CN114014292A - Preparation method of lithium iron manganese phosphate - Google Patents
Preparation method of lithium iron manganese phosphate Download PDFInfo
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- CN114014292A CN114014292A CN202111295859.6A CN202111295859A CN114014292A CN 114014292 A CN114014292 A CN 114014292A CN 202111295859 A CN202111295859 A CN 202111295859A CN 114014292 A CN114014292 A CN 114014292A
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- iron
- lithium
- raw material
- phosphate
- manganese
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- 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 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 29
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims abstract description 8
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 6
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 64
- 239000002994 raw material Substances 0.000 claims description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001238 wet grinding Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 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
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 230000009286 beneficial effect Effects 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
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 4
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910014985 LiMnxFe1-xPO4 Inorganic materials 0.000 description 1
- 229910014982 LiMnxFe1−xPO4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C01B25/45—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 lithium iron manganese phosphate, which comprises the steps of enabling a ferric salt and a phosphate to react more uniformly when being mixed through a premixing unit and a stirring unit in a reaction kettle, reducing local concentration, preparing and obtaining a uniform ferric phosphate precursor, preparing and obtaining the lithium iron manganese phosphate with uniform appearance through a mode of combining a wet method and a solid phase method, improving the conductivity of the lithium iron manganese phosphate through carbon coating, and being beneficial to improving the cycle life, the first discharge capacity and the charge-discharge efficiency of a lithium iron manganese phosphate anode material.
Description
Technical Field
The invention belongs to the field of new energy materials, and relates to a preparation method of lithium iron manganese phosphate.
Background
With the enhancement of public environmental awareness, the country supports the new energy field greatly, and the lithium ion battery gradually becomes a widely used power storage device. The lithium iron phosphate battery is widely applied to the fields of new energy automobiles and energy storage due to the advantages of good safety performance, long cycle life, low price and the like, and the lithium iron phosphate battery does not contain precious metals and rare elements, is rich in raw material reserves and relatively small in environmental pollution, and gradually receives market impactIs very popular. However, the discharge voltage platform of the lithium iron phosphate is low (-3.4V), and the compaction density is only 2.4g/cm3Resulting in lower energy density and limiting the development and application of lithium iron phosphate.
And lithium iron phosphate (LiFePO)4) Lithium manganese phosphate (LiMnPO) having the same structure4) Relative to Li+The electrode potential of the/Li is 4.1V, which is much higher than that of LiFePO4The voltage platform is positioned in an electrochemical stability window of the existing electrolyte system, and has wide future application prospect, so that the voltage platform is concerned. However, since LiMnPO4Is considered to be an insulator, resulting in the synthesis of reversibly chargeable and dischargeable LiMnPO4Is very difficult and limits the development and application of the method.
Lithium iron manganese phosphate LiMnxFe1-xPO4(0<x<1) Is in LiMnPO4Developed on the basis of modification, the preparation difficulty is large although Fe2+The introduction of the lithium manganese phosphate can improve the electrochemical performance of the lithium manganese phosphate, but the improvement range is limited, so that the electrochemical performance of the material is difficult to give full play, and the prepared lithium manganese phosphate is difficult to meet the application requirements.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of lithium iron manganese phosphate, the preparation method is simple, and the prepared lithium iron manganese phosphate has excellent electrochemical performance.
The invention provides a preparation method of lithium iron manganese phosphate, which comprises the following steps:
(1) at normal temperature, injecting an iron raw material and a phosphoric acid raw material into a premixing unit of a reaction kettle in a continuous parallel flow and top feeding mode to obtain premixed raw materials;
(2) feeding the premixed raw materials obtained in the step (1) into the bottom of a reaction kettle, carrying out precipitation reaction on the bottom of the reaction kettle, controlling the pH value of the reaction process to be 0.5-3, controlling the reaction temperature to be 40-75 ℃, reacting for 1-8 h, then heating to 80-99 ℃, and continuing to react for 0.5-8 h to obtain mixed slurry;
(3) filtering the mixed slurry obtained in the step (2), and washing the obtained filter residue to obtain an iron phosphate precursor;
(4) carrying out wet milling treatment on the iron phosphate precursor, the manganese source, the lithium source and the carbon source according to the molar ratio of elements in the lithium manganese iron phosphate to obtain a mixture, carrying out spray drying on the mixture to obtain a lithium manganese iron phosphate precursor, and calcining the lithium manganese iron phosphate precursor in an inert atmosphere to obtain the lithium manganese iron phosphate anode material.
