WO2022116692A1 - Method for preparing iron phosphate from lithium extraction slag of waste lithium iron phosphate positive electrode powder and application - Google Patents
Method for preparing iron phosphate from lithium extraction slag of waste lithium iron phosphate positive electrode powder and application Download PDFInfo
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- WO2022116692A1 WO2022116692A1 PCT/CN2021/123399 CN2021123399W WO2022116692A1 WO 2022116692 A1 WO2022116692 A1 WO 2022116692A1 CN 2021123399 W CN2021123399 W CN 2021123399W WO 2022116692 A1 WO2022116692 A1 WO 2022116692A1
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- iron phosphate
- iron
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 119
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 85
- 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 54
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000843 powder Substances 0.000 title claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- 239000002893 slag Substances 0.000 title claims abstract description 26
- 238000000605 extraction Methods 0.000 title abstract description 5
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 37
- 230000002378 acidificating effect Effects 0.000 claims abstract description 37
- 239000000047 product Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000007774 positive electrode material Substances 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 51
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- 238000001556 precipitation Methods 0.000 claims description 40
- 239000005955 Ferric phosphate Substances 0.000 claims description 34
- 229940032958 ferric phosphate Drugs 0.000 claims description 34
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 34
- 239000002002 slurry Substances 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- 239000011574 phosphorus Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 10
- 239000003570 air Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 claims description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 39
- 239000002244 precipitate Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 91
- 229910052742 iron Inorganic materials 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000010406 cathode material Substances 0.000 description 10
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- LEAMSPPOALICQN-UHFFFAOYSA-H iron(2+);diphosphate;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEAMSPPOALICQN-UHFFFAOYSA-H 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 1
- RQKNQWUJROKKEQ-UHFFFAOYSA-K iron(3+);phosphate;hydrate Chemical compound [OH-].[Fe+3].OP([O-])([O-])=O RQKNQWUJROKKEQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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
- 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
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/11—Powder tap density
-
- 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
Definitions
- the present disclosure relates to the technical field of new energy materials for lithium batteries, in particular to a method and application for preparing iron phosphate by using waste lithium iron phosphate positive electrode powder to extract lithium slag.
- Lithium iron phosphate battery is the mainstream power battery in the early stage of my country's new energy vehicle industry. It has outstanding advantages such as good safety performance, long cycle life and low cost. It has always been the preferred power source for electric commercial vehicles, special vehicles and energy storage. Although the energy density of lithium iron phosphate batteries is lower than that of ternary lithium batteries, lithium iron phosphate batteries have a great cost advantage in cathode materials compared with ternary lithium batteries. With the decline of national subsidies, lithium iron phosphate batteries have a cost advantage. highlighted.
- Iron phosphate is the core precursor for the preparation of lithium iron phosphate cathode material, and its preparation process generally includes two-step method and two-step method.
- the one-step method is to mix the iron source and the phosphorus source in one reaction tank to prepare iron phosphate.
- the preparation process has only one step of washing operation.
- the prepared iron phosphate is difficult to be used as a precursor of battery materials due to high impurities.
- the two-step method changes the one-step synthesis to two steps, aiming to improve the quality of iron phosphate.
- the two-step method includes two synthesis modes.
- the first synthesis mode is to adjust the pH value of ferrous source (such as FeSO 4 ⁇ 7H 2 O) and phosphorus source (such as (NH 4 ) 2 HPO 4 ) to 4 with ammonia water. After -5 precipitation to obtain ferrous phosphate octahydrate (Fe 3 (PO 4 ) 2 ⁇ 8H 2 O), after the ferrous phosphate octahydrate is washed, it is stirred and beaten with an aqueous solution, and phosphoric acid and hydrogen peroxide are added to the slurry, The slurry is heated to below 100 °C to obtain iron phosphate dihydrate crystals (FePO 4 ⁇ 2H 2 O), which will be washed again to improve the purity; the second synthesis mode is to first make a ferrous source (FePO 4 ⁇ 2H 2 O) Such as FeSO 4 ⁇ 7H 2 O) and phosphorus source (such as (NH 4 ) 2 HPO 4 ) react in an aqueous environment in the
- iron phosphate used as a cathode material for lithium iron phosphate batteries is generally prepared by a two-step method using iron sources and phosphorus sources with higher purity.
- the present disclosure provides a method for preparing iron phosphate by using waste lithium iron phosphate cathode powder to extract lithium slag, by dissolving the lithium extraction slag in an acid solution to obtain an acidic iron-phosphorus solution, heating the acidic iron-phosphorus solution, and stirring the heated acidic iron-phosphorus solution to precipitate phosphoric acid Iron precipitation, and further processing the iron phosphate precipitation to obtain iron phosphate, the method has low energy consumption, low cost, simple process, and realizes the resource utilization of waste cathode materials of lithium iron phosphate batteries.
- a method for preparing iron phosphate by utilizing waste lithium iron phosphate positive electrode powder to extract lithium slag comprising the following steps:
- described acid solution is one or more in sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, wherein non-limiting combination is: the combination of sulfuric acid and hydrochloric acid, sulfuric acid and phosphoric acid Combination, the combination of hydrochloric acid and phosphoric acid, the combination of hydrochloric acid and nitric acid, the combination of sulfuric acid, hydrochloric acid and phosphoric acid.
- the dissolving temperature is 20°C to 90°C, in another embodiment, 20°C to 80°C, and in another embodiment, 20°C to 70°C .
- the concentration of H + in the acid solution in step (1) is 0.7-12 mol/L, while in another embodiment, it is 0.7-10 mol/L, and in yet another embodiment, it is 0.7 ⁇ 6mol/L.
- the mass-volume ratio of the waste lithium iron phosphate positive electrode powder and acid solution dissolved is 1: (1-100) g/mL, and in another embodiment, it is 1: (1-50) g/mL, in yet another embodiment 1: (1-30) g/mL.
- the waste lithium iron phosphate cathode powder extraction slag is heat treated before dissolving, and then added to the acid solution;
- the time of the heat treatment is 0.5 ⁇ 9h
- the atmosphere of the heat treatment is one or more of air, oxygen, nitrogen, argon or helium, wherein the non-limiting combination is: the combination of oxygen and nitrogen, oxygen and Combination of Argon, Combination of Nitrogen and Argon, Combination of Argon and Helium, Combination of Oxygen, Nitrogen and Argon.
- the heating temperature is 40°C to 250°C, in another embodiment, 80°C to 200°C, and in yet another embodiment, 95°C to 160°C .
- the concentration of H + in the acidic iron-phosphorus solution is 0.1-10 mol/L, in another embodiment, 0.1-8.0 mol/L, in yet another embodiment Medium is 0.1 to 6.0 mol/L.
- step (2) the concentration of phosphorus element in the acidic iron-phosphorus solution is 0.05-2.5 mol/L.
- the concentration of iron element in the acidic iron-phosphorus solution is 0.05-2.5 mol/L.
- an oxidant is added to the acidic iron-phosphorus solution before heating, so that Fe 2+ in the acidic iron-phosphorus solution is oxidized to Fe 3+ , and the oxidant is hydrogen peroxide, oxygen, One or more of air, ozone, peroxymonosulfuric acid, peroxodisulfuric acid, ammonium persulfate, sodium persulfate, potassium persulfate, sodium hypochlorite or sodium perchlorate, wherein the non-limiting combination is: hydrogen peroxide and oxygen Combination, the combination of hydrogen peroxide and peroxymonosulfuric acid, the combination of peroxodisulfuric acid and ammonium persulfate, the combination of hydrogen peroxide, air and sodium hypochlorite.
- the iron in the acidic iron-phosphorus solution is sometimes all ferrous ions, sometimes partly ferrous ions, because the iron of iron phosphate is trivalent, and in order to make the Fe/P ratio in the precipitated product meet the requirements for preparing battery cathode materials, Therefore, the acid iron-phosphorus solution is oxidized before heating, so that Fe 2+ in the iron-phosphorus solution is oxidized to Fe 3+ .
- the stirring method is any one of conventional stirring paddle stirring, solution rotation along with the precipitation reactor, or self-aspirating stirring, and the stirring form can affect the particle size and morphological characteristics of the precipitate,
- Some special stirring forms also have the dual functions of oxidizing Fe 2+ and stirring due to the continuous inhalation of air or oxygen to generate microbubbles.
- the stirring time is 0.1-72 h, in another embodiment, 0.5-48 h, and in yet another embodiment, 1-24 h.
- the linear velocity of the end of the stirring paddle is 1-20 m/s.
- a precipitation aid is added to the acidic iron-phosphorus solution, because a certain energy barrier needs to be overcome microscopically when iron phosphate is precipitated in the acidic iron-phosphorus solution, which is To overcome this energy barrier, a precipitation aid can be added to the acidic iron-phosphorus solution before stirring the solution; in addition, some special elements need to be doped during the preparation of the lithium iron phosphate cathode material. In order to make the doping uniform, an appropriate amount can be added.
