CN117509583A - Preparation method of high-grinding-efficiency ferric phosphate and lithium iron phosphate - Google Patents
Preparation method of high-grinding-efficiency ferric phosphate and lithium iron phosphate Download PDFInfo
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- CN117509583A CN117509583A CN202311567741.3A CN202311567741A CN117509583A CN 117509583 A CN117509583 A CN 117509583A CN 202311567741 A CN202311567741 A CN 202311567741A CN 117509583 A CN117509583 A CN 117509583A
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- phosphate
- iron
- lithium
- iron phosphate
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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 66
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 32
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 32
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 32
- 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 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 34
- 238000000227 grinding Methods 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 20
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 20
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 20
- 239000006012 monoammonium phosphate Substances 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- 239000012065 filter cake Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011790 ferrous sulphate Substances 0.000 claims description 14
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 14
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000001488 sodium phosphate Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003337 fertilizer Substances 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 4
- 235000011009 potassium phosphates Nutrition 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 238000005056 compaction Methods 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 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 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 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 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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
- C01P2006/10—Solid 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
- C01P2006/40—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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of high-grinding-efficiency ferric phosphate and lithium iron phosphate. The iron phosphate with special morphology is obtained by controlling the solid content and controlling the amount of the added phosphoric acid and the added phosphate. The iron phosphate has high grinding efficiency, can improve the production efficiency of lithium iron phosphate, and the lithium iron phosphate product prepared by adopting the iron phosphate has the characteristics of high compaction and high capacity.
Description
Technical Field
The invention relates to the technical field of new energy and lithium batteries, in particular to a preparation method of high-grinding-efficiency ferric phosphate and lithium iron phosphate.
Background
The rapid development of the electric automobile industry drives the development of power batteries, and the capacity of the batteries of the electric automobile becomes a bottleneck for limiting the development of the electric automobile. In a power battery, a positive electrode material occupies an important position, and the positive electrode material determines the performance of the power battery. The existing power battery anode material mainly adopts a nickel-cobalt-manganese ternary material and a lithium iron phosphate material. The lithium iron phosphate battery has become the mainstream of the power battery because of the advantages of low cost, high safety, no toxicity, environmental friendliness and the like.
The existing lithium iron phosphate anode material is mainly prepared by grinding an iron phosphate precursor, a lithium source and a carbon source, then spray drying, calcining and crushing. The grinding process is a key process for limiting the productivity and the performance of the lithium iron phosphate material. The high-grinding-efficiency ferric phosphate material not only can greatly shorten the grinding time and improve the efficiency and the productivity, but also has nano-scale, and the lithium permeation and the carbon coating are more uniform and sufficient, so that the electrical property of the material is improved. The grinding performance of the existing ferric phosphate products needs to be further improved, so that the productivity and the electrical performance of the lithium iron phosphate material are improved.
Disclosure of Invention
The invention aims to solve one of the technical problems existing in the existing iron phosphate production process. The invention provides a preparation method of high-grinding-efficiency ferric phosphate and lithium iron phosphate.
The preparation method of the ferric phosphate comprises the following steps:
s1, preparing an iron source solution and a phosphorus source solution for later use;
s2, adding an oxidant into the phosphorus source solution;
s3, adding the iron source solution and the phosphorus source solution into a reaction kettle at the same time to prepare slurry, and adding alkali liquor to adjust the pH value to 5-7;
s4, filtering and washing the prepared slurry to obtain a filter cake;
s5, pulping a filter cake, controlling the solid content of the slurry, adding phosphoric acid and phosphonium salt, reacting for 3-5 hours at 90-100 ℃, and washing and calcining the reacted product to obtain the ferric phosphate.
Preferably, by controlling the solid content of the slurry and adding the phosphoric acid and the phosphate in the step S5, the iron phosphate product with special appearance and loose agglomeration can be obtained, and the secondary agglomeration is loose, so that the iron phosphate product has high grinding efficiency and good electric performance.
