CN116281932A - Lithium iron manganese phosphate and preparation method and application thereof - Google Patents
Lithium iron manganese phosphate and preparation method and application thereof Download PDFInfo
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- CN116281932A CN116281932A CN202310417133.8A CN202310417133A CN116281932A CN 116281932 A CN116281932 A CN 116281932A CN 202310417133 A CN202310417133 A CN 202310417133A CN 116281932 A CN116281932 A CN 116281932A
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- Prior art keywords
- phosphate
- manganese
- lithium iron
- lithium
- sintering
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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 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 13
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 13
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000011656 manganese carbonate Substances 0.000 claims description 10
- 229940093474 manganese carbonate Drugs 0.000 claims description 10
- 235000006748 manganese carbonate Nutrition 0.000 claims description 10
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 10
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 7
- 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 6
- 239000008103 glucose Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 6
- 239000002228 NASICON Substances 0.000 abstract description 5
- 238000005056 compaction Methods 0.000 abstract description 4
- 240000007817 Olea europaea Species 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000007600 charging Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 102220043159 rs587780996 Human genes 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- 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
- C01P2004/60—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
-
- 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 lithium iron manganese phosphate, a preparation method and application thereof. The lithium iron manganese phosphate comprises the following steps: the mixed gel containing mineralizer, lithium dihydrogen phosphate, iron source and solvent reacts to prepare an iron phosphate precursor; and sintering the mixture containing the ferric phosphate precursor, the carbon source and the manganese source to prepare the lithium iron manganese phosphate. According to the invention, the lithium iron phosphate with the NASICON configuration is used as a precursor, and is matched with other characteristics to synthesize the lithium iron manganese phosphate of olive Dan Gouxing, and the diffusion rate of lithium ions is increased by retaining the porous structure of phosphate with the NACION structure, so that the compaction density, the multiplying power performance and the cycle performance of the battery are improved.
Description
Technical Field
The invention relates to lithium iron manganese phosphate, a preparation method and application thereof.
Background
The current world is receiving more and more attention as new energy batteries due to the shortage of fossil fuel resources and the occurrence of environmental pollution. Especially, the development of new energy batteries is greatly stimulated by the rising of new energy automobiles and energy storage power stations.
The lithium iron phosphate battery is one of the most widely applied positive electrode materials of new energy batteries by virtue of the advantages of low cost, high safety and the like. As technology evolves, the energy density of lithium iron phosphate batteries encounters the "ceiling". Lithium iron manganese phosphate has attracted considerable attention as an upgrade to lithium iron phosphate battery technology. According to the research, the lithium iron manganese phosphate can improve the energy density of the new energy battery by more than 15 percent compared with the lithium iron phosphate. But the conductivity and the multiplying power of the lithium iron manganese phosphate material are poor due to the crystal structure characteristics of the lithium iron manganese phosphate material.
Disclosure of Invention
The invention aims to overcome the defect of poor conductivity and rate capability of a lithium iron manganese phosphate material in the prior art, and provides a lithium iron manganese phosphate and a preparation method and application thereof.
The invention solves the technical problems through the following technical proposal.
The invention provides a preparation method of lithium iron manganese phosphate, which comprises the following steps:
s1, carrying out a reaction on mixed gel containing a mineralizer, lithium dihydrogen phosphate, an iron source and a solvent to prepare an iron phosphate precursor;
s2, sintering the mixture containing the ferric phosphate precursor, the carbon source and the manganese source to prepare the lithium iron manganese phosphate.
In S1, the mineralizer may be oxalic acid.
In S1, the mineralizer can be used in amounts conventional in the art. The mineralizer may be used in an amount of 15 to 25g/L, for example 18g/L, in the mixed gel.
In the invention, the lithium source and the phosphorus source in the lithium manganese iron phosphate can be derived from lithium dihydrogen phosphate.
In S1, the iron source may be an iron source conventionally used in the art, preferably including one or more of ferric chloride, ferric sulfate, and ferric nitrate.
In S1, the solvent may be of a type conventional in the art, typically deionized water.
In S1, the preparation method of the mixed gel can be conventional in the art, and the mineralizer, the lithium dihydrogen phosphate and the iron source are generally added into a solvent and stirred for 1-2 h.
In S1, the reaction is generally carried out in an autoclave.
In S1, the temperature of the reaction is preferably 120 ℃ to 180 ℃, for example 130 ℃.
