CN111446436A - Carbon-coated lithium vanadium phosphate lithium ion battery positive electrode material and preparation method thereof - Google Patents

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

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CN111446436A
CN111446436A CN202010338160.2A CN202010338160A CN111446436A CN 111446436 A CN111446436 A CN 111446436A CN 202010338160 A CN202010338160 A CN 202010338160A CN 111446436 A CN111446436 A CN 111446436A
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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
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract

The invention relates to the technical field of lithium ion batteries, and discloses a carbon-coated lithium vanadium phosphate lithium ion battery anode material which comprises the following formula raw materials and components of Cr-doped L i3V2(PO4)32-aminoimidazole, p-chloromethyl styrene, p-divinylbenzene, an initiator, a cross-linking agent and polyvinyl alcohol, wherein Cr is doped with L i3V2(PO4)3The crystal grains have uniform and small grain diameter, higher ion diffusion coefficient and electronic conductivity, and are porousThe chloromethyl polystyrene microsphere is coated with Cr-doped L i3V2(PO4)3From AlCl3The lithium ion battery anode material is a cross-linking agent, 2-aminoimidazole is a nitrogen source, and is subjected to high-temperature thermal cracking carbonization to obtain the nitrogen-doped porous carbon coated lithium vanadium phosphate lithium ion battery anode material with large specific surface area and rich pore structures.

Description

Carbon-coated lithium vanadium 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 vanadium phosphate lithium ion battery anode material and a preparation method thereof.
Background
The lithium ion battery is a chargeable secondary battery, mainly rely on the lithium ion to move and insert and remove between positive pole and negative pole and move to work reciprocally, while charging, there are lithium ions produced on the positive pole of the battery, the lithium ion is extracted from the positive pole, move to the negative pole through the electrolyte, the negative pole carbon material has many micropores, the lithium ion is inserted into the micropore of the carbon layer, make the negative pole in the state of rich lithium, the more lithium ion that is inserted, the higher the charge capacity is when discharging; during discharging, lithium ions are extracted from the negative electrode carbon layer, the lithium ions are inserted into the positive electrode through the electrolyte, the positive electrode is in a lithium-rich state, the more the lithium ions return to the positive electrode, the higher the discharge capacity is, and the lithium ion battery has the advantages of high energy density, high average output voltage, excellent cycle performance, quick charge and discharge, no memory effect, long service life and the like, and is a novel efficient green battery.
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 accounts for a larger proportion, the electrochemical performance of the positive electrode material also directly influences the performance of the lithium ion battery, and the positive electrode material of the lithium ion battery mainly comprises transition metal oxides such as lithium cobaltate, lithium manganate, lithium nickel cobalt aluminate and the like at present; polyanionic compounds such as lithium iron phosphate, lithium vanadium phosphate, lithium iron fluorosulfate, and the like; metal halides such as iron fluoride, cobalt fluoride, lithium chloride, and the like; the lithium ion battery positive electrode material has great development potential, but the lithium vanadium phosphate has low electronic conductivity and ionic conductivity, so that the diffusion coefficient of electrons and lithium ions is low, the migration and transmission of electrons and lithium ions in electrode reaction are inhibited, the rate capability of the positive electrode material is reduced, and the volume expansion of the lithium vanadium phosphate is easily caused due to the deintercalation of lithium ions in the charging and discharging processes of the lithium vanadium phosphate, so that the loss and damage of the matrix structure of the positive electrode material are caused, and the electrochemical cycle stability of the positive electrode material and the safety performance of the lithium ion battery are influenced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a carbon-coated lithium vanadium phosphate lithium ion battery anode material and a preparation method thereof, which solve the problems that the electron conductivity and the ionic conductivity of the lithium vanadium phosphate anode material are low, and the transmission and the diffusion of electrons and lithium ions are influenced, and simultaneously solve the problem that the volume of the lithium vanadium phosphate can expand in the charging and discharging process.
(II) technical scheme
In order to realize the aim, the invention provides the following technical scheme that the carbon-coated lithium vanadium phosphate lithium ion battery anode material comprises the following formula raw materials and components of Cr-doped L i3V2(PO4)32-aminoimidazole, p-chloromethyl styrene, p-divinylbenzene, an initiator, a cross-linking agent and polyvinyl alcohol, wherein the cross-linking agent is AlCl3, and the initiator is azobisisobutyronitrile.
Preferably, the Cr is doped with L i3V2(PO4)3The preparation method comprises the following steps:
(1) adding distilled water solvent, vanadium pentoxide, ammonium dihydrogen phosphate, cadmium acetate and dispersant citric acid into a reaction bottle, uniformly stirring, adding lithium carbonate, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 40-60 ℃ for 2-4h, placing the reaction bottle into an oil bath pot, heating to 75-90 ℃, uniformly stirring for reaction for 4-10h until the solution forms a sol, fully drying the sol mixed product to remove water, placing the sol mixed product into a planetary ball mill, and ball-milling into fine powder until the fine powder passes through a 1500-mesh screen with 1000 meshes.
(2) Placing the ball-milled fine powder in an atmosphere furnace, introducing nitrogen, heating at the rate of 2-4 ℃/min, carrying out heat preservation treatment at the temperature of 300-340 ℃ for 3-5h, heating to the temperature of 720-760 ℃, carrying out heat preservation calcination for 8-10h, placing the calcination product in a planetary ball mill for ball milling until the product passes through a screen with 1500 meshes of 1000-plus, washing the ball-milled product by using distilled water and ethanol, and fully drying to prepare the Cr-doped L i3V2(PO4)3。
Preferably, the mass ratio of the vanadium pentoxide to the ammonium dihydrogen phosphate to the cadmium acetate to the citric acid to the lithium carbonate is 0.96-0.99:3-3.2:0.02-0.08:6-9:1.5, and the Cr is doped with L i3V2(PO4)3Has the chemical expression of L i3Cr0.02- 0.08V1.92-1.98(PO4)3。
Preferably, the preparation method of the carbon-coated lithium vanadium phosphate lithium ion battery positive electrode material comprises the following steps:
(1) adding distilled water solvent andadding Cr doped L i into the surfactant polyvinyl alcohol after stirring and dissolving3V2(PO4)3Uniformly stirring p-chloromethyl styrene, p-divinylbenzene, an initiator azodiisobutyronitrile and toluene, placing a reaction bottle in an oil bath pot, heating to 50-60 ℃, uniformly stirring for 30-60min, heating to 75-85 ℃, uniformly stirring for reaction for 12-18h, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product by using distilled water and diethyl ether, fully drying, and preparing the chloromethyl polystyrene microsphere coated Cr doped L i3V2(PO4)3。
(2) Adding dichloromethane solvent and chloromethyl polystyrene microsphere coated Cr-doped L i into a reaction bottle3V2(PO4)3And a crosslinking agent AlCl3Placing a reaction bottle in an oil bath pot, heating to 35-45 ℃, uniformly stirring for 10-15h, heating to 75-95 ℃, uniformly stirring for reaction for 15-20h, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and acetone in sequence, and fully drying to prepare the super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3。
(3) Introducing nitrogen into a reaction bottle, adding dichloromethane and 1, 4-dioxane mixed solvent with the volume ratio of 1.5-2.5:1, adding super-crosslinked porous polystyrene microspheres to coat Cr-doped L i3V2(PO4)3Placing a reaction bottle in an oil bath, heating to 40-60 ℃, uniformly stirring for 10-15h, adding 2-aminoimidazole, heating to 80-110 ℃, uniformly stirring for reaction for 15-25h, vacuum drying the solution to remove the solvent, washing the solid product by sequentially using 1, 4-dioxane and dichloromethane, and fully drying to prepare the porous polyimidazol styrene microsphere coated Cr doped L i3V2(PO4)3。
(4) Coating porous polyimidazol styrene microspheres with Cr-doped L i3V2(PO4)3Placing the mixture in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 3-8 ℃/min, and carrying out heat preservation and calcination at the temperature of 550-600 ℃ for 2-4h to prepare the lithium ion of the carbon-coated lithium vanadium phosphateA battery positive electrode material.
Preferably, the polyvinyl alcohol and the Cr are doped L i in the step (1)3V2(PO4)3The mass ratio of p-chloromethyl styrene, p-divinylbenzene, initiator azodiisobutyronitrile and toluene is 0.2-0.4:12-20:14-18:1.5-2:0.5-0.8: 1.
Preferably, the chloromethyl polystyrene microsphere in the step (2) is coated with Cr-doped L i3V2(PO4)3And a crosslinking agent AlCl3The mass ratio of (A) to (B) is 1: 35-45.
Preferably, the hypercrosslinked porous polystyrene microsphere in the step (2) is coated with Cr doped L i3V2(PO4) And 2-aminoimidazole in a mass ratio of 1: 8-14.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the carbon-coated lithium vanadium phosphate lithium ion battery anode material is prepared by taking citric acid as a dispersing agent and cadmium acetate as a cadmium source through a sol-gel method to obtain Cr-doped L i with uniform crystal grains and small particle size3V2(PO4)3The chemical expression is L i3Cr0.02-0.08V1.92-1.98(PO4)3Cr goes into L i3V2(PO4)3In the crystal lattices, partial V crystal lattices are replaced, structural defects are generated in the crystal, the ion diffusion coefficient is improved, the transmission and the migration of lithium ions are facilitated, the internal resistance and the impedance of lithium vanadium phosphate are reduced by doping Cr, the electronic conductivity of the lithium vanadium phosphate is improved, the migration rate of electrons in electrode reaction is improved, and the rate capability of the anode material is obviously enhanced.
The carbon-coated lithium vanadium phosphate lithium ion battery anode material is prepared by doping L i with Cr3V2(PO4)3Preparing porous chloromethyl polystyrene microsphere coated Cr doping by using a matrix, a p-chloromethyl styrene molecular chain matrix, p-divinylbenzene as a chain extender and toluene as a pore-foaming agent through an in-situ growth method and free radical polymerizationLi3V2(PO4)3So that the polymer completely covers the Cr doping L i3V2(PO4)3Then use AlCl3The preparation method comprises the steps of forming a hypercrosslinked porous chloromethyl polystyrene polymer with a three-dimensional structure by using chloromethyl polystyrene as a cross-linking agent, forming the hypercrosslinked porous polyimidazolyl styrene polymer by performing affinity substitution reaction on chloromethyl in the polystyrene and 2-aminoimidazole as a nitrogen source, and performing high-temperature thermal cracking carbonization to obtain the lithium ion battery anode material which is coated with lithium vanadium phosphate and is coated with nitrogen-doped porous carbon with huge specific surface area and rich pore structures, wherein the contact and wettability of the lithium vanadium phosphate anode material and electrolyte can be enhanced by the huge specific surface area and the large pore structures, the nitrogen-doped porous carbon has excellent conductivity, interface charge transfer is promoted under the synergistic action, the rich pore structures provide diffusion channels for lithium ions, the diffusion coefficient of the lithium ions is improved, and the rich pores and the pore structures of the porous carbon are Cr-doped L i3V2(PO4)3The growth sites are provided, the porous carbon layer has a uniform structure and completely covers the lithium vanadium phosphate, and the volume expansion phenomenon of the lithium vanadium phosphate in the charging and discharging process is effectively inhibited.
Detailed Description
In order to realize the aim, the invention provides the following specific implementation mode and embodiment that the positive electrode material of the carbon-coated lithium vanadium phosphate lithium ion battery comprises the following formula raw materials and components of Cr-doped L i3V2(PO4)32-aminoimidazole, p-chloromethyl styrene, p-divinylbenzene, an initiator, a cross-linking agent and polyvinyl alcohol, wherein the cross-linking agent is AlCl3The initiator is azobisisobutyronitrile.
Cr doping L i3V2(PO4)3The preparation method comprises the following steps:
(1) adding distilled water solvent into a reaction bottle, uniformly stirring vanadium pentoxide, ammonium dihydrogen phosphate, cadmium acetate and a dispersant citric acid, adding lithium carbonate, wherein the mass ratio of the vanadium pentoxide to the ammonium dihydrogen phosphate to the citric acid is 0.96-0.99:3-3.2:0.02-0.08:6-9:1.5, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 40-60 ℃ for 2-4h, placing the reaction bottle into an oil bath, heating to 75-90 ℃, uniformly stirring for reaction for 4-10h until the solution forms a sol state, fully drying the sol state mixed product to remove moisture, placing the mixture into a planetary ball mill, and performing ball milling to obtain fine powder until the fine powder passes through a 1500-mesh screen with 1000 meshes.
(2) Placing the ball-milled fine powder in an atmosphere furnace, introducing nitrogen, heating at the rate of 2-4 ℃/min, carrying out heat preservation treatment at the temperature of 300-340 ℃ for 3-5h, heating to the temperature of 720-760 ℃, carrying out heat preservation calcination for 8-10h, placing the calcination product in a planetary ball mill for ball milling until the product passes through a screen with 1500 meshes of 1000-plus, washing the ball-milled product by using distilled water and ethanol, and fully drying to prepare the Cr-doped L i3V2(PO4)3The chemical expression is L i3Cr0.02-0.08V1.92-1.98(PO4)3。
The preparation method of the carbon-coated lithium vanadium phosphate lithium ion battery anode material comprises the following steps:
(1) adding distilled water solvent and surfactant polyvinyl alcohol into a reaction bottle, stirring and dissolving, and adding Cr-doped L i3V2(PO4)3P-chloromethyl styrene, p-divinylbenzene, an initiator azobisisobutyronitrile and toluene in a mass ratio of 0.2-0.4:12-20:14-18:1.5-2:0.5-0.8:1, uniformly stirring, placing a reaction bottle in an oil bath pot, heating to 50-60 ℃, uniformly stirring for 30-60min, heating to 75-85 ℃, uniformly stirring for reaction for 12-18h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and diethyl ether, and fully drying to obtain the chloromethyl polystyrene microsphere coated Cr doped L i3V2(PO4)3。
(2) Adding dichloromethane solvent into a reaction bottle, and coating chloromethyl polystyrene microspheres with Cr-doped L i3V2(PO4)3And a crosslinking agent AlCl3Placing the reaction bottle in an oil bath pot according to the mass ratio of 1:35-45, heating to 35-45 ℃, uniformly stirring for 10-15h, heating to 75-95 ℃, uniformly stirring for reaction for 15-20h, distilling the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and acetone in sequence, and washing the solid product with acetoneFully drying to prepare the super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3。
(3) Introducing nitrogen into a reaction bottle, adding dichloromethane and 1, 4-dioxane mixed solvent with the volume ratio of 1.5-2.5:1, adding super-crosslinked porous polystyrene microspheres to coat Cr-doped L i3V2(PO4)3Placing a reaction bottle in an oil bath, heating to 40-60 ℃, uniformly stirring for 10-15h, adding 2-aminoimidazole, heating to 80-110 ℃, uniformly stirring for reaction for 15-25h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by sequentially using 1, 4-dioxane and dichloromethane, and fully drying to prepare the porous polyimidazolyl styrene microsphere coated Cr doped L i3V2(PO4)3。
(4) Coating porous polyimidazol styrene microspheres with Cr-doped L i3V2(PO4)3Placing the carbon-coated lithium vanadium phosphate anode material in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 3-8 ℃/min, and carrying out heat preservation and calcination at the temperature of 550-600 ℃ for 2-4h to prepare the carbon-coated lithium vanadium phosphate anode material for the lithium ion battery.
Uniformly dispersing a carbon-coated lithium vanadium phosphate lithium ion battery positive electrode material, a conductive agent acetylene black and an adhesive polyvinylidene fluoride in an N-methyl pyrrolidone solvent, uniformly coating the mixture on an aluminum foil, and fully drying to prepare the lithium ion battery positive electrode working electrode material.
Example 1
(1) The Cr doping L i is prepared3V2(PO4)3Component 1: adding distilled water solvent into a reaction bottle, uniformly stirring vanadium pentoxide, ammonium dihydrogen phosphate, cadmium acetate and a dispersant citric acid, adding lithium carbonate, wherein the mass ratio of the vanadium pentoxide to the ammonium dihydrogen phosphate to the cadmium acetate to the dispersant citric acid is 0.99:3:0.02:6:1.5, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 40 ℃ for 2 hours, placing the reaction bottle into an oil bath pot, heating to 75 ℃, uniformly stirring for reaction for 4 hours until the solution forms a sol state, fully drying the sol mixed product to remove water, placing the sol mixed product into a planetary ball mill, and ball-milling the sol mixed product into fine powder until the fine powder passes through a 1000-mesh sievePlacing the ball-milled fine powder in an atmosphere furnace, introducing nitrogen at the heating rate of 2 ℃/min, carrying out heat preservation treatment at the temperature of 300 ℃ for 3h, then heating to 720 ℃, carrying out heat preservation calcination for 8h, placing the calcined product in a planetary ball mill for ball milling until the product passes through a 1000-mesh screen, washing the ball-milled product by using distilled water and ethanol, and fully drying to prepare the Cr-doped L i3V2(PO4)3Component 1, chemical expression is L i3Cr0.02V1.98(PO4)3。
(2) Preparation of chloromethyl polystyrene microsphere coated Cr-doped L i3V2(PO4)3The component 1 is that distilled water solvent and surfactant polyvinyl alcohol are added into a reaction bottle, and Cr doped L i is added after stirring and dissolving3V2(PO4)3The preparation method comprises the following steps of uniformly stirring component 1, p-chloromethyl styrene, p-divinylbenzene, initiator azobisisobutyronitrile and toluene in a mass ratio of 0.2:12:14:1.5:0.5:1, placing a reaction bottle in an oil bath pot, heating to 50 ℃, uniformly stirring for 30min, heating to 75 ℃, uniformly stirring for reaction for 12h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and diethyl ether, and fully drying to obtain chloromethyl polystyrene microsphere coated Cr doped L i3V2(PO4)3And (3) component 1.
(3) Preparation of super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3Component 1, adding dichloromethane solvent into a reaction bottle, and coating chloromethyl polystyrene microspheres with Cr-doped L i3V2(PO4)3Component 1 and crosslinker AlCl3Placing a reaction bottle in an oil bath pot according to the mass ratio of 1:35, heating to 35 ℃, uniformly stirring for 10h, heating to 75 ℃, uniformly stirring for reaction for 15h, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and acetone in sequence, and fully drying to prepare the super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3And (3) component 1.
(4) Preparation of porous Polyimidazole styrene microsphere coating Cr doping L i3V2(PO4)3Introducing nitrogen into a reaction bottle, adding dichloromethane and 1, 4-dioxane mixed solvent with the volume ratio of 1.5:1, and adding hypercrosslinked porous polystyrene microspheres to coat Cr-doped L i3V2(PO4)3Placing a reaction bottle in an oil bath pot, heating to 40 ℃, uniformly stirring for 10h, adding 2-aminoimidazole according to the mass ratio of 1:8, heating to 80 ℃, uniformly stirring for reaction for 15h, drying the solution in vacuum to remove the solvent, washing the solid product by sequentially using 1, 4-dioxane and dichloromethane, and fully drying to prepare the porous polyimidazole styrene microsphere coated Cr doped L i3V2(PO4)3And (3) component 1.
(5) Preparing the lithium ion battery anode material 1 of carbon-coated lithium vanadium phosphate by coating porous polyimidazole styrene microspheres with Cr-doped L i3V2(PO4)3Placing the component 1 in an atmosphere resistance furnace, introducing nitrogen, keeping the temperature and calcining at 550 ℃ for 2h at the heating rate of 3 ℃/min to prepare a carbon-coated lithium vanadium phosphate lithium ion battery anode material 1, uniformly dispersing the carbon-coated lithium vanadium phosphate lithium ion battery anode material 1, a conductive agent acetylene black and an adhesive polyvinylidene fluoride in an N-methyl pyrrolidone solvent, uniformly coating the aluminum foil, and fully drying to prepare the lithium ion battery anode working electrode material 1.
Example 2
(1) The Cr doping L i is prepared3V2(PO4)3And (2) component: adding distilled water solvent into a reaction bottle, uniformly stirring vanadium pentoxide, ammonium dihydrogen phosphate, cadmium acetate and a dispersant citric acid, adding lithium carbonate, wherein the mass ratio of the vanadium pentoxide to the ammonium dihydrogen phosphate to the calcium acetate to the dispersant citric acid is 0.98:3:0.04:61.5, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 60 ℃ for 4 hours, placing the reaction bottle into an oil bath kettle, heating to 90 ℃, uniformly stirring for reaction for 10 hours until the solution forms a sol, fully drying the sol mixed product to remove water, placing the sol mixed product into a planetary ball mill, ball-milling into fine powder until the fine powder passes through a 1500-mesh screen, placing the ball-milled fine powder into an atmosphere furnace, introducing nitrogen, and raising the temperature at 4 DEG CAnd/min, carrying out heat preservation treatment at 340 ℃ for 3h, then heating to 760 ℃, carrying out heat preservation calcination for 10h, placing the calcined product in a planetary ball mill for ball milling until the product passes through a 1000-mesh screen, washing the ball-milled product by using distilled water and ethanol, and fully drying to prepare Cr-doped L i3V2(PO4)3Component 2, chemical expression is L i3Cr0.04V1.96(PO4)3。
(2) Preparation of chloromethyl polystyrene microsphere coated Cr-doped L i3V2(PO4)3Component 2, adding distilled water solvent and surfactant polyvinyl alcohol into a reaction bottle, stirring and dissolving, and adding Cr-doped L i3V2(PO4)3The preparation method comprises the following steps of uniformly stirring a component 2, p-chloromethyl styrene, p-divinylbenzene, an initiator azobisisobutyronitrile and toluene in a mass ratio of 0.4:12:14:1.5:0.5:1, placing a reaction bottle in an oil bath pot, heating to 60 ℃, uniformly stirring for 60min, heating to 75 ℃, uniformly stirring for reaction for 12h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and diethyl ether, and fully drying to obtain the chloromethyl polystyrene microsphere coated Cr doped L i3V2(PO4)3And (3) component 2.
(3) Preparation of super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3Component 2, methylene dichloride solvent is added into a reaction bottle, and chloromethyl polystyrene microspheres are coated with Cr-doped L i3V2(PO4)3Component 2 and crosslinker AlCl3Placing a reaction bottle in an oil bath pot according to the mass ratio of 1:35, heating to 45 ℃, uniformly stirring for 15h, heating to 95 ℃, uniformly stirring for reaction for 15h, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and acetone in sequence, and fully drying to prepare the super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3And (3) component 2.
(4) Preparation of porous polyimidazole styrene microsphere coated Cr-doped L i3V2(PO4)3And (2) component: is turned to the reverse directionIntroducing nitrogen into a bottle, adding dichloromethane and 1, 4-dioxane mixed solvent with the volume ratio of 1.5:1, and adding hypercrosslinked porous polystyrene microspheres to coat Cr-doped L i3V2(PO4)3And (2) placing the reaction bottle in an oil bath pot, heating to 60 ℃, uniformly stirring for 15h, adding 2-aminoimidazole according to the mass ratio of 1:8, heating to 110 ℃, uniformly stirring for reaction for 25h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by sequentially using 1, 4-dioxane and dichloromethane, and fully drying to prepare the porous polyimidazole styrene microsphere coated Cr doped L i3V2(PO4)3And (3) component 2.
(5) Preparing the carbon-coated lithium vanadium phosphate lithium ion battery cathode material 2, namely coating porous polyimidazol styrene microspheres with Cr-doped L i3V2(PO4)3And (2) placing the component 2 in an atmosphere resistance furnace, introducing nitrogen, keeping the temperature and calcining at 550 ℃ for 4h at the heating rate of 8 ℃/min to prepare the carbon-coated lithium vanadium phosphate lithium ion battery anode material 2, uniformly dispersing the carbon-coated lithium vanadium phosphate lithium ion battery anode material 2, a conductive agent acetylene black and an adhesive polyvinylidene fluoride in an N-methyl pyrrolidone solvent, uniformly coating the aluminum foil, and fully drying to prepare the lithium ion battery anode working electrode material 2.
Example 3
(1) The Cr doping L i is prepared3V2(PO4)3And (3) component: adding distilled water solvent into a reaction bottle, uniformly stirring vanadium pentoxide, ammonium dihydrogen phosphate, cadmium acetate and a dispersant citric acid, adding lithium carbonate, wherein the mass ratio of the vanadium pentoxide to the ammonium dihydrogen phosphate is 0.97:3.1:0.06:7.5:1.5, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 50 ℃ for 3h, placing the reaction bottle into an oil bath, heating to 85 ℃, uniformly stirring for reaction for 7h until the solution forms a sol, fully drying the sol mixed product to remove moisture, placing the sol mixed product into a planetary ball mill, grinding into fine powder until the fine powder passes through a 1200-mesh screen, placing the ball-milled fine powder into an atmosphere furnaceAnd 9h, placing the calcined product into a planetary ball mill for ball milling until the calcined product passes through a 1200-mesh screen, washing the ball-milled product by using distilled water and ethanol, and fully drying to prepare the Cr-doped L i3V2(PO4)3Component 3, chemical expression is L i3Cr0.06V1.94(PO4)3。
(2) Preparation of chloromethyl polystyrene microsphere coated Cr-doped L i3V2(PO4)3Component 3, adding distilled water solvent and surfactant polyvinyl alcohol into a reaction bottle, stirring and dissolving, and adding Cr-doped L i3V2(PO4)3The preparation method comprises the following steps of uniformly stirring a component 3, p-chloromethyl styrene, p-divinylbenzene, an initiator azobisisobutyronitrile and toluene in a mass ratio of 0.3:16: 1.8:0.7:1, placing a reaction bottle in an oil bath pot, heating to 55 ℃, uniformly stirring for 45min, heating to 80 ℃, uniformly stirring for reaction for 15h, cooling the solution to room temperature, filtering to remove the solvent, washing a solid product with distilled water and diethyl ether, and fully drying to obtain chloromethyl polystyrene microsphere coated Cr doped L i3V2(PO4)3And (3) component.
(3) Preparation of super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3Component 3, methylene dichloride solvent is added into a reaction bottle, and chloromethyl polystyrene microspheres are coated with Cr-doped L i3V2(PO4)3Component 3 and crosslinker AlCl3Placing a reaction bottle in an oil bath pot according to the mass ratio of 1:40, heating to 40 ℃, uniformly stirring for 12h, heating to 85 ℃, uniformly stirring for reaction for 17h, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and acetone in sequence, and fully drying to prepare the super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3And (3) component.
(4) Preparation of porous polyimidazole styrene microsphere coated Cr-doped L i3V2(PO4)3And (3) component: introducing nitrogen into a reaction bottle, adding a mixed solvent of dichloromethane and 1, 4-dioxaneAdding the super-crosslinked porous polystyrene microspheres to coat Cr-doped L i, wherein the volume ratio of the two is 2:13V2(PO4)3And (3) placing the reaction bottle in an oil bath, heating to 50 ℃, uniformly stirring for 12h, adding 2-aminoimidazole according to the mass ratio of 1:11, heating to 90 ℃, uniformly stirring for reaction for 20h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by sequentially using 1, 4-dioxane and dichloromethane, and fully drying to prepare the porous polyimidazole styrene microsphere coated Cr doped L i3V2(PO4)3And (3) component.
(5) Preparing the lithium ion battery anode material 3 of carbon-coated lithium vanadium phosphate by coating porous polyimidazole styrene microspheres with Cr-doped L i3V2(PO4)3Placing the component 3 in an atmosphere resistance furnace, introducing nitrogen, keeping the temperature and calcining at 580 ℃ for 3h at the heating rate of 5 ℃/min, preparing to obtain the carbon-coated lithium vanadium phosphate lithium ion battery anode material 3, uniformly dispersing the carbon-coated lithium vanadium phosphate lithium ion battery anode material 3, a conductive agent acetylene black and an adhesive polyvinylidene fluoride in an N-methyl pyrrolidone solvent, uniformly coating the aluminum foil, and fully drying to prepare the lithium ion battery anode working electrode material 3.
Example 4
(1) The Cr doping L i is prepared3V2(PO4)3And (4) component: adding distilled water solvent into a reaction bottle, uniformly stirring vanadium pentoxide, ammonium dihydrogen phosphate, cadmium acetate and a dispersant citric acid, adding lithium carbonate, wherein the weight ratio of the vanadium pentoxide to the ammonium dihydrogen phosphate to the calcium acetate to the dispersant citric acid is 0.965:3:0.07:6:1.5, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 40 ℃ for 4h, placing the reaction bottle into an oil bath, heating to 90 ℃, uniformly stirring for reaction for 10h until the solution forms a sol, fully drying the sol mixed product to remove moisture, placing the sol mixed product into a planetary ball mill, ball-milling into fine powder until the fine powder passes through a 1000-mesh screen, placing the ball-milled fine powder into an atmosphere furnace, introducing nitrogen, heating at the speed of 4 ℃/min, performing heat preservation treatment at 340 ℃ for 5h, heating to 760 ℃, performing heat preservation and calcinationSieving, washing the ball-milled product with distilled water and ethanol, and fully drying to obtain the Cr-doped L i3V2(PO4)3Component 4, chemical expression is L i3Cr0.07V1.93(PO4)3。
(2) Preparation of chloromethyl polystyrene microsphere coated Cr-doped L i3V2(PO4)3Component 4, adding distilled water solvent and surfactant polyvinyl alcohol into a reaction bottle, stirring and dissolving, and adding Cr-doped L i3V2(PO4)3The preparation method comprises the following steps of uniformly stirring a component 4, p-chloromethyl styrene, p-divinylbenzene, an initiator azobisisobutyronitrile and toluene in a mass ratio of 0.4:12:14:1.5:0.8:1, placing a reaction bottle in an oil bath pot, heating to 55 ℃, uniformly stirring for 45min, heating to 85 ℃, uniformly stirring for reaction for 18h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and diethyl ether, and fully drying to obtain chloromethyl polystyrene microsphere coated Cr doped L i3V2(PO4)3And (4) component.
(3) Preparation of super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3Component 4, methylene dichloride solvent is added into a reaction bottle, and chloromethyl polystyrene microspheres are coated with Cr-doped L i3V2(PO4)3Component 4 and crosslinker AlCl3Placing a reaction bottle in an oil bath pot according to the mass ratio of 1:35, heating to 45 ℃, uniformly stirring for 10h, heating to 95 ℃, uniformly stirring for 20h, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and acetone in sequence, and fully drying to prepare the super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3And (4) component.
(4) Preparation of porous polyimidazole styrene microsphere coated Cr-doped L i3V2(PO4)3And (4) component: introducing nitrogen into a reaction bottle, adding dichloromethane and 1, 4-dioxane mixed solvent with the volume ratio of 2.5:1, and adding the super-crosslinked porous polystyrene microspheres to coat CrHetero L i3V2(PO4)3And (4) placing the reaction bottle in an oil bath, heating to 60 ℃, uniformly stirring for 15h, adding 2-aminoimidazole according to the mass ratio of 1:14, heating to 110 ℃, uniformly stirring for reaction for 25h, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by sequentially using 1, 4-dioxane and dichloromethane, and fully drying to prepare the porous polyimidazole styrene microsphere coated Cr doped L i3V2(PO4)3And (4) component.
(5) Preparing the lithium ion battery anode material 4 of carbon-coated lithium vanadium phosphate by coating porous polyimidazole styrene microspheres with Cr-doped L i3V2(PO4)3And (2) placing the component 4 in an atmosphere resistance furnace, introducing nitrogen, keeping the temperature and calcining at the temperature of 600 ℃ for 4h at the heating rate of 8 ℃/min to prepare the carbon-coated lithium vanadium phosphate lithium ion battery anode material 4, uniformly dispersing the carbon-coated lithium vanadium phosphate lithium ion battery anode material 4, a conductive agent acetylene black and an adhesive polyvinylidene fluoride in an N-methyl pyrrolidone solvent, uniformly coating the aluminum foil, and fully drying to prepare the lithium ion battery anode working electrode material 4.
Example 5
(1) The Cr doping L i is prepared3V2(PO4)3And (5) component: adding distilled water solvent into a reaction bottle, uniformly stirring vanadium pentoxide, ammonium dihydrogen phosphate, cadmium acetate and a dispersant citric acid, adding lithium carbonate, wherein the mass ratio of the vanadium pentoxide to the ammonium dihydrogen phosphate to the citric acid is 0.96:3.2:0.08:9:1.5, placing the reaction bottle into an ultrasonic treatment instrument, performing ultrasonic dispersion treatment at 60 ℃ for 4h, placing the reaction bottle into an oil bath, heating to 90 ℃, uniformly stirring for reaction for 10h until the solution forms a sol, fully drying the sol mixed product to remove moisture, placing the sol mixed product into a planetary ball mill, performing ball milling to obtain fine powder, passing through a 1500-mesh screen, placing the ball-milled fine powder into an atmosphere furnace, introducing nitrogen, heating at the rate of 4 ℃/min, performing heat preservation treatment at 340 ℃ for 5h, heating to 760 ℃, performing heat preservation and calcination for 10h, placing the calcined product into the planetary ball mill, until the product passes through a 1500-mesh screen, washing the ball-milled product by using distilled water, and the mixture is fully dried,the Cr doping L i is prepared3V2(PO4)3Component 5, chemical expression is L i3Cr0.08V1.92(PO4)3。
(2) Preparation of chloromethyl polystyrene microsphere coated Cr-doped L i3V2(PO4)3Component 5, adding distilled water solvent and surfactant polyvinyl alcohol into a reaction bottle, stirring and dissolving, and adding Cr-doped L i3V2(PO4)3The preparation method comprises the following steps of uniformly stirring component 5, p-chloromethyl styrene, p-divinylbenzene, initiator azobisisobutyronitrile and toluene in a mass ratio of 0.4:20:18:2:0.8:1, placing a reaction bottle in an oil bath pot, heating to 60 ℃, uniformly stirring for 60min, heating to 85 ℃, uniformly stirring for 18h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water and diethyl ether, and fully drying to obtain chloromethyl polystyrene microsphere coated Cr doped L i3V2(PO4)3And (5) component.
(3) Preparation of super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3Component 5, methylene dichloride solvent is added into a reaction bottle, and chloromethyl polystyrene microspheres are coated with Cr-doped L i3V2(PO4)3Component 5 and crosslinker AlCl3Placing a reaction bottle in an oil bath pot according to the mass ratio of 1:45, heating to 45 ℃, uniformly stirring for 15h, heating to 95 ℃, uniformly stirring for 20h, distilling the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and acetone in sequence, and fully drying to prepare the super-crosslinked porous polystyrene microsphere coated Cr-doped L i3V2(PO4)3And (5) component.
(4) Preparation of porous polyimidazole styrene microsphere coated Cr-doped L i3V2(PO4)3The component 5 is that nitrogen is introduced into a reaction bottle, dichloromethane and 1, 4-dioxane mixed solvent are added, the volume ratio of the dichloromethane to the 1, 4-dioxane mixed solvent is 2.5:1, and the hypercrosslinked porous polystyrene microspheres are added to coat Cr doping L i3V2(PO4)3Component 5, will be reversedPlacing the mixture into an oil bath kettle, heating the mixture to 60 ℃, uniformly stirring the mixture for 15 hours, adding 2-aminoimidazole according to the mass ratio of 1:14, heating the mixture to 110 ℃, uniformly stirring the mixture for reaction for 25 hours, carrying out vacuum drying on the solution to remove the solvent, washing the solid product by sequentially using 1, 4-dioxane and dichloromethane, and fully drying the solid product to prepare the porous polyimidazol styrene microsphere coated Cr-doped L i3V2(PO4)3And (5) component.
(5) Preparing the carbon-coated lithium vanadium phosphate lithium ion battery cathode material 5, namely coating Cr-doped L i on porous polyimidazol styrene microspheres3V2(PO4)3Placing the component 5 in an atmosphere resistance furnace, introducing nitrogen, keeping the temperature and calcining at the temperature of 600 ℃ for 4h at the temperature rise rate of 8 ℃/min to prepare the carbon-coated lithium vanadium phosphate lithium ion battery anode material 5, uniformly dispersing the carbon-coated lithium vanadium phosphate lithium ion battery anode material 5, a conductive agent acetylene black and an adhesive polyvinylidene fluoride in an N-methyl pyrrolidone solvent, uniformly coating the aluminum foil, and fully drying to prepare the lithium ion battery anode working electrode material 5.
In summary, the carbon-coated lithium vanadium phosphate lithium ion battery cathode material is prepared by taking citric acid as a dispersant and cadmium acetate as a cadmium source through a sol-gel method to obtain Cr-doped L i with uniform crystal grains and small particle size3V2(PO4)3The chemical expression is L i3Cr0.02-0.08V1.92-1.98(PO4)3Cr goes into L i3V2(PO4)3In the crystal lattices, partial V crystal lattices are replaced, structural defects are generated in the crystal, the ion diffusion coefficient is improved, the transmission and the migration of lithium ions are facilitated, the internal resistance and the impedance of lithium vanadium phosphate are reduced by doping Cr, the electronic conductivity of the lithium vanadium phosphate is improved, the migration rate of electrons in electrode reaction is improved, and the rate capability of the anode material is obviously enhanced.
L i doped with Cr3V2(PO4)3Taking a p-chloromethyl styrene molecular chain matrix and p-divinylbenzene as chain extenders and toluene as pore-foaming agents as a matrix, and carrying out in-situ growth method and self-assemblyPreparing porous chloromethyl polystyrene microsphere coated Cr doped L i by radical polymerization3V2(PO4)3So that the polymer completely covers the Cr doping L i3V2(PO4)3Then use AlCl3The preparation method comprises the steps of forming a hypercrosslinked porous chloromethyl polystyrene polymer with a three-dimensional structure by using chloromethyl polystyrene as a cross-linking agent, forming the hypercrosslinked porous polyimidazolyl styrene polymer by performing affinity substitution reaction on chloromethyl in the polystyrene and 2-aminoimidazole as a nitrogen source, and performing high-temperature thermal cracking carbonization to obtain the lithium ion battery anode material which is coated with lithium vanadium phosphate and is coated with nitrogen-doped porous carbon with huge specific surface area and rich pore structures, wherein the contact and wettability of the lithium vanadium phosphate anode material and electrolyte can be enhanced by the huge specific surface area and the large pore structures, the nitrogen-doped porous carbon has excellent conductivity, interface charge transfer is promoted under the synergistic action, the rich pore structures provide diffusion channels for lithium ions, the diffusion coefficient of the lithium ions is improved, and the rich pores and the pore structures of the porous carbon are Cr-doped L i3V2(PO4)3The growth sites are provided, the porous carbon layer has a uniform structure and completely covers the lithium vanadium phosphate, and the volume expansion phenomenon of the lithium vanadium phosphate in the charging and discharging process is effectively inhibited.

Claims (8)

1. The carbon-coated lithium vanadium phosphate lithium ion battery anode material comprises the following formula raw materials and components, and is characterized in that the material is Cr-doped L i3V2(PO4)32-aminoimidazole, p-chloromethyl styrene, p-divinylbenzene, an initiator, a crosslinking agent and polyvinyl alcohol.
