the waste lithium iron phosphate anode powder to the metal complexing agent is (5-20): 1; and/or
The metal complexing agent is at least one of EDTA, PMA, PAA and HEDP; the first inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid.
In some embodiments, the temperature of the aluminum removing treatment is 40-100 ℃, and the time of the aluminum removing treatment is 2-7 hours.
In some embodiments, after the step of filtering in step S1 and before the step of obtaining the aluminum-removed lithium iron phosphate material, a step of washing filter residue is further included, so that the aluminum content in the aluminum-removed lithium iron phosphate material is controlled to be not more than 0.02% by mass.
In some embodiments, in step S2, the second inorganic acid and the hydrogen peroxide are added in such an amount that a molar ratio of lithium iron phosphate in the aluminum-removed lithium iron phosphate material, hydrogen ions in the second inorganic acid, and hydrogen peroxide in the hydrogen peroxide is 1: (1-5): (0.7-1).
In some embodiments, in step S2, the temperature of the oxidation reaction is 10 to 90 ℃, and the time of the oxidation reaction is 1 to 3 hours; and/or
And in the filtering step after the oxidation reaction step, the filter residue containing iron and phosphorus is obtained, and simultaneously, the filtrate containing soluble lithium salt is also obtained.
In some embodiments, in step S3, the third inorganic acid is added in an amount such that the molar ratio of the phosphorus atoms in the iron-phosphorus-containing filter residue to the hydrogen ions in the third inorganic acid is 1: (3-5) as the standard; and/or
The temperature of the mixing, pulping and dissolving is 30-90 ℃, and the time is 1-3 hours.
In some embodiments, before adjusting the ph value with the base in step S4, the method further includes the steps of: according to the actual molar weight of iron and phosphorus in the iron-phosphorus-containing filtrate, adding an iron source or a phosphorus source so that the molar ratio of iron to phosphorus is 1: (0.9 to 1.1); and/or
Adjusting the pH value to 1.5-2.5 by using alkali; and/or
The reaction temperature in the step S4 is 30-90 ℃, and the reaction time is 1-3 hours.
In some embodiments, after the step of filtering and extracting filter residue in step S4 and before the step of obtaining the iron phosphate, the method further includes the following steps:
and drying the filter residue, and calcining to obtain the anhydrous ferric orthophosphate.
In some embodiments, the drying temperature is 100-150 ℃, and the drying time is 3-5 hours; the calcining temperature is 400-650 ℃, and the calcining time is 2-4 hours.
Advantageous effects
The method for recycling the waste lithium iron phosphate anode powder uses the waste lithium iron phosphate anode powder as a raw material, and firstly, the waste lithium iron phosphate anode powder reacts with a metal complexing agent under the action of inorganic acid to remove aluminum and other impurity metals; mixing and pulping the aluminum-removed lithium iron phosphate material and a second inorganic acid, adding hydrogen peroxide for oxidation reaction to convert ferrous ions in the mixture into ferric ions, convert lithium into soluble lithium salt and enter filtrate, and filtering to obtain iron-phosphorus-containing filter residue; further mixing the obtained iron and phosphorus-containing filter residue with inorganic acid, pulping and dissolving, and filtering to remove insoluble impurities such as graphite and the like to obtain iron and phosphorus-containing filtrate; and finally, adjusting the pH value of the iron-phosphorus-containing filtrate for reaction, and separating out a precipitate to obtain the iron phosphate. The method for recycling the waste lithium iron phosphate positive electrode powder effectively reduces the production cost of the iron phosphate and solves the problem that the tailings are difficult to treat after the lithium is extracted from the waste lithium iron phosphate battery positive electrode powder.
The method for recycling the waste lithium iron phosphate positive electrode powder has simple operation, economy and reasonability, can prepare industrial anhydrous iron phosphate by taking the waste lithium iron phosphate positive electrode powder as a raw material, and can also prepare soluble lithium salt or further prepare lithium carbonate.