- the oxides of these doping elements are used as additives, which can not only promote the precipitation, but also ensure the uniformity of doping. In addition, the oxides of these doping elements have anisotropic adsorption characteristics and have the ability to control the morphology of the precipitated products. effect.
- the precipitation aid is one or more of metatitanic acid, titanium dioxide, aluminum oxide, aluminum hydroxide, anhydrous iron phosphate, iron phosphate dihydrate or iron phosphorus.
- non-limiting combinations are: a combination of metatitanic acid and iron phosphate dihydrate, titanium dioxide and iron phosphate anhydrous, a combination of aluminum hydroxide and iron phosphate dihydrate, a combination of anhydrous iron phosphate and iron phosphate dihydrate, no The combination of ferric phosphate hydrate and ferric phosphorus, the combination of ferric phosphate dihydrate and ferrophosphorus, the combination of metatitanic acid, aluminum hydroxide and ferric phosphate anhydrous, the combination of ferric phosphate anhydrous, ferric phosphate dihydrate and ferrophosphorus anhydrous The combination.
- the addition amount of the precipitation aid is 0.01-1000 g/L, and in another embodiment, it is 1-250 g/L.
- step (4) the selection in washing mode is based on the iron phosphate particle size obtained by precipitation, so as to meet the requirement to iron phosphate particle size during the preparation of lithium iron phosphate positive electrode material.
- the washing is one of conventional stirring washing or ball milling washing.
- step (4) in order to make the Fe/P ratio of the obtained iron phosphate meet the requirement of the Fe/P ratio of the lithium iron phosphate positive electrode material, adding phosphoric acid solution soaking and drying between the washing and drying filtering process.
- the concentration of the phosphoric acid solution is 0.01-5 mol/L.
- the embodiments of the present disclosure also provide applications of the preparation method in preparing lithium iron phosphate cathode materials, ceramics or coatings.
- an acid solution is used to dissolve waste lithium iron phosphate cathode powder to extract lithium slag to obtain an acid iron phosphorus solution, to heat up the acid iron phosphorus solution, and to precipitate the iron phosphate precipitate from the acid iron phosphorus solution after stirring and heating, and further process the described phosphoric acid.
- Iron is precipitated to obtain a finished product of iron phosphate.
- the method has low energy consumption, low cost and simple operation, and realizes the resource utilization of waste cathode materials of lithium iron phosphate batteries.
- the prepared iron phosphate can be used as a cathode material for lithium iron phosphate. Raw material, can also be used to manufacture ceramics, coatings, etc.
- the embodiment of the present disclosure realizes high-efficiency and high-quality precipitation of iron phosphate in a high-acid system, and improves the purity of iron phosphate by suppressing the co-precipitation of impurity ions or suppressing the lattice substitution of impurities and iron in the iron phosphate lattice.
- Fig. 1 is the SEM image of the 5000-fold magnification of the finished iron phosphate product obtained in Example 1 of the present disclosure
- Fig. 2 is the SEM image of 50,000 times magnification of the finished iron phosphate product obtained in Example 1 of the present disclosure
- Example 3 is an XRD pattern of the finished iron phosphate product obtained in Example 1 of the present disclosure.
- a preparation method of iron phosphate comprising the following steps:
- Fig. 1 and Fig. 2 are SEM images under different magnifications of the finished ferric phosphate obtained in Example 1. It can be seen from the figures that the particle size distribution of the synthesized ferric phosphate is relatively uniform, mainly due to the fact that the flaky primary particles are close to each other. Staggered to form spherical particles with a particle size of 3-6 ⁇ m.
- Fig. 3 is the XRD pattern of the finished iron phosphate obtained in Example 1. It can be seen from Fig. 3 that the prepared iron phosphate XRD pattern is compared with the standard card (50-1635) spectrum, and the characteristic peaks are consistent one by one, and the diffraction peaks are sharp and characteristic The peak is obvious, indicating that the product has good crystallinity.
- a preparation method of iron phosphate comprising the following steps:
- a preparation method of iron phosphate comprising the following steps:
- a preparation method of iron phosphate comprising the following steps:
- a preparation method of iron phosphate comprising the following steps:
- a preparation method of iron phosphate comprising the following steps:
- a preparation method of iron phosphate comprising the following steps:
- a preparation method of iron phosphate comprising the following steps:
- (2) acid iron phosphorus solution is transferred in the precipitation reactor of conventional stirring paddle, and is ferric iron with the ferrous iron in the ammonium persulfate oxidation solution, adds ferric phosphate dihydrate according to the amount of 600g/L, and the temperature of the solution is heated up. to 40°C and synchronously stirring, when the temperature reaches 40°C, start timing, and continue stirring for 72 hours to obtain a slurry containing iron phosphate precipitation;
- a traditional method for preparing iron phosphate adding reduced iron powder and H 3 PO 4 in a reaction kettle according to a certain amount of material ratio, dissolving the iron powder under the conditions of a certain temperature and stirring rate, and after the reaction is completed, the reaction solution is pumped.
- each physical and chemical index and impurity content of the iron phosphate obtained by the preparation method of the embodiment of the present disclosure all meet the standard of lithium iron phosphate positive electrode material.
- the compaction density and electrical properties of the lithium iron phosphate powder synthesized by the iron phosphate of the embodiment of the present disclosure are comparable to those of the comparative example, indicating that the iron phosphate of the embodiment of the present disclosure has reached the level of iron phosphate used for lithium iron phosphate. Using the standard, it can be directly used as a precursor for lithium iron phosphate production.
- Table 3 is a comparison of raw materials and auxiliary materials of Example 1 and Comparative Example.
- the method of the embodiment of the present disclosure has lower raw material cost and water treatment cost, produces less waste water, is more environmentally friendly, and is suitable for large-scale promotion and use.
Abstract
The present invention relates to the technical field of lithium battery new energy materials, and provides a method for preparing iron phosphate from lithium extraction slag of waste lithium iron phosphate positive electrode powder and an application. The method comprises: dissolving the lithium extraction slag of the waste lithium iron phosphate positive electrode powder by means of an acid solution to obtain an acidic iron-phosphorus solution, heating the acidic iron-phosphorus solution, stirring the heated acidic iron-phosphorus solution to separate out an iron phosphate precipitate, and further treating the iron phosphate precipitate to obtain a finished iron phosphate product. The method is low in energy consumption, low in costs and simple in operation, and implements resource utilization of a waste lithium iron phosphate battery positive electrode material; and the prepared iron phosphate can be used as a raw material for preparing the lithium iron phosphate positive electrode material, and can also be used for manufacturing ceramics, coatings and the like.
Description
本公开涉及锂电池新能源材料技术领域，特别是涉及一种利用废磷酸铁锂正极粉提锂渣制备磷酸铁的方法和应用。The present disclosure relates to the technical field of new energy materials for lithium batteries, in particular to a method and application for preparing iron phosphate by using waste lithium iron phosphate positive electrode powder to extract lithium slag.
磷酸铁锂电池是我国新能源汽车产业发展初期的主流动力电池，具有安全性能好、循环寿命长、成本低等突出优点，一直是电动商用车、专用车和储能领域的首选电源。虽然磷酸铁锂电池能量密度不及三元锂电池，但磷酸铁锂电池相比于三元锂电池在正极材料上具有很大的成本优势，随着国家补贴退坡，磷酸铁锂电池的成本优势突显。Lithium iron phosphate battery is the mainstream power battery in the early stage of my country's new energy vehicle industry. It has outstanding advantages such as good safety performance, long cycle life and low cost. It has always been the preferred power source for electric commercial vehicles, special vehicles and energy storage. Although the energy density of lithium iron phosphate batteries is lower than that of ternary lithium batteries, lithium iron phosphate batteries have a great cost advantage in cathode materials compared with ternary lithium batteries. With the decline of national subsidies, lithium iron phosphate batteries have a cost advantage. highlighted.
