CN117976849A - Titanium modified lithium iron manganese phosphate base material and preparation method and application thereof - Google Patents
Titanium modified lithium iron manganese phosphate base material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117976849A CN117976849A CN202311857644.8A CN202311857644A CN117976849A CN 117976849 A CN117976849 A CN 117976849A CN 202311857644 A CN202311857644 A CN 202311857644A CN 117976849 A CN117976849 A CN 117976849A
- Authority
- CN
- China
- Prior art keywords
- titanium
- source
- slurry
- base material
- manganese phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 68
- 239000010936 titanium Substances 0.000 title claims abstract description 53
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 53
- -1 Titanium modified lithium iron manganese phosphate Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 26
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910015645 LiMn Inorganic materials 0.000 claims abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 32
- 238000005245 sintering Methods 0.000 claims description 29
- 239000007921 spray Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001694 spray drying Methods 0.000 claims description 15
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical class [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 6
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 4
- 238000005056 compaction Methods 0.000 abstract description 9
- 239000007774 positive electrode material Substances 0.000 description 26
- 239000011159 matrix material Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910015831 LiMn0.6Fe0.4PO4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- CDRCPXYWYPYVPY-UHFFFAOYSA-N iron(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+2].[Fe+2].[Fe+2] CDRCPXYWYPYVPY-UHFFFAOYSA-N 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a titanium modified lithium iron manganese phosphate base material, a preparation method and application thereof, wherein the titanium modified lithium iron manganese phosphate base material comprises a base material and a titanium compound existing on the surface of the base material, the chemical formula of the base material is LiMn xFe1‑xPO4, x is more than or equal to 0.1 and less than or equal to 0.9, and the titanium compound comprises titanium dioxide and/or lithium titanate. The invention can improve the compaction density, ploidy and other performances of the titanium modified lithium iron manganese phosphate based material.
Description
Technical Field
The invention relates to the field of batteries, in particular to a titanium modified lithium iron manganese phosphate base material, a preparation method and application thereof.
Background
The power battery is a main power source of products such as new energy automobiles and the like, and mainly comprises components such as an anode, a cathode, electrolyte, a diaphragm and the like, wherein an anode material is an important factor influencing the performance of the power battery, and gradually becomes a main development direction of the power battery. At present, lithium iron phosphate is used as a main-flow positive electrode material, has the defects of poor electrochemical dynamics, poor low-temperature performance, low working voltage and the like, and can overcome the problems of poor low-temperature performance, low discharge voltage and the like of the lithium iron phosphate to a certain extent as an iterative product of the lithium iron phosphate.
However, the compaction density of the lithium iron manganese phosphate is lower and is generally less than 2.3cm 3/g, and the compaction density of the lithium iron manganese phosphate directly influences the energy density of the lithium iron manganese phosphate, which is a great obstacle for the application of the lithium iron manganese phosphate on electric automobiles, particularly the use of the lithium iron manganese phosphate on long-endurance automobile types, and meanwhile, the electrochemical properties such as the multiplying power performance and the like of the existing lithium iron manganese phosphate material are still to be further improved.
Disclosure of Invention
The invention provides a titanium modified lithium iron manganese phosphate base material, a preparation method and application thereof, which can improve the electrochemical properties such as compaction density, rate capability and the like of the titanium modified lithium iron manganese phosphate base material.
In one aspect of the invention, a titanium modified lithium iron manganese phosphate base material is provided, and comprises a base material and a titanium compound existing on the surface of the base material, wherein the chemical formula of the base material is LiMn xFe1-xPO4, x is more than or equal to 0.1 and less than or equal to 0.9, and the titanium compound comprises titanium dioxide and/or lithium titanate.
According to an embodiment of the present invention, the mass ratio of the titanium compound to the base material is 0.1% to 3%.
