CN116885172A - Method for circularly reconstructing lithium iron phosphate from phosphorus iron slag after lithium extraction, lithium iron phosphate and application thereof - Google Patents
Method for circularly reconstructing lithium iron phosphate from phosphorus iron slag after lithium extraction, lithium iron phosphate and application thereof Download PDFInfo
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- CN116885172A CN116885172A CN202311043951.2A CN202311043951A CN116885172A CN 116885172 A CN116885172 A CN 116885172A CN 202311043951 A CN202311043951 A CN 202311043951A CN 116885172 A CN116885172 A CN 116885172A
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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 82
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000002893 slag Substances 0.000 title claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000605 extraction Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 238000004064 recycling Methods 0.000 claims abstract description 23
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000004108 freeze drying Methods 0.000 claims abstract description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 16
- 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 14
- 239000008103 glucose Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 239000011775 sodium fluoride Substances 0.000 claims description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000001502 supplementing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000009469 supplementation Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 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 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940085288 combination potassium chloride Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- -1 salt ions Chemical class 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940073713 combination sodium fluoride Drugs 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Abstract
The invention provides a method for circularly reconstructing lithium iron phosphate from phosphorus iron slag after lithium extraction, lithium iron phosphate and application thereof, wherein the method comprises the following steps: (1) Mixing the lithium extracted ferrophosphorus slag, a carbon source and a lithium salt solution, and performing hydrothermal treatment to obtain a first mixture; (2) Freeze-drying the first mixture to obtain a second mixture; (3) Sintering the second mixture at high temperature to obtain a third mixture; (4) And sequentially washing and drying the third mixture to obtain the reconstituted carbon coated lithium iron phosphate. According to the method provided by the invention, the lithium iron phosphate is coated by the in-situ hydrothermal lithium supplementing recycled carbon of the phosphorus iron slag after lithium extraction, so that the efficient recycling of valuable elements in the waste phosphorus iron slag is realized, the applicability of raw materials is enhanced, meanwhile, the process flow is simplified, secondary pollution is avoided, the environmental protection and economic benefits are considered, and the method is beneficial to large-scale popularization and application.
Description
Technical Field
The invention belongs to the technical field of waste lithium ion battery recovery, relates to a method for recycling lithium iron phosphate by using ferrophosphorus slag, and particularly relates to a method for recycling lithium iron phosphate by using ferrophosphorus slag after lithium extraction, lithium iron phosphate and application thereof.
Background
Lithium iron phosphate (LiFePO) 4 ) Batteries have become one of the mainstream choices of power lithium ion batteries for vehicles due to their cost advantages and high safety, but due to the limited life of lithium ion batteries, a large amount of lithium iron phosphate batteries must be scrapped over time. The waste lithium iron phosphate battery is subjected to pretreatment procedures such as crushing, sorting and the like to obtain lithium iron phosphate waste (LiFePO) 4 and/C/Al/Cu/Fe, etc.), the waste contains rare noble metal element lithium and rich iron and phosphorus, and if the rare noble metal element lithium and the rich iron and phosphorus are reasonably recycled, the consumption of mineral resources can be slowed down, good social and economic benefits can be produced, and the technical staff can conduct extensive researches aiming at the problem.
In addition, as the value of lithium in the waste lithium iron phosphate black powder is higher, the existing waste lithium iron phosphate black powder recovery method mainly adopts an oxidation acid system to selectively extract lithium in the waste lithium iron phosphate black powder to further prepare battery-grade lithium carbonate for recycling, and the generated phosphorus iron slag contains rich phosphorus iron elements, is often piled up or directly used as solid waste treatment, and lacks effective recycling treatment technology or means.
CN 102208707a discloses a method for repairing and regenerating waste lithium iron phosphate battery anode materials, which comprises the steps of mixing and ball milling recovered lithium iron phosphate waste materials with lithium carbonate or placing the lithium iron phosphate waste materials in a lithium-containing solution for hydrothermal lithium supplementation, and performing solid phase repairing to obtain regenerated lithium iron phosphate. The solid phase repair regeneration provides a good way for recycling the lithium iron phosphate waste, but the method has high purity requirement on the lithium iron phosphate waste, and in actual industrial production, the lithium iron phosphate waste has complex material feeding and high impurity content, so that the lithium iron phosphate obtained by the solid phase regeneration has low coulomb efficiency and poor multiplying power performance, and further the application of the technology in industrialization is limited.