磷酸铁是磷酸铁锂正极材料制备的核心前驱体，其制备工艺大体上包括一步法和两步法两种。一步法是将铁源和磷源在一个反应罐中一步混合反应制得磷酸铁，制备过程只有一步洗涤操作，所制得的磷酸铁因杂质高而难以用作电池材料的前驱体。两步法将一步合成改为两步，旨在提高磷酸铁的质量。两步法包括两种合成模式，第一种合成模式为，先使亚铁源(如FeSO
4·7H
2O)和磷源(如(NH
4)
2HPO
4)经氨水调节pH值至4-5后沉淀制得八水磷酸亚铁(Fe
3(PO
4)
2·8H
2O)，八水磷酸亚铁经洗涤后，再用水溶液搅拌打浆，并往浆料中加入磷酸和双氧水、升温浆料至100℃以下，制得二水磷酸铁晶体(FePO
4·2H
2O)，该二水磷酸铁晶体会再次洗涤以提高纯度；第二种合成模式为，先使亚铁源(如FeSO
4·7H
2O)和磷源(如(NH
4)
2HPO
4)在氧化剂(如双氧水)存在的水溶液环境中反应生成无定形磷酸铁沉淀，并洗涤所获得的无定形磷酸铁沉淀，再将洗后的无定形磷酸铁沉淀加入至磷酸溶液中、于85-100℃下转晶，制得二水磷酸铁晶体，该二水磷酸铁晶体也会再次洗涤去除夹带的游离离子。现阶段，磷酸铁锂电池正极材料用磷酸铁一般采用纯度较高的铁源和磷源经两步法制得。
Iron phosphate is the core precursor for the preparation of lithium iron phosphate cathode material, and its preparation process generally includes two-step method and two-step method. The one-step method is to mix the iron source and the phosphorus source in one reaction tank to prepare iron phosphate. The preparation process has only one step of washing operation. The prepared iron phosphate is difficult to be used as a precursor of battery materials due to high impurities. The two-step method changes the one-step synthesis to two steps, aiming to improve the quality of iron phosphate. The two-step method includes two synthesis modes. The first synthesis mode is to adjust the pH value of ferrous source (such as FeSO 4 ·7H 2 O) and phosphorus source (such as (NH 4 ) 2 HPO 4 ) to 4 with ammonia water. After -5 precipitation to obtain ferrous phosphate octahydrate (Fe 3 (PO 4 ) 2 ·8H 2 O), after the ferrous phosphate octahydrate is washed, it is stirred and beaten with an aqueous solution, and phosphoric acid and hydrogen peroxide are added to the slurry, The slurry is heated to below 100 °C to obtain iron phosphate dihydrate crystals (FePO 4 ·2H 2 O), which will be washed again to improve the purity; the second synthesis mode is to first make a ferrous source (FePO 4 ·2H 2 O) Such as FeSO 4 ·7H 2 O) and phosphorus source (such as (NH 4 ) 2 HPO 4 ) react in an aqueous environment in the presence of an oxidizing agent (such as hydrogen peroxide) to generate amorphous iron phosphate precipitates, and wash the obtained amorphous iron phosphate precipitates Then, the washed amorphous iron phosphate precipitate is added to the phosphoric acid solution and crystallized at 85-100 ° C to obtain iron phosphate dihydrate crystals. The iron phosphate dihydrate crystals will also be washed again to remove entrained free ions. At this stage, iron phosphate used as a cathode material for lithium iron phosphate batteries is generally prepared by a two-step method using iron sources and phosphorus sources with higher purity.
此外，目前已经有公开报道了一种在盐酸介质中合成磷酸铁的方法，该法先将高纯铁粉溶解至适当浓度的盐酸中，再加入双氧水和磷酸，搅拌均匀后进入喷雾干燥回收盐酸、并制备磷酸铁。还有公开报道了一种利用硫酸法钛白行业产生的硫酸亚铁废渣为原料制备磷酸铁的方法，该法先用由氟化铵和还原铁粉组成的复合沉淀剂提纯硫酸亚铁，再将硫酸亚铁和磷酸溶液混合制成溶液、用双氧水氧化亚铁离子、用氨水和磷酸调节pH值至2.2-2.6，然后在120-180℃的水热条件反应6-10小时制得片状磷酸铁。In addition, a method for synthesizing iron phosphate in a hydrochloric acid medium has been publicly reported at present. This method first dissolves high-purity iron powder into hydrochloric acid of an appropriate concentration, then adds hydrogen peroxide and phosphoric acid, and after stirring, enters spray drying to recover hydrochloric acid, and Preparation of iron phosphate. There is also a public report on a method for preparing iron phosphate by using the ferrous sulfate waste residue produced by the titanium dioxide industry of the sulfuric acid method as a raw material. Mix ferrous sulfate and phosphoric acid solution to make a solution, oxidize ferrous ion with hydrogen peroxide, adjust pH value to 2.2-2.6 with ammonia water and phosphoric acid, and then react at 120-180 ℃ hydrothermal conditions for 6-10 hours to obtain flakes Iron Phosphate.
近年来，我国早年使用的磷酸铁锂电池已大量进入退役期，目前退役磷酸铁锂电池废正极材料以回收锂为主，铁磷组分尚未有效回收，造成铁磷资源浪费。In recent years, a large number of lithium iron phosphate batteries used in my country in the early years have entered the decommissioning period. At present, the waste cathode materials of decommissioned lithium iron phosphate batteries are mainly recycled lithium, and the iron and phosphorus components have not been effectively recovered, resulting in a waste of iron and phosphorus resources.
发明内容SUMMARY OF THE INVENTION
本公开提供一种利用废磷酸铁锂正极粉提锂渣制备磷酸铁的方法，通过酸液溶解提锂渣得酸性铁磷溶液、升温酸性铁磷溶液、搅动升温后的酸性铁磷溶液析出磷酸铁沉淀、进一步处理所述的磷酸铁沉淀，即得磷酸铁，该方法能耗低，成本低，工艺简单，实现磷酸铁锂电池废正极材料的资源化利用。The present disclosure provides a method for preparing iron phosphate by using waste lithium iron phosphate cathode powder to extract lithium slag, by dissolving the lithium extraction slag in an acid solution to obtain an acidic iron-phosphorus solution, heating the acidic iron-phosphorus solution, and stirring the heated acidic iron-phosphorus solution to precipitate phosphoric acid Iron precipitation, and further processing the iron phosphate precipitation to obtain iron phosphate, the method has low energy consumption, low cost, simple process, and realizes the resource utilization of waste cathode materials of lithium iron phosphate batteries.
本公开实施例提供了：Embodiments of the present disclosure provide:
一种利用废磷酸铁锂正极粉提锂渣制备磷酸铁的方法，包括如下步骤：A method for preparing iron phosphate by utilizing waste lithium iron phosphate positive electrode powder to extract lithium slag, comprising the following steps:
(1)将废磷酸铁锂正极粉提锂渣溶解于酸液中，再过滤，收集滤液，得到酸性铁磷溶液；(1) dissolving waste lithium iron phosphate cathode powder extracting lithium residue in acid solution, filtering again, collecting filtrate to obtain acid iron phosphorus solution;
(2)将所述酸性铁磷溶液进行加热，搅拌，得到含磷酸铁的料浆；(2) the acidic iron-phosphorus solution is heated and stirred to obtain a slurry containing iron phosphate;
(3)将所述料浆进行过滤，得到磷酸铁固体和沉淀母液；(3) filter described slurry, obtain ferric phosphate solid and precipitation mother liquor;
(4)将磷酸铁固体进行洗涤，过滤，干燥，即得磷酸铁成品。(4) washing the iron phosphate solid, filtering and drying to obtain the iron phosphate finished product.
在一实施例中，步骤(1)中，所述酸液为硫酸、盐酸、磷酸、硝酸中的一种或几种，其中非限制性的组合为：硫酸和盐酸的组合，硫酸和磷酸的组合，盐酸和磷酸的组合，盐酸和硝酸的组合，硫酸、盐酸和磷酸三者的组合。In one embodiment, in step (1), described acid solution is one or more in sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, wherein non-limiting combination is: the combination of sulfuric acid and hydrochloric acid, sulfuric acid and phosphoric acid Combination, the combination of hydrochloric acid and phosphoric acid, the combination of hydrochloric acid and nitric acid, the combination of sulfuric acid, hydrochloric acid and phosphoric acid.
在另一实施例中，步骤(1)中，所述溶解的温度为20℃～90℃，在又一实施例中为20℃～80℃，在又一实施例中为20℃～70℃。In another embodiment, in step (1), the dissolving temperature is 20°C to 90°C, in another embodiment, 20°C to 80°C, and in another embodiment, 20°C to 70°C .
在又一实施例中，步骤(1)所述酸液中H
+的浓度为0.7～12mol/L，而在另一实施例中为0.7～10mol/L，在又一实施例中，为0.7～6mol/L。
In yet another embodiment, the concentration of H + in the acid solution in step (1) is 0.7-12 mol/L, while in another embodiment, it is 0.7-10 mol/L, and in yet another embodiment, it is 0.7 ~6mol/L.
在又一实施例中，步骤(1)中，所述废磷酸铁锂正极粉和酸液溶解的质量体积比为1：(1-100)g/mL，在另一实施例中为1：(1～50)g/mL，在又一实施例中为1：(1～30)g/mL。In yet another embodiment, in step (1), the mass-volume ratio of the waste lithium iron phosphate positive electrode powder and acid solution dissolved is 1: (1-100) g/mL, and in another embodiment, it is 1: (1-50) g/mL, in yet another embodiment 1: (1-30) g/mL.
