CN116692817A - Preparation method of ferric manganese phosphate precursor - Google Patents
Preparation method of ferric manganese phosphate precursor Download PDFInfo
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- CN116692817A CN116692817A CN202310782786.6A CN202310782786A CN116692817A CN 116692817 A CN116692817 A CN 116692817A CN 202310782786 A CN202310782786 A CN 202310782786A CN 116692817 A CN116692817 A CN 116692817A
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- iron phosphate
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- phosphate precursor
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- 239000002243 precursor Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 title claims description 5
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 claims abstract description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- -1 SP-80 Substances 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019439 ethyl acetate Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 23
- 239000002245 particle Substances 0.000 abstract description 13
- 238000001914 filtration Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 7
- 150000001768 cations Chemical class 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- 239000005955 Ferric phosphate Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009827 uniform distribution 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
- C01B25/45—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
- C01P2004/51—Particles with a specific particle size distribution
-
- 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
- C01P2006/80—Compositional purity
-
- 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 application discloses a preparation method of a manganese iron phosphate precursor, relates to the technical field of lithium ion battery anode materials, and solves the problem that other metal cation impurities and other acid radical impurities are easy to introduce in the preparation process. The preparation method comprises the following steps: dissolving manganese powder and iron powder in phosphoric acid solution, adding the solution into a reaction kettle, adding an oxidant for oxidation, adding alkali liquor for regulating the pH value, controlling the pH value to be 1-6, reacting at 20-60 ℃, stirring at 200-800 r/min for 3-8 h, filtering and washing the suspension after the reaction is finished, drying at 75-130 ℃, and roasting at 200-800 ℃ for 2-5 h to remove crystal water, thereby obtaining the manganese iron phosphate precursor without crystal water. The ferromanganese phosphate precursor prepared by the method has the advantages of high purity, uniform element distribution, good crystallinity, narrow particle size distribution, simple process method and less pollution.
Description
Technical Field
The application relates to the technical field of lithium ion battery anode materials, in particular to a preparation method of a manganese iron phosphate precursor.
Background
The olivine-structured lithium iron manganese phosphate is a kind of positive electrode material of lithium ion batteries with phosphate systems, and is mainly used for various lithium ion batteries. The lithium iron manganese phosphate battery has the advantages of safety, environmental protection, high cycle performance, low price, no toxicity, no environmental pollution and the like, and has obvious advantages compared with the traditional lead-acid battery, and the novel fuel battery, nickel-hydrogen battery and lithium manganate battery. The lithium iron manganese phosphate has the advantages of lithium iron phosphate and lithium manganese phosphate, has the same theoretical capacity of 170mAh/g, is high in safety and stability, has higher working voltage, can reach about 4.1V and is far higher than 3.4V of the lithium iron phosphate, and therefore has the potential advantage of high energy density. When the actual capacity of the lithium iron manganese phosphate is exerted to the same extent as that of the lithium iron phosphate, the energy density of the lithium iron manganese phosphate is improved by 15-20% compared with that of the lithium iron phosphate, and the upper limit of the endurance mileage is further broken through. The lithium iron manganese phosphate is regarded as an upgrade of lithium iron phosphate, is a novel positive electrode material obtained by adding manganese element on the basis of lithium iron phosphate, obtains the best material performance by adjusting the proportion of Fe-Mn, has higher voltage platform, higher energy density and longer cycle life, and is increasingly popular in the power battery market.
The preparation method of the lithium iron manganese phosphate mainly comprises a high-temperature solid phase method, a sol-gel method and a coprecipitation method. The high-temperature solid-phase method for synthesizing the lithium iron phosphate material is mainly formed by mechanically and uniformly mixing a lithium source, an iron source, a manganese source and a phosphorus source and then carrying out solid-phase sintering. In order to solve the problems, a coprecipitation method is adopted to prepare a manganese iron phosphate precursor, and the key point of research is that people study. The manganese iron phosphate is used as a precursor for preparing the manganese iron phosphate lithium material, and the performances of element distribution, morphology, granularity and the like are key factors for determining the performance of the manganese iron phosphate lithium material. Because the solubility product of ferric phosphate and manganese phosphate has larger difference, the pH difference of initial precipitation in a liquid phase is larger, and the ferric phosphate precursor is difficult to form by coprecipitation under a conventional liquid phase reaction system, the preparation of the ferric phosphate precursor with evenly mixed ferric and manganese has certain difficulty, the process is complex, the cost is higher, a large amount of waste water and waste acid can be generated in the preparation process, and the industrial production is difficult.