In a specific embodiment, the reaction kettle comprises a kettle body, a premixing unit arranged at the upper part of the kettle body and a stirring unit arranged at the lower part of the kettle body;
the premixing unit comprises a feed hopper and a first stirrer, wherein the feed hopper and the first stirrer are arranged on the inner side of the top of the kettle body, the first stirrer is arranged at the lower position of the middle part of the feed hopper, a first motor is arranged above the top of the kettle body, the first stirrer is driven by the first motor, and the top wall of the kettle body is communicated with the iron raw material inlet and the phosphoric acid raw material inlet;
the stirring unit comprises a second stirrer and a second motor which are arranged at the bottom of the kettle body, the second stirrer is driven by the second motor, and a rotating shaft of the second stirrer is connected with the output end of the second motor through a coupler;
a feeding port is formed in the middle of the side face of the kettle body, and a discharging port is formed in the bottom of the kettle body;
the rotating shaft of the second stirrer penetrates through the bottom of the kettle body and extends to the lower part of the kettle body, and the rotating shaft is arranged at the center of the bottom of the kettle body;
the iron raw material inlet is communicated with the iron raw material storage box, and a first valve is arranged on a pipeline between the iron raw material inlet and the iron raw material storage box; the phosphoric acid raw material inlet is communicated with the phosphoric acid raw material storage box, and a second valve is arranged on a pipeline between the phosphoric acid raw material inlet and the phosphoric acid raw material storage box.
In a specific embodiment, the iron raw material is at least one of ferrous sulfate, ferrous chloride and ferrous nitrate solution; preferably a ferrous sulfate solution;
the phosphoric acid raw material is at least one of phosphoric acid, ammonium dihydrogen phosphate and sodium dihydrogen phosphate, and phosphoric acid is preferred;
injecting an oxidant from a feed inlet in the middle of the reaction kettle, wherein the oxidant is one or more of sodium hypochlorite, sodium chlorate and hydrogen peroxide; preferably hydrogen peroxide.
In a specific embodiment, the molar ratio of ferrous iron, phosphoric acid and hydrogen peroxide in the reaction kettle is 1: (1.0-1.3): (0.5 to 1.5).
In a specific example, in the step (3), the iron phosphate precursor is washed with pure water.
In a specific embodiment, in the step (4), the manganese source is one or both of manganese nitrate and manganese chloride.
In a specific embodiment, in the step (4), the lithium source is one or both of lithium carbonate and lithium acetate.
In a specific embodiment, in the step (4), the carbon source is one or more of glucose, PVA, PVB, polypropylene and citric acid, and the addition amount of the carbon source is 1-20 wt% of ferric phosphate in the ferric phosphate precursor.
In a specific embodiment, in the step (4), the calcination temperature of the lithium iron manganese phosphate precursor is 500-900 ℃ for 2-24 hours.
The beneficial technical effects of the invention are as follows:
the invention provides a preparation method of lithium iron manganese phosphate, which comprises the steps of enabling a ferric salt and a phosphate to react more uniformly when being mixed through a premixing unit and a stirring unit in a reaction kettle, reducing local concentration, preparing and obtaining a uniform ferric phosphate precursor, preparing and obtaining lithium iron manganese phosphate with uniform appearance in a mode of combining a wet method and a solid phase method, improving the conductivity of the lithium iron manganese phosphate through carbon coating, and being beneficial to improving the electrochemical performance of a lithium iron manganese phosphate anode material.
Drawings
FIG. 1 is a schematic structural view of a reaction vessel in example 1 of the present invention.
Fig. 2 is an electron microscope scanning image of the lithium iron manganese phosphate prepared in embodiment 1 of the present invention.