In another aspect of the present invention, a preparation method of the above titanium-modified lithium iron manganese phosphate-based material is provided, comprising the steps of: mixing a lithium source, a manganese source, an iron source, a phosphorus source and water to obtain a first slurry; sequentially performing first spray drying and first sintering on the first slurry to prepare a precursor; mixing the precursor, a titanium source and water to obtain second slurry; and sequentially carrying out second spray drying and second sintering on the second slurry to obtain the titanium modified lithium iron manganese phosphate based material.
According to an embodiment of the present invention, after mixing a lithium source, a manganese source, an iron source, a phosphorus source and water, performing first grinding to obtain the first slurry; wherein the average particle diameter of the particles in the first slurry is set to 0.25 to 0.55 μm by the first polishing.
According to one embodiment of the invention, a first spray dryer is adopted for carrying out the first spray drying, wherein the inlet temperature of the first spray dryer is 70-180 ℃ and the outlet temperature of the first spray dryer is 50-120 ℃; and/or the temperature of the first sintering is 350-600 ℃, and the time of the first sintering is 5-10 h.
According to an embodiment of the invention, the titanium source comprises one or more of titanium dioxide, titanic acid, tetrabutyl titanate, lithium titanate.
According to an embodiment of the present invention, after the precursor, the titanium source and the water are mixed, a second grinding is performed to obtain the second slurry; wherein the average particle diameter of the particles in the second slurry is set to 0.3 to 0.4 μm by the second polishing.
According to an embodiment of the present invention, a second spray dryer is used for the second spray drying, wherein the inlet temperature of the second spray dryer is 150-300 ℃ and the outlet temperature is 80-100 ℃; and/or the temperature of the second sintering is 400-900 ℃, and the time of the second sintering is 2-10 h.
In another aspect of the invention, a positive electrode sheet is provided, comprising the above titanium modified lithium iron manganese phosphate based material.
In another aspect of the present invention, a battery is provided, including the positive electrode sheet described above.
According to the titanium modified lithium manganese iron phosphate and the preparation method and application thereof, provided by the invention, the matrix material is LiMn xFe1-xPO4 (x is more than or equal to 0.1 and less than or equal to 0.9), and the specific titanium compound (including titanium dioxide and/or lithium titanate) exists on the surface of the matrix material, so that the compaction density (more specifically, not less than 2.3cm 3/g) of the titanium modified lithium manganese iron phosphate base material can be improved, and the energy density of a positive plate or a battery adopting the titanium modified lithium manganese iron phosphate base material can be improved, and meanwhile, the rate performance and other electrochemical performances of the positive plate or the battery can be improved. The titanium modified lithium iron manganese phosphate material can be used as a positive electrode active material of a battery, and can be particularly applied to a power battery to improve the endurance of the power battery.
Detailed Description
The present invention will be described in further detail below for the purpose of better understanding of the aspects of the present invention by those skilled in the art. The following detailed description is merely illustrative of the principles and features of the present invention, and examples are set forth for the purpose of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the examples of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides a titanium modified lithium iron manganese phosphate base material, which comprises a base material and a titanium compound existing on the surface of the base material, wherein the chemical formula of the base material is LiMn xFe1-xPO4, x is more than or equal to 0.1 and less than or equal to 0.9, and the titanium compound comprises titanium dioxide and/or lithium titanate.
In general, the titanium compound may be coated on the surface of the base material. Specifically, the titanium modified lithium iron manganese phosphate-based material is granular, the granule can comprise a core and a shell layer existing on the surface of the core, the core comprises a matrix material, the shell layer comprises a titanium compound, and the shell layer can be coated on the surface of the core (matrix material).
In the embodiment of the invention, the titanium compound comprising titanium dioxide and/or lithium titanate is used for coating the matrix material with the composition, so that the structural stability of the titanium modified lithium manganese iron phosphate matrix material can be improved, the compaction density of the titanium modified lithium manganese iron phosphate matrix material can be more particularly not lower than 2.3cm 3/g (namely, the phenomenon of particle breakage and the like can not occur under the compaction density higher than 2.3cm 3/g), and the energy density of a positive plate or a battery adopting the titanium modified lithium manganese iron phosphate matrix material can be improved, and meanwhile, the electrochemical performances such as the multiplying power performance of the positive plate or the battery can be improved.