Disclosure of Invention
Aiming at the defects, the application provides the preparation method of the manganese iron phosphate precursor, which avoids introducing other metal cation impurities and other acid radical impurities, does not generate a large amount of wastewater in the preparation process, and has the advantages of simple process operation, high purity, narrow granularity distribution and good crystallinity. The specific technical scheme is as follows:
a preparation method of a manganese iron phosphate precursor comprises the following steps:
(1) Iron powder and manganese powder are respectively added into phosphoric acid solution according to a certain solid-liquid weight ratio to be dissolved, so as to obtain iron source solution A and manganese source solution B;
(2) Placing the solution A and the solution B into a reaction kettle for stirring and mixing, adding an oxidant, adding alkali liquor to adjust the pH value of a reaction system to be 1-6, and stirring for 3-8 hours at 20-60 ℃ to obtain a suspension;
(3) And (3) filter-pressing the suspension, washing a filter cake, drying at 75-130 ℃, and roasting at 200-800 ℃ for 2-5 hours to obtain the ferromanganese phosphate precursor.
Preferably, in the step (1), the weight ratio of the solid to the liquid is 1:5-1:20, and the weight ratio of the iron powder to the manganese powder is 1-4:1.
Preferably, in the step (1), the mass concentration of the phosphoric acid solution is 20-85%.
Preferably, in the step (2), the oxidant is at least one of hydrogen peroxide, sodium hypochlorite and ammonium persulfate.
Preferably, in the step (2), the addition amount of the oxidant is 5-50% of the weight of the mixed solution in the reaction kettle.
Preferably, in the step (2), the alkali liquor is at least one of ammonia water, ammonium carbonate, ammonium bicarbonate, sodium hydroxide, sodium carbonate and potassium hydroxide.
Preferably, the alkali liquor contains a dispersing agent, and the dispersing agent is at least one of ethanol, n-butanol, polyethylene glycol, polyvinyl alcohol, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, carboxymethyl cellulose, SP-80, polydimethylsiloxane, ammonium polyacrylate, ethyl acetate, glycerin, sodium acetate and stearic acid.
Preferably, the concentration of the dispersing agent is 1-20 g/L.
Preferably, in the step (3), the washing is carried out by soaking in deionized water for 0.5-3 hours and then washing with deionized water for three times; the stirring rotating speed in the step (2) is 200-800 r/min.
The ferromanganese phosphate precursor prepared by the preparation method is prepared.
Compared with the prior art, the application has the beneficial effects that:
1. the application can avoid rapid agglomeration and growth of crystals by controlling the reaction temperature to be 20-60 ℃ and the lower reaction temperature, thereby reducing entrainment of metal cations; the pH is controlled to be 1-6, metal cations can be prevented from entering the crystal lattice by the lower pH, and cationic impurities and acid radical impurities are prevented from being introduced by controlling the reaction temperature and the pH, so that a large amount of waste water and waste acid cannot be generated in the preparation process, pollution is not easy to generate, the method is more environment-friendly, the process operation is simple, and the method is suitable for industrial mass production.
2. The addition of the dispersing agent can lead the agglomeration degree of the ferric manganese phosphate precursor to be small, and solve the problem that particles are easy to agglomerate.
3. The ferromanganese phosphate precursor prepared by the method has uniform particle size distribution, high purity and uniform distribution of iron and manganese elements, and forms uniform single crystal phase compound.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the description of the embodiments will be briefly described below.