在又一实施例中，步骤(1)中，所述废磷酸铁锂正极粉提锂渣在溶解前先进行热处理，再加入酸液中；所述热处理的温度为200℃～600℃，所述热处理的时间为0.5～9h，所述热处理的气氛为空气、氧气、氮气、氩气或氦气中的一种或几种，其中非限制性的组合为：氧气和氮气的组合，氧气和氩气的组合，氮气和氩气的组合，氩气和氦气的组合，氧气、氮气和氩气三者的组合。由于废磷酸铁锂正极粉提锂渣所属的晶型有时酸溶性能不佳，为帮助转晶以提高酸溶性能，故在溶解前先进行热处理。In yet another embodiment, in step (1), the waste lithium iron phosphate cathode powder extraction slag is heat treated before dissolving, and then added to the acid solution; The time of the heat treatment is 0.5～9h, and the atmosphere of the heat treatment is one or more of air, oxygen, nitrogen, argon or helium, wherein the non-limiting combination is: the combination of oxygen and nitrogen, oxygen and Combination of Argon, Combination of Nitrogen and Argon, Combination of Argon and Helium, Combination of Oxygen, Nitrogen and Argon. Because the crystal form of the waste lithium iron phosphate cathode powder to extract the lithium slag sometimes has poor acid solubility, in order to help the crystal transformation to improve the acid solubility, heat treatment is performed before dissolving.
在又一实施例中，步骤(2)中，所述加热的温度为40℃～250℃，在另一实施例中为80℃～200℃，在又一实施例中为95℃～160℃。In yet another embodiment, in step (2), the heating temperature is 40°C to 250°C, in another embodiment, 80°C to 200°C, and in yet another embodiment, 95°C to 160°C .
在又一实施例中，步骤(2)中，所述酸性铁磷溶液中H
+的浓度为0.1～10mol/L，在另一实施例中为0.1～8.0mol/L，在又一实施例中为0.1～6.0mol/L。
In yet another embodiment, in step (2), the concentration of H + in the acidic iron-phosphorus solution is 0.1-10 mol/L, in another embodiment, 0.1-8.0 mol/L, in yet another embodiment Medium is 0.1 to 6.0 mol/L.
在又一实施例中，步骤(2)中，所述酸性铁磷溶液中磷元素的浓度为0.05～2.5mol/L。In yet another embodiment, in step (2), the concentration of phosphorus element in the acidic iron-phosphorus solution is 0.05-2.5 mol/L.
在又一实施例中，步骤(2)中，所述酸性铁磷溶液中铁元素的浓度为0.05～2.5mol/L。In yet another embodiment, in step (2), the concentration of iron element in the acidic iron-phosphorus solution is 0.05-2.5 mol/L.
在又一实施例中，步骤(2)中，所述酸性铁磷溶液在加热前先加入氧化剂，使酸性铁磷溶液中的Fe
2+氧化为Fe
3+，所述氧化剂为双氧水、氧气、空气、臭氧、过一硫酸、过二硫酸、过硫酸铵、过硫酸钠、过硫酸钾、次氯酸钠或高氯酸钠中的一种或几种，其中非限制性的组合为：双氧水和氧气的组合，双氧水和过一硫酸的组合，过二硫酸和过硫酸铵的组合，双氧水、空气和次氯酸钠三者的组合。酸性铁磷溶液中的铁有时全部为亚铁离子、有时部分为亚铁离子，因磷酸铁的铁为三价，且为使沉淀产物中的Fe/P配比满足制备电池正极材料用要求，故在加热所述酸性铁磷溶液前先氧化，使铁磷溶液中的Fe
2+氧化为Fe
3+。
In another embodiment, in step (2), an oxidant is added to the acidic iron-phosphorus solution before heating, so that Fe 2+ in the acidic iron-phosphorus solution is oxidized to Fe 3+ , and the oxidant is hydrogen peroxide, oxygen, One or more of air, ozone, peroxymonosulfuric acid, peroxodisulfuric acid, ammonium persulfate, sodium persulfate, potassium persulfate, sodium hypochlorite or sodium perchlorate, wherein the non-limiting combination is: hydrogen peroxide and oxygen Combination, the combination of hydrogen peroxide and peroxymonosulfuric acid, the combination of peroxodisulfuric acid and ammonium persulfate, the combination of hydrogen peroxide, air and sodium hypochlorite. The iron in the acidic iron-phosphorus solution is sometimes all ferrous ions, sometimes partly ferrous ions, because the iron of iron phosphate is trivalent, and in order to make the Fe/P ratio in the precipitated product meet the requirements for preparing battery cathode materials, Therefore, the acid iron-phosphorus solution is oxidized before heating, so that Fe 2+ in the iron-phosphorus solution is oxidized to Fe 3+ .
在又一实施例中，所述搅拌的方式为常规搅拌桨搅动、溶液随沉淀反应器一起回转或自吸气搅动中的任意一种，搅拌的形式可影响沉淀的颗粒大小及形貌特征，一些特殊的搅动形式还因持续地吸入空气或氧气产生微气泡而具有氧化Fe
2+及搅拌的双重作用。
In yet another embodiment, the stirring method is any one of conventional stirring paddle stirring, solution rotation along with the precipitation reactor, or self-aspirating stirring, and the stirring form can affect the particle size and morphological characteristics of the precipitate, Some special stirring forms also have the dual functions of oxidizing Fe 2+ and stirring due to the continuous inhalation of air or oxygen to generate microbubbles.
在又一实施例中，步骤(2)中，所述搅拌的时间为0.1～72h，在另一实施例中为0.5～48h，在又一实施例中为1～24h。In yet another embodiment, in step (2), the stirring time is 0.1-72 h, in another embodiment, 0.5-48 h, and in yet another embodiment, 1-24 h.
在又一实施例中，当所述搅拌的方式为搅拌桨搅动时，搅拌桨叶端线速度为1-20m/s。In yet another embodiment, when the stirring mode is stirring by a stirring paddle, the linear velocity of the end of the stirring paddle is 1-20 m/s.
在又一实施例中，在步骤(2)中所述加热前，往酸性铁磷溶液中添加沉淀助剂，由于酸性铁磷溶液中析出磷酸铁时在微观上需要克服一定的能垒，为克服该能量障碍，可以在搅动溶液前，往酸性铁磷溶液中添加沉淀助剂；并且，磷酸铁锂正极材料制备过程中还需掺杂某些特种元素，为使掺杂均匀，可适量加入这些掺杂元素的氧化物作为助剂，不仅能促进沉淀，还能保证掺杂的均匀性，此外，这些掺杂元素的氧化物因具有各向异性吸附特性而具有调控沉淀产物形貌特征的作用。In yet another embodiment, before the heating described in the step (2), a precipitation aid is added to the acidic iron-phosphorus solution, because a certain energy barrier needs to be overcome microscopically when iron phosphate is precipitated in the acidic iron-phosphorus solution, which is To overcome this energy barrier, a precipitation aid can be added to the acidic iron-phosphorus solution before stirring the solution; in addition, some special elements need to be doped during the preparation of the lithium iron phosphate cathode material. In order to make the doping uniform, an appropriate amount can be added. The oxides of these doping elements are used as additives, which can not only promote the precipitation, but also ensure the uniformity of doping. In addition, the oxides of these doping elements have anisotropic adsorption characteristics and have the ability to control the morphology of the precipitated products. effect.
在又一实施例中，所述沉淀助剂为偏钛酸、二氧化钛、氧化铝、氢氧化铝、无水磷酸铁、二水磷酸铁或磷铁中的一种或几种。其中非限制性的组合为：偏钛酸和二水磷酸铁的组合，二氧化钛和无水磷酸铁，氢氧化铝和二水磷酸铁的组合，无水磷酸铁和二水磷酸铁的组合，无水磷酸铁和磷铁的组合，二水磷酸铁和磷铁的组合，偏钛酸、氢氧化铝和无水磷酸铁三者的组合，无水磷酸铁、二水磷酸铁和磷铁三者的组合。In yet another embodiment, the precipitation aid is one or more of metatitanic acid, titanium dioxide, aluminum oxide, aluminum hydroxide, anhydrous iron phosphate, iron phosphate dihydrate or iron phosphorus. Among them, non-limiting combinations are: a combination of metatitanic acid and iron phosphate dihydrate, titanium dioxide and iron phosphate anhydrous, a combination of aluminum hydroxide and iron phosphate dihydrate, a combination of anhydrous iron phosphate and iron phosphate dihydrate, no The combination of ferric phosphate hydrate and ferric phosphorus, the combination of ferric phosphate dihydrate and ferrophosphorus, the combination of metatitanic acid, aluminum hydroxide and ferric phosphate anhydrous, the combination of ferric phosphate anhydrous, ferric phosphate dihydrate and ferrophosphorus anhydrous The combination.