In addition, the titanium compound coats the matrix material, so that the contact of the matrix material with electrolyte and side reactions caused by the contact can be avoided, and the performance of the matrix material in the application of a battery can be further ensured.
Specifically, the shell layer may be a titanium compound layer formed of a titanium compound, for example, a titanium oxide layer formed of titanium oxide or a lithium titanate layer formed of lithium titanate, the main component of which is a titanium compound.
Illustratively, in the chemical formula of the matrix material, x may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or a range of any two of these
Specifically, the mass ratio of the titanium compound to the base material may be in the range of 0.1% to 3%, for example, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% or any two thereof.
The embodiment of the invention also provides a preparation method of the titanium modified lithium iron manganese phosphate based material, which comprises the following steps: mixing a lithium source, a manganese source, an iron source, a phosphorus source and water to obtain a first slurry; sequentially performing first spray drying and first sintering on the first slurry to prepare a precursor; mixing the precursor, a titanium source and water to obtain second slurry; and sequentially carrying out second spray drying and second sintering on the second slurry to obtain the titanium modified lithium iron manganese phosphate based material.
In the preparation process, after the first sintering, the prepared precursor is used for forming a matrix material (inner core), the matrix material is mixed with a titanium source and water to prepare second slurry, and the second slurry is subjected to second spray drying and second sintering in sequence to prepare the titanium modified lithium iron manganese phosphate base material comprising the matrix material and the titanium compound (shell layer) existing on the surface of the matrix material. Compared with the traditional modes of carbon coating and the like of lithium iron phosphate, the embodiment of the invention adopts the titanium compound to coat the matrix material (lithium manganese iron phosphate material), and can improve the compaction density, ploidy and other performances of the prepared titanium modified lithium manganese iron phosphate material.
According to the research of the inventor, the density of material growth can be improved by coating the matrix material with the titanium compound, the compaction density of the prepared titanium modified lithium iron manganese phosphate-based material is improved, and meanwhile, the particle size of the material is reduced to a certain extent by coating the titanium compound, the electrochemical performance is increased, and the multiplying power performance is improved.
Embodiments of the invention may employ a lithium source, a manganese source, an iron source, and a phosphorus source conventional in the art, e.g., the lithium source may include one or more of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate, the phosphorus source may include one or more of lithium dihydrogen phosphate, manganese iron phosphate, phosphoric acid, etc., the iron source may include an iron salt and/or an iron oxide, e.g., one or more of manganese iron phosphate, iron oxalate, iron phosphate, etc., the iron oxide may include a manganese oxide, e.g., three iron tetraoxide, and/or a manganese salt, the manganese oxide may include a manganese oxide, e.g., three manganese tetraoxide, the manganese salt may include a manganese iron phosphate, e.g., manganese iron phosphate.
In the specific implementation, the dosage of each raw material can be regulated and controlled according to the chemical formula of a preset matrix material, so that the molar quantity of each element or group accords with the preset chemical formula, and the titanium modified lithium manganese iron phosphate based material with corresponding composition is obtained. For example, the amounts of lithium source and phosphoric acid used are as follows: the molar ratio of the lithium element to the phosphorus element (Li/P molar ratio) is (1-1.03): 1; the dosages of the iron source and the phosphorus source are as follows: the molar ratio of the iron element to the phosphorus element (Fe/P molar ratio) is (0.1-0.9): 1; the dosage of the manganese source and the phosphorus source is as follows: the molar ratio of manganese element to phosphorus element (Mn/P molar ratio) is (0.1-0.9): 1.
Further, the titanium source may include one or more of titanium dioxide, titanic acid, tetrabutyl titanate, lithium titanate.
Specifically, the amounts of the titanium source and the precursor may be as follows: the mass ratio of the titanium compound to the precursor is 0.1-3%, so that the mass ratio of the titanium compound to the matrix material in the prepared titanium modified lithium iron manganese phosphate base material can be 0.1-3%.