The test shows that: according to the method for recycling the waste lithium iron phosphate anode powder, the content of aluminum in the prepared anhydrous ferric phosphate is as low as less than 40ppm, even less than 30 ppm; and the yield is high, and the content of other impurities is also greatly reduced. The anhydrous ferric orthophosphate has high purity and better product quality.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The embodiment of the invention provides a recycling method of waste lithium iron phosphate anode powder, which comprises the following steps of S1-S4.
S1, mixing the lithium iron phosphate positive powder with a first inorganic acid, a metal complexing agent and water for aluminum removal treatment, and filtering to obtain the aluminum-removed lithium iron phosphate material.
Step S1 is to react with a metal complexing agent under the action of an inorganic acid to remove aluminum (Al) and other impurity metals, such as calcium (Ca), cobalt (Co), chromium (Cr), copper (Cu), and the like.
In some embodiments, in step S1, the mass ratio of the waste lithium iron phosphate positive electrode powder to water is 1 (2-5). In some embodiments, the adding amount of the first inorganic acid and the metal complexing agent is based on the molar ratio of the lithium iron phosphate in the waste lithium iron phosphate positive electrode powder to the first inorganic acid (100-500): 1, and the molar ratio of the lithium iron phosphate in the waste lithium iron phosphate positive electrode powder to the metal complexing agent (5-20): 1. The aluminum removal effect can be improved by controlling the aluminum removal treatment under the optimized process parameters.
Furthermore, the adding amount of the first inorganic acid and the metal complexing agent is based on the molar ratio of the lithium iron phosphate in the waste lithium iron phosphate anode powder to the first inorganic acid (100-200): 1, and the molar ratio of the lithium iron phosphate in the waste lithium iron phosphate anode powder to the metal complexing agent (5-20): 1. The aluminum removal effect can be improved by controlling the aluminum removal treatment under the optimized process parameters.
In some of these embodiments, the metal complexing agent is at least one of EDTA (ethylenediaminetetraacetic acid), PMA (maleic-acrylic acid copolymer), PAA (sodium polyacrylate), and HEDP (hydroxyethylidene diphosphonic acid).
In some of these embodiments, the first mineral acid is at least one of hydrochloric acid, sulfuric acid, and nitric acid.
In some embodiments, the temperature of the aluminum removing treatment is 40-100 ℃, and the time of the aluminum removing treatment is 2-7 h. Further, the temperature of the aluminum removing treatment is 60-100 ℃, and more preferably 80-95 ℃. In some examples, the time for the dealumination treatment may be 6 to 7 hours.
It is understood that the mixing step in step S1 is performed under mechanical agitation.
In some embodiments, after the step of filtering in step S1 and before the step of obtaining the aluminum-removed lithium iron phosphate material, a step of washing the filter residue is further included, so that the aluminum content in the aluminum-removed lithium iron phosphate material is controlled to be not more than 0.02% by mass.
In some embodiments, the waste lithium iron phosphate battery positive electrode powder is obtained by discharging, crushing, winnowing and grading the waste lithium iron phosphate battery.
And S2, mixing and pulping the aluminum-removed lithium iron phosphate material and a second inorganic acid, adding hydrogen peroxide for oxidation reaction, and filtering to obtain iron-phosphorus-containing filter residue.
Step S2, mixing and pulping the aluminum-removed lithium iron phosphate material and a second inorganic acid, adding hydrogen peroxide for oxidation reaction to convert ferrous ions in the mixture into ferric ions, convert lithium into soluble lithium salt, and feeding the soluble lithium salt into filtrate to realize lithium extraction, and filtering to obtain a solid, namely the iron-phosphorus-containing filter residue.
In some embodiments, in step S2, the second inorganic acid and the hydrogen peroxide are added in such an amount that the molar ratio of the lithium iron phosphate in the aluminum-removed lithium iron phosphate material, the hydrogen ions in the second inorganic acid, and the hydrogen peroxide in the hydrogen peroxide is 1: (1-5): (0.7-1).
Further, the second inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid.
In some embodiments, the temperature of the oxidation reaction is 10 to 90 ℃ and the time of the oxidation reaction is 1 to 3 hours. Further, the temperature of the oxidation reaction is preferably 40 to 80 ℃, and more preferably 50 to 60 ℃.