Preferably, the iron source in the step S1 is at least one selected from titanium white byproduct ferrous sulfate, ferrous nitrate, ferrous oxalate and ferrous chloride.
Preferably, the phosphorus source in the step S1 is at least one selected from the group consisting of a phosphorus-containing compound fertilizer, phosphoric acid, monoammonium phosphate, ammonium phosphate, sodium phosphate monobasic, sodium phosphate, potassium phosphate monobasic, and potassium phosphate.
Preferably, the molar ratio of iron to phosphorus in the iron source and phosphorus source solution prepared in the step S1 is 2 (1.6-1.8).
Preferably, the oxidant in the step S2 is at least one selected from potassium permanganate, hydrogen peroxide, peracetic acid and ammonium persulfate;
preferably, in the step S3, the adding time of the phosphorus source solution and the iron source solution into the reaction kettle is 40-60 min; preferably 50min. The stirring speed of the reaction kettle is 150-300 rpm; preferably 250rpm.
Preferably, the alkaline solution in the step S3 is at least one selected from sodium hydroxide, ammonia water, trisodium phosphate and tri-ammonium phosphate.
Preferably, in the step S5, the solid content of the slurry is 3-7%, preferably 5%, and the slurry is stirred at 250-350 rpm.
Preferably, the phosphate salt in the step S5 is at least one selected from the group consisting of a phosphate-containing compound fertilizer, monoammonium phosphate, ammonium phosphate, monosodium phosphate, sodium phosphate, monopotassium phosphate and potassium phosphate.
Preferably, the reaction temperature in the step S5 is 90-100 ℃, preferably 95 ℃; the reaction time is 3 to 5 hours, preferably 4 hours.
Preferably, the calcination temperature in the step S5 is 500-650 ℃, and the calcination time is 3-7 hours.
A method for preparing lithium iron phosphate, comprising the following steps:
t1, preparing ferric phosphate according to the preparation method;
and T2, adding water, a lithium source and a carbon source into the iron phosphate prepared by the method T1, performing sanding treatment, performing spray drying on the sanded material, and calcining the spray dried material at a high temperature in a protective atmosphere to obtain the lithium iron phosphate.
Preferably, the lithium source is at least one of lithium hydroxide, lithium carbonate and lithium phosphate, and the carbon source is at least one of saccharides, organic acids and other carbon-containing high polymer compounds.
Preferably, the granularity of the obtained material after sanding is 200-500 nm.
Preferably, in the high-temperature calcination operation of T2, the calcination temperature is 700-800 ℃ and the time is 10-20 h.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a flow chart of the operation of the present invention;
FIG. 2 is an XRD pattern of iron phosphate prepared in example 3;
FIG. 3 is an SEM image of the iron phosphate prepared in example 3;
FIG. 4 is an SEM image of iron phosphate prepared in a comparative example;
FIG. 5 is a graph showing the polishing efficiency of iron phosphate prepared in examples 1, 2 and 3 and comparative example.
Description of the embodiments
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the embodiments of the present invention, it should be noted that, if the terms "upper," "lower," "inner," "outer," and the like indicate an azimuth or a positional relationship based on the azimuth or the positional relationship shown in the drawings, or the azimuth or the positional relationship in which the inventive product is conventionally put in use, it is merely for convenience of describing the present invention and simplifying the description, and does not indicate or imply that the apparatus or element to be referred to must have a specific azimuth, be configured and operated in a specific azimuth, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like in the description of the present invention, if any, are used for distinguishing between the descriptions and not necessarily for indicating or implying a relative importance.
In the description of the embodiments of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "connected," and "connected" should be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Example 1 ]
The preparation method of the high grinding efficiency ferric phosphate comprises the following steps:
1. 3L of ferrous sulfate solution is prepared, and the concentration of the ferrous sulfate solution is 1.2mol/L.
2. 3L of monoammonium phosphate solution is prepared, the concentration of the monoammonium phosphate solution is 1.0mol/L, and 275.3g of hydrogen peroxide is added into the monoammonium phosphate solution.
