CN116495716A - Method for preparing sodium ion battery anode material by using waste lithium iron phosphate - Google Patents
Method for preparing sodium ion battery anode material by using waste lithium iron phosphate Download PDFInfo
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- CN116495716A CN116495716A CN202310754594.4A CN202310754594A CN116495716A CN 116495716 A CN116495716 A CN 116495716A CN 202310754594 A CN202310754594 A CN 202310754594A CN 116495716 A CN116495716 A CN 116495716A
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- Prior art keywords
- lithium iron
- iron phosphate
- ion battery
- waste lithium
- sodium
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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 99
- 239000002699 waste material Substances 0.000 title claims abstract description 77
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 38
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000010405 anode material Substances 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 64
- 238000002386 leaching Methods 0.000 claims abstract description 61
- 238000000498 ball milling Methods 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 19
- 239000012498 ultrapure water Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 239000005955 Ferric phosphate Substances 0.000 claims description 4
- 229940032958 ferric phosphate Drugs 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000010406 cathode material Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000011268 mixed slurry Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006012 monoammonium phosphate Substances 0.000 description 3
- 229920000447 polyanionic polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000010926 waste battery Substances 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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
A method for preparing a sodium ion battery anode material by using waste lithium iron phosphate comprises the following steps: (1) Pre-extracting lithium from waste lithium iron phosphate powder to obtain a lithium iron phosphate leaching material, and ball-milling the leaching material to 200-500 nm; (2) Mixing and stirring the lithium iron phosphate leaching material subjected to ball milling in the step (1) with a certain amount of carbon source, sodium source, phosphorus source or other anion sources and ultrapure water, and evaporating and drying to prepare a mixed precursor; (3) Carbonizing, annealing and washing the precursor prepared in the step (2) in an inert atmosphere to obtain the sodium ion battery anode material. The invention utilizes the waste lithium iron phosphate to prepare the positive electrode material of the sodium ion battery, can effectively inherit the shape of the nano particles, simplifies the synthesis process, effectively solves the technical difficulties of single recovery product, low economic benefit, more wastes and the like of the traditional lithium iron phosphate battery, and fills the process gap of direct conversion and regeneration of the waste lithium iron phosphate. The invention has simple process flow and is easy to realize large-scale production.
Description
Technical Field
The invention belongs to the field of waste battery recovery, and relates to a method for preparing a sodium ion battery anode material by using waste lithium iron phosphate.
Background
The lithium iron phosphate battery has wide application in the fields of energy storage and electric automobiles due to the advantages of high safety, low cost, long service life and the like. The future application and the duty ratio of the lithium iron phosphate power battery in the field of electric automobiles are expected to continuously increase, and the volume of the future retired lithium iron phosphate battery is expected to continuously increase.
The lithium iron phosphate anode material does not contain noble metals and mainly comprises lithium, iron, phosphorus and oxygen elements. The existing data show that the waste lithium iron phosphate power battery is mainly used for recovering lithium elements through element extraction. The residual materials are generally disposed of by discarding, landfilling and other low-value treatments due to the low commercial value of the materials. In the long term, the volume of the lithium iron phosphate battery retired in the future can be very large, if the lithium iron phosphate battery cannot be properly disposed after being retired, on one hand, environmental pressure and potential safety hazard can be brought to the society; on the other hand, the resource waste is also caused, which is unfavorable for the continuous healthy development of the new energy industry.
The polyanion compound with low cost and high safety has an open frame structure and a good ion migration path, is expected to become a sodium ion battery anode material with wide application prospect, is synthesized by a solid phase method at present, and has realized industrialized mass production, but the prepared material has poor multiplying power performance, cycle life and conductivity due to the shape agglomeration and low phase purity.
Disclosure of Invention
In order to solve the problems and other technical problems which are not solved, the invention aims to provide a method for preparing a positive electrode material of a sodium ion battery by utilizing waste lithium iron phosphate, and the positive electrode material for manufacturing the sodium ion battery is prepared.
The invention is realized by the following technical scheme.
The invention relates to a method for preparing a sodium ion battery anode material from waste lithium iron phosphate, which comprises the following steps of.
(1) Pre-extracting lithium from waste lithium iron phosphate powder to obtain a lithium iron phosphate leaching material, and ball-milling the leaching material to 200-500 nm.
(2) Mixing and stirring the lithium iron phosphate leaching material subjected to ball milling in the step (1) with a certain amount of carbon source, sodium source, phosphorus source or other anion sources and ultrapure water, evaporating and drying to prepare a mixed precursor.
(3) Carbonizing, annealing and washing the precursor prepared in the step (2) in an inert atmosphere to obtain the sodium ion battery anode material.
The lithium leached lithium iron phosphate waste material of step (1) mainly comprises: one or more of lithium iron phosphate, ferric phosphate dihydrate and ferric phosphate.
The carbon source in the step (2) is one or more of glucose, ascorbic acid, polyvinylpyrrolidone, polyacrylic acid and the like, and the carbon source accounts for 1-10% of the mass ratio of the mixed leaching materials. Preferably glucose and polyacrylic acid, and the carbon source mass ratio is 3-7%.
The sodium source in the step (2) comprises one or more of sodium hydroxide, sodium carbonate, sodium acetate, sodium phosphate and the like, and the addition amount is 100-150% of the stoichiometric ratio of the product. Sodium hydroxide and sodium carbonate are preferred.
The phosphorus source in the step (2) comprises one or more of phosphoric acid, sodium phosphate, ammonium dihydrogen phosphate and the like, and the addition amount is 100-150% of the stoichiometric ratio of the product. Ammonium dihydrogen phosphate is preferred.
The anion source in step (2) includes, but is not limited to, one or more of fluorine source, sulfate source, carbonate source, etc., preferably sodium fluoride.
The solid-liquid ratio of the lithium iron phosphate leaching material to the ultrapure water in the step (2) is 1:1-1:6.
The annealing process in the step (3) comprises carbonization for 1-3 hours at 300-450 ℃, and then heating to 550-750 ℃ continuously, and annealing for 4-12 h. Preferably at a carbonization temperature of 400 ℃,2 h and an annealing temperature of 600 ℃ for 10 hours.
The washing solvent of step (3) comprises: one or more solvents of acetone, methanol, ethanol, toluene, etc., preferably ethanol.
The positive electrode material of the sodium ion battery prepared by regeneration of the invention comprises and is not limited to polyanion compounds, preferably Na 3.12 Fe 2.44 (P 2 O 7 ) 2 。
According to the invention, different polyanion compounds can be prepared by adjusting the proportion and adding other elements: na (Na) 3.12 Fe 2.44 (P 2 O 7 ) 2 、Na 2 FePO 4 F、Na 2 FePO 4 、Na 7 Fe 4 (P 2 O 7 ) 4 PO 4 、Na 2 FePO 4 F or Na 4 Fe 3 (SO 4 ) 2 (P 2 O 7 ) Etc.
The invention utilizes the waste lithium iron phosphate to prepare the positive electrode material of the sodium ion battery, can effectively inherit the shape of the nano particles, simplifies the synthesis process, effectively solves the technical difficulties of single recovery product, low economic benefit, more wastes and the like of the traditional lithium iron phosphate battery, and fills the process gap of direct conversion and regeneration of the waste lithium iron phosphate. The invention has simple process flow and is easy to realize large-scale production.
Drawings
FIG. 1 is a schematic view of an example 1 of a method for preparing Na-ion battery cathode material using waste lithium iron phosphate 3.12 Fe 2.44 (P 2 O 7 ) 2 Is a flow chart of (a).
Fig. 2 is a diagram showing preparation of sodium ion battery positive electrode material Na using waste lithium iron phosphate according to example 1 3.12 Fe 2.44 (P 2 O 7 ) 2 Scanning electron microscope photographs of (2).
FIG. 3 is a schematic diagram of an example 1 of a method for preparing Na-ion battery cathode material from waste lithium iron phosphate 3.12 Fe 2.44 (P 2 O 7 ) 2 Is a XRD pattern of (C).
Fig. 4 shows preparation of sodium ion battery positive electrode material Na by using waste lithium iron phosphate according to examples 2 and 3 3.12 Fe 2.44 (P 2 O 7 ) 2 Is a XRD pattern of (C).
FIG. 5 is a schematic diagram of the method for preparing Na-ion battery cathode material from waste lithium iron phosphate in example 1 3.12 Fe 2.44 (P 2 O 7 ) 2 Is a cyclic voltammogram of (c).
FIG. 6 is a diagram showing the preparation of sodium ion battery cathode material Na using waste lithium iron phosphate according to example 1 3.12 Fe 2.44 (P 2 O 7 ) 2 Constant current charge-discharge curve of (2).
FIG. 7 shows the preparation of sodium ion battery cathode material Na from waste lithium iron phosphate according to examples 1-3 3.12 Fe 2.44 (P 2 O 7 ) 2 Is a cyclic test curve of (2).
FIG. 8 is a diagram showing the preparation of Na-ion battery cathode material using waste lithium iron phosphate according to example 5 2 FePO 4 F scanning electron micrograph.
FIG. 9 is a diagram showing the preparation of Na-ion battery cathode material using waste lithium iron phosphate according to example 5 2 FePO 4 XRD pattern of F.
Fig. 10 is a diagram of a method for preparing Na-ion battery cathode material using waste lithium iron phosphate according to example 6 2 FePO 4 Scanning electron microscope photographs of (2).
FIG. 11 is a diagram showing the preparation of Na-ion battery cathode material using waste lithium iron phosphate according to example 6 2 FePO 4 Is a XRD pattern of (C).
FIG. 12 is a diagram showing the preparation of Na-ion battery cathode material using waste lithium iron phosphate according to example 7 7 Fe 4 (P 2 O 7 ) 4 PO 4 Scanning electron microscope photographs of (2).
FIG. 13 is a schematic diagram showing the preparation of Na-ion battery cathode material using waste lithium iron phosphate according to example 7 7 Fe 4 (P 2 O 7 ) 4 PO 4 Is a XRD pattern of (C).
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
Characterization tests for preparing a positive electrode material of a sodium ion battery from waste lithium iron phosphate provided in the following examples are as follows.
(1) Scanning electron microscope test: scanning Electron Microscope (SEM) instrument model SU8020.
(2) X-ray diffraction (XRD) test, using the model number: smartlab (9), the test parameters used Cu/K alpha rays, lambda= 1.4506A, voltage 40 kV, current 100 mA, scanning speed 10 DEG/min step size 0.02 DEG, and scanning angle 10 DEG-70 deg.
(3) The cyclic voltammetry test is a Chenhua electrochemical workstation, the model of the instrument is CHI600E, the scanning rate is 0.1 mV/s, and the voltage interval is 1.6-4V.
(4) And the constant current charge and discharge test is that the LAND battery test system has the instrument model of CT2001A, the current density of 1C and the voltage interval of 1.6-4V.
Example 1
(1) Pre-extracting lithium from waste lithium iron phosphate powder to obtain a lithium iron phosphate leaching material, mixing the 50 g waste lithium iron phosphate leaching material with 500 mL ultrapure water solution, loading the mixture into a ball milling tank, ball milling the mixture on a planetary ball mill at 600 rpm for 6h, taking out the ball milling liquid, placing the ball milling liquid into an oven, and drying the ball milling liquid at 80 ℃ for 12 h. Obtaining refined waste lithium iron phosphate leaching material.
(2) Weighing 46.1 and g of waste lithium iron phosphate leaching materials, mixing the waste lithium iron phosphate leaching materials with 26.3 g of polyacrylic acid with 25 percent and 50 mL of ultrapure water until the waste lithium iron phosphate leaching materials are completely dispersed and mixed, adding 17.3 g ammonium dihydrogen phosphate and 13.5 g sodium hydroxide into the mixed leaching materials, mixing and stirring for 30 min, placing the mixed slurry on a heating table at 80 ℃, stirring and heating at 500rpm until the solvent is completely volatilized, and obtaining a mixed precursor.
(3) Grinding the mixture, transferring the mixture into an alumina magnetic boat, and placing the alumina magnetic boat in a tube furnace, and heating the mixture at 400 ℃ for 3 h at a heating rate of 4 ℃/min; then heating to 600 ℃ to heat 10 h, wherein the heating rate is 10 ℃/min. Cooling, washing and drying the reaction product with ethanol for multiple times to obtain sodium ion battery anode material Na with 7% carbon coating amount 3.12 Fe 2.44 (P 2 O 7 ) 2 And (3) powder.
Example 2
(1) Pre-extracting lithium from waste lithium iron phosphate powder to obtain a lithium iron phosphate leaching material, mixing the 50 g waste lithium iron phosphate leaching material with 500 mL ultrapure water solution, loading the mixture into a ball milling tank, ball milling the mixture on a planetary ball mill at 600 rpm for 6h, taking out the ball milling liquid, placing the ball milling liquid into an oven, and drying the ball milling liquid at 80 ℃ for 12 h. Obtaining refined waste lithium iron phosphate leaching material.
(2) Weighing 46.1 and g waste lithium iron phosphate leaching materials, mixing the waste lithium iron phosphate leaching materials with 6.6 g ascorbic acid and 100 mL ultrapure water until the waste lithium iron phosphate leaching materials are dispersed and mixed, adding 17.1 g monoammonium phosphate and 19.3 g sodium carbonate into the mixed leaching materials, mixing and stirring for 30 min, placing the mixed slurry on a heating table at 80 ℃, stirring and heating at 500rpm until the solvent is completely volatilized, and obtaining a mixed precursor.
(3) Grinding the mixture, transferring the mixture into an alumina magnetic boat, and placing the alumina magnetic boat in a tube furnace, heating the mixture at 400 ℃ for 2 h, wherein the heating rate is 4 ℃/min; then heating to 550 ℃ and heating to 10 h, wherein the heating rate is 10 ℃/min. Cooling, washing and drying the reaction product with toluene for multiple times to obtain sodium ion battery anode material Na with 5% carbon coating amount 3.12 Fe 2.44 (P 2 O 7 ) 2 And (3) powder.
Example 3
(1) Pre-extracting lithium from waste lithium iron phosphate powder to obtain a lithium iron phosphate leaching material, mixing the 50 g waste lithium iron phosphate leaching material with 500 mL ultrapure water solution, loading the mixture into a ball milling tank, ball milling the mixture on a planetary ball mill at 600 rpm for 6 hours, taking out the ball milling liquid, placing the ball milling liquid into an oven, and drying the ball milling liquid at 80 ℃ for 12 h. Obtaining refined waste lithium iron phosphate leaching material.
(2) Weighing 46.1 and g of waste lithium iron phosphate leaching materials, mixing the waste lithium iron phosphate leaching materials with 11.2 g of polyacrylic acid with 25 percent of content and 150 mL of ultrapure water until the waste lithium iron phosphate leaching materials are dispersed and mixed, adding 12.3 g of sodium phosphate and 9.1 and g of sodium hydroxide into the mixed leaching materials, mixing and stirring for 30 min, placing the mixed slurry on a heating table at 80 ℃, stirring and heating at 500rpm until the solvent is completely volatilized, and obtaining a mixed precursor.
(3) Grinding the mixture, transferring the mixture into an alumina magnetic boat, and placing the alumina magnetic boat in a tube furnace, heating the mixture at 400 ℃ for 1 h, wherein the heating rate is 4 ℃/min; then heat up to 650Heating at 6 deg.C and h at a rate of 10deg.C/min. Cooling, washing and drying the reaction product with ethanol for multiple times to obtain sodium ion battery anode material Na with 3% carbon coating amount 3.12 Fe 2.44 (P 2 O 7 ) 2 And (3) powder.
Example 4
(1) Pre-extracting lithium from waste lithium iron phosphate powder to obtain a lithium iron phosphate leaching material, mixing the 50 g waste lithium iron phosphate leaching material with 500 mL ultrapure water solution, loading the mixture into a ball milling tank, ball milling the mixture on a planetary ball mill at 600 rpm for 6h, taking out the ball milling liquid, placing the ball milling liquid into an oven, and drying the ball milling liquid at 80 ℃ for 12 h. Obtaining refined waste lithium iron phosphate leaching material.
(2) Weighing 46.1 and g waste lithium iron phosphate leaching materials, mixing with 6.2 and g glucose and 200 and mL ultrapure water until the waste lithium iron phosphate leaching materials are dispersed and mixed, adding 13.3 and g phosphoric acid and 14.1 and g sodium acetate into the mixed leaching materials, mixing and stirring for 30 min, placing the mixed slurry on a heating table at 80 ℃, stirring and heating at 500rpm until the solvent is completely volatilized, and obtaining a mixed precursor.
(3) Grinding the mixture, transferring the mixture into an alumina magnetic boat, and placing the alumina magnetic boat in a tube furnace, heating the mixture at 400 ℃ for 2 h, wherein the heating rate is 4 ℃/min; then heating to 600 ℃ to heat 8 h, wherein the heating rate is 10 ℃/min. After cooling, washing and drying the reaction product for multiple times by using acetone to obtain the Na-ion battery anode material with 7% carbon coating quantity 3.12 Fe 2.44 (P 2 O 7 ) 2 And (3) powder.
Example 5
(1) Pre-extracting lithium from waste lithium iron phosphate powder to obtain a lithium iron phosphate leaching material, mixing the 50 g waste lithium iron phosphate leaching material with 500 mL ultrapure water solution, loading the mixture into a ball milling tank, ball milling the mixture on a planetary ball mill at 600 rpm for 6h, taking out the ball milling liquid, placing the ball milling liquid into an oven, and drying the ball milling liquid at 80 ℃ for 12 h. Obtaining refined waste lithium iron phosphate leaching material.
(2) Weighing 46.1 and g of waste lithium iron phosphate leaching materials, mixing the waste lithium iron phosphate leaching materials with 3.1g of polyvinylpyrrolidone and 200 mL of ultrapure water until the waste lithium iron phosphate leaching materials are dispersed and mixed, adding 1.3 g of monoammonium phosphate, 21.5 g of sodium hydroxide and 10.4 g of sodium fluoride into the mixed leaching materials, mixing and stirring for 30 min, placing the mixed slurry on a heating table at 80 ℃, stirring and heating at 500rpm until the solvent is completely volatilized, and obtaining a mixed precursor.
(3) Grinding the mixture, transferring the mixture into an alumina magnetic boat, and placing the alumina magnetic boat in a tube furnace, heating the mixture at 400 ℃ for 2 h, wherein the heating rate is 4 ℃/min; then heating to 650 ℃ to heat 8 h, wherein the heating rate is 10 ℃/min. After cooling, washing and drying the reaction product for multiple times by using acetone to obtain the Na-ion battery anode material with 7% carbon coating quantity 2 FePO 4 F powder.
Example 6
(1) Pre-extracting lithium from waste lithium iron phosphate powder to obtain a lithium iron phosphate leaching material, mixing the 50 g waste lithium iron phosphate leaching material with 500 mL ultrapure water solution, loading the mixture into a ball milling tank, ball milling the mixture on a planetary ball mill at 600 rpm for 6h, taking out the ball milling liquid, placing the ball milling liquid into an oven, and drying the ball milling liquid at 80 ℃ for 12 h. Obtaining refined waste lithium iron phosphate leaching material.
(2) Weighing 46.1 and g of waste lithium iron phosphate leaching materials, mixing the waste lithium iron phosphate leaching materials with 6.6 g glucose and 200 mL of ultrapure water until the waste lithium iron phosphate leaching materials are dispersed and mixed, adding 2.8 and g of monoammonium phosphate and 23.1g of sodium carbonate into the mixed leaching materials, mixing and stirring for 30 min, placing the mixed slurry on a heating table at 80 ℃, stirring and heating at 500rpm until the solvent is completely volatilized, and obtaining a mixed precursor.
(3) Grinding the mixture, transferring the mixture into an alumina magnetic boat, and placing the alumina magnetic boat in a tube furnace, heating the mixture at 400 ℃ for 2 h, wherein the heating rate is 4 ℃/min; then heating to 600 ℃ to heat 8 h, wherein the heating rate is 10 ℃/min. After cooling, washing and drying the reaction product for multiple times by using acetone to obtain the Na-ion battery anode material with 7% carbon coating quantity 2 FePO 4 And (3) powder.
Example 7
(1) Pre-extracting lithium from waste lithium iron phosphate powder to obtain a lithium iron phosphate leaching material, mixing the 50 g waste lithium iron phosphate leaching material with 500 mL ultrapure water solution, loading the mixture into a ball milling tank, ball milling the mixture on a planetary ball mill at 600 rpm for 6h, taking out the ball milling liquid, placing the ball milling liquid into an oven, and drying the ball milling liquid at 80 ℃ for 12 h. Obtaining refined waste lithium iron phosphate leaching material.