It is understood that the system is acidic in step S2, and the o-phenanthroline may be used for color development to indicate whether the oxidation reaction is complete. The phenanthroline will react with ferrous ion (Fe) at pH 2-92+) Forming stable orange red o-diazaphenanthrene ferrous ions. If the o-phenanthroline is added, the color is not developed, that is, the ferrous ions in the o-phenanthroline are all oxidized into ferric ions, and the oxidation reaction is terminated; the subsequent filtration and washing can be carried out.
In some embodiments, the step of filtering after the step of oxidizing reaction is performed to obtain the iron-phosphorus-containing filter residue and the soluble lithium salt-containing filtrate. Further, in other examples, the method further comprises the following steps: and preparing lithium carbonate by using the filtrate containing soluble lithium salt as a raw material. Therefore, comprehensive recycling of waste lithium iron phosphate anode powder is realized.
In one specific example, the lithium carbonate may be prepared by using a filtrate containing a soluble lithium salt as a raw material, as follows: and adding a sodium carbonate solution into the filtrate containing the soluble lithium salt for reaction, filtering to obtain a solid, washing and drying to obtain the lithium carbonate.
And S3, mixing the iron and phosphorus-containing filter residue with a third inorganic acid, pulping, dissolving, and filtering to remove graphite to obtain iron and phosphorus-containing filtrate.
Step S3 is further mixing the obtained iron and phosphorus-containing filter residue with inorganic acid, pulping and dissolving, and filtering to remove insoluble impurities therein, such as graphite, carbon powder and pvdf, to obtain iron and phosphorus-containing filtrate.
In some embodiments, in step S3, the third inorganic acid is added in an amount such that the molar ratio of the phosphorus atoms in the iron-phosphorus-containing filter residue to the hydrogen ions in the third inorganic acid is 1: (3-5) for the most part.
Further, the third inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid.
In some embodiments, in step S3, the temperature for mixing, beating and dissolving is 30-90 ℃ for 1-3 hours. The temperature for further mixing, pulping and dissolving is 40-80 ℃, and the more preferable temperature is 70-80 ℃.
And S4, adjusting the pH value of the filtrate containing iron and phosphorus by alkali for reaction, separating out precipitate, and filtering to obtain filter residue to obtain the iron phosphate.
And step S4, adjusting the pH value of the iron and phosphorus-containing filtrate obtained in the step S3 to react, and separating out a precipitate to obtain the iron phosphate.
In some embodiments, before adjusting the ph value with the base in step S4, the method further includes the steps of: adding an iron source or a phosphorus source according to the actual molar amount of iron and phosphorus in the iron-phosphorus-containing filtrate to ensure that the molar ratio of iron to phosphorus is 1: (0.9 to 1.1), preferably 1: 1. among them, the alkali is preferably ammonia water.
In some embodiments, the pH value is adjusted to 1.5-2.5 by alkali; preferably 1.5 to 2.0, and more preferably 1.8 to 1.9.
In some embodiments, in step S4, the reaction temperature is 30 to 90 ℃, preferably 40 to 80 ℃, and more preferably 70 to 80 ℃; the reaction time is 1-3 hours.
In some embodiments, after the step of filtering and taking out the filter residue in step S4 and before the step of obtaining the iron phosphate, the method further includes the following steps:
and drying the filter residue, and calcining in a dehydration furnace to obtain the anhydrous ferric orthophosphate.
Wherein the filter residue is light yellow hydrated ferric orthophosphate with the general formula of FePO4·nH2Hydrated iron orthophosphate of O.
Further, in the step S4, the drying temperature is 100-150 ℃, and the drying time is 3-5 hours; the drying temperature is preferably 110 ℃ to 140 ℃, more preferably 120 ℃ to 130 ℃. Further, the drying manner is flash drying.
Further, in step S4, the calcining temperature is 400-650 ℃, and the calcining time is 2-4 hours; the calcination temperature is preferably 450 ℃ to 600 ℃, more preferably 530 ℃ to 560 ℃.
