CN113270575A - Ternary lithium manganese iron phosphate coated composite material and preparation method thereof - Google Patents
Ternary lithium manganese iron phosphate coated composite material and preparation method thereof Download PDFInfo
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- CN113270575A CN113270575A CN202110490524.3A CN202110490524A CN113270575A CN 113270575 A CN113270575 A CN 113270575A CN 202110490524 A CN202110490524 A CN 202110490524A CN 113270575 A CN113270575 A CN 113270575A
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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 38
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims abstract description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000011572 manganese Substances 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910016096 LiMn0.5Fe0.5PO4 Inorganic materials 0.000 description 1
- 229910015855 LiMn0.7Fe0.3PO4 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000009818 secondary granulation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Classifications
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- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a ternary lithium manganese iron phosphate coated composite material and a preparation method thereof, wherein the ternary lithium manganese iron phosphate coated composite material comprises a coating material, a ternary material, lithium manganese iron phosphate, a dispersing agent and deionized water, wherein the coating material is graphene and metal elements, and the metal elements are at least one of oxides of AL, Mg, Ti, V, Nb, Sr, Y, Ru, Zn, Mo and Zr; the ternary material is LiNiXCoYMn1‑x‑yO2，0.3≤x≤0.9,0.3≤x+y≤0.9; the lithium iron manganese phosphate is LiMnzFe1‑zPO4Z is more than or equal to 0.1 and less than or equal to 0.9; the dispersing agent is at least one of hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride polyethylene glycol, polyvinyl alcohol, polyethylene oxide, propylene glycol, sodium polystyrene sulfonate and ethanol. The invention relates to the technical field of lithium ion battery anode materials, and particularly provides a coated ternary lithium manganese iron phosphate composite material and a preparation method thereof, which can reduce the cost of ternary materials, improve the safety performance and simultaneously improve the conductivity of the lithium manganese iron phosphate material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a coated ternary/lithium iron manganese phosphate composite material and a preparation method thereof.
Background
Lithium ion batteries have been widely used in the fields of digital products, electric vehicles, energy storage base stations, and the like. With the great application of lithium ion batteries, higher requirements are put on the anode materials of the lithium ion batteries, wherein the ternary anode material (LiNi)XCoYMn1-x-yO2X is more than or equal to 0.3 and less than or equal to 0.9, and x + y is more than or equal to 0.3 and less than or equal to 0.9), has higher energy density, has a theoretical specific gram capacity value of about 278mAh/g, has a voltage platform of 3.6V, is widely applied to electric automobiles, but has higher cost, limited resources and poorer safety performance, and has the thermal stability of reducing from 300 ℃ to 240 ℃ or even lower along with the increase of the nickel content of the ternary material. And the other positive electrode material of lithium manganese iron phosphate (LiMnxFe)1-xPO4X is more than or equal to 0.1 and less than or equal to 0.9), the theoretical gram specific capacity value is about 170mAh/g, the voltage platform is 4.1V, the phase transformation point is about 760 ℃, and the method is more and more emphasized by people. However, the lithium manganese iron phosphate has low conductivity and poor ion diffusion rate, and the large-scale application of the lithium manganese iron phosphate is restricted.
The particle size of the ternary material is usually 6-15 mu m, the particle size of the lithium manganese iron phosphate is usually 1-3 mu m, and in order to better fuse the two materials, the two materials are ground into primary particles of 0.1-1 mu m, graphene and a coating metal element are added, and then the agglomerated particles with the particle size of 4-25 mu m are prepared in a secondary granulation mode. The two anode materials are mutually jointed with the graphene and the coating metal element through primary particles, and secondary agglomerated particles are integrated, so that the diffusion distance of lithium ions of the anode can be effectively shortened, the internal resistance of the materials is reduced, and the overall thermal stability is improved.
Chinese patent CN107546379A is to use a fine lithium iron manganese phosphate material to partially or completely coat the surface of a ternary material large particle to form a core-shell structure. However, the problem that the conductivity of the lithium manganese iron phosphate is poor cannot be solved, and the lithium manganese iron phosphate on the surface layer of the material is peeled off due to the expansion of the charging and discharging volume of the battery, so that the shell can not be well protected.
In the chinese patent CN108321385A, lithium iron manganese phosphate and a ternary positive electrode material are mechanically mixed in proportion when the battery is used for pulping, and a conductive agent is added to reduce the resistivity of the material, which cannot improve the resistivity of the material between primary particles.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides the coated ternary/lithium iron manganese phosphate composite material and the preparation method thereof, so that the cost of the ternary material is reduced, the safety performance is improved, and the conductivity of the lithium iron manganese phosphate material is improved.
The technical scheme adopted by the invention is as follows: the coating material is graphene and metal elements, and the metal elements are at least one of oxides of AL, Mg, Ti, V, Nb, Sr, Y, Ru, Zn, Mo and Zr; the ternary material is LiNiXCoYMn1-x-yO2X is more than or equal to 0.3 and less than or equal to 0.9, and x + y is more than or equal to 0.3 and less than or equal to 0.9; the lithium iron manganese phosphate is LiMnzFe1-zPO4Z is more than or equal to 0.1 and less than or equal to 0.9; the dispersing agent is at least one of hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride polyethylene glycol, polyvinyl alcohol, polyethylene oxide, propylene glycol, sodium polystyrene sulfonate and ethanol.
Furthermore, the molar ratio of the ternary material to the lithium iron manganese phosphate is 0.1-2: 0.1-2.
Further, the graphene coating amount accounts for 0.1-5% of the total mass.
Further, the coating amount of the metal element accounts for 0.1-5% of the total molar amount.
Further, the dispersant accounts for 0.1-5% of the total mass.
Further, the deionized water is 1-10 times of the total mass of the ternary material, the lithium iron manganese phosphate, the graphene and the metal elements.
The invention also discloses a preparation method of the coated ternary/lithium iron manganese phosphate composite material, which comprises the following steps:
1) dry-mixing and stirring the ternary material, the lithium manganese phosphate, the graphene and the metal element coating material in a vacuum stirrer according to a ratio until the materials are uniform;
2) grinding the mixture obtained in the step 1) uniformly, drying, adding deionized water, adding a dispersing agent, and stirring to form slurry;
3) putting the slurry obtained in the step 2) into a sand mill for grinding, wherein the rotating speed of the grinding machine is 100-3000 r/min, the grinding time is 0.2-4 h, grinding is carried out until the particle diameter is 0.1-1 mu m, and then water is added to adjust the viscosity to 20-300 cps;
4) carrying out high-speed spray drying on the slurry obtained in the step 3) at the temperature of 220-300 ℃ under the pressure of 0.1-1 Mpa, and controlling the particle size to be 4-35 mu m;
5) carrying out heat treatment on the dried material obtained in the step 4) in an atmosphere furnace at the temperature of 300-450 ℃ for 1-4 hours, and then sieving to obtain a finished product.
Further, the stirring speed of the vacuum stirrer in the step 2) is 50-800 r/min.
The invention with the structure has the following beneficial effects: according to the scheme, the ternary material with poor safety and the lithium manganese iron phosphate with good safety are combined together through grinding and re-granulating, the primary particle size of the lithium manganese iron phosphate is ground to small particles, the ion migration distance is shortened, the graphene composite metal element is added for coating, the contact area between the surface of the ternary material and electrolyte is reduced, and the safety performance is improved. Meanwhile, the conductivity of the lithium manganese iron phosphate is increased, the high energy density of the ternary material and the high safety characteristic of the lithium manganese iron phosphate material are considered, the two are cooperatively optimized, and the graphene is assisted to cooperate with the metal element for coating, so that the safety performance of the material is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of an embodiment of a preparation method of a coated ternary/lithium iron manganese phosphate composite material according to the present invention;
FIG. 2 is a scanning electron microscope image of a coated ternary/lithium iron manganese phosphate composite material of the present invention;
FIG. 3 is a charging and discharging curve diagram of the coated ternary/lithium iron manganese phosphate composite material of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1, 1.0kg of a ternary material LiNi was weighed0.5Co0.2Mn0.3O21.0kg of lithium iron manganese phosphate LiMn0.7Fe0.3PO40.01kg of titanium dioxide and 0.04kg of graphene are put into a vacuum stirrer and are uniformly stirred for 30 minutes at the speed of 50 revolutions per minute until the mixed powder is uniformly stirred; putting 4kg of deionized water into a stirrer, adding 0.02kg of propylene glycol, and stirring at the speed of 300 revolutions per minute for 10 minutes to prepare slurry for later use; taking out the slurry, putting into a grinder for 2000 r/m, grinding until D50 is 0.2 μm, and adding water to adjust the viscosity to 50 cps; drying the slurry in a fluid dryer at 260 ℃ under the pressure of 0.4Mpa to obtain a precursor material with the granularity D50 being 6-8 mu m; will be provided withAnd (3) carrying out heat treatment on the precursor material in an atmosphere drying furnace at 350 ℃ to obtain a finished product material.
The tap density of the finished product material is 1.8g/cm3The resistivity of the material is 22.3 omega cm, a half cell is prepared, the charge-discharge capacity of 0.1C/0.1C is 162mAh/g, the discharge medium voltage is 3.8V, and the material has good physical and chemical properties.
Example 2 weighing 1.0kg of ternary material LiNi0.8Co0.15Al0.05O25kg of lithium iron manganese phosphate LiMn0.5Fe0.5PO40.08kg of zirconium oxide and 0.06kg of graphene are put into a vacuum stirrer and are uniformly stirred for 60 minutes at the speed of 200 r/min until the mixed powder is uniformly stirred; putting 10kg of deionized water into a stirrer, adding 0.01kg of polyvinyl alcohol, and stirring at the speed of 200 rpm for 30 minutes to prepare slurry for later use; taking out the slurry, putting into a grinder for 1000 r/min, grinding until D50 is 0.6 μm, and adding water to adjust the viscosity to 200 cps; drying the slurry in a fluid dryer at 280 ℃ under the pressure of 0.2Mpa to obtain a precursor material with the particle size D50 being 15 mu m; and (3) carrying out heat treatment on the precursor material in an atmosphere drying furnace at 450 ℃ to obtain a finished product material, wherein a scanning electron microscope image of the finished product is shown in figure 2.
The tap density of the finished product material is 1.3g/cm3And a half cell is prepared at 16.3 omega.cm, the charge-discharge capacity of 0.1C/0.1C is 156.3mAh/g, the discharge medium voltage is 3.8V, and the material has good physical and chemical properties.
Example 3, 1.0kg of a ternary material LiNi was weighed0.8Co0.1Mn0.1O20.2kg of LiMn-Fe-Mn phosphate0.6Fe0.4PO40.04kg of alumina and 0.01kg of graphene are put into a vacuum stirrer and are uniformly stirred at the speed of 100 revolutions per minute for 20 minutes until the mixed powder is uniformly stirred; putting 1.5kg of deionized water into a stirrer, adding 0.01kg of ethanol, and stirring at the speed of 500 revolutions per minute for 20 minutes to prepare slurry for later use; taking out the slurry, putting into a grinder for 1500 r/min, grinding until D50 is 0.4 μm, and adding water to adjust the viscosity to 100 cps; drying the slurry in a fluid dryer at 230 ℃ under the pressure of 0.3Mpa to obtain a precursor material with the particle size D50 being 8 mu m; mixing the aboveAnd (4) carrying out heat treatment on the precursor material in an atmosphere drying furnace at 400 ℃ to obtain a finished product material.
The tap density of the finished product material is 1.7g/cm3And the resistivity of the material is 12.7 omega-cm, the prepared half-cell has the charge-discharge capacity of 188.4mAh/g at 0.2C/0.2C and the discharge medium voltage of 3.7V, the material has good physical and chemical properties, and a charge-discharge curve graph of the half-cell is shown in figure 3.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The coated ternary lithium manganese iron phosphate composite material is characterized by comprising a coating material, a ternary material, lithium manganese iron phosphate, a dispersing agent and deionized water, wherein the coating material is graphene and metal elements, and the metal elements are at least one of oxides of AL, Mg, Ti, V, Nb, Sr, Y, Ru, Zn, Mo and Zr; the ternary material is LiNiXCoYMn1-x-yO2X is more than or equal to 0.3 and less than or equal to 0.9, and x + y is more than or equal to 0.3 and less than or equal to 0.9; the lithium iron manganese phosphate is LiMnzFe1-zPO4Z is more than or equal to 0.1 and less than or equal to 0.9; the dispersing agent is at least one of hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride polyethylene glycol, polyvinyl alcohol, polyethylene oxide, propylene glycol, sodium polystyrene sulfonate and ethanol.
2. The coated ternary lithium iron manganese phosphate composite material of claim 1, wherein the molar ratio of the ternary material to the lithium iron manganese phosphate is 0.1-2: 0.1-2.
3. The coated ternary lithium iron manganese phosphate composite material of claim 2, wherein the graphene coating amount accounts for 0.1-5% of the total mass.
4. The coated ternary lithium iron manganese phosphate composite material of claim 3, wherein the amount of the metal element coating is 0.1-5% of the total molar amount.
5. The coated ternary lithium iron manganese phosphate composite material of claim 4, wherein the dispersant accounts for 0.1-5% of the total mass.
6. The coated ternary lithium manganese iron phosphate composite material of claim 5, wherein the deionized water is 1-10 times of the total mass of the ternary material, the lithium manganese iron phosphate, the graphene and the metal element.
7. A preparation method of a ternary lithium iron manganese phosphate-coated composite material is characterized by comprising the following steps:
1) dry-mixing and stirring the ternary material, the lithium manganese phosphate, the graphene and the metal element coating material in a vacuum stirrer according to a ratio until the materials are uniform;
2) grinding the mixture obtained in the step 1) uniformly, drying, adding deionized water, adding a dispersing agent, and stirring to form slurry;
3) putting the slurry obtained in the step 2) into a sand mill for grinding, wherein the rotating speed of the grinding machine is 100-3000 r/min, the grinding time is 0.2-4 h, grinding is carried out until the particle diameter is 0.1-1 mu m, and then water is added to adjust the viscosity to 20-300 cps;
4) carrying out high-speed spray drying on the slurry obtained in the step 3) at the temperature of 220-300 ℃ under the pressure of 0.1-1 Mpa, and controlling the particle size to be 4-35 mu m;
5) carrying out heat treatment on the dried material obtained in the step 4) in an atmosphere furnace at the temperature of 300-450 ℃ for 1-4 hours, and then sieving to obtain a finished product.
8. The preparation method of the coated ternary lithium iron manganese phosphate composite material of claim 7, wherein the stirring speed of the vacuum stirrer is 50-800 r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114843507A (en) * | 2022-03-28 | 2022-08-02 | 佛山市德方纳米科技有限公司 | Single-core multi-shell lithium manganese iron phosphate positive electrode material, preparation method and secondary battery |
| US11888154B2 (en) | 2022-03-04 | 2024-01-30 | Contemporary Amperex Technology Co., Limited | Positive electrode sheet, secondary battery, battery module, battery pack and electrical apparatus |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035887A (en) * | 2012-12-17 | 2013-04-10 | 鸿纳（东莞）新材料科技有限公司 | High-concentration few-layer graphene composite material, component of lithium battery electrode and preparation |
| CN104377353A (en) * | 2014-11-18 | 2015-02-25 | 长沙理工大学 | Method for preparing lithium iron phosphate and lithium nickel cobalt manganese oxide composite cathode material |
| JP2016025077A (en) * | 2014-07-22 | 2016-02-08 | シーナノ テクノロジー リミテッド | Electrode composition for battery |
| CN106129365A (en) * | 2016-08-19 | 2016-11-16 | 骆驼集团新能源电池有限公司 | A kind of high security iron manganese phosphate lithium battery |
| US20190372093A1 (en) * | 2018-06-01 | 2019-12-05 | Nanotek Instruments, Inc. | Multi-level graphene-protected battery cathode active material particles |
-
2021
- 2021-05-06 CN CN202110490524.3A patent/CN113270575A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035887A (en) * | 2012-12-17 | 2013-04-10 | 鸿纳（东莞）新材料科技有限公司 | High-concentration few-layer graphene composite material, component of lithium battery electrode and preparation |
| JP2016025077A (en) * | 2014-07-22 | 2016-02-08 | シーナノ テクノロジー リミテッド | Electrode composition for battery |
| CN104377353A (en) * | 2014-11-18 | 2015-02-25 | 长沙理工大学 | Method for preparing lithium iron phosphate and lithium nickel cobalt manganese oxide composite cathode material |
| CN106129365A (en) * | 2016-08-19 | 2016-11-16 | 骆驼集团新能源电池有限公司 | A kind of high security iron manganese phosphate lithium battery |
| US20190372093A1 (en) * | 2018-06-01 | 2019-12-05 | Nanotek Instruments, Inc. | Multi-level graphene-protected battery cathode active material particles |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11888154B2 (en) | 2022-03-04 | 2024-01-30 | Contemporary Amperex Technology Co., Limited | Positive electrode sheet, secondary battery, battery module, battery pack and electrical apparatus |
| CN114843507A (en) * | 2022-03-28 | 2022-08-02 | 佛山市德方纳米科技有限公司 | Single-core multi-shell lithium manganese iron phosphate positive electrode material, preparation method and secondary battery |
| CN114843507B (en) * | 2022-03-28 | 2023-04-11 | 佛山市德方纳米科技有限公司 | Single-core multi-shell lithium manganese iron phosphate positive electrode material, preparation method and secondary battery |
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