3. Adding the ferrous sulfate solution in 1 and the monoammonium phosphate solution containing hydrogen peroxide in 2 into a reaction kettle, wherein the stirring speed of the reaction kettle is 250rpm, and the adding time is 50min.
4. After the addition, the reaction is carried out for 1 hour to obtain ferric phosphate slurry, and ammonia water is added to adjust the pH value of the slurry to 7.
5. The ferric phosphate slurry is filtered and washed to have the conductivity below 8000 uS/cm.
6. Adding water into the filter cake obtained in step 5 to slurry, controlling the solid content to be 5%, adding the filter cake into a reaction kettle, setting the stirring rotation speed to be 300rpm, adding 45.2g of phosphoric acid with the mass concentration of 85%, and adding 18.5g of ammonium phosphate with the purity of 98%.
7. Heating to 95 ℃, and preserving heat for 4 hours to obtain the sizing agent of ferric phosphate.
8. The slurry of iron phosphate obtained in 7 was washed and filtered to a conductivity of 2000uS/cm or less.
9. And (3) calcining the filter cake obtained after the filtration in step 8 for 5 hours at 550 ℃ to obtain an anhydrous ferric phosphate product.
Example 2 ]
The preparation method of the high grinding efficiency ferric phosphate comprises the following steps:
1. 4L of ferrous sulfate solution is prepared, and the concentration of the ferrous sulfate solution is 1.2mol/L.
2. 4L monoammonium phosphate solution is prepared, the concentration of the monoammonium phosphate solution is 1.0mol/L, and 367.1g of hydrogen peroxide is added into the monoammonium phosphate solution.
3. Adding the ferrous sulfate solution in 1 and the monoammonium phosphate solution containing hydrogen peroxide in 2 into a reaction kettle, wherein the stirring speed of the reaction kettle is 250rpm, and the adding time is 50min.
4. After the addition, the reaction was completed for 1 hour to obtain a slurry of iron phosphate, and the pH of the slurry was adjusted to 7 by adding sodium hydroxide.
5. The ferric phosphate slurry is filtered and washed to have the conductivity below 8000 uS/cm.
6. Pulping the filter cake obtained in step 5 by adding water, controlling the solid content to be 5%, adding the filter cake into a reaction kettle, setting the stirring rotation speed to be 300rpm, adding 60.27g of phosphoric acid with the mass concentration of 85%, and adding 24.67g of diammonium phosphate with the purity of 94%.
7. Heating to 95 ℃, and preserving heat for 4 hours to obtain the sizing agent of ferric phosphate.
8. The iron phosphate slurry obtained in step 7 was washed by filtration to a conductivity of 2000uS/cm or less.
9. And (3) calcining the filter cake obtained after the filtration in step 8 for 6 hours at 550 ℃ to obtain an anhydrous ferric phosphate product.
Example 3 ]
The preparation method of the high grinding efficiency ferric phosphate comprises the following steps:
1. preparing 25L of ferrous sulfate solution, wherein the concentration of the ferrous sulfate solution is 1.2mol/L.
2. 25L of monoammonium phosphate solution is prepared, the concentration of the monoammonium phosphate solution is 1.0mol/L, and 2.754 kg hydrogen peroxide is added into the monoammonium phosphate solution.
3. And (3) simultaneously adding the ferrous sulfate solution in the step (1) and the monoammonium phosphate solution containing hydrogen peroxide in the step (2) into a reaction kettle, wherein the stirring speed of the reaction kettle is 250rpm, and the adding time is 80min.
4. After the addition, the reaction was completed for 1 hour to obtain a slurry of iron phosphate, and the pH of the slurry was adjusted to 7 by adding sodium hydroxide.
5. The ferric phosphate slurry is filtered and washed until the conductivity is less than 10000 uS/cm.
6. Adding water into the filter cake obtained in step 5 to pulpify, controlling the solid content to be 3%, adding the filter cake into a reaction kettle, setting the stirring rotation speed to be 350rpm, adding 951.5g of 85% phosphoric acid by mass and 123.5g of ammonium phosphate with the purity of 98%.
7. Heating to 95 ℃, and preserving heat for 5 hours to obtain the sizing agent of ferric phosphate.
8. The slurry of iron phosphate obtained in 7 was washed and filtered to a conductivity of 2000uS/cm or less.
9. And (3) calcining the filter cake obtained after the filtration in step 8 for 6 hours at 550 ℃ to obtain an anhydrous ferric phosphate product. The material was cooled and inspected for X-ray diffraction measurements, the results of which are shown in FIG. 2. As can be seen from fig. 2, the iron phosphate product obtained after calcination is pure phase iron phosphate. The material was examined by scanning electron microscopy, see figure 3. As can be seen from FIG. 3, the calcined iron phosphate primary particles were small particles (200 to 300 nm) plus flakes (length: 200 to 300nm, thickness: 10 to 20 nm).
< comparative example >
A method for preparing ferric phosphate, comprising the following steps:
1. preparing 25L of ferrous sulfate solution, wherein the concentration of the ferrous sulfate solution is 1.2mol/L.
2. 25L of monoammonium phosphate solution is prepared, the concentration of the monoammonium phosphate solution is 1.0mol/L, and 2.754 kg hydrogen peroxide is added into the monoammonium phosphate solution.
3. Adding the ferrous sulfate solution in 1 and the monoammonium phosphate solution containing hydrogen peroxide in 2 into a reaction kettle, wherein the stirring speed of the reaction kettle is 250rpm, and the adding time is 80min.
4. After the addition, the reaction was completed for 1 hour to obtain a slurry of iron phosphate, and the pH of the slurry was adjusted to 7 by adding sodium hydroxide.
5. The ferric phosphate slurry is filtered and washed until the conductivity is less than 10000 uS/cm.
6. Adding water into the filter cake obtained in step 5 to pulpify, controlling the solid content to be 12%, adding the filter cake into a reaction kettle, setting the stirring rotation speed to be 350rpm, and adding 951.5g of phosphoric acid with the mass concentration of 85%.
7. Heating to 95 ℃, and preserving heat for 5 hours to obtain the sizing agent of ferric phosphate.
8. The slurry of iron phosphate obtained in 7 was filtered and washed to a conductivity of 2000uS/cm or less.
9. And (3) calcining the filter cake obtained after the filtration in step 8 for 6 hours at 550 ℃ to obtain an anhydrous ferric phosphate product. The material was examined by scanning electron microscopy, see figure 4.
The iron phosphate prepared in examples 1 to 3 and comparative example was used to prepare lithium iron phosphate under the same conditions. Iron phosphate, deionized water, lithium carbonate and glucose are prepared into a mixture, the mixture is sanded, granularity is sampled and detected in different time periods, and the grinding efficiency of the iron phosphate of examples 1-3 and the grinding efficiency of the iron phosphate of a comparison example (figure 5) are obtained, the iron phosphate prepared in examples 1-3 has high grinding efficiency, the grinding efficiency can be lower than 400nm in 30min, the grinding efficiency of the iron phosphate of the comparison example needs 60min, and the grinding efficiency of the iron phosphate prepared in examples 1-3 is doubled compared with that of the comparison example.
And (3) carrying out spray drying on the slurry after sanding, and then sintering the material for 20 hours at 720 ℃ in a nitrogen atmosphere to obtain the lithium iron phosphate. The prepared lithium iron phosphate was prepared into a button cell under the same conditions according to a conventional method, and then tested for electrical properties under the same conditions according to a conventional method in the art. The electrical property test results of examples 1 to 3 and the comparative example are shown in table 1 below:
table 1 electrical property comparison
As can be seen from table 1, the charge and discharge properties and the compacted density of the lithium iron phosphate prepared by examples were significantly improved as compared to the comparative examples. Compared with the comparative example, the charging capacity is improved by 4-5 mAh/g, the discharging capacity is improved by 6-7 mAh/g, and the compaction density is improved by 0.14-0.16. The iron phosphate product prepared by the embodiment has the characteristics of high grinding efficiency, high compaction and high capacity due to the special appearance, and has the advantages of simple and convenient operation and industrialized production capacity.