在又一实施例中，所述沉淀助剂的添加量为0.01～1000g/L，在另一实施例中为1～250g/L。In yet another embodiment, the addition amount of the precipitation aid is 0.01-1000 g/L, and in another embodiment, it is 1-250 g/L.
在又一实施例中，步骤(4)中，在洗涤方式上的选择依据为沉淀获得的磷酸铁颗粒尺寸 大小，以满足磷酸铁锂正极材料制备时对磷酸铁粒度的要求。In yet another embodiment, in step (4), the selection in washing mode is based on the iron phosphate particle size obtained by precipitation, so as to meet the requirement to iron phosphate particle size during the preparation of lithium iron phosphate positive electrode material.
在又一实施例中，所述洗涤为常规搅拌洗涤或边球磨边洗涤中的一种。In yet another embodiment, the washing is one of conventional stirring washing or ball milling washing.
在又一实施例中，步骤(4)中，为使获得的磷酸铁的Fe/P比满足磷酸铁锂正极材料Fe/P比的要求，在所述洗涤和干燥之间增加磷酸溶液浸泡和过滤的工序。In yet another embodiment, in step (4), in order to make the Fe/P ratio of the obtained iron phosphate meet the requirement of the Fe/P ratio of the lithium iron phosphate positive electrode material, adding phosphoric acid solution soaking and drying between the washing and drying filtering process.
在又一实施例中，所述磷酸溶液的浓度为0.01～5mol/L。In yet another embodiment, the concentration of the phosphoric acid solution is 0.01-5 mol/L.
本公开实施例还提供所述的制备方法在制备磷酸铁锂正极材料、陶瓷或涂料中的应用。The embodiments of the present disclosure also provide applications of the preparation method in preparing lithium iron phosphate cathode materials, ceramics or coatings.
本公开实施例的优点：Advantages of embodiments of the present disclosure:
1、本公开实施例通过酸液溶解废磷酸铁锂正极粉提锂渣得酸性铁磷溶液、升温酸性铁磷溶液、搅拌升温后的酸性铁磷溶液析出磷酸铁沉淀、进一步处理所述的磷酸铁沉淀，得到磷酸铁成品，该方法能耗低，成本低，操作简单，实现了磷酸铁锂电池废正极材料的资源化利用，所制得的磷酸铁可用作磷酸铁锂正极材料制备的原料，也可用作制造陶瓷、涂料等。1. In the embodiment of the present disclosure, an acid solution is used to dissolve waste lithium iron phosphate cathode powder to extract lithium slag to obtain an acid iron phosphorus solution, to heat up the acid iron phosphorus solution, and to precipitate the iron phosphate precipitate from the acid iron phosphorus solution after stirring and heating, and further process the described phosphoric acid. Iron is precipitated to obtain a finished product of iron phosphate. The method has low energy consumption, low cost and simple operation, and realizes the resource utilization of waste cathode materials of lithium iron phosphate batteries. The prepared iron phosphate can be used as a cathode material for lithium iron phosphate. Raw material, can also be used to manufacture ceramics, coatings, etc.
2、本公开实施例实现了磷酸铁在高酸体系下的高效高质沉淀，通过抑制杂质离子的共沉淀或抑制杂质与磷酸铁晶格中铁的晶格替代以提高磷酸铁纯度。2. The embodiment of the present disclosure realizes high-efficiency and high-quality precipitation of iron phosphate in a high-acid system, and improves the purity of iron phosphate by suppressing the co-precipitation of impurity ions or suppressing the lattice substitution of impurities and iron in the iron phosphate lattice.
本公开实施例的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：The above and/or additional aspects and advantages of embodiments of the present disclosure will become apparent and readily understood from the following description of the embodiments in conjunction with the accompanying drawings, wherein:
图1为本公开实施例1制得磷酸铁成品放大5000倍的SEM图；Fig. 1 is the SEM image of the 5000-fold magnification of the finished iron phosphate product obtained in Example 1 of the present disclosure;
图2为本公开实施例1制得磷酸铁成品放大50000倍的SEM图；Fig. 2 is the SEM image of 50,000 times magnification of the finished iron phosphate product obtained in Example 1 of the present disclosure;
图3为本公开实施例1制得磷酸铁成品的XRD图。3 is an XRD pattern of the finished iron phosphate product obtained in Example 1 of the present disclosure.
为了对本公开进行深入的理解，下面结合实例对本公开若干实验方案进行描述，以进一步的说明本公开的特点和优点，任何不偏离本公开主旨的变化或者改变能够为本领域的技术人员理解，本公开的保护范围由所属权利要求范围确定。In order to have an in-depth understanding of the present disclosure, several experimental schemes of the present disclosure will be described below in conjunction with examples to further illustrate the features and advantages of the present disclosure. The scope of protection disclosed is determined by the scope of the appended claims.
实施例1Example 1
一种磷酸铁的制备方法，包括以下步骤：A preparation method of iron phosphate, comprising the following steps:
(1)称取100g废磷酸铁锂正极粉提锂渣，配置H
+浓度10mol/L的盐酸溶液，量取120mL配置好的盐酸溶液，将称好的废磷酸铁锂正极粉提锂渣在20℃下溶解至盐酸溶液中，过滤，获得酸性铁磷溶液；
(1) Weigh 100g of waste lithium iron phosphate cathode powder to extract lithium slag, prepare a hydrochloric acid solution with a H + concentration of 10mol/L, measure 120mL of the prepared hydrochloric acid solution, and place the weighed waste lithium iron phosphate cathode powder to extract lithium slag in Dissolve in hydrochloric acid solution at 20°C, filter to obtain acid iron-phosphorus solution;
(2)往获得的酸性铁磷溶液中加入适量的去离子水，将铁和磷浓度控制在1.0mol/L，将稀释后的酸性铁磷溶液倒入至配备了自吸式搅拌桨的沉淀反应器中，按照100g/L的量加入 无水磷酸铁，沉淀反应器配备冷凝回流装置，加热溶液温度至90℃并同步搅拌，待温度达到90℃后开始计时，并持续搅拌12h，得到含磷酸铁沉淀的料浆；(2) Add an appropriate amount of deionized water to the obtained acidic iron-phosphorus solution, control the concentration of iron and phosphorus at 1.0 mol/L, and pour the diluted acidic iron-phosphorus solution into a precipitation equipped with a self-priming stirring paddle In the reactor, anhydrous ferric phosphate was added in an amount of 100 g/L, the precipitation reactor was equipped with a condensing reflux device, the temperature of the solution was heated to 90 °C and stirred synchronously. Ferric phosphate precipitated slurry;
(3)将获得的料浆过滤，得到磷酸铁固体和沉淀母液；(3) the obtained slurry is filtered to obtain ferric phosphate solid and precipitation mother liquor;
(4)将磷酸铁固体用水浆化，倒入耐酸的反应罐完成边磨边洗、过滤，再进一步用2mol/L H
3PO
4的磷酸溶液浸泡、过滤，干燥后得到磷酸铁成品。
(4) slurrying the iron phosphate solid with water, pouring it into an acid-resistant reaction tank to complete washing and filtering while grinding, and then soaking and filtering with a phosphoric acid solution of 2mol/L H 3 PO 4 , and drying to obtain a finished iron phosphate product.
图1和图2为实施例1制得磷酸铁成品不同放大倍数下的SEM图，由图中可以看出，合成的磷酸铁的颗粒大小分布较为均匀，主要是由片状一次粒子彼此靠近相互交错，形成粒径为3～6μm的类球状颗粒。Fig. 1 and Fig. 2 are SEM images under different magnifications of the finished ferric phosphate obtained in Example 1. It can be seen from the figures that the particle size distribution of the synthesized ferric phosphate is relatively uniform, mainly due to the fact that the flaky primary particles are close to each other. Staggered to form spherical particles with a particle size of 3-6 μm.
图3为实施例1制得磷酸铁成品的XRD图，由图3可知制备的磷酸铁XRD图与标准卡片(50-1635)谱图相比，特征峰一一吻合，其衍射峰尖锐，特征峰明显，表明产品结晶度好。Fig. 3 is the XRD pattern of the finished iron phosphate obtained in Example 1. It can be seen from Fig. 3 that the prepared iron phosphate XRD pattern is compared with the standard card (50-1635) spectrum, and the characteristic peaks are consistent one by one, and the diffraction peaks are sharp and characteristic The peak is obvious, indicating that the product has good crystallinity.