FIG. 1 is an SEM image of a manganese iron phosphate precursor prepared according to example 1 of the present application;
FIG. 2 is an SEM image of a manganese iron phosphate precursor according to example 2 of the present application;
FIG. 3 is an SEM image of a manganese iron phosphate precursor according to example 3 of the present application;
FIG. 4 is an XRD pattern of a manganese iron phosphate precursor prepared in example 3 of the present application;
FIG. 5 is an XRD pattern of the manganese iron phosphate precursor prepared in comparative example 1;
FIG. 6 is an XRD pattern of the manganese iron phosphate precursor prepared in comparative example 2;
Detailed Description
The following detailed description of specific embodiments of the application is, but it should be understood that the application is not limited to specific embodiments.
Example 1
A preparation method of a manganese iron phosphate precursor comprises the following steps:
39.2g of iron powder and 359ml of 65% phosphoric acid are taken and placed in a container for stirring, and after the iron powder is completely dissolved, the obtained solution is filtered to obtain solution A; placing 16.5g of manganese powder and 153.9ml of 65% phosphoric acid into a container for stirring, and filtering the obtained solution after the manganese powder is completely dissolved to obtain a solution B; placing the solution A and the solution B into a reaction kettle, stirring and mixing, adding 65ml of 28% hydrogen peroxide, adjusting the pH value of the reaction to 2.6-3.0 by using 5mol/L sodium hydroxide solution containing 5g/L polyethylene glycol, and stirring at the reaction temperature of 40 ℃ for 5 hours at the rotating speed of 300r/min to obtain a suspension; and (3) carrying out filter pressing on the suspension, soaking a filter cake in deionized water for 0.5h, washing with pure water for three times, drying at 100 ℃ in a vacuum drying oven, and roasting at 350 ℃ in a muffle furnace for 3h to remove crystal water, thus obtaining the manganese iron phosphate precursor without crystal water.
The particle diameter D10 of the manganese iron phosphate precursor prepared in this example was 4.51 μm, D50 was 6.61 μm and D90 was 10.12. Mu.m, (Fe+Mn): p=0.981. The observation result by a Scanning Electron Microscope (SEM) is shown in fig. 1.
Example 2
A preparation method of a manganese iron phosphate precursor comprises the following steps:
89.6g of iron powder and 820.5ml of 65% phosphoric acid are taken and placed in a container for stirring, and after the iron powder is completely dissolved, the obtained solution is filtered to obtain solution A; 22g of manganese powder and 205.1ml of 65% phosphoric acid are placed in a container for stirring, and after the manganese powder is completely dissolved, the obtained solution is filtered to obtain a solution B; placing the solution A and the solution B into a reaction kettle, stirring and mixing, adding 150ml of 28% hydrogen peroxide, adjusting the pH value of the reaction to 2.6-3.0 by using 20% ammonia water containing 10g/L sodium dodecyl benzene sulfonate, and stirring at the reaction temperature of 50 ℃ and the rotation speed of 500r/min for 5 hours to obtain a suspension; and (3) carrying out filter pressing on the suspension, soaking a filter cake in deionized water for 3 hours, washing with pure water for three times, drying at 100 ℃ in a vacuum drying oven, and roasting at 600 ℃ in a muffle furnace for 3 hours to remove crystal water, thereby obtaining the manganese iron phosphate precursor without crystal water.
The particle diameter D10 of the manganese iron phosphate precursor prepared in this example was 3.41 μm, D50 was 5.14 μm, and D90 was 8.24 μm, (Fe+Mn): p=0.992. The observation result by a Scanning Electron Microscope (SEM) is shown in fig. 2.
Example 3
A preparation method of a manganese iron phosphate precursor comprises the following steps:
67.2g of iron powder and 880.9ml of 50% phosphoric acid are taken and placed in a container for stirring, and after the iron powder is completely dissolved, the obtained solution is filtered to obtain solution A; placing 44g of manganese powder and 587.3ml of 50% phosphoric acid into a container for stirring, and filtering the obtained solution after the manganese powder is completely dissolved to obtain a solution B; placing the solution A and the solution B into a reaction kettle, stirring and mixing, adding 150ml of 28% hydrogen peroxide, adjusting the pH value of the reaction to 3.4-4.0 by using 5mol/L sodium hydroxide containing 7g/L ammonium polyacrylate, and stirring at the reaction temperature of 30 ℃ for 5 hours at the rotating speed of 500r/min to obtain a suspension; and (3) carrying out filter pressing on the suspension, soaking a filter cake in deionized water for 2 hours, washing with pure water for three times, drying at 100 ℃ in a vacuum drying oven, and roasting at 600 ℃ in a muffle furnace for 3 hours to remove crystal water, thereby obtaining the manganese iron phosphate precursor without crystal water.