In general, when lithium titanate is adopted, in the prepared titanium modified lithium manganese iron phosphate based material, the titanium compound is lithium titanate; when titanium dioxide is adopted, the titanium compound in the prepared titanium modified lithium iron manganese phosphate-based material is titanium dioxide; when tetrabutyl titanate and/or titanic acid are adopted, the titanium oxide is converted into titanium dioxide after treatment such as second sintering, so that the titanium compound in the prepared titanium modified lithium iron manganese phosphate-based material is titanium dioxide.
According to the research of the inventor, when titanium dioxide is adopted as a titanium source, the titanium dioxide not only can play a role in coating, but also can be doped in a crystal lattice of a matrix material at high temperature, so that the material structure is further stabilized, and the performance of the prepared titanium modified lithium iron manganese phosphate based material is improved. Thus, it is preferred that the titanium source used comprises titanium dioxide.
In the preparation process, after mixing the lithium source, the manganese source, the iron source, the phosphorus source and the water, the first grinding can be performed so as to uniformly mix the components, thereby obtaining the first slurry. Wherein the average particle diameter D50 of the particles in the first slurry is made to be in the range of 0.25 to 0.55 μm, for example, 0.25 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm, 0.5 μm, 0.55 μm or any two thereof by the first polishing.
In practice, the first milling may be carried out using a conventional ball mill in the art such as a planetary ball mill, for example, the ingredients and water may be added to the planetary ball mill for milling.
In some embodiments, during the first grinding, the rotational speed of the ball mill may be in the range of 300-1000 r/min, such as 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, or any two thereof, and the time of the second grinding may be in the range of 1-4 hours, such as1 hour, 2 hours, 3 hours, 4 hours, or any two thereof.
The first spray drying may be performed by using a first spray dryer having an inlet temperature of 70 to 180 ℃, for example, 70 ℃,90 ℃, 100 ℃, 120 ℃, 140 ℃,150 ℃, 160 ℃, 170 ℃, 180 ℃ or any two thereof, and an outlet temperature of 50 to 120 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃,90 ℃, 100 ℃, 110 ℃, 120 ℃ or any two thereof.
In the preparation process, after the first sintering, each metal element in the prepared precursor generally exists in an oxide form, and in general, the first sintering can be performed in an air atmosphere, and in the specific implementation, a muffle furnace can be used for the first sintering.
Further, the temperature of the first sintering may be 350 to 600 ℃, for example 350 ℃, 400 ℃, 430 ℃, 450 ℃, 480 ℃, 500 ℃, 530 ℃, 550 ℃, 580 ℃, 600 ℃ or any two of them, and the time of the first sintering may be 5 to 10 hours, for example 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or any two of them.
In addition, after mixing the precursor, the titanium source and the water, a second grinding can be performed to uniformly mix the components to obtain a second slurry; wherein the average particle diameter of the particles in the second slurry is made to be in the range of 0.3 to 0.4 μm, for example, 0.3 μm, 0.33 μm, 0.35 μm, 0.38 μm, 0.4 μm or any two thereof by the second polishing.
In practice, the second milling may be performed using a conventional ball mill in the art, such as a planetary ball mill, for example, the ingredients and water may be added to the planetary ball mill for milling.
In some embodiments, during the second grinding, the rotational speed of the ball mill may be in the range of 300-1000 r/min, such as 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, or any two thereof, and the time of the second grinding may be in the range of 1-4 hours, such as1 hour, 2 hours, 3 hours, 4 hours, or any two thereof.
Further, the second spray drying may be performed using a second spray dryer having an inlet temperature of 150 to 300 ℃, for example, 150 ℃, 170 ℃, 200 ℃, 230 ℃, 250 ℃, 280 ℃, 300 ℃ or any two thereof, and an outlet temperature of 80 to 100 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or any two thereof.
Typically, the second sintering is performed at a temperature greater than that of the first sintering, and the second sintering may be performed under an inert gas atmosphere, including, for example, nitrogen and/or argon.
In some embodiments, the temperature of the second sintering may be in the range of 400-900 ℃, such as 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, or any two thereof, and the time of the second sintering may be in the range of 2-10 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or any two thereof.