The method for recycling the waste lithium iron phosphate anode powder uses the waste lithium iron phosphate anode powder as a raw material, and firstly, the waste lithium iron phosphate anode powder reacts with a metal complexing agent under the action of inorganic acid to remove aluminum and other impurity metals; mixing and pulping the aluminum-removed lithium iron phosphate material and a second inorganic acid, adding hydrogen peroxide for oxidation reaction to convert ferrous ions in the mixture into ferric ions, convert lithium into soluble lithium salt and enter filtrate, and filtering to obtain iron-phosphorus-containing filter residue; further mixing the obtained iron and phosphorus-containing filter residue with inorganic acid, pulping and dissolving, and filtering to remove insoluble impurities such as graphite and the like to obtain iron and phosphorus-containing filtrate; and finally, adjusting the pH value of the iron-phosphorus-containing filtrate for reaction, and separating out a precipitate to obtain the iron phosphate. The method for recycling the waste lithium iron phosphate positive electrode powder effectively reduces the production cost of the iron phosphate and solves the problem that the tailings are difficult to treat after the lithium is extracted from the waste lithium iron phosphate battery positive electrode powder.
The method for recycling the waste lithium iron phosphate positive electrode powder has simple operation, economy and reasonability, can prepare industrial anhydrous iron phosphate by taking the waste lithium iron phosphate positive electrode powder as a raw material, and can also prepare soluble lithium salt or further prepare lithium carbonate.
The test shows that: according to the method for recycling the waste lithium iron phosphate anode powder, the content of aluminum in the prepared anhydrous ferric phosphate is as low as less than 40ppm, even less than 30 ppm; and the yield is high, and the content of other impurities is also greatly reduced. The anhydrous ferric orthophosphate has high purity and better product quality.
The invention solves the problem that a large amount of waste residues containing iron and phosphorus cannot be recycled to generate solid waste due to higher aluminum content after lithium is recovered from the anode powder of the waste lithium iron phosphate batteries, and comprehensively utilizes the anode powder of the waste lithium iron phosphate batteries to prepare the industrial anhydrous iron phosphate and the lithium carbonate, thereby realizing resource recycling while solving the problem of environmental pollution caused by the upstream waste lithium iron phosphate batteries, and providing a new idea and a new way for reducing the production cost for downstream iron phosphate and lithium carbonate manufacturers.
In order to better illustrate the invention, the following examples are given to further illustrate the invention. The following are specific examples.
The used anode powder of the waste lithium iron phosphate batteries in each example is the same, and the detection shows that the mass of lithium iron phosphate contained in each 100g of the anode powder of the waste lithium iron phosphate batteries is 85g, and the content of each impurity is shown in table 1 below.
Example 1
A method for recycling waste lithium iron phosphate anode powder comprises the following steps:
(1) weighing 100g of waste lithium iron phosphate battery positive electrode powder into a reaction kettle, adding 200mL of distilled water, adding 0.053g (0.02mol) of concentrated hydrochloric acid and 11g (0.05mol) of HEDP, stirring at 20r/min, heating to 80 ℃ under continuous stirring, reacting for 2h, and filtering to obtain lithium iron phosphate containing less than 100ppm of aluminum. The amount of lithium iron phosphate in 100g of waste lithium iron phosphate battery anode powder and lithium iron phosphate containing less than 100ppm of aluminum is about 0.54 mol.
(2) 200mL of distilled water and 55g (0.55mol) of concentrated hydrochloric acid are added into a reaction kettle, the lithium iron phosphate is pulped, the stirring speed is 20r/min, 47g (0.38mol) of hydrogen peroxide (content: 27.5%) is dripped, and the reaction temperature is controlled to be less than 70 ℃. Completely coloring and oxidizing with phenanthroline, reacting for 1h, filtering the mother liquor to obtain a lithium chloride solution, and filtering a filter cake to obtain iron and phosphorus-containing waste residues. Wherein the lithium chloride solution can be further used for preparing lithium carbonate. Wherein the amount of phosphorus atom-containing substances in the iron-phosphorus-containing waste slag is about 0.54 mol.
(3) The iron-phosphorus waste residue is put into 200mL of distilled water for pulping, 81g (0.81mol) of concentrated sulfuric acid (content: 98%) is added, the stirring speed is 20r/min, the reaction is carried out for 1h, 15g of insoluble impurities (graphite and PVDF) are removed by filtration, and the mother liquor is the iron-phosphorus-containing filtrate.