The particle diameter D10 of the manganese iron phosphate precursor prepared in this example was 3.15. Mu.m, D50 was 4.71. Mu.m, and D90 was 7.42. Mu.m, (Fe+Mn): p=0.996. The results of Scanning Electron Microscope (SEM) observation are shown in fig. 3, and the XRD pattern of the obtained manganese iron phosphate precursor is shown in fig. 4.
Example 4
A preparation method of a manganese iron phosphate precursor comprises the following steps:
placing 40g of iron powder and 1190.5ml of 20% phosphoric acid in a container, stirring, and filtering the obtained solution after the iron powder is completely dissolved to obtain a solution A; placing 9.8g of manganese powder and 298.1ml of 20% phosphoric acid into a container for stirring, and filtering the obtained solution after the manganese powder is completely dissolved to obtain a solution B; placing the solution A and the solution B in a reaction kettle, stirring and mixing, adding 36.9g of sodium hypochlorite, adjusting the pH value of the reaction to 1 by using 5g/L of ammonium carbonate and ammonium bicarbonate which contain 5g/L of ethanol, n-butyl alcohol, polyvinyl alcohol and sodium dodecyl sulfate, and stirring at the speed of 200r/min for 3 hours at the reaction temperature of 20 ℃ to obtain a suspension; and (3) carrying out filter pressing on the suspension, soaking a filter cake in deionized water for 2 hours, washing with pure water for three times, drying at 75 ℃ in a vacuum drying oven, and roasting in a muffle furnace at 200 ℃ for 2 hours to remove crystal water, thus obtaining the manganese iron phosphate precursor without crystal water.
The particle size DD10 of the manganese iron phosphate precursor prepared in the example is 3.55 μm, D50 is 5.25 μm, D90 is 8.68 μm, (Fe+Mn): p=0.995.
Example 5
A preparation method of a manganese iron phosphate precursor comprises the following steps:
50g of iron powder and 350.1ml of 85% phosphoric acid are taken and placed in a container for stirring, and after the iron powder is completely dissolved, the obtained solution is filtered to obtain solution A; placing 12.3g of manganese powder and 87.7ml of 85% phosphoric acid into a container for stirring, and filtering the obtained solution after the manganese powder is completely dissolved to obtain a solution B; placing the solution A and the solution B in a reaction kettle, stirring and mixing, adding 140g of ammonium persulfate, adjusting the pH value of the reaction to 1 by using ammonium bicarbonate, sodium carbonate and potassium hydroxide containing 5g/L of carboxymethyl cellulose, SP-80, polydimethylsiloxane, ethyl acetate, glycerol, sodium acetate and 5mol/L of stearic acid, and stirring at the reaction temperature of 60 ℃ for 8 hours at the rotation speed of 800r/min to obtain a suspension; and (3) carrying out filter pressing on the suspension, soaking a filter cake in deionized water for 2 hours, washing with pure water for three times, drying at 130 ℃ in a vacuum drying oven, and roasting at 800 ℃ in a muffle furnace for 5 hours to remove crystal water, thus obtaining the manganese iron phosphate precursor without crystal water.
The particle diameter D10 of the manganese iron phosphate precursor prepared in this example was 4.01. Mu.m, D50 was 6.05. Mu.m, and D90 was 9.16. Mu.m, (Fe+Mn): p=0.994.