Description of reference numerals: 1-kettle body, 2-premixing unit, 201-feed hopper, 202-first stirrer, 203-first motor, 3-stirring mechanism, 301-second stirrer, 302-second motor, 303-coupler, 4-iron raw material inlet, 5-phosphoric acid raw material inlet, 6-discharge port, 7-iron raw material storage box, 8-first valve, 9-phosphoric acid raw material storage box, 10-second valve and 11-feed inlet.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
In this example, unless otherwise specified, all reagents used were common commercial products or prepared by conventional means, and the equipment used was conventional in the art, and the following are some examples of the inventors in the experiment:
example 1
The invention relates to a preparation method of lithium iron manganese phosphate, which comprises the following steps:
(1) at normal temperature, injecting ferrous sulfate solution and phosphoric acid into a premixing unit of a reaction kettle in a continuous parallel flow and top feeding mode to obtain premixed raw materials;
(2) the premixed raw materials enter the bottom of the reaction kettle, hydrogen peroxide is injected from a feed inlet in the middle of the side surface of the kettle body, and the molar ratio of ferrous iron to phosphoric acid to the hydrogen peroxide in the reaction kettle is controlled to be 1: 1.2: 1, carrying out precipitation reaction at the bottom of a reaction kettle, controlling the pH value of the reaction process to be 1-2, controlling the reaction temperature to be 60 ℃, reacting for 1 hour, then heating to 90 ℃, and continuing to react for 6 hours to obtain mixed slurry;
(3) filtering the mixed slurry obtained in the step (2), and washing the obtained filter residue to obtain an iron phosphate precursor;
(4) according to the molar ratio of elements in the lithium manganese iron phosphate, carrying out wet grinding treatment on the iron phosphate precursor, a manganese source, a lithium source and a carbon source (the mass ratio of glucose to PVA is 5: 5), wherein the addition amount of the carbon source is 5 wt% of the iron phosphate, obtaining a mixture, carrying out spray drying on the mixture to obtain a lithium manganese iron phosphate precursor, placing the lithium manganese iron phosphate precursor under the protection of nitrogen atmosphere, and calcining at the temperature of 700 ℃ for 8 hours to obtain the lithium manganese iron phosphate anode material.
As shown in fig. 1, the reaction kettle comprises a kettle body 1, a premixing unit 2 arranged at the upper part of the kettle body and a stirring unit 3 arranged at the lower part of the kettle body;
the premixing unit 2 comprises a feed hopper 201 and a first stirrer 202 which are arranged on the inner side of the top of the kettle body, the first stirrer 202 is arranged at the lower position of the middle part of the feed hopper 201, a first motor 203 is arranged above the top of the kettle body 1, the first stirrer is driven by the first motor, and the top wall of the kettle body is communicated with an iron raw material inlet 4 and a phosphoric acid raw material inlet 5;
the stirring unit 3 comprises a second stirrer 301 and a second motor 302 which are arranged at the bottom of the kettle body, the second stirrer is driven by the second motor, and a rotating shaft of the second stirrer is connected with the output end of the second motor through a coupler 303;
the intermediate position of the side surface of the kettle body is provided with a feed inlet 11, and the bottom of the kettle body is provided with a discharge outlet 6.
The rotating shaft of the second stirrer 301 penetrates through the bottom of the kettle body and extends to the lower part of the kettle body, and the rotating shaft is installed at the center of the bottom of the kettle body.
The iron raw material inlet 4 is communicated with an iron raw material storage box 7, and a first valve 8 is arranged on a pipeline between the iron raw material inlet and the iron raw material storage box; the phosphoric acid raw material inlet 5 is communicated with a phosphoric acid raw material storage tank 9, and a second valve 10 is arranged on a pipeline between the phosphoric acid raw material inlet and the phosphoric acid raw material storage tank.
Fig. 2 is an electron microscope scanning image of the lithium iron manganese phosphate prepared in example 1, and it can be seen from fig. 2 that the lithium iron manganese phosphate particles are uniform, and the average particle size (D50) is 200-500 nm.