The embodiment of the invention also provides a positive plate which comprises the titanium modified lithium iron manganese phosphate-based material, has the advantages corresponding to the lithium iron manganese phosphate-based composite material, and is not repeated.
Specifically, the positive plate comprises a positive current collector and a positive active material layer arranged on the surface of the positive current collector, wherein the positive active material layer comprises a positive active material, a binder and a conductive agent, and the positive active material comprises the titanium modified lithium iron manganese phosphate-based material.
In general, the positive electrode active material layer may have a compacted density of greater than 2.3g/cm 3, specifically may be in the range of 2.31 to 2.45g/cm 3, such as 2.31g/cm3、2.33g/cm3、2.35g/cm3、2.38g/cm3、2.4g/cm3、2.43g/cm3、2.45g/cm3, or any two of these.
Specifically, the positive electrode active material layer is mainly a positive electrode active material (titanium modified lithium iron manganese phosphate-based material), and therefore, the compacted density of the positive electrode active material layer is also a compacted density of the positive electrode active material (titanium modified lithium iron manganese phosphate-based material).
In some embodiments, the mass ratio of the positive electrode active material may be in the range of 70% to 99%, such as 70%, 75%, 80%, 85%, 90%, 95%, 99% or any two thereof, the mass ratio of the conductive agent may be in the range of 0.5% to 15%, such as 0.5%, 1%, 3%, 5%, 7%, 10%, 13%, 15% or any two thereof, and the mass ratio of the binder may be in the range of 0.5% to 15%, such as 0.5%, 1%, 3%, 5%, 7%, 10%, 13%, 15% or any two thereof, based on the total mass of the positive electrode active material layer.
Specifically, the positive electrode active material layer may be disposed on one surface of the positive electrode current collector, or on both the front and back surfaces of the positive electrode current collector, and the positive electrode current collector may include a conventional positive electrode current collector in the art such as aluminum foil.
The positive electrode sheet according to the embodiment of the present invention may be manufactured by a conventional method in the art such as a coating method, for example, by placing materials such as a positive electrode active material, a conductive agent, and a binder in a solvent, for example, including N-methylpyrrolidone (NMP), and then coating the slurry on the surface of a positive electrode current collector, and forming a positive electrode active material layer on the surface of the current collector after processes such as drying and rolling.
The embodiment of the invention also provides a battery, which comprises the positive plate, and has the advantages corresponding to the positive plate and is not repeated.
Specifically, the battery also comprises a diaphragm and a negative electrode plate, wherein the diaphragm is positioned between the positive electrode plate and the negative electrode plate and is used for spacing the positive electrode plate and the negative electrode plate so as to prevent the positive electrode plate and the negative electrode plate from being in contact short circuit.
Specifically, the battery comprises a battery core, wherein the battery core comprises the positive plate, the diaphragm and the negative plate, and the battery core can be a laminated battery core, namely, the positive plate, the diaphragm and the negative plate are sequentially stacked, or the battery core can be a coiled battery core, namely, the positive plate, the diaphragm and the negative plate are stacked and placed and then coiled to form a coiled structure.
In the embodiment of the invention, the separator may be a conventional separator in the art, and the negative electrode sheet may be a conventional negative electrode sheet in the art, for example, the negative electrode sheet includes a negative electrode current collector, and a negative electrode active material layer disposed on the surface of the negative electrode current collector, the negative electrode active material layer includes a negative electrode active material, a binder, and a conductive agent, and the negative electrode active material may include one or more of graphite, mesophase carbon microspheres, soft carbon, hard carbon, a silicon material, a silicon oxygen material, a silicon carbon material, lithium titanate, and the like.
The conductive agent and the binder in the positive or negative electrode sheet may be conventional materials in the art, for example, the conductive agent includes at least one of conductive carbon black (Super P), acetylene black, carbon nanotubes, conductive graphite, and graphene, and the binder includes at least one of polyvinylidene fluoride (PVDF), a copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, and Styrene Butadiene Rubber (SBR).