(4) Performing color development on the iron and phosphorus-containing filtrate by using o-phenanthroline again to ensure complete oxidation, stirring at the speed of 20r/min, dropwise adding ammonia water until the pH value is 2, reacting for 2h, separating out a large amount of yellow precipitate, filtering and washing to obtain a yellow filter cake, namely hydrated iron phosphate (FePO)4·nH2O); and (3) drying the filter cake in an oven at 105 ℃ for 4 hours, transferring the dried filter cake into a muffle furnace at 550 ℃ for calcining for 3 hours to obtain the filter cake which is the iron phosphate, and obtaining 80g of industrial anhydrous iron phosphate.
The impurity content of the industrial anhydrous iron phosphate obtained in example 1 was analyzed to find that:
Al:39ppm/Ca:9ppm/Co:8ppm/Cr:3ppm/Cu:n.d./K:3ppm/Mg:8ppm/
mn 8ppm/Na 9ppm/Ni 6ppm/Ti 25ppm/Zn 17/magnetic material: 0.3 ppm.
Example 2
A method for recycling waste lithium iron phosphate anode powder comprises the following steps:
(1) weighing 100g of waste lithium iron phosphate battery positive electrode powder into a reaction kettle, adding 200mL of distilled water, adding 0.5g (0.005mol) of concentrated sulfuric acid and 15.7g (0.053mol) of EDTA, stirring at 20r/min, heating to 80 ℃ under continuous stirring, reacting for 3h, and filtering to obtain lithium iron phosphate containing less than 100ppm of aluminum. The amount of lithium iron phosphate in 100g of waste lithium iron phosphate battery anode powder and lithium iron phosphate containing less than 100ppm of aluminum is about 0.54 mol.
(2) 200mL of distilled water and 27g (0.27mol) of concentrated sulfuric acid are added into a reaction kettle, the lithium iron phosphate is pulped, the stirring speed is 20r/min, 47g (0.38mol) of hydrogen peroxide (content: 27.5%) is dripped, and the reaction temperature is controlled to be less than 70 ℃. Completely coloring and oxidizing with phenanthroline, reacting for 1h, and filtering the mother liquor to obtain a filter cake which is iron and phosphorus-containing waste residue. Wherein the lithium sulfate solution can be further used for preparing lithium carbonate. Wherein the content of phosphorus atom in the waste slag containing iron and phosphorus is 0.54 mol.
(3) The iron-phosphorus waste residue is put into 200mL of distilled water for pulping, 81g of concentrated sulfuric acid (content: 98%) is added, the stirring speed is 20r/min, the reaction is carried out for 1h, 15g of insoluble impurities (graphite and PVDF) are removed by filtration, and the mother liquor is the iron-phosphorus-containing filtrate.
(4) Performing color development on the iron and phosphorus-containing filtrate by using o-phenanthroline again to ensure complete oxidation, stirring at the speed of 20r/min, dropwise adding ammonia water until the pH value is 2, reacting for 2h, separating out a large amount of yellow precipitate, filtering and washing to obtain a yellow filter cake, namely hydrated iron phosphate (FePO)4·nH2O), drying the filter cake in an oven at 105 ℃ for 4 hours, transferring the dried filter cake into a muffle furnace at 550 ℃ for calcining for 3 hours, and obtaining the filter cake which is 80g of industrial anhydrous iron phosphate.
The impurity content of the industrial anhydrous iron phosphate prepared in example 2 was analyzed to find that:
Al:37ppm/Ca:6ppm/Co:6ppm/Cr:5ppm/Cu:n.d./K:3ppm/Mg:8ppm/
mn 5ppm/Na 10ppm/Ni 8ppm/Ti 20ppm/Zn 16/magnetic material: 0.2 ppm.