Example 2
The invention relates to a preparation method of lithium iron manganese phosphate, which comprises the following steps:
(1) at normal temperature, injecting ferrous sulfate solution and phosphoric acid into a premixing unit of a reaction kettle in a continuous parallel flow and top feeding mode to obtain premixed raw materials;
(2) the premixed raw materials enter the bottom of the reaction kettle, hydrogen peroxide is injected from a feed inlet in the middle of the side surface of the kettle body, and the molar ratio of ferrous iron to phosphoric acid to the hydrogen peroxide in the reaction kettle is controlled to be 1: 1.1: 0.8, carrying out precipitation reaction at the bottom of the reaction kettle, controlling the pH value of the reaction process to be 1-2, controlling the reaction temperature to be 50 ℃, reacting for 1 hour, then heating to 95 ℃, and continuing to react for 4 hours to obtain mixed slurry;
(3) filtering the mixed slurry obtained in the step (2), and washing the obtained filter residue to obtain an iron phosphate precursor;
(4) according to the molar ratio of elements in the lithium manganese iron phosphate, carrying out wet grinding treatment on the iron phosphate precursor, a manganese source, a lithium source and a carbon source (the mass ratio of polypropylene to citric acid is 5: 5), wherein the addition amount of the carbon source is 8 wt% of the iron phosphate, so as to obtain a mixture, carrying out spray drying on the mixture so as to obtain a lithium manganese iron phosphate precursor, and calcining the lithium manganese iron phosphate precursor at the temperature of 900 ℃ for 4 hours under the protection of a nitrogen atmosphere so as to obtain the lithium manganese iron phosphate anode material.
Example 3
The invention relates to a preparation method of lithium iron manganese phosphate, which comprises the following steps:
(1) at normal temperature, injecting ferrous sulfate solution and phosphoric acid into a premixing unit of a reaction kettle in a continuous parallel flow and top feeding mode to obtain premixed raw materials;
(2) the premixed raw materials enter the bottom of the reaction kettle, hydrogen peroxide is injected from a feed inlet in the middle of the side surface of the kettle body, and the molar ratio of ferrous iron to phosphoric acid to the hydrogen peroxide in the reaction kettle is controlled to be 1: 1.25: 0.7, carrying out precipitation reaction at the bottom of the reaction kettle, controlling the pH value of the reaction process to be 1-2, controlling the reaction temperature to be 40 ℃, reacting for 2 hours, then heating to 85 ℃, and continuing to react for 8 hours to obtain mixed slurry;
(3) filtering the mixed slurry obtained in the step (2), and washing the obtained filter residue to obtain an iron phosphate precursor;
(4) according to the molar ratio of elements in the lithium manganese iron phosphate, carrying out wet grinding treatment on the iron phosphate precursor, a manganese source, a lithium source and a carbon source (the mass ratio of PVB to citric acid is 5: 5), wherein the addition amount of the carbon source is 2 wt% of the iron phosphate, so as to obtain a mixture, carrying out spray drying on the mixture so as to obtain a lithium manganese iron phosphate precursor, placing the lithium manganese iron phosphate precursor under the protection of nitrogen atmosphere, and calcining at 650 ℃ for 12 hours so as to obtain the lithium manganese iron phosphate anode material.
Mixing the lithium iron manganese phosphate positive electrode material prepared in the embodiment 1-3, a polyvinylidene fluoride adhesive and a carbon black conductive agent according to a mass ratio of 92:4:4 to obtain a mixture, adding the mixture into an NMP (N-methyl pyrrolidone) solvent to obtain mixed slurry, coating the mixed slurry on the surface of an aluminum substrate, and drying to obtain a positive plate; assembling the positive plate, the lithium negative electrode, the diaphragm and electrolyte into a button lithium battery, wherein the electrolyte comprises ethylene carbonate, methyl ethyl carbonate and lithium hexafluorophosphate, the volume ratio of the ethylene carbonate to the methyl ethyl carbonate is 3:7, and the concentration of the lithium hexafluorophosphate is 1M.
The lithium manganese iron phosphate obtained in the examples 1 to 3 was prepared into a button lithium battery for electrochemical performance test, and specifically shown in table 1:
TABLE 1 electrochemical Performance test data for lithium batteries
In conclusion, the iron salt and the phosphate react more uniformly when mixed through the premixing unit and the stirring unit in the reaction kettle, the local concentration is reduced, the uniform iron phosphate precursor is prepared, the lithium manganese iron phosphate with uniform morphology is prepared in a mode of combining a wet method and a solid phase method, the conductivity of the lithium manganese iron phosphate is improved through carbon coating, and the cycle life, the first discharge capacity and the charge-discharge efficiency of the lithium manganese iron phosphate anode material are improved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the lithium iron manganese phosphate is characterized by comprising the following steps of:
(1) at normal temperature, injecting an iron raw material and a phosphoric acid raw material into a premixing unit of a reaction kettle in a continuous parallel flow and top feeding mode to obtain premixed raw materials;
(2) feeding the premixed raw materials obtained in the step (1) into the bottom of a reaction kettle, carrying out precipitation reaction on the bottom of the reaction kettle, controlling the pH value of the reaction process to be 0.5-3, controlling the reaction temperature to be 40-75 ℃, reacting for 1-8 h, then heating to 80-99 ℃, and continuing to react for 0.5-8 h to obtain mixed slurry;
(3) filtering the mixed slurry obtained in the step (2), and washing the obtained filter residue to obtain an iron phosphate precursor;
(4) carrying out wet milling treatment on the iron phosphate precursor, the manganese source, the lithium source and the carbon source according to the molar ratio of elements in the lithium manganese iron phosphate to obtain a mixture, carrying out spray drying on the mixture to obtain a lithium manganese iron phosphate precursor, and calcining the lithium manganese iron phosphate precursor in an inert atmosphere to obtain the lithium manganese iron phosphate anode material.