Example 6
A preparation method of a manganese iron phosphate precursor comprises the following steps:
placing 50g of iron powder and 1488.1ml of 20% phosphoric acid in a container, stirring, and filtering the obtained solution after the iron powder is completely dissolved to obtain a solution A; placing 12.3g of manganese powder and 272.6ml of 20% phosphoric acid into a container for stirring, and filtering the obtained solution after the manganese powder is completely dissolved to obtain a solution B; placing the solution A and the solution B in a reaction kettle, stirring and mixing, adding 45.9g of sodium hypochlorite and ammonium persulfate, adjusting the pH value of the reaction to 1 by using 5mol/L ammonium bicarbonate and ammonium bicarbonate containing 5g/L ethyl acetate and glycerol, and stirring at the reaction temperature of 50 ℃ for 7 hours at the rotation speed of 500r/min to obtain a suspension; and (3) carrying out filter pressing on the suspension, soaking a filter cake in deionized water for 2 hours, washing with pure water for three times, drying at 120 ℃ in a vacuum drying oven, and roasting at 600 ℃ in a muffle furnace for 4 hours to remove crystal water, thereby obtaining the manganese iron phosphate precursor without crystal water.
The particle diameter D10 of the manganese iron phosphate precursor prepared in this example was 3.59 μm, D50 was 5.68 μm and D90 was 9.22 μm, (Fe+Mn): p=1.001.
Comparative example 1
A preparation method of a manganese iron phosphate precursor comprises the following steps:
67.2g of iron powder and 880.9ml of 50% phosphoric acid are taken and placed in a container for stirring, and after the iron powder is completely dissolved, the obtained solution is filtered to obtain solution A; placing 44g of manganese powder and 587.3ml of 50% phosphoric acid into a container for stirring, and filtering the obtained solution after the manganese powder is completely dissolved to obtain a solution B; placing the solution A and the solution B into a reaction kettle, stirring and mixing, adding 150ml of 28% hydrogen peroxide, adjusting the pH value of the reaction to 3.4-4.0 by using 5mol/L sodium hydroxide containing 7g/L ammonium polyacrylate, and stirring at the reaction temperature of 70 ℃ for 5 hours at the rotation speed of 500r/min to obtain a suspension; and (3) carrying out filter pressing on the suspension, soaking a filter cake in deionized water for 2 hours, washing with pure water for three times, drying at 100 ℃ in a vacuum drying oven, and roasting at 600 ℃ in a muffle furnace for 3 hours to remove crystal water, thereby obtaining the manganese iron phosphate precursor without crystal water.
The reaction temperature of this comparative example was higher than that of the present application, and other reaction data were the same as in example 3.
The particle diameter D50 of the ferromanganese phosphate precursor prepared in the comparative example is 7.9 mu m, (Fe+Mn): p=0.975.
The XRD pattern of the prepared manganese iron phosphate precursor is shown in figure 5, and the impurities are more after the reaction temperature is higher.
Comparative example 2
A preparation method of a manganese iron phosphate precursor comprises the following steps:
67.2g of iron powder and 880.9ml of 50% phosphoric acid are taken and placed in a container for stirring, and after the iron powder is completely dissolved, the obtained solution is filtered to obtain solution A; placing 44g of manganese powder and 587.3ml of 50% phosphoric acid into a container for stirring, and filtering the obtained solution after the manganese powder is completely dissolved to obtain a solution B; placing the solution A and the solution B into a reaction kettle, stirring and mixing, adding 150ml of 28% hydrogen peroxide, adjusting the pH value of the reaction to 7.5-8.5 by using 5mol/L sodium hydroxide containing 7g/L ammonium polyacrylate, and stirring at the reaction temperature of 30 ℃ for 5 hours at the rotating speed of 500r/min to obtain a suspension; and (3) carrying out filter pressing on the suspension, soaking a filter cake in deionized water for 2 hours, washing with pure water for three times, drying at 100 ℃ in a vacuum drying oven, and roasting at 600 ℃ in a muffle furnace for 3 hours to remove crystal water, thereby obtaining the manganese iron phosphate precursor without crystal water.
The comparative example shows a reaction pH higher than that of the present application, and the other data are the same as in example 3.