Example 3
A method for recycling waste lithium iron phosphate anode powder comprises the following steps:
(1) weighing 3000g of waste lithium iron phosphate battery positive electrode powder into a reaction kettle, adding 6000mL of distilled water, then adding 60g of concentrated sulfuric acid and 300g of EDTA, stirring at 20r/min, heating to 90 ℃ under continuous stirring, reacting for 3h, and filtering to obtain lithium iron phosphate with the aluminum content less than 100 ppm. The amount of lithium iron phosphate in 100g of waste lithium iron phosphate battery anode powder and lithium iron phosphate containing less than 100ppm of aluminum is about 0.54 mol.
(2) 6000mL of distilled water and 810g of concentrated sulfuric acid are added into a reaction kettle, the lithium iron phosphate is pulped, the stirring speed is 20r/min, 1410g of hydrogen peroxide (the content: 27.5%) is dripped, and the reaction temperature is controlled to be lower than 70 ℃. And (3) completely carrying out color development and oxidation by using phenanthroline, reacting for 1h, and obtaining a filtered mother solution which is a lithium sulfate solution (the filter cake is the waste residue containing iron and phosphorus), wherein the lithium sulfate solution can be further used for preparing lithium carbonate.
(3) The iron-phosphorus waste residue is put into 60000mL of distilled water for pulping, 2430g of concentrated sulfuric acid (content: 98%) is added, the stirring speed is 20r/min, the reaction is carried out for 1h, 450g of insoluble impurities (graphite and PVDF) are removed by filtration, and the mother liquor is the iron-phosphorus-containing filtrate.
(4) Performing color development on the iron and phosphorus-containing filtrate by using o-phenanthroline again to ensure complete oxidation, stirring at the speed of 20r/min, dropwise adding ammonia water until the pH value is 2, reacting for 2h, separating out a large amount of yellow precipitate, filtering and washing to obtain a yellow filter cake, namely hydrated iron phosphate (FePO)4·nH2O), drying the filter cake in an oven at 105 ℃ for 4 hours, transferring the dried filter cake into a muffle furnace at 550 ℃ for calcining for 3 hours, and obtaining 2400g of industrial anhydrous iron phosphate as the filter cake.
The impurity content of the industrial anhydrous iron phosphate prepared in example 3 was analyzed to find that:
Al:37ppm/Ca:6ppm/Co:6ppm/Cr:5ppm/Cu:n.d./K:3ppm/Mg:8ppm/
mn 5ppm/Na 10ppm/Ni 8ppm/Ti 20ppm/Zn 16/magnetic material: 0.2 ppm.
Example 4
A method for recycling waste lithium iron phosphate anode powder comprises the following steps:
(1) 10000g of waste lithium iron phosphate battery positive electrode powder is weighed in a reaction kettle, 20000mL of distilled water is added, 200g of concentrated sulfuric acid and 1000g of EDTA are added, the stirring speed is 20r/min, the temperature is raised to 80 ℃ under continuous stirring, the reaction is carried out for 3h, and lithium iron phosphate containing less than 100ppm of aluminum is obtained by filtering. The amount of lithium iron phosphate in 100g of waste lithium iron phosphate battery anode powder and lithium iron phosphate containing less than 100ppm of aluminum is about 0.54 mol.
(2) 20000mL of distilled water and 2700g of concentrated sulfuric acid are added into a reaction kettle, the lithium iron phosphate is pulped, the stirring speed is 20r/min, 4700g of hydrogen peroxide (content: 27.5%) is dropwise added, and the reaction temperature is controlled to be lower than 70 ℃. Completely coloring and oxidizing with phenanthroline, reacting for 1h, wherein a filtered mother solution is a lithium sulfate solution (used for preparing lithium carbonate), and a filter cake is iron and phosphorus-containing waste residue.
(3) Pulping the iron-phosphorus waste residue in 20000mL of distilled water, adding 8100g of concentrated sulfuric acid (content: 98%), stirring at 20r/min, reacting for 1h, and filtering to remove 1500g of insoluble impurities (graphite and PVDF), wherein the mother liquor is the iron-phosphorus-containing filtrate.