The invention is further described below by means of specific examples.
Example 1
(1) Mixing lithium carbonate, manganous oxide, ferric phosphate, lithium dihydrogen phosphate and water, and putting the mixture into a planetary ball mill for ball milling and mixing for 1h at the rotating speed of 550r/min to obtain first slurry (wherein the average particle diameter D50 of solid particles is 0.45 mu m); wherein the molar ratio of Li to P is 1.01, the molar ratio of Fe to P is 0.4, and the molar ratio of Mn to P is 0.6;
(2) Performing first spray drying on the first slurry by adopting a first spray dryer, wherein the inlet temperature of the first spray dryer is 170 ℃, and the outlet temperature of the first spray dryer is 90 ℃;
(3) Then, placing the obtained first dry material in a muffle furnace, and sintering for about 5.5 hours at 450 ℃ in an air atmosphere to obtain a precursor;
(4) Mixing titanium dioxide and a precursor according to a mass ratio of 3:100, adding the mixture into a planetary ball mill, and ball-milling and mixing the mixture in the ball mill for 1.5 hours at a rotating speed of 550r/min to obtain second slurry (wherein the average particle size D50 of solid particles is 0.35 mu m);
(5) Performing second spray drying on the second slurry by adopting a second spray dryer, wherein the inlet temperature of the second spray dryer is 210 ℃, and the outlet temperature of the second spray dryer is 100 ℃;
(6) Subsequently, the obtained second dried material is put into a sintering furnace and sintered for 6 hours at 760 ℃ under the protection of nitrogen gas, so as to obtain the titanium modified lithium iron manganese phosphate-based material (the chemical formula of which can be expressed as LiMn 0.6Fe0.4PO4@TiO2).
Example 2: the difference from example 1 is that in step (4), tetrabutyl titanate is used in place of titanium dioxide, and the amount of tetrabutyl titanate is as follows: the ratio of the mass of titanium dioxide converted from tetrabutyl titanate to the mass of the precursor is 3:100; the other conditions were the same as in example 1.
Example 3: the difference from example 1 is that in step (4), lithium titanate is used instead of titanium dioxide, and the other conditions are the same as in example 1.
Comparative example 1: the difference from example 1 is that in step (4), no titanium source is added, and only the precursor is sequentially subjected to steps (4) to (6) to prepare the lithium iron manganese phosphate material; the other conditions were the same as in example 1.
Comparative example 2: the difference from example 1 is that comparative example 2 was carbon coated, i.e., in step (4), super P was used instead of silica, and the other conditions were the same as in example 1;
Performance testing
The lithium iron manganese phosphate-based materials prepared in each example and comparative example were used as positive electrode active materials, and positive electrode sheets and batteries were prepared according to the following procedures, and the cycle performance of the batteries was tested.
1. Preparation of positive plate
Mixing positive active materials PVDF and Super P according to a mass ratio of 95:2:3, and placing the mixture in NMP to prepare positive slurry;
Coating positive electrode slurry on the front and back surfaces of an aluminum foil (positive electrode current collector) by using a coating machine, drying and rolling to form positive electrode active material layers on the front and back surfaces of the aluminum foil, and preparing a positive electrode plate; wherein the surface density of the positive electrode active material layer was about 300mg/cm 2, and the compacted density was shown in Table 1.
2. Preparation of a Battery
The positive plate, the diaphragm made of PP material and the lithium plate (negative plate) are assembled into a battery after being stacked, electrolyte consists of EC, DMC, EMC, liPF 6, and the molar ratio of EC, DMC, EMC is 1:1: the concentration of 1, liPF 6 was 1mol/L.
3. Performance testing
(1) 0.2C rate cycle test: the cyclic charge and discharge test was performed on a blue electric test system at a rate of 0.2C (1c=150 mA/g) at room temperature (about 25 ℃) and a voltage range of 2.0 to 4.5V, and the specific capacity of the first-turn discharge and the capacity retention after 100-turn cycle were measured and are shown in table 1.