The particle diameter D50 of the ferromanganese phosphate precursor prepared in the comparative example is 9.67 mu m, (Fe+Mn): p=1.201.
The XRD pattern of the obtained manganese iron phosphate precursor is shown in figure 6.
By comparing the XRD patterns of example 3, comparative example 1, comparative example 2, the results show that: according to the application, by controlling the reaction temperature and controlling the pH value, the lower reaction temperature can prevent crystals from being quickly agglomerated and grown, so that metal cations are reduced, the lower pH value can prevent the metal cations from entering crystal lattices, the introduction of cationic impurities and acid radical impurities is effectively avoided, and the high-quality manganese iron phosphate precursor is obtained.
The particle sizes D10, D50 and D90 of the manganese iron phosphate precursors prepared in examples 1 to 6 show that the manganese iron phosphate precursors prepared by the method have uniform particle size distribution.
The foregoing descriptions of specific exemplary embodiments of the present application are presented for purposes of illustration and description. It is not intended to limit the application to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the application and its practical application to thereby enable one skilled in the art to make and utilize the application in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the application be defined by the claims and their equivalents.
Claims (10)
1. The preparation method of the ferric manganese phosphate precursor is characterized by comprising the following steps of:
(1) Iron powder and manganese powder are respectively added into phosphoric acid solution according to a certain solid-liquid weight ratio to be dissolved, so as to obtain iron source solution A and manganese source solution B;
(2) Placing the solution A and the solution B into a reaction kettle for stirring and mixing, adding an oxidant, adding alkali liquor to adjust the pH value of a reaction system to be 1-6, and stirring for 3-8 hours at 20-60 ℃ to obtain a suspension;
(3) And (3) filter-pressing the suspension, washing a filter cake, drying at 75-130 ℃, and roasting at 200-800 ℃ for 2-5 hours to obtain the ferromanganese phosphate precursor.
2. The method for preparing a manganese iron phosphate precursor according to claim 1, wherein in the step (1), the weight ratio of the solid to the liquid is 1:5-1:20, and the weight ratio of the iron powder to the manganese powder is 1-4:1.
3. The method for preparing a manganese iron phosphate precursor according to claim 1, wherein in the step (1), the mass concentration of the phosphoric acid solution is 20-85%.
4. The method for preparing a precursor of manganese iron phosphate according to claim 1, wherein in the step (2), the oxidizing agent is at least one of hydrogen peroxide, sodium hypochlorite and ammonium persulfate.
5. The method for preparing a precursor of manganese iron phosphate according to claim 1, wherein in the step (2), the addition amount of the oxidant is 5-50% of the weight of the mixed solution in the reaction kettle.
6. The method for preparing a precursor of manganese iron phosphate according to claim 1, wherein in the step (2), the alkali solution is at least one of ammonia water, ammonium carbonate, ammonium bicarbonate, ammonium dihydrogen carbonate, sodium hydroxide, sodium carbonate and potassium hydroxide.
7. The method for preparing a precursor of manganese iron phosphate according to claim 6, wherein the alkali solution contains a dispersant, and the dispersant is at least one of ethanol, n-butanol, polyethylene glycol, polyvinyl alcohol, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, carboxymethyl cellulose, SP-80, polydimethylsiloxane, ammonium polyacrylate, ethyl acetate, glycerin, sodium acetate and stearic acid.
8. The method for preparing a precursor of manganese iron phosphate according to claim 7, wherein the concentration of the dispersing agent is 1-20 g/L.
9. The method for preparing a manganese iron phosphate precursor according to claim 1, wherein in the step (3), the washing is carried out by immersing the precursor in deionized water for 0.5-3 hours, and then washing with deionized water three times; the stirring rotating speed in the step (2) is 200-800 r/min.
10. A manganese iron phosphate precursor prepared by the preparation method of any one of claims 1 to 9.
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| CN116924377B (en) * | 2023-09-18 | 2024-01-02 | 宁波容百新能源科技股份有限公司 | Ammonium ferromanganese phosphate, lithium ferromanganese phosphate, and preparation methods and applications thereof |
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