The above embodiments are only for illustrating the technical solution and features of the present invention, and are intended to be better implemented by those skilled in the art, but not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention are within the scope of the present invention, wherein the prior art is not specifically illustrated.
Claims (10)
1. The preparation method of the high-grinding-efficiency ferric phosphate is characterized by comprising the following steps of:
s1, preparing an iron source solution and a phosphorus source solution for later use;
s2, adding an oxidant into the phosphorus source solution;
s3, adding the iron source solution and the phosphorus source solution into a reaction kettle at the same time to prepare slurry, and adding alkali liquor to adjust the pH value to 5-7;
s4, washing and filtering the prepared slurry to obtain a filter cake;
s5, pulping a filter cake, controlling the solid content of the slurry, adding phosphoric acid and phosphonium salt, reacting for 3-5 hours at 90-100 ℃, and washing and calcining the reacted product to obtain the ferric phosphate.
2. The method for preparing iron phosphate with high grinding efficiency according to claim 1, wherein the iron source in S1 is at least one of titanium white byproduct ferrous sulfate, ferrous nitrate, ferrous oxalate and ferrous chloride.
3. The method for preparing iron phosphate with high grinding efficiency according to claim 1, wherein the phosphorus source in S1 is at least one selected from the group consisting of a phosphorus-containing compound fertilizer, phosphoric acid, monoammonium phosphate, ammonium phosphate, monosodium phosphate, sodium phosphate, monopotassium phosphate and potassium phosphate.
4. The method for preparing high grinding efficiency ferric phosphate according to claim 1, wherein the molar ratio of iron to phosphorus in the prepared iron source and phosphorus source solution is 2 (1.6-1.8).
5. The method for preparing high grinding efficiency ferric phosphate according to claim 1, wherein the oxidant in S2 is at least one selected from the group consisting of potassium permanganate, hydrogen peroxide, peracetic acid and ammonium persulfate; the alkali liquor in the step S3 is at least one selected from sodium hydroxide solution, ammonia water, trisodium phosphate solution and tri-ammonium phosphate solution.
6. The method for preparing iron phosphate with high grinding efficiency according to claim 1, wherein the adding time of the iron source solution and the phosphorus source solution in S3 is 40-60 min, and the stirring speed of the reaction kettle is 150-300 rpm;
s5, the solid content of the slurry after pulping is 3-7%, the slurry is in a stirring state, and the stirring speed is 250-350 rpm; s5, the phosphate salt is at least one of a phosphorus-containing compound fertilizer, monoammonium phosphate, ammonium phosphate, sodium phosphate monobasic, sodium phosphate, potassium phosphate monobasic and potassium phosphate; and S5, the calcination temperature is 500-650 ℃, and the calcination time is 3-7 h.
7. The preparation method of the lithium iron phosphate is characterized by comprising the following steps of:
t1, preparing iron phosphate according to the preparation method of any one of claims 1-6;
and T2, adding water, a lithium source and a carbon source into the ferric phosphate prepared by the T1, performing sanding treatment, performing spray drying on the sanded material, and calcining the spray dried material at a high temperature in a protective atmosphere to obtain the lithium iron phosphate.
8. The method for producing lithium iron phosphate according to claim 7, wherein the lithium source is at least one of lithium hydroxide, lithium carbonate and lithium phosphate, and the carbon source is at least one of saccharides, organic acids and other carbon-containing high molecular compounds.
9. The method for preparing lithium iron phosphate according to claim 7, wherein the granularity of the obtained material after sanding is 200-500 nm.
10. The method for preparing lithium iron phosphate according to claim 7, wherein the protective atmosphere in T2 is at least one of hydrogen, argon, nitrogen and carbon monoxide, and the calcination temperature is 700-800 ℃ and the calcination time is 10-20 h in the high-temperature calcination operation.
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