(2) 1C rate cycle test: the cyclic charge and discharge test was performed on a blue electric test system at a rate of 1C (1c=150ma/g) at room temperature (about 25 ℃), and the voltage range was 2.0 to 4.5V, and the specific capacity of the first-turn discharge and the capacity retention after 100-turn cycle were measured and are shown in table 1.
TABLE 1
As can be seen from table 1, examples 1 to 3 can effectively increase the compacted density of the positive electrode active material and increase the specific discharge capacity and the capacity retention rate of the battery under different rate conditions, relative to comparative example 1. Wherein, comparative example 1 was not coated, and the positive electrode active material was subjected to side reaction with the electrolyte during the battery cycle, and the structure of the positive electrode active material was also changed, resulting in deterioration of electrochemical properties, and examples 1 to 3 were coated with the matrix material by the titanium compound, so that the problems could be effectively overcome.
Further, examples 1 to 3 can effectively improve the compacted density of the positive electrode active material, while simultaneously achieving both of the performance of maintaining a high specific discharge capacity, a high capacity retention rate, and the like, as compared to comparative example 2.
In addition, in example 1, titanium dioxide was used as a titanium source, so that the compacted density of the positive electrode active material could be further increased, and the specific discharge capacity and the capacity retention rate of the battery could be improved, as compared with example 2 and example 3. The analytical reasons are that tetrabutyl titanate is relatively unstable, and can be hydrolyzed in the grinding process, and titanium dioxide can overcome the problems, so that the coating effect on a matrix material can be improved; in addition, lithium titanate only plays a coating role, and titanium dioxide can be doped into the crystal lattice of the matrix material at high temperature besides the coating role, so that the material structure is further stabilized, and the performance of the prepared positive electrode active material is optimized.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The titanium modified lithium iron manganese phosphate base material is characterized by comprising a base material and a titanium compound existing on the surface of the base material, wherein the chemical formula of the base material is LiMn xFe1-xPO4, x is more than or equal to 0.1 and less than or equal to 0.9, and the titanium compound comprises titanium dioxide and/or lithium titanate.
2. The titanium-modified lithium iron manganese phosphate based material according to claim 1, wherein the mass ratio of the titanium compound to the base material is 0.1% to 3%.
3. A method for preparing the titanium-modified lithium iron manganese phosphate-based material according to claim 1 or 2, comprising the steps of:
Mixing a lithium source, a manganese source, an iron source, a phosphorus source and water to obtain a first slurry;
sequentially performing first spray drying and first sintering on the first slurry to prepare a precursor;
mixing the precursor, a titanium source and water to obtain second slurry;
And sequentially carrying out second spray drying and second sintering on the second slurry to obtain the titanium modified lithium iron manganese phosphate based material.
4. The method according to claim 3, wherein the first slurry is obtained by mixing a lithium source, a manganese source, an iron source, a phosphorus source and water and then performing a first grinding; wherein the average particle diameter of the particles in the first slurry is set to 0.25 to 0.55 μm by the first polishing.
5. A process according to claim 3, wherein,
The first spray drying is carried out by adopting a first spray dryer, wherein the inlet temperature of the first spray dryer is 70-180 ℃ and the outlet temperature of the first spray dryer is 50-120 ℃;
And/or the temperature of the first sintering is 350-600 ℃, and the time of the first sintering is 5-10 h.
6. The method of claim 3, wherein the titanium source comprises one or more of titanium dioxide, titanic acid, tetrabutyl titanate, lithium titanate.
7. The method according to any one of claims 3 to 6, wherein the second slurry is obtained by mixing the precursor, a titanium source and water and then performing a second grinding; wherein the average particle diameter of the particles in the second slurry is set to 0.3 to 0.4 μm by the second polishing.
8. The process according to any one of claim 3 to 6, wherein,
Carrying out second spray drying by adopting a second spray dryer, wherein the inlet temperature of the second spray dryer is 150-300 ℃ and the outlet temperature of the second spray dryer is 80-100 ℃;
and/or the temperature of the second sintering is 400-900 ℃, and the time of the second sintering is 2-10 h.