CN 110459828A discloses a comprehensive recovery method of waste lithium iron phosphate battery anode materials, wherein dilute acid and oxidant are utilized to leach waste lithium iron phosphate battery anode powder to obtain lithium enrichment liquid, and then precipitation method is adopted to purify and remove impurities to obtain lithium carbonate. The method realizes the selective recovery of lithium in the waste lithium iron phosphate battery, is a method commonly adopted in the current industrial production, but has few reports on how to carry out high-value green disposal on the ferrophosphorus slag generated after the lithium extraction.
Therefore, how to provide a method for recycling lithium iron phosphate by using the phosphorus iron slag after extracting lithium, the applicability of raw materials is enhanced, meanwhile, the process flow is simplified, secondary pollution is avoided, environmental protection and economic benefits are considered, and the method becomes a urgent problem to be solved by the current technicians in the field.
Disclosure of Invention
The invention aims to provide a method for recycling lithium iron phosphate by using phosphorus iron slag after lithium extraction, lithium iron phosphate and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for recycling lithium iron phosphate from phosphorus iron slag after lithium extraction, comprising the following steps:
(1) Mixing the lithium extracted ferrophosphorus slag, a carbon source and a lithium salt solution, and performing hydrothermal treatment to obtain a first mixture;
(2) Freeze-drying the first mixture to obtain a second mixture;
(3) Sintering the second mixture at high temperature to obtain a third mixture;
(4) And sequentially washing and drying the third mixture to obtain the reconstituted carbon coated lithium iron phosphate.
According to the invention, the carbon source is mixed in the hydrothermal treatment process, so that the full mixing between the ferrophosphorus slag and the lithium source is facilitated, the in-situ hydrothermal lithium supplementation is realized, the smooth conversion from the waste ferrophosphorus slag to the lithium iron phosphate is realized through high-temperature sintering, the finally prepared carbon-coated lithium iron phosphate is realized, the efficient recycling of valuable elements in the waste ferrophosphorus slag is realized, the raw material applicability is strong, the process flow is simple, the repeatability is good, and the method is suitable for industrial scale-up production.
In addition, the method provided by the invention forms a closed-circuit flow, does not produce secondary pollution, and has low production cost, thereby taking into account environmental protection and economy and being beneficial to large-scale popularization and application.
Preferably, the carbon source of step (1) comprises any one or a combination of at least two of glucose, water-soluble starch or absolute ethanol, and typical but non-limiting combinations include a combination of glucose and water-soluble starch, a combination of water-soluble starch and absolute ethanol, a combination of glucose and absolute ethanol, or a combination of glucose, water-soluble starch and absolute ethanol.
Preferably, the mixing ratio of the carbon source in step (1) is 10 to 30wt%, for example, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt% or 30wt%, based on the total amount of the mixture, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In the invention, the mixing ratio of the carbon sources needs to be controlled within a reasonable range. When the mixing ratio is less than 10wt%, too little carbon source cannot completely wrap the surface of the ferrophosphorus slag particles, thereby resulting in a decrease in electrochemical properties of the finally obtained lithium iron phosphate material; when the mixing ratio is more than 30wt%, not only is the raw material redundant caused, the treatment cost is unnecessarily increased, but also excessive carbon is mixed in the ferrophosphorus slag to reduce the compacted density of the regenerated lithium iron phosphate material, thereby affecting the electrochemical performance thereof.
Preferably, the solute in the lithium salt solution of step (1) comprises lithium hydroxide and/or lithium nitrate.
Preferably, the concentration of the lithium salt solution in the step (1) is 1 to 5mol/L, for example, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L or 5mol/L, but not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the solid-to-liquid ratio of the phosphorus iron slag and the lithium salt solution after the lithium extraction in the step (1) is 50-300g/L, for example, 50g/L, 60g/L, 80g/L, 100g/L, 120g/L, 140g/L, 160g/L, 180g/L, 200g/L, 220g/L, 240g/L, 260g/L, 280g/L or 300g/L, but the solid-to-liquid ratio is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the mixed material of step (1) further comprises an inorganic salt in order to further enhance the electrochemical properties of the finally obtained lithium iron phosphate.
Preferably, the inorganic salt comprises any one or a combination of at least two of sodium chloride, potassium chloride or sodium fluoride, typically but not limited to combinations of sodium chloride and potassium chloride, combinations of potassium chloride and sodium fluoride, combinations of sodium chloride and sodium fluoride, or combinations of sodium chloride, potassium chloride and sodium fluoride.
Preferably, the inorganic salt is mixed in an amount of 1 to 10wt% based on the total amount of the mixture, and may be, for example, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The temperature of the hydrothermal treatment in the step (1) is preferably 100 to 200 ℃, and may be, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, or 200 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
In the invention, the temperature of the hydrothermal treatment needs to be controlled within a reasonable range. When the temperature is lower than 100 ℃, active sites on the surfaces of the ferrophosphorus slag particles in the solution are too few, so that the carbon source of the solution and the contact degree between salt ions of the aqueous solution and the particles are insufficient, and the mixing uniformity among different components in the whole system is further reduced; when the temperature is higher than 200 ℃, the pressure in the system is too high, the operation difficulty is increased, and meanwhile, the extra energy consumption is unnecessarily increased.
Preferably, the time of the hydrothermal treatment in step (1) is 1-5h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the hydrothermal treatment in step (1) is carried out with stirring at a stirring speed of 100 to 500rpm, for example, 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm or 500rpm, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are equally applicable.
Preferably, the temperature of the freeze-drying in step (2) is-10 to 0 ℃, for example, -10 ℃, -9 ℃, -8 ℃, -7 ℃, -6 ℃, -5 ℃, -4 ℃, -3 ℃, -2 ℃, -1 ℃ or 0 ℃, but is not limited to the recited values, other non-recited values within the range of values being equally applicable.
Preferably, the time of the freeze-drying in the step (2) is 1-5h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the freeze-drying in step (2) has an absolute vacuum of 10 -5 -10 -1 MPa, for example, can be 10 -5 、5×10 -4 、10 -4 、5×10 -3 、10 -3 、5×10 -2 、10 -2 、5×10 -1 Or 10 -1 But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the high temperature sintering of step (3) is performed in an inert gas atmosphere.
Preferably, the inert gas comprises any one or a combination of at least two of nitrogen, argon or helium, typically but not limited to combinations comprising nitrogen and argon, argon and helium, nitrogen and helium, or nitrogen, argon and helium.
Preferably, the high temperature sintering in step (3) has a temperature of 500 to 800 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, but the sintering temperature is not limited to the values listed, and other values not listed in the range are equally applicable.
In the invention, the temperature of the high-temperature sintering needs to be controlled within a reasonable range. When the temperature is lower than 500 ℃, the carbonization of the carbon source is insufficient, and the reduction degree of iron in the ferrophosphorus slag is reduced, so that the electrochemical performance of the prepared lithium iron phosphate material is affected; when the temperature is higher than 800 ℃, the generated lithium iron phosphate material is unstable and decomposed, and the energy consumption is unnecessarily increased.
Preferably, the high temperature sintering time in step (3) is 3-20h, for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the solid-to-liquid ratio of the water washing in the step (4) is 50-300g/L, for example, 50g/L, 60g/L, 80g/L, 100g/L, 120g/L, 140g/L, 160g/L, 180g/L, 200g/L, 220g/L, 240g/L, 260g/L, 280g/L or 300g/L, but not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
The temperature of the washing with water in the step (4) is preferably 0 to 100 ℃, and may be, for example, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, or 100 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the time of the washing in the step (4) is 0.5-2h, for example, but not limited to, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, and other non-enumerated values in the numerical range are equally applicable.
Preferably, the temperature of the drying in the step (4) is 40 to 80 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but the method is not limited to the listed values, and other non-listed values within the range are applicable.
Preferably, the drying time in step (4) is 6-12h, for example, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h or 12h, but not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferred technical solution of the first aspect of the present invention, the method includes the following steps:
(1) Adding the lithium-extracted ferrophosphorus slag into a lithium salt solution with the concentration of 1-5mol/L, controlling the solid-to-liquid ratio of the ferrophosphorus slag to be 50-300g/L, adding a carbon source and inorganic salt, fully dissolving and mixing, and then placing the mixture into a hydrothermal reaction kettle, setting the hydrothermal treatment temperature to be 100-200 ℃, the hydrothermal time to be 1-5h and the hydrothermal rotating speed to be 100-500rpm, so as to obtain a first mixture; the solute in the lithium salt solution comprises lithium hydroxide and/or lithium nitrate, the carbon source comprises any one or a combination of at least two of glucose, water-soluble starch or absolute ethyl alcohol, and the inorganic salt comprises any one or a combination of at least two of sodium chloride, potassium chloride or sodium fluoride; the mixing ratio of the carbon source is 10-30wt% and the mixing ratio of the inorganic salt is 1-10wt% based on the total amount of the mixed materials;
(2) Freeze-drying the first mixture in a freeze dryer at-10deg.C to 0deg.C for 1-5 hr with absolute vacuum degree of 10 -5 -10 -1 MPa, obtaining a second mixture;
(3) Placing the second mixture into a tubular furnace for high-temperature sintering, and introducing any one or a combination of at least two of nitrogen, argon and helium into the tubular furnace, setting the sintering temperature to be 500-800 ℃ and the sintering time to be 3-20h to obtain a third mixture;
(4) Washing and drying the third mixture in sequence to obtain reconstituted lithium iron phosphate; the solid-liquid ratio of the water washing is 50-300g/L, the temperature is 0-100 ℃ and the time is 0.5-2h; the temperature of the drying is 40-80 ℃ and the time is 6-12h.
In a second aspect, the present invention provides a lithium iron phosphate reconstituted by the method of the first aspect, and the surface of the lithium iron phosphate is coated with a carbon layer.
In a third aspect, the present invention provides the use of a lithium iron phosphate as described in the second aspect as a positive electrode material for a lithium iron phosphate battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the carbon source is mixed in the hydrothermal treatment process, so that the full mixing between the ferrophosphorus slag and the lithium source is facilitated, the in-situ hydrothermal lithium supplementation is realized, the smooth conversion from the waste ferrophosphorus slag to the lithium iron phosphate is realized through high-temperature sintering, the finally prepared carbon-coated lithium iron phosphate is realized, the efficient recycling of valuable elements in the waste ferrophosphorus slag is realized, the raw material applicability is strong, the process flow is simple, the repeatability is good, and the method is suitable for industrial amplification production;
(2) The method provided by the invention forms a closed-circuit flow, does not produce secondary pollution, and has low production cost, thereby taking into account environmental protection and economy and being beneficial to large-scale popularization and application.
Drawings
FIG. 1 is a flow chart of a method for recycling and reproducing lithium iron phosphate from phosphorus iron slag after lithium extraction.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a method for circularly reconstructing lithium iron phosphate from phosphorus iron slag after lithium extraction, as shown in fig. 1, comprising the following steps:
(1) Adding the lithium-extracted ferrophosphorus slag into a lithium hydroxide solution with the concentration of 3mol/L, controlling the solid-to-liquid ratio of the ferrophosphorus slag to 175g/L, adding glucose and sodium chloride, wherein the mixing ratio of the glucose is 20wt%, the mixing ratio of the sodium chloride is 5wt%, fully dissolving and mixing, and then placing the mixture into a hydrothermal reaction kettle, wherein the hydrothermal treatment temperature is set to 150 ℃, the hydrothermal time is set to 3h, and the hydrothermal rotating speed is set to 300rpm, so as to obtain a first mixture;
(2) Freeze-drying the first mixture in a freeze dryer at-5deg.C for 3 hr with absolute vacuum degree of 10 -3 MPa, obtaining a second mixture;
(3) Placing the second mixture into a tube furnace for high-temperature sintering, introducing nitrogen into the tube furnace, setting the sintering temperature to 650 ℃ and the sintering time to 10 hours, and obtaining a third mixture;
(4) Washing and drying the third mixture in sequence to obtain reconstituted lithium iron phosphate; the solid-liquid ratio of the water washing is 175g/L, the temperature is 50 ℃, and the time is 1h; the temperature of the drying is 60 ℃ and the time is 9 hours.
Example 2
The embodiment provides a method for circularly reconstructing lithium iron phosphate from phosphorus iron slag after lithium extraction, as shown in fig. 1, comprising the following steps:
(1) Adding the lithium-extracted ferrophosphorus slag into a lithium nitrate solution with the concentration of 1mol/L, controlling the solid-to-liquid ratio of the ferrophosphorus slag to be 50g/L, then adding water-soluble starch and potassium chloride, wherein the mixing ratio of the water-soluble starch is 10wt%, the mixing ratio of the potassium chloride is 1wt%, fully dissolving and mixing, and then placing the mixture into a hydrothermal reaction kettle, wherein the hydrothermal treatment temperature is set to be 100 ℃, the hydrothermal time is set to be 5h, and the hydrothermal rotating speed is set to be 100rpm, so as to obtain a first mixture;
(2) Freeze-drying the first mixture in a freeze dryer at-10deg.C for 1 hr under absolute vacuum of 10 -1 MPa, obtaining a second mixture;
(3) Placing the second mixture into a tubular furnace for high-temperature sintering, introducing argon into the tubular furnace, setting the sintering temperature to be 500 ℃ and the sintering time to be 20 hours, and obtaining a third mixture;
(4) Washing and drying the third mixture in sequence to obtain reconstituted lithium iron phosphate; the solid-liquid ratio of the water washing is 50g/L, the temperature is 0 ℃, and the time is 2h; the temperature of the drying is 80 ℃ and the time is 6 hours.
Example 3
The embodiment provides a method for circularly reconstructing lithium iron phosphate from phosphorus iron slag after lithium extraction, as shown in fig. 1, comprising the following steps:
(1) Adding lithium-extracted ferrophosphorus slag into a lithium hydroxide solution with the concentration of 5mol/L, controlling the solid-to-liquid ratio of the ferrophosphorus slag to be 300g/L, adding glucose and sodium fluoride, wherein the mixing ratio of glucose is 30wt%, the mixing ratio of sodium fluoride is 10wt%, fully dissolving and mixing, and then placing the mixture into a hydrothermal reaction kettle, wherein the hydrothermal treatment temperature is set to be 200 ℃, the hydrothermal time is set to be 1h, and the hydrothermal rotating speed is set to be 500rpm, so as to obtain a first mixture;
(2) Freeze-drying the first mixture in a freeze dryer at 0deg.C for 5 hr under absolute vacuum of 10 -5 MPa, obtaining a second mixture;
(3) Placing the second mixture into a tube furnace for high-temperature sintering, introducing helium into the tube furnace, setting the sintering temperature to 800 ℃ and the sintering time to 3 hours, and obtaining a third mixture;
(4) Washing and drying the third mixture in sequence to obtain reconstituted lithium iron phosphate; the solid-liquid ratio of the water washing is 300g/L, the temperature is 100 ℃, and the time is 0.5h; the temperature of the drying is 40 ℃ and the time is 12 hours.
Example 4
The embodiment provides a method for recycling lithium iron phosphate by using phosphorus iron slag after extracting lithium, which is not described herein, except that the mixing ratio of glucose in the step (1) is changed to 8wt%, and the rest steps and conditions are the same as those in the embodiment 1.
Example 5
The embodiment provides a method for recycling lithium iron phosphate by using phosphorus iron slag after extracting lithium, which is not described herein, except that the mixing ratio of glucose in the step (1) is changed to 35wt%, and the rest steps and conditions are the same as those in the embodiment 1.
Example 6
The present embodiment provides a method for recycling lithium iron phosphate from phosphorus iron slag after extracting lithium, and the rest steps and conditions are the same as those in embodiment 1 except that the temperature of the hydrothermal treatment in step (1) is reduced to 80 ℃, so that no description is given here.
Example 7
The present embodiment provides a method for recycling lithium iron phosphate from phosphorus iron slag after extracting lithium, and the rest steps and conditions are the same as those in embodiment 1 except that the temperature of the hydrothermal treatment in step (1) is raised to 250 ℃, so that no description is given here.
Example 8
The present embodiment provides a method for recycling lithium iron phosphate from phosphorus iron slag after extracting lithium, and the rest steps and conditions are the same as those of embodiment 1 except that the temperature of high-temperature sintering in step (3) is reduced to 400 ℃, so that no description is given here.
Example 9
The present embodiment provides a method for recycling lithium iron phosphate from phosphorus iron slag after extracting lithium, and the other steps and conditions are the same as those in embodiment 1 except that the high temperature sintering temperature in step (3) is increased to 900 ℃, so that no description is given here.
Example 10
The present embodiment provides a method for recycling lithium iron phosphate from phosphorus iron slag after extracting lithium, and the rest steps and conditions are the same as those in embodiment 1 except that sodium chloride is not added in step (1), so that no description is given here.
Comparative example 1
The comparative example provides a method for recycling lithium iron phosphate by using phosphorus iron slag after extracting lithium, and the rest steps and conditions are the same as those of example 1 except that glucose is not added in step (1), so that no description is repeated here.
Comparative example 2
The comparative example provides a method for recycling lithium iron phosphate by using phosphorus iron slag after extracting lithium, except that in the step (1), the hydrothermal treatment is not performed, the freeze drying of the step (2) is not performed, the high-temperature sintering of the step (3) is directly performed on the mixed material, and other steps and conditions are the same as those of the embodiment 1, so that the description is omitted here.
The lithium iron phosphate obtained in examples 1 to 10 and comparative examples 1 to 2 were used as positive electrode materials, respectively, to prepare lithium iron phosphate batteries, the preparation process mainly comprising: firstly, uniformly mixing a lithium iron phosphate material, acetylene black and PVDF according to the mass ratio of 8:1:1, coating the mixture on an aluminum foil current collector, and then cutting the mixture into 1cm by a cutter 2 The wafer, the graphite cathode wafer and the electrolyte hexafluorophosphate lithium are pressed into the buckling shell in sequence to assemble the button cell.
The battery capacities of the batteries prepared using the lithium iron phosphate obtained in examples 1 to 10 and comparative examples 1 to 2 as a positive electrode material under the condition of 0.1C were examined as shown in table 1 below.
TABLE 1
| Lithium iron phosphate material | Battery capacity (mAh/g) |
| Example 1 | 160.2 |
| Example 2 | 158.9 |
| Example 3 | 159.3 |
| Example 4 | 158.6 |
| Example 5 | 161.4 |
| Implementation of the embodimentsExample 6 | 160.8 |
| Example 7 | 159.7 |
| Example 8 | 158.8 |
| Example 9 | 160.6 |
| Example 10 | 159.4 |
| Comparative example 1 | 151.1 |
| Comparative example 2 | 152.5 |
As can be seen from table 1: the electrochemical performance of the commercial lithium iron phosphate anode material generally requires that the discharge capacity of 0.1C is more than or equal to 155mAh/g, the electrochemical performance of the lithium iron phosphate material prepared by the synthesis of examples 1-10 meets the commercial requirements, and the electrochemical performance of the lithium iron phosphate material prepared by the synthesis of comparative examples 1-2 is lower than the commercial electrochemical performance requirements.
Therefore, the carbon source is mixed in the hydrothermal treatment process, so that the full mixing between the ferrophosphorus slag and the lithium source is facilitated, the in-situ hydrothermal lithium supplementation is realized, the smooth conversion from the waste ferrophosphorus slag to the lithium iron phosphate is realized through the subsequent high-temperature sintering, the finally prepared carbon-coated lithium iron phosphate is realized, the efficient recycling of valuable elements in the waste ferrophosphorus slag is realized, the raw material applicability is strong, the process flow is simple, the repeatability is good, and the method is suitable for industrial scale-up production.
In addition, the method provided by the invention forms a closed-circuit flow, does not produce secondary pollution, and has low production cost, thereby taking into account environmental protection and economy and being beneficial to large-scale popularization and application.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. A method for recycling and reconstructing lithium iron phosphate from phosphorus iron slag after lithium extraction, which is characterized by comprising the following steps:
(1) Mixing the lithium extracted ferrophosphorus slag, a carbon source and a lithium salt solution, and performing hydrothermal treatment to obtain a first mixture;
(2) Freeze-drying the first mixture to obtain a second mixture;
(3) Sintering the second mixture at high temperature to obtain a third mixture;
(4) And sequentially washing and drying the third mixture to obtain the reconstituted carbon coated lithium iron phosphate.