(4) Performing color development on the iron and phosphorus-containing filtrate by using o-phenanthroline again to ensure complete oxidation, stirring at the speed of 20r/min, dropwise adding ammonia water until the pH value is 2, reacting for 2h, separating out a large amount of yellow precipitate, filtering and washing to obtain a yellow filter cake, namely hydrated iron phosphate (FePO)4·nH2O), drying the filter cake, transferring the filter cake into a muffle furnace to calcine for 3 hours at 550 ℃, wherein the filter cake is 8000g of industrial anhydrous iron phosphate.
The impurity content of the industrial anhydrous iron phosphate prepared in example 4 was analyzed to find that:
Al:27ppm/Ca:9ppm/Co:5ppm/Cr:5ppm/Cu:n.d./K:3ppm/Mg:10ppm/
mn 5ppm/Na 11ppm/Ni 8ppm/Ti 20ppm/Zn 19/magnetic material: 0.2 ppm.
Example 5
The procedure of example 5 is substantially the same as example 1 except that: the concentrated sulfuric acid (content: 98%) added in the step (3) of example 5 is 60g, that is, the molar ratio of phosphorus atoms in the iron-phosphorus-containing filter residue to hydrogen ions of the concentrated sulfuric acid is 1: 2.2. stirring speed is 20r/min, reaction is carried out for 1h, and filtered mother liquor is iron-phosphorus-containing filtrate and filter cake is 37 g.
(4) Performing color development on the iron and phosphorus-containing filtrate by using o-phenanthroline again to ensure complete oxidation, stirring at the speed of 20r/min, dropwise adding ammonia water until the pH value is 2, reacting for 2h, separating out a large amount of yellow precipitate, filtering and washing to obtain a yellow filter cake, namely hydrated iron phosphate (FePO)4·nH2O), drying the filter cake, transferring the filter cake into a muffle furnace to calcine for 3 hours at 550 ℃, and obtaining 60g of industrial anhydrous iron phosphate as the filter cake.
Example 6
The procedure of example 6 is substantially the same as example 1 except that: before the pH value is adjusted by adopting alkali in the step (4), the method also comprises the following steps: based on the actual molar amounts of iron (0.53mol) and phosphorus (0.5mol) of the iron-phosphorus containing filtrate, 0.03mol of phosphoric acid was added to give a molar ratio of iron to phosphorus of 1: 1.
Example 7
The procedure of example 7 is substantially the same as example 1 except that: the adding amount of the concentrated hydrochloric acid in the step (1) is 0.25g (0.25 mol); the aluminum removal effect is poor, and the lithium iron phosphate containing more than 300ppm of aluminum is obtained by filtering.
Comparative example 1
The procedure of comparative example 1 is substantially the same as example 1 except that: step (3) in example 1 was omitted, and accordingly step (2) and step (4) were all different; the method comprises the following specific steps:
after the o-phenanthroline is subjected to color development and oxidation reaction for 1h in the step (2), ammonia water is directly added dropwise in the step (4) until the pH value is 2, the reaction is carried out for 2h, a large amount of yellow precipitate is separated out, and the yellow precipitate is filtered and washed to obtain a yellow filter cake, namely hydrated iron phosphate (FePO)4·nH2O); the filtrate was a lithium sulfate solution.
In comparative example 1, a mixture of carbon powder and PVDF, which accounts for 15% of the total battery powder weight, was introduced into the anhydrous iron phosphate product, resulting in a product with too low purity to be acceptable.
Comparative example 2
The procedure of comparative example 2 is substantially the same as example 1 except that: in step S1, aluminum is removed by alkaline leaching. Step S1 specifically includes: 100g of waste lithium iron phosphate material is immersed into 0.5mol/L sodium hydroxide solution, heated to 90 ℃, reacted for 2 hours, subjected to alkaline leaching to remove aluminum, and filtered to obtain the aluminum-removed lithium iron phosphate, wherein the amount of lithium iron phosphate is 0.3mol, the yield is low, and the aluminum content is 200 ppm. Among them, phosphorus is largely lost in the form of sodium phosphate.
The iron phosphate product of comparative example 2 was low in yield and high in impurity content.
The following are performance tests.