(2) Weighing 46.1 g g of waste lithium iron phosphate leaching material, mixing the waste lithium iron phosphate leaching material with 26.3 g of 25% content polyacrylic acid aqueous solution and 200 mL of ultrapure water until the waste lithium iron phosphate leaching material is dispersed and mixed, adding 18.1 g ammonium dihydrogen phosphate and 19.1 g sodium hydroxide into the mixed leaching material, mixing and stirring for 30 min, placing the mixed slurry on a heating table at 80 ℃, stirring and heating at 500rpm until the solvent is completely volatilized, and obtaining a mixed precursor.
(3) Grinding the mixture, transferring the mixture into an alumina magnetic boat, and placing the alumina magnetic boat in a tube furnace, heating the mixture at 400 ℃ for 2 h, wherein the heating rate is 4 ℃/min; then heating to 650 ℃ to heat 8 h, wherein the heating rate is 10 ℃/min. After cooling, washing and drying the reaction product for multiple times by using acetone to obtain the Na-ion battery anode material with 7% carbon coating quantity 7 Fe 4 (P 2 O 7 ) 4 PO 4 And (3) powder.
Claims (3)
1. A method for preparing a sodium ion battery anode material by using waste lithium iron phosphate is characterized by comprising the following steps:
(1) Pre-extracting lithium from waste lithium iron phosphate powder to obtain a lithium iron phosphate leaching material, and ball-milling the leaching material to 200-500 nm;
(2) Mixing and stirring the lithium iron phosphate leaching material subjected to ball milling in the step (1) with a certain amount of carbon source, sodium source, phosphorus source or other anion sources and ultrapure water, and evaporating and drying to prepare a mixed precursor;
(3) Carbonizing, annealing and washing the precursor prepared in the step (2) under inert atmosphere to obtain a sodium ion battery anode material;
the lithium leached lithium iron phosphate waste material of step (1) comprises: one or more of lithium iron phosphate, ferric phosphate dihydrate or ferric phosphate;
the carbon source in the step (2) is one or more of glucose, ascorbic acid, polyvinylpyrrolidone or polyacrylic acid, and the carbon source accounts for 1-10% of the mass ratio of the mixed leaching materials;
the sodium source in the step (2) comprises one or more of sodium hydroxide, sodium carbonate, sodium acetate or sodium phosphate, and the addition amount is 100% -150% of the stoichiometric ratio of the product;
the phosphorus source in the step (2) comprises one or more of phosphoric acid, sodium phosphate, ammonium dihydrogen phosphate and the like, and the addition amount is 100-150% of the stoichiometric ratio of the product;
the anion source of step (2) includes, but is not limited to, one or more of a fluoride source, a sulfate source, or a carbonate source;
the solid-to-liquid ratio of the lithium iron phosphate leaching material to the ultrapure water in the step (2) is 1:1-1:6
The annealing process in the step (3) is carried out under the conditions that the carbonization temperature is 300-450 ℃, the carbonization is carried out for 1-3 hours, then the temperature is continuously increased to 550-750 ℃, and the annealing is carried out for 4-12 h;
the washing solvent in the step (3) comprises one or more solvents selected from acetone, methanol, ethanol or toluene.
2. The method for preparing the sodium ion battery positive electrode material by utilizing the waste lithium iron phosphate, which is disclosed in claim 1, is characterized in that the carbon source mass ratio in the step (2) is 3-7%.
3. The method for preparing the positive electrode material of the sodium ion battery by utilizing the waste lithium iron phosphate, which is disclosed in claim 1, is characterized in that the annealing process in the step (3) is carried out at a carbonization temperature of 400 ℃, a heating temperature of 2 h and an annealing temperature of 600 ℃ for 10 hours.
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| US20130244100A1 (en) * | 2012-03-15 | 2013-09-19 | Imra America, Inc. | Iron phosphates: negative electrode materials for aqueous rechargeable sodium ion energy storage devices |
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| US20130244100A1 (en) * | 2012-03-15 | 2013-09-19 | Imra America, Inc. | Iron phosphates: negative electrode materials for aqueous rechargeable sodium ion energy storage devices |
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