In S1, the reaction time is preferably 8h to 36h, for example 24h.
In S2, the carbon source is preferably one or more of glucose, sucrose, citric acid and polyethylene glycol, for example glucose, polyethylene glycol or citric acid.
In S2, the amount of carbon source generally controls the amount of carbon residue in the product. In the lithium iron manganese phosphate, the carbon residue amount is preferably 1.0% -2.0% by mass of the lithium iron manganese phosphate, for example 1.0%, 1.5% or 1.7%.
In S2, the manganese source may be a manganese source conventionally used in the art, preferably including one or more of manganese powder, manganese dioxide, manganomanganic oxide, manganese carbonate and manganese oxalate, for example manganese powder or manganese carbonate.
In the invention, the dosage of the lithium source, the iron source, the manganese source and the phosphorus source in the raw materials can be adjusted by a person skilled in the art according to the structural formula of the lithium iron manganese phosphate. The molar ratio of the lithium source, the iron source, the manganese source, and the phosphorus source may be 1:0.66:0.33:1.
In S2, the mixture preferably further includes a doping element.
Wherein the doping element is preferably one or more of titanium, magnesium and vanadium.
Wherein the doping element is generally added in the form of a metal oxide, such as titanium dioxide, magnesium oxide or vanadium oxide.
In the lithium manganese iron phosphate, the doping amount of the doping element is preferably 0.5% -1.2%, for example 0.7%, 0.9% or 1.0%, and the percentage is the mass percentage of the doping element relative to the lithium manganese iron phosphate.
In S2, the mixture is generally obtained by grinding and mixing the materials.
In S2, the particle size D50 of the mixture may be 500-600nm.
In S2, the sintering operation and conditions may be conventional in the art, typically performed in a muffle furnace.
In S2, the sintering procedure is preferably two-stage sintering, more preferably, the first sintering is performed in air, and then the second sintering is performed in an inert atmosphere.
The temperature of the first sintering is preferably 300-500 ℃, for example 400 ℃.
The time for the first sintering is preferably 8 to 24 hours, for example 12 hours.
The temperature of the second sintering is preferably 650 ℃ to 750 ℃, for example 700 ℃.
The time for the second sintering is preferably 8h to 24h, for example 12h.
The inert atmosphere in the second sintering process generally refers to an atmosphere that does not participate in the system reaction during the sintering process, such as a nitrogen atmosphere or a helium atmosphere.
In S2, the sintered product is generally subjected to air current disruption. After the gas stream has been broken up, the particle size D50 of the product is preferably 500-700nm.
The invention provides lithium iron manganese phosphate prepared by the preparation method.
The invention provides lithium iron manganese phosphate, which has the structural formula as follows: liFe 0.66 Mn 0.33 PO 4 The morphology of the lithium manganese iron phosphate is in a NASCION configuration, and the olivine Dan Gouxing is formed in the NASCION configuration.
In the present invention, the NASICHON configuration may be defined by PO 4 Tetrahedra and FeO 6 The regular octahedron co-vertices are connected to form a three-dimensional network frame, ions in the frame gap can freely and rapidly move in the three-dimensional tunnel structure, and the aperture is about 1 nm.
In the invention, the particle size of the lithium iron manganese phosphate can be 500-700nm.
In the present invention, the lithium iron manganese phosphate may have a cubic structure.
The invention also provides application of the lithium iron manganese phosphate serving as a positive electrode material in the field of batteries.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
according to the invention, the lithium iron phosphate with the NASICON configuration is used as a precursor, and is matched with other characteristics to synthesize the lithium iron manganese phosphate of olive Dan Gouxing, and the diffusion rate of lithium ions is increased by retaining the porous structure of phosphate with the NACION structure, so that the compaction density, the multiplying power performance and the cycle performance of the battery are improved.
Drawings
FIG. 1 is a scanning electron micrograph of lithium iron manganese phosphate of example 1.
Fig. 2 is a buckling charge-discharge curve of lithium iron manganese phosphate prepared in example 2 at a 1C magnification at room temperature.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1 undoped lithium manganese iron phosphate
S1, 3.6g of oxalic acid, 31.2g of lithium dihydrogen phosphate and 48.4g of ferric nitrate are added into 200mL of deionized water step by step, and the mixture is stirred for 1h to obtain gel, and then reacted for 24 hours at 130 ℃ in an autoclave to form an iron phosphate precursor with a NASICON configuration.
S2, filtering the ferric phosphate precursor, washing with deionized water, drying in a baking oven at 120 ℃ for 12 hours, putting 15g of the dried ferric phosphate precursor, 0.7g of glucose and 4.1g of manganese carbonate into a mortar, grinding and mixing (the ground particle size D50=500-600 nm) uniformly, pouring into a crucible, sintering in a muffle furnace at 400 ℃ in air atmosphere for 12 hours, sintering in a nitrogen atmosphere at 700 ℃ for 12 hours, and obtaining lithium manganese phosphate (the structural formula is LiFe) after air flow crushing (the particle size D50=500-700 nm after air flow crushing) 0.66 Mn 0.33 PO 4 ) The carbon residue is 1.7%.
Example 2
S1 is the same as step S1 of example 1;
s2, filtering the ferric phosphate precursor, washing with deionized water, drying in a baking oven at 120 ℃ for 12 hours, putting 15g of the dried ferric phosphate precursor, 0.9g of polyethylene glycol, 4.1g of manganese carbonate and 0.24g of titanium dioxide into a mortar, grinding and mixing uniformly, pouring into a crucible, sintering in a muffle furnace at 400 ℃ for 12 hours in an air atmosphere, sintering in a nitrogen atmosphere at 700 ℃ for 12 hours, and crushing by air flow to obtain lithium manganese iron phosphate (with the structural formula of LiFe) 0.66 Mn 0.33 PO 4 ) The carbon residue is 1.5%.
In the lithium iron manganese phosphate, the content of the doping element Ti is 0.7 percent, and the percentage is the mass percentage of Ti in the lithium iron manganese phosphate.
Example 3
S1, adding 3.6g of oxalic acid, 131.2g of lithium dihydrogen phosphate and 40g of ferric sulfate into 200mL of deionized water step by step, stirring to obtain gel, and reacting at 130 ℃ in an autoclave for 24 hours to form an iron phosphate precursor with a NASICON configuration.
S2, filtering the ferric phosphate precursor, washing with deionized water, drying in a baking oven at 120 ℃ for 12 hours, putting 15g of the dried ferric phosphate precursor, 0.65g of citric acid, 2.0g of manganese powder and 0.24g of titanium dioxide into a mortar, grinding and mixing uniformly, pouring into a crucible, sintering in a muffle furnace at 400 ℃ for 12 hours in an air atmosphere, sintering in a nitrogen atmosphere at 700 ℃ for 12 hours, and crushing by air flow to obtain lithium manganese iron phosphate (with the structural formula of LiFe) 0.66 Mn 0.33 PO 4 ) The carbon residue is 1.0%.
In the lithium iron manganese phosphate, the content of the doping element Ti is 0.7 percent, and the percentage is the mass percentage of Ti in the lithium iron manganese phosphate.
Example 4
S1 is the same as step S1 of example 1;
s2, filtering the ferric phosphate precursor, washing with deionized water, drying in a baking oven at 120 ℃ for 12 hours, putting 15g of the dried ferric phosphate precursor, 0.9g of polyethylene glycol, 4.1g of manganese carbonate and 0.3g of magnesium oxide into a mortar, grinding and mixing uniformly, pouring into a crucible, sintering in a muffle furnace at 400 ℃ for 12 hours in an air atmosphere, sintering in a nitrogen atmosphere at 700 ℃ for 12 hours, and crushing by air flow to obtain lithium manganese iron phosphate (with the structural formula of LiFe) 0.66 Mn 0.33 PO 4 ) The carbon residue is 1.5%.
In the lithium iron manganese phosphate, the content of the doping element Mg is 0.9 percent, and the percentage is the mass percentage of Mg in the lithium iron manganese phosphate.
Example 5
S1 is the same as step S1 of example 1;
s2, filtering the ferric phosphate precursor, washing with deionized water, drying in an oven at 120 ℃ for 12 hours, and taking 15g of the dried ferric phosphate precursorThe iron phosphate precursor, 0.9g polyethylene glycol, 4.1g manganese carbonate and 0.35g vanadium oxide are put into a mortar for grinding and mixing uniformly, then poured into a crucible, sintered for 12 hours in an air atmosphere at 400 ℃ and sintered for 12 hours in a nitrogen atmosphere at 700 ℃ in a muffle furnace, and crushed by air flow to obtain lithium manganese phosphate (with the structural formula of LiFe) 0.66 Mn 0.33 PO 4 ) The carbon residue is 1.5%.
In the lithium iron manganese phosphate, the content of the doped element vanadium is 1.0 percent, and the percentage is the mass percentage of vanadium in the lithium iron manganese phosphate.
Comparative example 1
S1 to 200mL of deionized water, 331.2g of lithium dihydrogen phosphate and 48.4g of ferric nitrate were added in steps, and reacted at 130℃for 24 hours in an autoclave to form a precipitate.
S2 is the same as in step S2 of example 1, the carbon residue is 1.7%.
Comparative example 2
S1 is the same as step S1 of example 5;
s2 As compared with step S2 of example 5, the procedure and conditions were the same as those of S2 of example 5 except that polyethylene glycol was not added, and lithium iron manganese phosphate was produced with a carbon residue of 0%.
Comparative example 3 (preparation of lithium iron manganese phosphate by sol-gel method)
According to 1:0.66:0.33:1 molar ratio of lithium carbonate (Li 2 CO 3 ) Manganese carbonate (MnCO) 3 ) Ferrous oxalate (FeC) 2 O 4 ·2H 2 O), diammonium phosphate ((NH) 4 ) 2 HPO 4 ) Taking glucose as a carbon source (carbon residue amount is 1.5%) and ethanol as a solvent, putting into a ball mill, ball milling for 20 hours (particle size D50=500-600 nm after grinding), and putting the obtained slurry into a blast drying box for 1 hour after suction filtration and preliminary drying. The resulting powder was placed in a vacuum oven for 4h to obtain the final dry precursor.
Sintering the precursor powder in a muffle furnace at 400 ℃ in air atmosphere for 12h, at 700 ℃ in nitrogen atmosphere for 12h, and crushing the precursor powder by air flow (the particle size D50=500-700 nm after crushing the precursor powder by air flow) to obtain lithium manganese iron phosphate (the structural formula is LiFe) 0.66 Mn 0.33 PO 4 ) The carbon residue is 1.5%.
Effect examples
FIG. 1 is a scanning electron micrograph of lithium iron manganese phosphate prepared in example 1. As can be seen from FIG. 1, the morphology is in the NASCION configuration, the primary particle size is 500-600nm, and the cube; olive Dan Gouxing is formed in the nasicon configuration.
The lithium iron manganese phosphate prepared in examples 2 to 5 had the same structure as in example 1.
Electrochemical performance testing method:
1) Gram capacity test method:
charging: and (3) charging to the cut-off voltage of 4.2V by constant current corresponding to 0.1C, converting to constant voltage charging to the current corresponding to the cut-off current of 0.05C, and standing for 60S. Discharging: and discharging the constant current with the current corresponding to 0.1C to the cut-off voltage of 2.0V, and standing for 60S. The charging and discharging are sequentially carried out from small multiplying power to large multiplying power, the corresponding relation of different charging and discharging multiplying power is that 0.1C, 0.2C and 0.5C are charged and discharged at the same multiplying power, 1C, 2C, 5C and 10C are charged and discharged at the corresponding multiplying power, and the cut-off voltage and cut-off current are consistent with 0.1C. The gram capacity is the gram capacity corresponding to the discharge curve of 2.5V.
2) Gram capacity retention and cycle performance test method:
the charge and discharge test of the battery was performed in an incubator at 50C, and the charge and discharge were cycled at a current corresponding to 1C.
3) Method for testing compacted density of powder:
the powder compaction density was measured at a pressure of 30KN using an electronic pressure tester (model: UTM7305Z 09).
Fig. 2 is a buckling charge-discharge curve of lithium iron manganese phosphate prepared in example 2 at a 1C magnification at room temperature.
The battery properties of the lithium iron manganese phosphate prepared in examples 1 to 5 are shown in the following table 1.
TABLE 1
As can be seen from table 1, example 1 was free of doping elements and had relatively poor gram capacity, cycle performance and compacted density effects compared to other examples.
In the case of the same carbon residue in examples 2 to 5, the effect of example 5 in which the doping element is vanadium and the doping amount is 1.0% was better than that of example 4 in which the doping element is Mg and the doping amount is 0.9%, and the gram capacity and 50 ℃ cycle performance of example 4 were better than those of example 2 in which the doping element is Ti and the doping amount is 0.7%.
Comparative example 1 was not added with oxalic acid and the amount of lithium dihydrogen phosphate was increased as compared with example 1, but since comparative example 1 did not have oxalic acid as a mineralizer to form a mesophase of NASICON structure, the overall structure of the obtained product was completely different from example 1, and the effect was inferior as a whole to example 1.
Comparative example 2 was not carbon-coated, and the residual carbon content was 0%, and the gram capacity, cycle performance, compaction density, and the like were far inferior to those of example 5.
Comparative example 3 was inferior to example 5 in terms of effect of gram capacity, cycle performance, compacted density, etc., compared with example 5 in that the doping amount was reduced from 1% to 0.1%.
Claims (10)
1. The preparation method of the lithium iron manganese phosphate is characterized by comprising the following steps of:
s1, carrying out a reaction on mixed gel containing a mineralizer, lithium dihydrogen phosphate, an iron source and a solvent to prepare an iron phosphate precursor;
s2, sintering the mixture containing the ferric phosphate precursor, the carbon source and the manganese source to prepare the lithium iron manganese phosphate.
2. The method for preparing lithium iron manganese phosphate according to claim 1, wherein in S1, the mineralizer is oxalic acid;
and/or S1, the mineralizer is used in an amount of 15-25 g/L, such as 18g/L, in the mixed gel;
and/or, in S1, the iron source comprises one or more of ferric chloride, ferric sulfate, and ferric nitrate;
and/or, in S1, the temperature of the reaction is 120 ℃ to 180 ℃, e.g. 130 ℃;
and/or, in S1, the reaction time is 8h-36h, such as 24h.
3. The method for preparing lithium iron manganese phosphate according to claim 1, wherein in S2, the carbon source is one or more of glucose, sucrose, citric acid and polyethylene glycol;
and/or S2, wherein the carbon residue in the lithium iron manganese phosphate is 1.0-2.0% of the mass of the lithium iron manganese phosphate;
and/or, in S2, the manganese source includes one or more of manganese powder, manganese dioxide, manganous oxide, manganese carbonate and manganese oxalate;
and/or, in the lithium iron manganese phosphate, the molar ratio of the lithium source to the iron source to the manganese source to the phosphorus source is 1:0.66:0.33:1.
4. The method for preparing lithium iron manganese phosphate according to claim 3, wherein in S2, the carbon source is glucose, polyethylene glycol or citric acid;
and/or, in S2, the carbon residue in the lithium iron manganese phosphate is 1.0%, 1.5% or 1.7% of the mass of the lithium iron manganese phosphate;
and/or, in S2, the manganese source comprises manganese powder or manganese carbonate.
5. The method for preparing lithium iron manganese phosphate according to claim 1, wherein in S2, the mixture further comprises a doping element;
and/or, in S2, the particle size D50 of the mixture is 500-600nm;
and/or, in S2, the sintering procedure is two-stage sintering, preferably, first sintering is performed in air, and then second sintering is performed in inert atmosphere;
and/or S2, carrying out airflow crushing on the product obtained by sintering; after the airflow is broken, the particle size D50 of the product is 500-700nm.
6. The method for preparing lithium iron manganese phosphate according to claim 5, wherein the doping element is one or more of titanium, magnesium and vanadium;
and/or the doping element is added in the form of a metal oxide, such as titanium dioxide, magnesium oxide or vanadium oxide;
and/or the doping amount of the doping element in the lithium manganese iron phosphate is 0.5% -1.2%, for example 0.7%, 0.9% or 1.0%, and the percentage is the mass percentage of the doping element relative to the lithium manganese iron phosphate.
7. The method of preparing lithium iron manganese phosphate according to claim 5, wherein the temperature of the first sintering is 300-500 ℃, such as 400 ℃;
and/or the time of the first sintering is 8-24 hours, for example 12 hours;
and/or the temperature of the second sintering is 650 ℃ to 750 ℃, e.g. 700 ℃;
and/or the second sintering is performed for 8h-24h, for example 12h.
8. A lithium iron manganese phosphate produced by the production process according to any one of claims 1 to 7.
9. The lithium iron manganese phosphate is characterized in that the structural formula comprises: liFe 0.66 Mn 0.33 PO 4 The morphology of the lithium manganese iron phosphate is in a NASCION configuration, and the olivine Dan Gouxing is formed in the NASCION configuration.
10. Use of a lithium iron manganese phosphate according to claim 8 or 9 as a positive electrode material in the field of batteries.
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