实施例2Example 2
一种磷酸铁的制备方法，包括以下步骤：A preparation method of iron phosphate, comprising the following steps:
(1)称取100g废磷酸铁锂正极粉提锂渣，在250℃的空气中先煅烧2h，配置H
+浓度3mol/L的硫酸溶液，量取1000mL配置好的硫酸溶液，将煅烧后的废磷酸铁锂正极粉提锂渣在60℃下溶解至硫酸溶液中，过滤，获得酸性铁磷溶液，其中铁和磷的浓度大约在0.5mol/L；
(1) Weigh 100g of waste lithium iron phosphate cathode powder to extract lithium slag, calcinate in air at 250°C for 2 hours, prepare a sulfuric acid solution with a H + concentration of 3 mol/L, measure 1000 mL of the prepared sulfuric acid solution, and calcine the calcined sulfuric acid solution. The lithium slag extracted from the waste lithium iron phosphate cathode powder is dissolved in a sulfuric acid solution at 60 ° C, and filtered to obtain an acidic iron and phosphorus solution, wherein the concentration of iron and phosphorus is about 0.5mol/L;
(2)将酸性铁磷溶液倒入至配备了常规搅拌桨的沉淀反应器中，按照300g/L的量加入偏钛酸和二水磷酸铁，升温溶液温度至100℃并同步搅拌，待温度达到100℃后开始计时，并持续搅拌4h，得到含磷酸铁沉淀的料浆；(2) Pour the acidic iron-phosphorus solution into a precipitation reactor equipped with a conventional stirring paddle, add metatitanic acid and ferric phosphate dihydrate in an amount of 300 g/L, raise the temperature of the solution to 100°C and stir synchronously, wait for the temperature Start timing after reaching 100 °C, and continue stirring for 4 h to obtain a slurry containing iron phosphate precipitate;
(3)将获得的料浆过滤，得到磷酸铁固体和沉淀母液；(3) the obtained slurry is filtered to obtain ferric phosphate solid and precipitation mother liquor;
(4)将磷酸铁固体用水浆化，完成洗涤、过滤，再进一步用5mol/L H
3PO
4的磷酸溶液浸泡、过滤，干燥后得到磷酸铁成品。
(4) Slurry the solid iron phosphate with water, complete washing and filtration, further soak and filter with a phosphoric acid solution of 5mol/L H 3 PO 4 , and dry to obtain a finished product of ferric phosphate.
实施例3Example 3
一种磷酸铁的制备方法，包括以下步骤：A preparation method of iron phosphate, comprising the following steps:
(1)称取10g废磷酸铁锂正极粉提锂渣，在200℃的氮气中先煅烧3h，配置H
+浓度2.5mol/L的硫酸溶液，量取100mL配置好的硫酸溶液，将煅烧后的废磷酸铁锂正极粉在40℃下溶解至硫酸溶液中，过滤，获得酸性铁磷溶液，其中铁和磷的浓度大约在0.5mol/L；
(1) Weigh 10g of waste lithium iron phosphate cathode powder to extract lithium slag, calcinate in nitrogen at 200°C for 3h, prepare a sulfuric acid solution with a H + concentration of 2.5mol/L, and measure 100mL of the prepared sulfuric acid solution. The waste lithium iron phosphate cathode powder was dissolved in a sulfuric acid solution at 40°C, and filtered to obtain an acidic iron-phosphorus solution, in which the concentration of iron and phosphorus was about 0.5mol/L;
(2)将酸性铁磷溶液倒入至均相反应器中，不添加沉淀助剂，将盛有溶液的均相反应器安置在均相反应釜中，将盛有溶液的均相反应器安置在均相反应釜中，升温反应釜温度至180℃，待温度达到180℃后开始计时，并持续转动6h，得到含磷酸铁沉淀的料浆；(2) Pour the acidic iron-phosphorus solution into the homogeneous reactor, without adding a precipitation aid, place the homogeneous reactor containing the solution in the homogeneous reactor, and place the homogeneous reactor containing the solution In the homogeneous reaction kettle, the temperature of the reaction kettle is raised to 180 °C, and the time is started after the temperature reaches 180 °C, and the rotation is continued for 6 hours to obtain a slurry containing iron phosphate precipitation;
(3)将获得的料浆过滤，得到磷酸铁固体和沉淀母液；(3) the obtained slurry is filtered to obtain ferric phosphate solid and precipitation mother liquor;
(4)将磷酸铁固体用水浆化，完成洗涤、过滤，干燥后得到磷酸铁成品。(4) Slurry the iron phosphate solid with water, complete washing, filtration, and obtain the finished iron phosphate product after drying.
实施例4Example 4
一种磷酸铁的制备方法，包括以下步骤：A preparation method of iron phosphate, comprising the following steps:
(1)称取100g废磷酸铁锂正极粉提锂渣，配置H
+浓度8mol/L的盐酸和硫酸的混合溶液，量取200mL配置好的混合酸溶液，将磷酸铁废料在90℃下溶解至混合酸溶液中，过滤，获得酸性铁磷溶液；
(1) Weigh 100g of waste lithium iron phosphate cathode powder to extract lithium slag, configure a mixed solution of hydrochloric acid and sulfuric acid with a H concentration of 8mol/L, measure 200mL of the configured mixed acid solution, and dissolve the iron phosphate waste at 90 °C into a mixed acid solution, filtered to obtain an acidic iron-phosphorus solution;
(2)往获得的酸性铁磷溶液中加入适量的去离子水，将铁和磷浓度控制在1.5mol/L，往稀释后的酸性铁磷溶液中加入双氧水，实现Fe
2+的氧化，然后将氧化后的酸性铁磷溶液倒入至耐酸耐压的搅拌沉淀釜中，不需添加沉淀助剂，升温搅拌沉淀釜中溶液的温度至250℃，待温度达到250℃后开始计时，并持续搅拌0.1h，得到含磷酸铁沉淀的料浆；
(2) adding an appropriate amount of deionized water to the obtained acidic iron-phosphorus solution, controlling the concentration of iron and phosphorus at 1.5 mol/L, adding hydrogen peroxide to the diluted acidic iron-phosphorus solution to realize the oxidation of Fe 2+ , then Pour the oxidized acidic iron-phosphorus solution into the acid-resistant and pressure-resistant stirring and precipitation kettle, without adding precipitation aids, raise the temperature of the solution in the stirring and precipitation kettle to 250°C, start timing when the temperature reaches 250°C, and continue Stir for 0.1h to obtain a slurry containing iron phosphate precipitate;
(3)将获得的料浆过滤，得到磷酸铁固体和沉淀母液；(3) the obtained slurry is filtered to obtain ferric phosphate solid and precipitation mother liquor;
(4)将磷酸铁固体用水浆化，完成洗涤、过滤，干燥后得到磷酸铁成品。(4) Slurry the iron phosphate solid with water, complete washing, filtration, and obtain the finished iron phosphate product after drying.
实施例5Example 5
一种磷酸铁的制备方法，包括以下步骤：A preparation method of iron phosphate, comprising the following steps:
(1)称取50g废磷酸铁锂正极粉提锂渣，在600℃的空气中先煅烧0.5h，配置H
+浓度0.7mol/L的硫酸溶液，量取5L配置好的硫酸溶液，将煅烧后的物料在70℃下溶解至硫酸溶液中，过滤，获得酸性铁磷溶液，其中铁和磷浓度约为0.054mol/L；
(1) Weigh 50g of waste lithium iron phosphate cathode powder to extract lithium slag, calcinate in the air at 600°C for 0.5h, prepare a sulfuric acid solution with a H + concentration of 0.7mol/L, measure 5L of the prepared sulfuric acid solution, and calcine The latter material is dissolved in a sulfuric acid solution at 70° C., and filtered to obtain an acidic iron-phosphorus solution, wherein the iron and phosphorus concentrations are about 0.054 mol/L;
(2)将酸性铁磷溶液倒入至耐酸耐压的搅拌沉淀釜中，按照500g/L的量加入二水磷酸铁，升温搅拌沉淀釜中溶液的温度至220℃，待温度达到220℃后开始计时，并持续搅拌3h，得到含磷酸铁沉淀的料浆；(2) Pour the acid iron-phosphorus solution into the acid-resistant and pressure-resistant stirring precipitation kettle, add ferric phosphate dihydrate according to the amount of 500g/L, heat up the temperature of the solution in the stirring precipitation kettle to 220 ℃, after the temperature reaches 220 ℃ Start timing, and continue to stir for 3h to obtain a slurry containing iron phosphate precipitation;
(3)将获得的料浆过滤，得到磷酸铁固体和沉淀母液；(3) the obtained slurry is filtered to obtain ferric phosphate solid and precipitation mother liquor;
(4)将磷酸铁固体用水浆化，倒入耐酸的反应罐完成边磨边洗、过滤，再进一步用0.01mol/L H
3PO
4的磷酸溶液浸泡、过滤，干燥后得到磷酸铁成品。
(4) Slurry the ferric phosphate solid with water, pour it into an acid-resistant reaction tank to complete washing and filtering while grinding, then further soak and filter with a phosphoric acid solution of 0.01mol/L H 3 PO 4 , and dry to obtain a finished product of ferric phosphate.
实施例6Example 6
一种磷酸铁的制备方法，包括以下步骤：A preparation method of iron phosphate, comprising the following steps:
(1)称取50g废磷酸铁锂正极粉提锂渣，在200℃的空气中先煅烧9h，配置H
+浓度0.7mol/L的盐酸溶液，量取5L配置好的硫酸溶液，将煅烧后的废磷酸铁锂正极粉提锂渣在80℃下溶解至硫酸溶液中，过滤，获得酸性铁磷溶液，其中铁和磷浓度约为0.054mol/L；
(1) Weigh 50g of waste lithium iron phosphate cathode powder to extract lithium slag, calcinate in air at 200°C for 9 hours, prepare a hydrochloric acid solution with a H + concentration of 0.7mol/L, measure 5L of the prepared sulfuric acid solution, and calcinate the calcined The waste lithium iron phosphate cathode powder extracted lithium slag was dissolved in a sulfuric acid solution at 80 ° C, and filtered to obtain an acidic iron and phosphorus solution, wherein the iron and phosphorus concentrations were about 0.054mol/L;
(2)将酸性铁磷溶液倒入至耐酸耐压的搅拌沉淀釜中，按照1000g/L的量加入偏钛酸、氢氧化铝和二水磷酸铁，升温搅拌沉淀釜中溶液的温度至160℃，待温度达到160℃后开始计 时，并持续搅拌5h，得到含磷酸铁沉淀的料浆；(2) Pour the acidic iron-phosphorus solution into the stirring and precipitation tank of acid resistance and pressure resistance, add metatitanic acid, aluminum hydroxide and ferric phosphate dihydrate according to the amount of 1000g/L, and heat up the temperature of the solution in the stirring and precipitation tank to 160 ℃ ℃, start timing after the temperature reaches 160℃, and continue to stir for 5 hours to obtain a slurry containing iron phosphate precipitate;
(3)将获得的料浆过滤，得到磷酸铁固体和沉淀母液；(3) the obtained slurry is filtered to obtain ferric phosphate solid and precipitation mother liquor;
(4)将磷酸铁固体用水浆化，倒入耐酸的反应罐完成边磨边洗、过滤，再进一步用1mol/L H
3PO
4的磷酸溶液浸泡、过滤，干燥后得到磷酸铁成品。
(4) slurry the ferric phosphate solid with water, pour it into an acid-resistant reaction tank to complete washing and filtering while grinding, then further soak and filter with a phosphoric acid solution of 1 mol/L H 3 PO 4 , and dry to obtain a finished product of ferric phosphate.
实施例7Example 7
一种磷酸铁的制备方法，包括以下步骤：A preparation method of iron phosphate, comprising the following steps:
(1)称取100g废磷酸铁锂正极粉提锂渣，配置H
+浓度5mol/L的磷酸溶液，量取200mL配置好的磷酸溶液，将称好的废磷酸铁锂正极粉提锂渣在65℃下溶解至磷酸溶液中，过滤，获得酸性铁磷溶液；
(1) Weigh 100g of waste lithium iron phosphate cathode powder to extract lithium slag, prepare a phosphoric acid solution with a H + concentration of 5mol/L, measure 200mL of the prepared phosphoric acid solution, and place the weighed waste lithium iron phosphate cathode powder to extract lithium slag in Dissolve into phosphoric acid solution at 65°C, filter to obtain acidic iron-phosphorus solution;
(2)往获得的酸性铁磷溶液中加入适量的去离子水，将铁和磷浓度控制在2.0mol/L，将稀释后的酸性铁磷溶液转移至配备了自吸式搅拌桨的沉淀反应器中，按照300g/L的量加入无水磷酸铁和磷铁，升温溶液温度至80℃并同步搅拌，待温度达到80℃后开始计时，并持续搅拌48h，得到含磷酸铁沉淀的料浆；(2) Add an appropriate amount of deionized water to the obtained acidic iron-phosphorus solution, control the concentration of iron and phosphorus at 2.0 mol/L, and transfer the diluted acidic iron-phosphorus solution to a precipitation reaction equipped with a self-priming stirring paddle Add anhydrous ferric phosphate and ferrophosphorus in the amount of 300g/L, raise the temperature of the solution to 80°C and stir synchronously, start timing when the temperature reaches 80°C, and continue stirring for 48h to obtain a slurry containing ferric phosphate precipitation ;
(3)将获得的料浆过滤，得到磷酸铁固体和沉淀母液；(3) the obtained slurry is filtered to obtain ferric phosphate solid and precipitation mother liquor;
(4)将磷酸铁固体用水浆化，完成洗涤、过滤，干燥后得到磷酸铁成品。(4) Slurry the iron phosphate solid with water, complete washing, filtration, and obtain the finished iron phosphate product after drying.
实施例8Example 8
一种磷酸铁的制备方法，包括以下步骤：A preparation method of iron phosphate, comprising the following steps:
(1)称取100g废磷酸铁锂正极粉提锂渣，配置H
+浓度0.7mol/L的磷酸溶液，量取4.5L配置好的硫酸、磷酸混合溶液，将称好的废磷酸铁锂正极粉提锂渣在75℃下溶解至硫酸、磷酸混合溶液中，过滤，获得酸性铁磷溶液，其中铁和磷浓度约为0.13mol/L；
(1) Weigh 100g of waste lithium iron phosphate cathode powder to extract lithium slag, configure a phosphoric acid solution with H + concentration of 0.7mol/L, weigh 4.5L of the prepared mixed solution of sulfuric acid and phosphoric acid, and weigh the weighed waste lithium iron phosphate cathode The powdered lithium slag is dissolved in a mixed solution of sulfuric acid and phosphoric acid at 75°C, and filtered to obtain an acidic iron-phosphorus solution, wherein the iron and phosphorus concentrations are about 0.13 mol/L;
(2)将酸性铁磷溶液转移至常规搅拌桨的沉淀反应器中，并用过硫酸铵氧化溶液中的二价铁为三价铁，按照600g/L的量加入二水磷酸铁，升温溶液温度至40℃并同步搅拌，待温度达到40℃后开始计时，并持续搅拌72h，得到含磷酸铁沉淀的料浆；(2) acid iron phosphorus solution is transferred in the precipitation reactor of conventional stirring paddle, and is ferric iron with the ferrous iron in the ammonium persulfate oxidation solution, adds ferric phosphate dihydrate according to the amount of 600g/L, and the temperature of the solution is heated up. to 40°C and synchronously stirring, when the temperature reaches 40°C, start timing, and continue stirring for 72 hours to obtain a slurry containing iron phosphate precipitation;
(3)将获得的料浆过滤，得到磷酸铁固体和沉淀母液；(3) the obtained slurry is filtered to obtain ferric phosphate solid and precipitation mother liquor;
(4)将磷酸铁固体用水浆化，完成洗涤、过滤，干燥后得到磷酸铁成品。(4) Slurry the iron phosphate solid with water, complete washing, filtration, and obtain the finished iron phosphate product after drying.
对比例：(采用传统方法制备的磷酸铁)Comparative example: (iron phosphate prepared by traditional method)
一种制备磷酸铁的传统方法，按一定物质的量比加入还原铁粉、H
3PO
4于反应釜中，在一定温度和搅拌速率条件下溶解铁粉，待反应结束后，将反应液抽滤，得到澄清的滤液；将滤液倒入反应釜，水浴加热，搅拌速度为350r/min，控制体系pH＝2.0；反应过程中缓慢滴加一定量的H
2O
2(过量10％)溶液，直到有白色沉淀产生；反应结束后，陈化4h，将产物抽滤 分离，用去离子水洗涤沉淀直至最后一次抽滤后滤液的pH＝7.0；最后将得到的产物在80℃下干燥12h。
A traditional method for preparing iron phosphate, adding reduced iron powder and H 3 PO 4 in a reaction kettle according to a certain amount of material ratio, dissolving the iron powder under the conditions of a certain temperature and stirring rate, and after the reaction is completed, the reaction solution is pumped. Filter to obtain a clear filtrate; pour the filtrate into the reaction kettle, heat in a water bath, the stirring speed is 350r/min, and the pH of the control system is 2.0; a certain amount of H 2 O 2 (excess 10%) solution is slowly added dropwise in the reaction process, Until a white precipitate was formed; after the reaction was over, aged for 4 hours, the product was separated by suction filtration, and the precipitate was washed with deionized water until the pH of the filtrate after the last suction filtration was 7.0; finally, the obtained product was dried at 80 °C for 12 hours.