9. A positive electrode sheet comprising the titanium-modified lithium iron manganese phosphate-based material according to claim 1 or 2.
10. A battery comprising the positive electrode sheet according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311857644.8A CN117976849A (en) | 2023-12-29 | 2023-12-29 | Titanium modified lithium iron manganese phosphate base material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311857644.8A CN117976849A (en) | 2023-12-29 | 2023-12-29 | Titanium modified lithium iron manganese phosphate base material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117976849A true CN117976849A (en) | 2024-05-03 |
Family
ID=90857325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311857644.8A Pending CN117976849A (en) | 2023-12-29 | 2023-12-29 | Titanium modified lithium iron manganese phosphate base material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117976849A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119038513A (en) * | 2024-10-31 | 2024-11-29 | 四川富临新能源科技有限公司 | Composite lithium iron manganese phosphate positive electrode material and preparation method thereof |
-
2023
- 2023-12-29 CN CN202311857644.8A patent/CN117976849A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119038513A (en) * | 2024-10-31 | 2024-11-29 | 四川富临新能源科技有限公司 | Composite lithium iron manganese phosphate positive electrode material and preparation method thereof |
| CN119038513B (en) * | 2024-10-31 | 2025-02-11 | 四川富临新能源科技有限公司 | A composite lithium iron manganese phosphate positive electrode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20220092556A (en) | Anode active material for battery and manufacturing method thereof, battery negative electrode, battery | |
| CN111430687B (en) | Carbon-coated lithium iron phosphate composite material, preparation method thereof and lithium ion battery | |
| CN111463419B (en) | Silicon-based @ titanium niobium oxide core-shell structure anode material and preparation method thereof | |
| CN110400929B (en) | A phosphate-coated metal-doped ternary cathode active material and its preparation and application | |
| CN111342023B (en) | Positive electrode material and preparation method and application thereof | |
| CN107623112B (en) | Lithium-doped boron phosphate modified carbon-coated lithium manganese iron phosphate cathode material and preparation method thereof | |
| CN115513515B (en) | Secondary battery and preparation method thereof | |
| CN115863623A (en) | Multi-site co-doped lithium manganese iron phosphate composite material, preparation method, and secondary battery | |
| CN114512655A (en) | Lithium ion battery anode composite material and preparation method and application thereof | |
| CN115893363A (en) | Composite cathode material and preparation method and application thereof | |
| CN116230932A (en) | Preparation method of carbon and lithium phosphate double-coated lithium manganese iron phosphate material | |
| WO2025044783A1 (en) | Lithium manganese iron phosphate modified material, and positive electrode and lithium ion battery using same | |
| CN116565164A (en) | A preparation method of functional polymer-coated high-nickel cathode material | |
| CN114937770B (en) | Double-layer lithium ion conductor coated modified lithium cobalt oxide positive electrode material, preparation method thereof, lithium ion battery and electric equipment | |
| CN117976849A (en) | Titanium modified lithium iron manganese phosphate base material and preparation method and application thereof | |
| CN116779847B (en) | Positive electrode plate, preparation method thereof, energy storage device and power utilization device | |
| CN119008877A (en) | In-situ polymerization coated sodium ferric pyrophosphate composite material and preparation method and application thereof | |
| CN111864189B (en) | Lithium battery positive electrode material and preparation method thereof | |
| CN115775885B (en) | Silicon-oxygen anode material and preparation method and application thereof | |
| CN108878823B (en) | Preparation method of metal olivine coated nano silicon | |
| WO2024221957A1 (en) | Preparation method for and use of naxfe3-0.5x(so4)3@c positive electrode material | |
| CN116835670A (en) | Sodium ion positive electrode material and preparation method thereof | |
| CN110783544A (en) | Carbon nanotube coated H 3PO 4Modified lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN114566647B (en) | Calcium phosphate coated high-nickel ternary positive electrode material and preparation method and application thereof | |
| CN113097458A (en) | Ternary cathode material @ titanium nitride core-shell structure composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |