CN111477862A - Carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material and preparation method thereof - Google Patents

Carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material and preparation method thereof Download PDF

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CN111477862A
CN111477862A CN202010394646.8A CN202010394646A CN111477862A CN 111477862 A CN111477862 A CN 111477862A CN 202010394646 A CN202010394646 A CN 202010394646A CN 111477862 A CN111477862 A CN 111477862A
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lithium
carbon
iron phosphate
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何家均
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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
    • H01M4/362—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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 relates to the technical field of lithium ion batteries, and discloses a carbon-coated lithium manganese iron phosphate positive electrode material for a lithium ion battery, which comprises the following formula raw materials and components of tartaric acid, urea and three-dimensional porous lithium manganese iron phosphate, wherein porous lithium manganese iron phosphate L iMn is prepared from the carbon-coated lithium manganese iron phosphate positive electrode material for the lithium ion battery0.6‑0.9Fe0.1‑0.4PO4，Fe2+Insert L iMnPO4The crystal lattice limits the excessive growth of the crystal, is beneficial to forming a micro-nano morphology structure, shortens the diffusion path of lithium ions, and the lithium manganese iron phosphate forms a rich pore structure, is beneficial to the diffusion and transmission of the lithium ions, and improves the lithium ion yieldThe diffusion rate of the ions, the nitrogen-doped carbon-coated lithium manganese iron phosphate, and the N element which is rich in electrons in the carbon layer structure form a large number of structural defects and active sites, so that the conductivity of the carbon layer structure and the anode material is improved, the transmission of electrons is promoted, and the anode material shows excellent actual specific capacitance and rate performance.

Description

Carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a carbon-coated lithium manganese iron phosphate lithium ion battery anode material and a preparation method thereof.
Background
In recent years, the problem of energy crisis and environmental pollution caused by overuse of fossil fuels is attracting more and more attention, and a new energy device and a new energy system which are green, environment-friendly and economical are urgently needed to relieve the problem of the environment and the problem of the energy crisis.
The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte and the like, wherein the positive electrode material has great influence on the electrochemical performance of the lithium ion battery, the current positive electrode material of the lithium ion battery mainly comprises lithium cobaltate, lithium manganate, lithium iron phosphate, lithium manganese phosphate and the like, wherein the lithium manganese phosphate with an olivine structure is L iMnPO4The lithium manganese phosphate anode material has the advantages of high energy density, low cost and the like, is a lithium ion battery anode material with great development potential, but the conductivity of the lithium manganese phosphate is low, the electronic conductivity and the lithium ion diffusion coefficient are low, the transmission and the diffusion of electrons and lithium ions in electrode reaction are not facilitated, and the practical application of the lithium manganese phosphate is limited.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a carbon-coated lithium manganese iron phosphate lithium ion battery anode material and a preparation method thereof, and solves the problems of low conductivity, electronic conductivity and lithium ion diffusion coefficient of lithium manganese phosphate.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material comprises the following formula raw materials in parts by weight: 20-30 parts of tartaric acid, 2-5 parts of urea and 65-78 parts of three-dimensional porous lithium manganese iron phosphate.
Preferably, the preparation method of the three-dimensional porous lithium manganese iron phosphate comprises the following steps:
(1) adding a mixed solvent of distilled water and ethylene glycol into a reaction bottle, wherein the volume ratio of the distilled water to the ethylene glycol is 2-4:1, adding biological pollen, uniformly dispersing by ultrasonic wave, adding a dispersing agent, lithium hydroxide, ferric oxalate, manganese acetate and ammonium dihydrogen phosphate, placing the mixture into a constant-temperature water bath kettle, heating to 50-80 ℃, uniformly stirring for 3-6h, pouring the solution into a polytetrafluoroethylene reaction kettle, heating to 180 ℃ for 10-20h, filtering the solution to remove the solvent, placing a solid mixed product into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 2-8 ℃/min, carrying out heat preservation and calcination for 2-4h at 580 ℃ of 650 ℃, grinding the calcined product into fine powder, and preparing the three-dimensional porous lithium manganese iron phosphate.
Preferably, atmosphere resistance furnace includes that furnace body, furnace body left side fixedly connected with intake pipe, intake pipe right side fixed connection breather pipe, breather pipe surface are provided with the inlet port, inlet port right side fixedly connected with outlet duct, the inside downside fixedly connected with insulating layer of furnace body, insulating in-process is provided with the circulator, circulator and rotation axis fixed connection, rotation axis top fixedly connected with crucible.
Preferably, the biological pollen is rapeseed pollen, the mass ratio of the rapeseed pollen to the lithium hydroxide is 0.5-1.5:1, the dispersing agent is citric acid, the mass ratio of the substances of the citric acid, the lithium hydroxide, the ferric oxalate, the manganese acetate and the ammonium dihydrogen phosphate is 2.5-4:1:0.1-0.4:0.6-0.9:1, and the chemical expression of the three-dimensional porous lithium manganese iron phosphate is L iMn0.6-0.9Fe0.1-0.4PO4。
Preferably, the preparation method of the carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol, 20-30 parts of tartaric acid, 2-5 parts of urea and 65-78 parts of three-dimensional porous lithium manganese iron phosphate into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 60-80 ℃, stirring at constant speed until the reaction bottle is in a gel state, fully drying the gel-state mixed product to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 2-8 ℃/min, keeping the temperature at 340 ℃ for 1-3h, heating to 560 ℃ for 620 ℃, keeping the temperature, and calcining for 3-5h, wherein the calcined product is the carbon-coated lithium manganese iron phosphate lithium ion battery anode material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the carbon-coated lithium manganese iron phosphate lithium ion battery anode material takes biological rapeseed pollen as a template,preparing porous lithium manganese iron phosphate L iMn by a high-pressure hot solvent method and a high-temperature thermal cracking method0.6-0.9Fe0.1-0.4PO4，Fe2+Insert L iMnPO4In the crystal lattice, the overgrowth of the crystal is limited, the formation of a micro-nano morphology structure is facilitated, the diffusion path of lithium ions is shortened due to the small particle size, meanwhile, rapeseed pollen is used as a template and a pore-foaming agent, so that the manganese lithium iron phosphate forms a rich pore structure, the diffusion and the transmission of the lithium ions are facilitated, the diffusion rate of the lithium ions is improved, the nitrogen-doped carbon-coated manganese lithium iron phosphate is prepared by using urea as a nitrogen source and tartaric acid as a carbon source through an in-situ synthesis method and a sol-gel method and high-temperature carbonization, a large number of structural defects and active sites are formed by an electron-rich N element in the carbon layer structure, the conductivity of the carbon layer structure and the conductivity of an anode material are greatly improved, the transmission of electrons is promoted, and the anode material shows excellent actual specific.
Drawings
FIG. 1 is a schematic front view of a furnace body.
1. A furnace body; 2. an air inlet pipe; 3. a breather pipe; 4. an air inlet; 5. an air outlet pipe; 6. a rotator; 7. a rotating shaft; 8. a crucible is provided.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material comprises the following formula raw materials in parts by weight: 20-30 parts of tartaric acid, 2-5 parts of urea and 65-78 parts of three-dimensional porous lithium manganese iron phosphate.
The preparation method of the three-dimensional porous lithium manganese iron phosphate comprises the following steps:
(1) adding a mixed solvent of distilled water and ethylene glycol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent of ethylene glycol is 2-4:1, adding biological pollen which is rapeseed pollen, ultrasonically dispersing uniformly, and adding dispersing agents of citric acid, lithium hydroxide, ferric oxalate, manganese acetate and ammonium dihydrogen phosphate, wherein the mass ratio of the rapeseed pollen to the lithium hydroxide is 0.5-1.5:1, and the mass ratio of the substances of citric acid, lithium hydroxide, ferric oxalate, manganese acetate and ammonium dihydrogen phosphate is that2.5-4:1:0.1-0.4:0.6-0.9:1, heating to 50-80 ℃ in a constant-temperature water bath kettle, stirring at a constant speed for 3-6h, pouring the solution into a polytetrafluoroethylene reaction kettle, heating to 160-0.6-0.9Fe0.1-0.4PO4。
The preparation method of the carbon-coated lithium manganese iron phosphate lithium ion battery anode material comprises the following steps of:
(1) adding a mixed solvent of distilled water and ethanol, 20-30 parts of tartaric acid, 2-5 parts of urea and 65-78 parts of three-dimensional porous lithium manganese iron phosphate into a reaction bottle, placing the reaction bottle in a constant-temperature water bath kettle, heating to 60-80 ℃, stirring at constant speed until the reaction bottle is in a gel state, fully drying the gel-state mixed product to remove the solvent, placing the solid product in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 2-8 ℃/min, keeping the temperature at 340 ℃ for 1-3h, heating to 560 ℃ for 620 ℃, keeping the temperature, and calcining for 3-5h, wherein the calcined product is the carbon-coated lithium manganese iron phosphate lithium ion battery anode material.
Adding a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material serving as an active substance into an N-methyl pyrrolidone solvent, uniformly stirring polyvinylidene fluoride serving as an adhesive and carbon black serving as a conductive agent, uniformly coating the slurry on an aluminum foil, and fully drying to prepare the lithium ion battery positive electrode working electrode material.
Example 1
(1) Preparing a three-dimensional porous ferromanganese phosphate component 1: adding a mixed solvent of distilled water and ethylene glycol into a reaction bottle, wherein the volume ratio of the distilled water to the mixed solvent is 2:1, and adding biological pollen into the reaction bottle to obtain rapeAfter uniformly dispersing seed pollen by ultrasonic, adding dispersing agent citric acid, lithium hydroxide, ferric oxalate, manganese acetate and ammonium dihydrogen phosphate, wherein the mass ratio of the rapeseed pollen to the lithium hydroxide is 0.5:1, the mass ratio of the substances of the citric acid, the lithium hydroxide, the ferric oxalate, the manganese acetate and the ammonium dihydrogen phosphate is 2.5:1:0.1:0.9:1, placing the mixture into a constant-temperature water bath, heating to 50 ℃, stirring at a constant speed for 3 hours, then pouring the solution into a polytetrafluoroethylene reaction kettle, heating to 160 ℃, reacting for 10 hours, filtering the solution to remove a solvent, placing a solid mixed product into an atmosphere resistance furnace, introducing nitrogen, wherein the atmosphere resistance furnace comprises a furnace body, an air inlet pipe fixedly connected to the left side of the furnace body, an air inlet pipe fixedly connected to the right side of the air inlet pipe, an air outlet pipe fixedly connected to the surface of the air outlet pipe, a heat insulation layer fixedly connected to the lower side of the inner side of the furnace body, a rotator arranged in the heat insulation layer, a rotator fixedly connected to a rotating shaft, a crucible connected to the upper part of the rotating shaft, heating at a heating rate of 2 ℃/min, calcining for 2 hours under 5800.9Fe0.1PO4。
(2) Preparing a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material 1: adding a mixed solvent of distilled water and ethanol, 20 parts of tartaric acid, 2 parts of urea and 78 parts of three-dimensional porous lithium manganese iron phosphate component 1 into a reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed until a gel state is formed, fully drying the gel-like mixed product to remove the solvent, placing a solid product into an atmosphere resistance furnace, introducing nitrogen, heating at a rate of 2 ℃/min, carrying out heat preservation treatment at 300 ℃ for 1h, then heating to 560 ℃, and carrying out heat preservation calcination for 3h, wherein the calcination product is the carbon-coated lithium manganese iron phosphate lithium ion battery anode material 1.
(3) Preparing a working electrode material 1 of the anode of the lithium ion battery: adding a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material 1 serving as an active substance, polyvinylidene fluoride serving as an adhesive and carbon black serving as a conductive agent into an N-methyl pyrrolidone solvent, uniformly stirring, uniformly coating the slurry on an aluminum foil, and fully drying to prepare the lithium ion battery positive electrode working electrode material 1.
Example 2
(1) Preparing a three-dimensional porous ferromanganese phosphate component 2, adding a mixed solvent of distilled water and ethylene glycol into a reaction bottle, wherein the volume ratio of the distilled water to the ethylene glycol is 4:1, adding biological pollen serving as rapeseed pollen, ultrasonically dispersing the rapeseed pollen uniformly, adding a dispersing agent of citric acid, lithium hydroxide, iron oxalate, manganese acetate and ammonium dihydrogen phosphate, wherein the mass ratio of the rapeseed pollen to the lithium hydroxide is 0.5:1, the mass ratio of the citric acid, the lithium hydroxide, the iron oxalate, the manganese acetate and the ammonium dihydrogen phosphate is 3:1:0.15:0.85:1, placing the mixture into a constant-temperature water bath, heating to 80 ℃, uniformly stirring for 6 hours, pouring the solution into a polytetrafluoroethylene reaction kettle, heating to 180 ℃, reacting for 10 hours, filtering the solution to remove the solvent, placing a solid mixed product into an atmosphere resistance furnace, introducing nitrogen, wherein the atmosphere resistance furnace comprises a furnace body, a gas inlet pipe is fixedly connected to the left side, a vent pipe is fixedly connected to the right side of the gas inlet pipe, a gas inlet hole is arranged on the surface of the vent pipe and fixedly connected to the right side of a gas outlet pipe, a manganese thermal insulation layer is fixedly connected to the lower side of the inside of the furnace body, a rotating shaft is fixedly connected to a rotating shaft, a rotating shaft is fixedly connected to a rotating crucible0.85Fe0.15PO4。
(2) Preparing a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material 2: adding a mixed solvent of distilled water and ethanol, 22.5 parts of tartaric acid, 2.5 parts of urea and 75 parts of three-dimensional porous lithium manganese iron phosphate component 2 into a reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed until the reaction bottle is in a gel state, fully drying the gel-state mixed product to remove the solvent, placing a solid product into an atmosphere resistance furnace, introducing nitrogen, heating at a rate of 5 ℃/min, carrying out heat preservation treatment at 310 ℃ for 2h, heating to 560 ℃, carrying out heat preservation and calcining for 5h, and obtaining a calcined product, namely the carbon-coated lithium manganese iron phosphate lithium ion battery anode material 2.
(3) Preparing a working electrode material 2 of the anode of the lithium ion battery: adding a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material 2 serving as an active substance, polyvinylidene fluoride serving as an adhesive and carbon black serving as a conductive agent into an N-methyl pyrrolidone solvent, uniformly stirring, uniformly coating the slurry on an aluminum foil, and fully drying to prepare the lithium ion battery positive electrode working electrode material 2.
Example 3
(1) Preparing a three-dimensional porous ferromanganese phosphate component 3, adding a mixed solvent of distilled water and ethylene glycol into a reaction bottle, wherein the volume ratio of the distilled water to the ethylene glycol is 3:1, adding biological pollen serving as rapeseed pollen, ultrasonically dispersing the rapeseed pollen uniformly, adding a dispersing agent of citric acid, lithium hydroxide, iron oxalate, manganese acetate and ammonium dihydrogen phosphate, wherein the mass ratio of the rapeseed pollen to the lithium hydroxide is 2:1, the mass ratio of the citric acid, the lithium hydroxide, the iron oxalate, the manganese acetate and the ammonium dihydrogen phosphate is 3.2:1:0.25:0.75:1, placing the mixture into a constant-temperature water bath, heating the mixture to 65, uniformly stirring the mixture for 5 hours, pouring the solution into a polytetrafluoroethylene reaction kettle, heating the mixture to 170 ℃, reacting for 15 hours, filtering the solution to remove the solvent, placing the solid mixture into an atmosphere resistance furnace, introducing nitrogen, wherein the atmosphere resistance furnace comprises a furnace body, the left side is fixedly connected with an air inlet pipe, the right side of the air inlet pipe is fixedly connected with an air inlet hole, the right side of the air hole is fixedly connected with an air outlet pipe, the lower side of the inside of the furnace body is fixedly connected with a thermal insulation layer, a rotator is arranged in the thermal insulation layer, the upper side of the rotary shaft is fixedly connected with a rotary shaft, the rotary0.7Fe0.3PO4。
(2) Preparing a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material 3: adding a mixed solvent of distilled water and ethanol, 25 parts of tartaric acid, 3 parts of urea and 72 parts of three-dimensional porous lithium manganese iron phosphate component 3 into a reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, stirring at a constant speed until a gel state is formed, fully drying the gel-like mixed product to remove the solvent, placing a solid product into an atmosphere resistance furnace, introducing nitrogen, heating at a rate of 5 ℃/min, carrying out heat preservation treatment at 320 ℃ for 2 hours, heating to 590 ℃, carrying out heat preservation and calcination for 4 hours, and obtaining a calcination product, namely the carbon-coated lithium manganese iron phosphate lithium ion battery anode material 3.
(3) Preparing a working electrode material 3 of the anode of the lithium ion battery: adding a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material 3 serving as an active substance, polyvinylidene fluoride serving as an adhesive and carbon black serving as a conductive agent into an N-methyl pyrrolidone solvent, uniformly stirring, uniformly coating the slurry on an aluminum foil, and fully drying to prepare the lithium ion battery positive electrode working electrode material 3.
Example 4
(1) Preparing a three-dimensional porous ferromanganese phosphate component 4, adding a mixed solvent of distilled water and ethylene glycol into a reaction bottle, wherein the volume ratio of the distilled water to the ethylene glycol is 4:1, adding biological pollen serving as rapeseed pollen, ultrasonically dispersing the rapeseed pollen uniformly, adding a dispersing agent of citric acid, lithium hydroxide, iron oxalate, manganese acetate and ammonium dihydrogen phosphate, wherein the mass ratio of the rapeseed pollen to the lithium hydroxide is 1:1, the mass ratio of the citric acid, the lithium hydroxide, the iron oxalate, the manganese acetate and the ammonium dihydrogen phosphate is 3.5:1:0.35:0.65:1, placing the mixture into a constant-temperature water bath, heating to 80 ℃, uniformly stirring for 6 hours, pouring the solution into a polytetrafluoroethylene reaction kettle, heating to 180 ℃, reacting for 10 hours, filtering the solution to remove the solvent, placing the solid mixed product into an atmosphere resistance furnace and introducing nitrogen, wherein the atmosphere resistance furnace comprises a furnace body, the left side is fixedly connected with an air inlet pipe, the right side is fixedly connected with an air vent pipe, the surface of the air inlet pipe is arranged on the right side and is fixedly connected with an air outlet pipe, the lower side of the furnace body is fixedly connected with a thermal insulation layer, a rotating shaft is fixedly connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating shaft, calcining speed crucible for 352 min0.65Fe0.35PO4。
(2) Preparing a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material 4: adding a mixed solvent of distilled water and ethanol, 28 parts of tartaric acid, 4 parts of urea and 68 parts of three-dimensional porous lithium manganese iron phosphate component 4 into a reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed until a gel state is formed, fully drying the gel-like mixed product to remove the solvent, placing a solid product into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 8 ℃/min, carrying out heat preservation treatment at 300 ℃ for 3 hours, heating to 560 ℃, and carrying out heat preservation calcination for 3 hours, wherein the calcination product is the carbon-coated lithium manganese iron phosphate lithium ion battery anode material 4.
(3) Preparing a working electrode material 4 of the anode of the lithium ion battery: adding a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material 4 serving as an active substance, polyvinylidene fluoride serving as an adhesive and carbon black serving as a conductive agent into an N-methyl pyrrolidone solvent, uniformly stirring, uniformly coating the slurry on an aluminum foil, and fully drying to prepare the lithium ion battery positive electrode working electrode material 4.
Example 5
(1) Preparing a three-dimensional porous ferromanganese phosphate component 5, adding a mixed solvent of distilled water and ethylene glycol into a reaction bottle, wherein the volume ratio of the distilled water to the ethylene glycol is 4:1, adding biological pollen serving as rapeseed pollen, ultrasonically dispersing the rapeseed pollen uniformly, adding a dispersing agent of citric acid, lithium hydroxide, iron oxalate, manganese acetate and ammonium dihydrogen phosphate, wherein the mass ratio of the rapeseed pollen to the lithium hydroxide is 1.5:1, the mass ratio of the citric acid, the lithium hydroxide, the iron oxalate, the manganese acetate and the ammonium dihydrogen phosphate is 4:1:0.4:0.9:1, placing the mixture into a constant-temperature water bath, heating to 80 ℃, uniformly stirring for 6 hours, pouring the solution into a polytetrafluoroethylene reaction kettle, heating to 180 ℃, reacting for 20 hours, filtering the solution to remove the solvent, placing a solid mixed product into an atmosphere resistance furnace, introducing nitrogen, wherein the atmosphere resistance furnace comprises a furnace body, a gas inlet pipe is fixedly connected to the left side of the furnace body, a vent pipe is fixedly connected to the right side of the gas inlet pipe, a vent hole is arranged on the surface of the vent pipe and a gas outlet pipe is fixedly connected to the lower side of the inside of the furnace body, a rotating shaft is fixedly connected with a rotating device, a rotating shaft is fixedly connected with a rotating shaft, heating crucible, calcining speed expression0.6Fe0.4PO4。
(2) Preparing a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material 5: adding a mixed solvent of distilled water and ethanol, 30 parts of tartaric acid, 5 parts of urea and 65 parts of three-dimensional porous lithium manganese iron phosphate component 5 into a reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed until a gel state is formed, fully drying the gel-like mixed product to remove the solvent, placing a solid product into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 8 ℃/min, carrying out heat preservation treatment at 340 ℃ for 3 hours, heating to 620 ℃, carrying out heat preservation calcination for 5 hours, and obtaining a calcination product, namely the carbon-coated lithium manganese iron phosphate lithium ion battery anode material 5.
(3) Preparing a working electrode material 5 of the anode of the lithium ion battery: adding a carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material 5 serving as an active substance into an N-methyl pyrrolidone solvent, uniformly stirring the mixture with polyvinylidene fluoride serving as an adhesive and carbon black serving as a conductive agent, uniformly coating the slurry on an aluminum foil, and fully drying to prepare the lithium ion battery positive electrode working electrode material 5.
Using working electrode materials 1-5 of the anode of the lithium ion battery as the anode of the battery, a metal lithium sheet as the cathode, a Celgard2400 polypropylene film as a diaphragm, and the mass concentration of the substances is L iPF mol/L6The mixed solution of ethylene carbonate and dimethyl carbonate is used as an electrolyte to be assembled into a CR2032 button cell, and the electrochemical performance and the rate capability of the cell are tested by using an L ANHE CT2001A cell testing system and a CHI600E electrochemical workstation.
Figure BDA0002487024040000091
Figure BDA0002487024040000101
In summary, the carbon-coated lithium manganese iron phosphate lithium ion battery cathode material is prepared by taking biological rapeseed pollen as a template through a high-pressure hot solvent method and a high-temperature thermal cracking method to obtain porous lithium manganese iron phosphate L iMn0.6-0.9Fe0.1- 0.4PO4，Fe2+Insert L iMnPO4The crystal lattice of (2) limits the overgrowth of the crystal,is beneficial to forming a micro-nano morphology structure, the smaller particle size shortens the diffusion path of lithium ions, and rapeseed pollen is used as a template and a pore-forming agent, so that the manganese lithium iron phosphate forms a rich pore structure, is beneficial to the diffusion and transmission of the lithium ions, improves the diffusion rate of the lithium ions, the nitrogen-doped carbon-coated lithium manganese iron phosphate is prepared by an in-situ synthesis method, urea is used as a nitrogen source, tartaric acid is used as a carbon source, a sol-gel method and high-temperature carbonization are adopted, a large number of structural defects and active sites are formed by electron-rich N elements in the carbon layer structure, the conductivity of the carbon layer structure and the anode material is greatly improved, the transmission of electrons is promoted, under the multiplying power of 0.5C, the specific capacity is up to 142.6-151.6 mA.h/g, under the high rate of 2C, the specific capacity is still 112.8-118.6 mA.h/g, so that the anode material has excellent actual specific capacitance and rate capability.

Claims (5)

1. The carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 20-30 parts of tartaric acid, 2-5 parts of urea and 65-78 parts of three-dimensional porous lithium manganese iron phosphate.
2. The carbon-coated lithium iron manganese phosphate positive electrode material for the lithium ion battery according to claim 1, wherein the carbon-coated lithium iron manganese phosphate positive electrode material comprises: the preparation method of the three-dimensional porous lithium manganese iron phosphate comprises the following steps:
(1) adding biological pollen into a mixed solvent of distilled water and ethylene glycol in a volume ratio of 2-4:1, ultrasonically dispersing uniformly, adding a dispersing agent, lithium hydroxide, ferric oxalate, manganese acetate and ammonium dihydrogen phosphate, heating to 50-80 ℃, uniformly stirring for 3-6h, heating a solution reaction kettle to 160-650 ℃, reacting for 10-20h, removing the solvent, placing a solid mixed product into an atmosphere resistance furnace, introducing nitrogen, heating at a rate of 2-8 ℃/min, carrying out heat preservation and calcination for 2-4h at 580-650 ℃, grinding the calcined product into fine powder, and preparing the three-dimensional porous lithium manganese iron phosphate.
3. The carbon-coated lithium iron manganese phosphate positive electrode material for the lithium ion battery according to claim 2, wherein the carbon-coated lithium iron manganese phosphate positive electrode material comprises: atmosphere resistance furnace includes furnace body, furnace body left side fixedly connected with intake pipe, intake pipe right side fixed connection breather pipe, breather pipe surface are provided with inlet port, inlet port right side fixedly connected with outlet duct, the inside downside fixedly connected with insulating layer of furnace body, be provided with the circulator in the insulating layer, circulator and rotation axis fixed connection, rotation axis top fixedly connected with crucible.
4. The carbon-coated lithium manganese iron phosphate positive electrode material of the lithium ion battery as claimed in claim 2, wherein the biological pollen is rapeseed pollen, the mass ratio of the rapeseed pollen to the lithium hydroxide is 0.5-1.5:1, the dispersing agent is citric acid, the mass ratio of the citric acid to the lithium hydroxide to the ferric oxalate to the manganese acetate to the ammonium dihydrogen phosphate is 2.5-4:1:0.1-0.4:0.6-0.9:1, and the chemical expression of the three-dimensional porous lithium manganese iron phosphate is L iMn0.6-0.9Fe0.1-0.4PO4。
5. The carbon-coated lithium iron manganese phosphate positive electrode material for the lithium ion battery according to claim 1, wherein the carbon-coated lithium iron manganese phosphate positive electrode material comprises: the preparation method of the carbon-coated lithium manganese iron phosphate lithium ion battery anode material comprises the following steps of:
(1) adding 20-30 parts of tartaric acid, 2-5 parts of urea and 65-78 parts of three-dimensional porous lithium manganese iron phosphate into a mixed solvent of distilled water and ethanol, heating to 60-80 ℃, stirring until a gel is formed, removing the solvent, placing a solid product into an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 2-8 ℃/min, carrying out heat preservation treatment at 340 ℃ for 1-3h at 300-620 ℃, heating to 620 ℃ for 560-620 ℃, and carrying out heat preservation calcination for 3-5h, wherein the calcination product is the carbon-coated lithium manganese iron phosphate lithium ion battery anode material.
CN202010394646.8A 2020-05-11 2020-05-11 Carbon-coated lithium manganese iron phosphate lithium ion battery positive electrode material and preparation method thereof Withdrawn CN111477862A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114068889A (en) * 2020-08-06 2022-02-18 东莞新能安科技有限公司 Cathode material, electrochemical device and electronic device containing the same
CN114204030A (en) * 2021-12-02 2022-03-18 南昌大学 Modification method of lithium ferric manganese phosphate positive electrode material
CN115020685A (en) * 2022-07-26 2022-09-06 湖北亿纬动力有限公司 Lithium iron manganese phosphate positive electrode material and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114068889A (en) * 2020-08-06 2022-02-18 东莞新能安科技有限公司 Cathode material, electrochemical device and electronic device containing the same
CN114204030A (en) * 2021-12-02 2022-03-18 南昌大学 Modification method of lithium ferric manganese phosphate positive electrode material
CN115020685A (en) * 2022-07-26 2022-09-06 湖北亿纬动力有限公司 Lithium iron manganese phosphate positive electrode material and preparation method and application thereof
CN115020685B (en) * 2022-07-26 2023-09-01 湖北亿纬动力有限公司 Lithium iron manganese phosphate positive electrode material, and preparation method and application thereof

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