2. The carbon-coated lithium vanadium phosphate positive electrode material for lithium ion batteries according to claim 1, characterized in that: the cross-linking agent is AlCl3, and the initiator is azobisisobutyronitrile.
3. The carbon-coated lithium vanadium phosphate positive electrode material for lithium ion batteries according to claim 1, characterized in that: the above-mentionedCr doping L i3V2(PO4)3The preparation method comprises the following steps:
(1) adding vanadium pentoxide, ammonium dihydrogen phosphate, cadmium acetate, a dispersing agent citric acid and lithium carbonate into a distilled water solvent, performing ultrasonic dispersion treatment for 2-4h at 40-60 ℃, heating to 75-90 ℃, reacting for 4-10h until the solution forms a sol, fully drying a sol mixed product to remove water, and performing ball milling to obtain fine powder until the fine powder passes through a 1000-mesh 1500-mesh screen;
(2) placing the ball-milled fine powder in an atmosphere furnace, introducing nitrogen, heating at the rate of 2-4 ℃/min, carrying out heat preservation treatment at the temperature of 300-340 ℃ for 3-5h, heating to the temperature of 720-760 ℃, carrying out heat preservation calcination for 8-10h, carrying out ball milling on the calcination product until the calcination product passes through a 1000-mesh 1500-mesh screen, washing and drying the ball-milled product, and preparing the Cr-doped L i3V2(PO4)3。
4. The carbon-coated lithium vanadium phosphate positive electrode material for the lithium ion battery as claimed in claim 3, wherein the mass ratio of the vanadium pentoxide to the ammonium dihydrogen phosphate to the cadmium acetate to the citric acid to the lithium carbonate is 0.96-0.99:3-3.2:0.02-0.08:6-9:1.5, and the Cr is doped with L i3V2(PO4)3Has the chemical expression of L i3Cr0.02-0.08V1.92-1.98(PO4)3。
5. The carbon-coated lithium vanadium phosphate positive electrode material for lithium ion batteries according to claim 1, characterized in that: the preparation method of the carbon-coated lithium vanadium phosphate lithium ion battery anode material comprises the following steps:
(1) adding surfactant polyvinyl alcohol and Cr doped L i into distilled water solvent3V2(PO4)3Heating p-chloromethyl styrene, p-divinylbenzene, initiator azobisisobutyronitrile and toluene to 50-60 ℃, uniformly stirring for 30-60min, heating to 75-85 ℃, reacting for 12-18h, cooling, filtering, washing and drying to prepare the chloromethyl polystyrene microsphere coated Cr doped L i3V2(PO4)3；
(2) Adding chloromethyl polystyrene microsphere coated Cr doping L i into dichloromethane solvent3V2(PO4)3And a crosslinking agent AlCl3Heating to 35-45 ℃, stirring at constant speed for 10-15h, heating to 75-95 ℃, reacting for 15-20h, removing the solvent, washing and drying to prepare the super-crosslinked porous polystyrene microsphere coated Cr doped L i3V2(PO4)3；
(3) Adding the super-crosslinked porous polystyrene microspheres coated with Cr doped L i into a mixed solvent of dichloromethane and 1, 4-dioxane with the volume ratio of 1.5-2.5:13V2(PO4)3Heating to 40-60 ℃ in nitrogen atmosphere, uniformly stirring for 10-15h, adding 2-aminoimidazole, heating to 80-110 ℃, reacting for 15-25h, removing solvent, washing and drying to obtain porous polyimidazol styrene microsphere coated Cr doped L i3V2(PO4)3；
(4) Coating porous polyimidazol styrene microspheres with Cr-doped L i3V2(PO4)3Placing the carbon-coated lithium vanadium phosphate anode material in an atmosphere resistance furnace, introducing nitrogen, heating at the rate of 3-8 ℃/min, and carrying out heat preservation and calcination at the temperature of 550-600 ℃ for 2-4h to prepare the carbon-coated lithium vanadium phosphate anode material for the lithium ion battery.
6. The carbon-coated lithium vanadium phosphate lithium ion battery positive electrode material as claimed in claim 5, wherein the polyvinyl alcohol and Cr in the step (1) are doped with L i3V2(PO4)3The mass ratio of p-chloromethyl styrene, p-divinylbenzene, initiator azodiisobutyronitrile and toluene is 0.2-0.4:12-20:14-18:1.5-2:0.5-0.8: 1.
7. The carbon-coated lithium vanadium phosphate lithium ion battery positive electrode material as claimed in claim 5, wherein the chloromethyl polystyrene microsphere coated with Cr is doped with L i in the step (2)3V2(PO4)3And a crosslinking agent AlCl3The mass ratio of (A) to (B) is 1: 35-45.
8. The carbon-coated lithium vanadium phosphate lithium ion battery positive electrode material as claimed in claim 1, wherein the hypercrosslinked porous polystyrene microsphere coated with Cr doped L i in the step (2)3V2(PO4) And 2-aminoimidazole in a mass ratio of 1: 8-14.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112018373A (en) * 2020-08-05 2020-12-01 嵊州市森拓新材料有限公司 Carbon-coated Li with shell-core structure3VO4Lithium ion battery cathode material and preparation method thereof
CN112919446A (en) * 2021-01-22 2021-06-08 益诺鑫电气(深圳)有限公司 Nitrogen-doped porous carbon loaded MoS2Electrode material of nanometer flower and its preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112018373A (en) * 2020-08-05 2020-12-01 嵊州市森拓新材料有限公司 Carbon-coated Li with shell-core structure3VO4Lithium ion battery cathode material and preparation method thereof
CN112919446A (en) * 2021-01-22 2021-06-08 益诺鑫电气(深圳)有限公司 Nitrogen-doped porous carbon loaded MoS2Electrode material of nanometer flower and its preparation method

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