2. The method for preparing lithium iron manganese phosphate according to claim 1, wherein the reaction kettle comprises a kettle body, a premixing unit arranged at the upper part of the kettle body and a stirring unit arranged at the lower part of the kettle body;
the premixing unit comprises a feed hopper and a first stirrer, wherein the feed hopper and the first stirrer are arranged on the inner side of the top of the kettle body, the first stirrer is arranged at the lower position of the middle part of the feed hopper, a first motor is arranged above the top of the kettle body, the first stirrer is driven by the first motor, and the top wall of the kettle body is communicated with the iron raw material inlet and the phosphoric acid raw material inlet;
the stirring unit comprises a second stirrer and a second motor which are arranged at the bottom of the kettle body, the second stirrer is driven by the second motor, and a rotating shaft of the second stirrer is connected with the output end of the second motor through a coupler;
a feeding port is formed in the middle of the side face of the kettle body, and a discharging port is formed in the bottom of the kettle body;
the rotating shaft of the second stirrer penetrates through the bottom of the kettle body and extends to the lower part of the kettle body, and the rotating shaft is arranged at the center of the bottom of the kettle body;
the iron raw material inlet is communicated with the iron raw material storage box, and a first valve is arranged on a pipeline between the iron raw material inlet and the iron raw material storage box; the phosphoric acid raw material inlet is communicated with the phosphoric acid raw material storage box, and a second valve is arranged on a pipeline between the phosphoric acid raw material inlet and the phosphoric acid raw material storage box.
3. The method for preparing lithium iron manganese phosphate according to claim 2, wherein the iron raw material is at least one of ferrous sulfate, ferrous chloride and ferrous nitrate solution; preferably a ferrous sulfate solution;
the phosphoric acid raw material is at least one of phosphoric acid, ammonium dihydrogen phosphate and sodium dihydrogen phosphate, and phosphoric acid is preferred;
injecting an oxidant from a feed inlet in the middle of the reaction kettle, wherein the oxidant is one or more of sodium hypochlorite, sodium chlorate and hydrogen peroxide; preferably hydrogen peroxide.
4. The preparation method of lithium iron manganese phosphate according to claim 3, wherein the molar ratio of ferrous iron, phosphoric acid and hydrogen peroxide in the reaction kettle is 1: (1.0-1.3): (0.5 to 1.5).
5. The method for preparing lithium iron manganese phosphate according to claim 1, wherein in step (3), the iron phosphate precursor is washed with pure water.
6. The method for preparing lithium iron manganese phosphate according to claim 1, wherein in step (4), the manganese source is one or both of manganese nitrate and manganese chloride.
7. The method for preparing lithium iron manganese phosphate according to claim 1, wherein in step (4), the lithium source is one or both of lithium carbonate and lithium acetate.
8. The preparation method of lithium iron manganese phosphate according to claim 1, wherein in the step (4), the carbon source is one or more of glucose, PVA, PVB, polypropylene and citric acid, and the addition amount of the carbon source is 1-20 wt% of ferric phosphate in the ferric phosphate precursor.
9. The preparation method of lithium iron manganese phosphate according to claim 1, wherein in the step (4), the calcination temperature of the lithium iron manganese phosphate precursor is 500-900 ℃ for 2-24 hours.
10. Lithium iron manganese phosphate, characterized in that it is produced by the method for producing lithium iron manganese phosphate according to any one of claims 1 to 9.
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