取上述实施例1～3制得的磷酸铁成品进行理化指标检测，结果如下表1所示：Get the ferric phosphate finished product that above-mentioned embodiment 1～3 makes and carry out physical and chemical index detection, the result is as shown in table 1 below:
表1本公开实施例1-3制备的无水磷酸铁理化指标检测结果Table 1 Test results of physical and chemical indexes of anhydrous iron phosphate prepared in Examples 1-3 of the present disclosure
从表1可以看出，采用本公开实施例的制备方法得到的磷酸铁的各项理化指标和杂质含量均符合磷酸铁锂正极材料的标准。As can be seen from Table 1, each physical and chemical index and impurity content of the iron phosphate obtained by the preparation method of the embodiment of the present disclosure all meet the standard of lithium iron phosphate positive electrode material.
取上述实施例1-3制得的磷酸铁与对比例制备的磷酸铁按照常规方法在同等条件下制备成磷酸铁锂，对制得的磷酸铁锂的压实密度及其他电性能进行检测，结果如下表2所示：Get the ferric phosphate that the above-mentioned embodiment 1-3 makes and the ferric phosphate that the comparative example prepares to prepare into lithium iron phosphate under the same conditions according to the conventional method, the compaction density and other electrical properties of the obtained lithium iron phosphate are detected, The results are shown in Table 2 below:
表2实施例1-3的磷酸铁与对比例磷酸铁合成磷酸铁锂粉末压实密度及电性能检测结果对比表The iron phosphate of table 2 embodiment 1-3 and comparative example iron phosphate synthesis lithium iron phosphate powder compaction density and electrical property test result comparison table
从表2可以看出，本公开实施例的磷酸铁合成的磷酸铁锂粉末的压实密度及电性能与对比例的相当，表明本公开实施例的磷酸铁达到了磷酸铁锂用磷酸铁的使用标准，可以直接作为磷酸铁锂生产的前驱体。As can be seen from Table 2, the compaction density and electrical properties of the lithium iron phosphate powder synthesized by the iron phosphate of the embodiment of the present disclosure are comparable to those of the comparative example, indicating that the iron phosphate of the embodiment of the present disclosure has reached the level of iron phosphate used for lithium iron phosphate. Using the standard, it can be directly used as a precursor for lithium iron phosphate production.
表3为实施例1与对比例的原辅料对比。Table 3 is a comparison of raw materials and auxiliary materials of Example 1 and Comparative Example.
表3table 3
从表3可以看出，本公开实施例方法的原料成本和水处理成本更低，产生的废水量更少，对环境更加友好，适合大规模推广使用。As can be seen from Table 3, the method of the embodiment of the present disclosure has lower raw material cost and water treatment cost, produces less waste water, is more environmentally friendly, and is suitable for large-scale promotion and use.
以上对本公开实施例提供的利用废磷酸铁锂正极粉提锂渣制备磷酸铁的方法和应用进行了详细的介绍，本文中应用了具体实施例对本公开的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本公开的方法及其核心思想，包括若干方式，并且也使得本领域的任何技术人员都能够实践本公开，包括制造和使用任何装置或***，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本公开原理的前提下，还可以对本公开进行若干改进和修饰，这些改进和修饰也落入本公开权利要求的保护范围内。本公开专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。The method and application of preparing iron phosphate by extracting lithium slag from waste lithium iron phosphate cathode powder provided by the embodiments of the present disclosure have been described in detail above. In this paper, specific examples are used to illustrate the principles and implementations of the present disclosure. The descriptions of the examples are only used to assist in understanding the methods of the present disclosure and the core ideas thereof, including several ways, and also to enable any person skilled in the art to practice the present disclosure, including making and using any devices or systems, and implementing any combination thereof. method. It should be pointed out that for those skilled in the art, without departing from the principles of the present disclosure, several improvements and modifications can also be made to the present disclosure, and these improvements and modifications also fall within the protection scope of the claims of the present disclosure. The scope of patent protection of this disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
- 一种利用废磷酸铁锂正极粉提锂渣制备磷酸铁的方法，包括如下步骤：A method for preparing iron phosphate by utilizing waste lithium iron phosphate positive electrode powder to extract lithium slag, comprising the following steps:(1)将废磷酸铁锂正极粉提锂渣溶解于酸液中，再过滤，收集滤液，得到酸性铁磷溶液；(1) dissolving waste lithium iron phosphate cathode powder extracting lithium residue in acid solution, filtering again, collecting filtrate to obtain acid iron phosphorus solution;(2)将所述酸性铁磷溶液进行加热，搅拌，得到含磷酸铁的料浆；(2) the acidic iron-phosphorus solution is heated and stirred to obtain a slurry containing iron phosphate;(3)将所述料浆进行过滤，得到磷酸铁固体和沉淀母液；(3) filter described slurry, obtain ferric phosphate solid and precipitation mother liquor;(4)将磷酸铁固体进行洗涤，过滤，干燥，即得磷酸铁成品。(4) washing the iron phosphate solid, filtering and drying to obtain the iron phosphate finished product.
- 根据权利要求1所述的方法，其中，步骤(1)中，所述酸液为硫酸、盐酸、磷酸、硝酸中的一种或几种；所述酸液中H +的浓度为0.7～12mol/L。 The method according to claim 1, wherein, in step (1), the acid solution is one or more of sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid; the concentration of H in the acid solution is 0.7～12mol /L.
- 根据权利要求1所述的方法，其中，步骤(1)中，所述溶解的温度为20℃～90℃。The method according to claim 1, wherein, in step (1), the temperature of the dissolving is 20°C to 90°C.
- 根据权利要求1所述的方法，其中，步骤(1)中，在所述废磷酸铁锂正极粉提锂渣溶解前先进行热处理；所述热处理的温度为200℃～600℃，所述热处理的时间为0.5～9h，所述热处理的气氛为空气、氧气、氮气、氩气或氦气中的一种或几种。The method according to claim 1, wherein, in step (1), heat treatment is performed before the dissolving of the waste lithium iron phosphate cathode powder for extracting lithium slag; the temperature of the heat treatment is 200°C-600°C, and the heat treatment The time of the heat treatment is 0.5-9h, and the atmosphere of the heat treatment is one or more of air, oxygen, nitrogen, argon or helium.
- 根据权利要求1所述的方法，其中，步骤(1)中，所述酸性铁磷溶液中的磷元素的浓度为0.05～2.5mol/L，铁元素的浓度为0.05～2.5mol/L。The method according to claim 1, wherein, in step (1), the concentration of phosphorus element in the acidic iron-phosphorus solution is 0.05-2.5 mol/L, and the concentration of iron element is 0.05-2.5 mol/L.
- 根据权利要求1所述的方法，其中，步骤(2)中，所述酸性铁磷溶液在加热前先加入氧化剂，所述氧化剂为双氧水、氧气、空气、臭氧、过一硫酸、过二硫酸、过硫酸铵、过硫酸钠、过硫酸钾、次氯酸钠或高氯酸钠中的一种或几种。The method according to claim 1, wherein, in step (2), an oxidant is added to the acidic iron-phosphorus solution before heating, and the oxidant is hydrogen peroxide, oxygen, air, ozone, peroxymonosulfuric acid, peroxodisulfuric acid, One or more of ammonium persulfate, sodium persulfate, potassium persulfate, sodium hypochlorite or sodium perchlorate.
- 根据权利要求1所述的方法，其中，步骤(2)中，所述加热的温度为40℃～250℃。The method according to claim 1, wherein, in step (2), the heating temperature is 40°C to 250°C.
- 根据权利要求1所述的方法，其中，步骤(2)中，在所述加热前，还包括往酸性铁磷溶液中添加沉淀助剂，所述沉淀助剂为偏钛酸、二氧化钛、氧化铝、氢氧化铝、无水磷酸铁、二水磷酸铁或磷铁中的一种或几种。The method according to claim 1, wherein, in step (2), before the heating, it further comprises adding a precipitation aid to the acidic iron-phosphorus solution, and the precipitation aid is metatitanic acid, titanium dioxide, alumina , one or more of aluminum hydroxide, anhydrous ferric phosphate, ferric phosphate dihydrate or ferrophosphorus.
- 根据权利要求1所述的方法，其中，步骤(4)中，在所述洗涤和干燥之间增加磷酸溶液浸泡和过滤的工序，所述磷酸溶液的浓度为0.01～5mol/L。The method according to claim 1, wherein, in step (4), a process of soaking and filtering a phosphoric acid solution is added between the washing and drying, and the concentration of the phosphoric acid solution is 0.01-5 mol/L.
- 权利要求1-9任一项所述的方法在制备磷酸铁锂正极材料、陶瓷或涂料中的应用。Application of the method according to any one of claims 1-9 in preparing lithium iron phosphate positive electrode material, ceramic or coating.
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