The impurity content analysis of the waste lithium iron phosphate positive electrode powder and the prepared anhydrous iron phosphate used in each example was carried out, and the obtained impurity content was as shown in table 1 below:
TABLE 1
Wherein n.d. represents no detection, and the detection limit is 0.02 ppm.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A recycling method of waste lithium iron phosphate anode powder is characterized by comprising the following steps:
s1, mixing the lithium iron phosphate positive electrode powder with a first inorganic acid, a metal complexing agent and water for aluminum removal treatment, and filtering to obtain a lithium iron phosphate material after aluminum removal;
s2, mixing and pulping the aluminum-removed lithium iron phosphate material and a second inorganic acid, adding hydrogen peroxide for oxidation reaction, and filtering to obtain iron-phosphorus-containing filter residues;
s3, mixing the iron and phosphorus-containing filter residue with a third inorganic acid, pulping, dissolving, and filtering to remove graphite to obtain iron and phosphorus-containing filtrate; and
and S4, adjusting the pH value of the filtrate containing the iron and the phosphorus by using alkali for reaction, separating out a precipitate, and filtering to obtain filter residue to obtain the iron phosphate.
2. The recycling method according to claim 1, wherein in step S1, the mass ratio of the waste lithium iron phosphate positive electrode powder to the water is 1 (2-5); and/or
The adding amount of the first inorganic acid and the metal complexing agent is based on the molar ratio of the lithium iron phosphate in the waste lithium iron phosphate anode powder to the first inorganic acid (100-500): 1, and the molar ratio of the lithium iron phosphate in the waste lithium iron phosphate anode powder to the metal complexing agent is (5-20): 1; and/or
The metal complexing agent is at least one of EDTA, PMA, PAA and HEDP; the first inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid.
3. The recycling method according to claim 1, wherein the temperature of the dealumination treatment is 40 to 100 ℃, and the time of the dealumination treatment is 2 to 7 hours.
4. The recycling method according to claim 1, further comprising a step of washing the filter residue after the step of filtering in step S1 and before the step of obtaining the aluminum-removed lithium iron phosphate material, so as to control the aluminum content in the aluminum-removed lithium iron phosphate material to be not more than 0.02% by mass.
5. The recycling method according to any one of claims 1 to 4, wherein in step S2, the second inorganic acid and the hydrogen peroxide are added in such an amount that the molar ratio of the lithium iron phosphate in the aluminum-removed lithium iron phosphate material, the hydrogen ions in the second inorganic acid, and the hydrogen peroxide in the hydrogen peroxide is 1: (1-5): (0.7-1).
6. The recycling method according to any one of claims 1 to 4, wherein in step S2, the temperature of the oxidation reaction is 10 to 90 ℃, and the time of the oxidation reaction is 1 to 3 hours; and/or
And in the filtering step after the oxidation reaction step, the filter residue containing iron and phosphorus is obtained, and simultaneously, the filtrate containing soluble lithium salt is also obtained.
7. The recycling method according to any one of claims 1 to 4, wherein in step S3, the third inorganic acid is added in an amount such that the molar ratio of phosphorus atoms in the iron-phosphorus-containing filter residue to hydrogen ions in the third inorganic acid is 1: (3-5) as the standard; and/or
The temperature of the mixing, pulping and dissolving is 30-90 ℃, and the time is 1-3 hours.
8. The recycling method according to any one of claims 1 to 4, further comprising, before adjusting pH with a base in step S4, the steps of: according to the actual molar weight of iron and phosphorus in the iron-phosphorus-containing filtrate, adding an iron source or a phosphorus source so that the molar ratio of iron to phosphorus is 1: (0.9 to 1.1); and/or
Adjusting the pH value to 1.5-2.5 by using alkali; and/or
The reaction temperature in the step S4 is 30-90 ℃, and the reaction time is 1-3 hours.
9. The recycling method according to any one of claims 1 to 4, further comprising, after the step of filtering the filter residue in step S4 and before the step of obtaining the iron phosphate, the steps of:
and drying the filter residue, and calcining to obtain the anhydrous ferric orthophosphate.
10. The recycling method according to claim 9, wherein the drying temperature is 100 ℃ to 150 ℃, and the drying time is 3 to 5 hours; the calcining temperature is 400-650 ℃, and the calcining time is 2-4 hours.
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