2. The method of claim 1, wherein the carbon source of step (1) comprises any one or a combination of at least two of glucose, water-soluble starch, or absolute ethanol;
preferably, the mixing ratio of the carbon source in the step (1) is 10-30wt% based on the total amount of the mixture;
preferably, the solute in the lithium salt solution of step (1) comprises lithium hydroxide and/or lithium nitrate;
preferably, the concentration of the lithium salt solution in the step (1) is 1-5mol/L;
preferably, the solid-to-liquid ratio of the phosphorus iron slag and the lithium salt solution after the lithium extraction in the step (1) is 50-300g/L.
3. The method of claim 1 or 2, wherein the mixed material of step (1) further comprises an inorganic salt;
preferably, the inorganic salt comprises any one or a combination of at least two of sodium chloride, potassium chloride or sodium fluoride;
preferably, the inorganic salt is mixed in an amount of 1 to 10wt% based on the total amount of the mixed materials.
4. A method according to any one of claims 1 to 3, wherein the temperature of the hydrothermal treatment of step (1) is 100 to 200 ℃;
preferably, the hydrothermal treatment in step (1) takes 1 to 5 hours;
preferably, the hydrothermal treatment in step (1) is accompanied by stirring at a stirring speed of 100-500rpm.
5. The method of any one of claims 1-4, wherein the temperature of the freeze drying of step (2) is from-10 to 0 ℃;
preferably, the freeze drying time of step (2) is 1-5 hours;
preferably, the freeze-drying in step (2) has an absolute vacuum of 10 -5 -10 -1 MPa。
6. The method according to any one of claims 1 to 5, wherein the high temperature sintering of step (3) is performed in an atmosphere of inert gas;
preferably, the inert gas comprises any one or a combination of at least two of nitrogen, argon or helium;
preferably, the high temperature sintering temperature in the step (3) is 500-800 ℃;
preferably, the high temperature sintering time in the step (3) is 3-20h.
7. The method according to any one of claims 1 to 6, wherein the solid to liquid ratio of the water wash of step (4) is 50 to 300g/L;
preferably, the temperature of the water washing in the step (4) is 0-100 ℃;
preferably, the time of the water washing in the step (4) is 0.5-2h;
preferably, the temperature of the drying in the step (4) is 40-80 ℃;
preferably, the drying time in the step (4) is 6-12h.
8. The method according to any one of claims 1-7, characterized in that the method comprises the steps of:
(1) Adding the lithium-extracted ferrophosphorus slag into a lithium salt solution with the concentration of 1-5mol/L, controlling the solid-to-liquid ratio of the ferrophosphorus slag to be 50-300g/L, adding a carbon source and inorganic salt, fully dissolving and mixing, and then placing the mixture into a hydrothermal reaction kettle, setting the hydrothermal treatment temperature to be 100-200 ℃, the hydrothermal time to be 1-5h and the hydrothermal rotating speed to be 100-500rpm, so as to obtain a first mixture; the solute in the lithium salt solution comprises lithium hydroxide and/or lithium nitrate, the carbon source comprises any one or a combination of at least two of glucose, water-soluble starch or absolute ethyl alcohol, and the inorganic salt comprises any one or a combination of at least two of sodium chloride, potassium chloride or sodium fluoride; the mixing ratio of the carbon source is 10-30wt% and the mixing ratio of the inorganic salt is 1-10wt% based on the total amount of the mixed materials;
(2) Freeze-drying the first mixture in a freeze dryer at-10deg.C to 0deg.C for 1-5 hr with absolute vacuum degree of 10 -5 -10 -1 MPa, obtaining a second mixture;
(3) Placing the second mixture into a tubular furnace for high-temperature sintering, and introducing any one or a combination of at least two of nitrogen, argon and helium into the tubular furnace, setting the sintering temperature to be 500-800 ℃ and the sintering time to be 3-20h to obtain a third mixture;
(4) Washing and drying the third mixture in sequence to obtain reconstituted lithium iron phosphate; the solid-liquid ratio of the water washing is 50-300g/L, the temperature is 0-100 ℃ and the time is 0.5-2h; the temperature of the drying is 40-80 ℃ and the time is 6-12h.
9. A lithium iron phosphate, wherein the lithium iron phosphate is reconstituted by the method of any one of claims 1-8, and the surface of the lithium iron phosphate is coated with a carbon layer.
10. Use of the lithium iron phosphate according to claim 9 as a positive electrode material for a lithium iron phosphate battery.
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