CN112838214A - Mesoporous carbon in-situ modified FeP lithium ion battery cathode material and preparation method thereof - Google Patents

Mesoporous carbon in-situ modified FeP lithium ion battery cathode material and preparation method thereof Download PDF

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CN112838214A
CN112838214A CN202110100708.4A CN202110100708A CN112838214A CN 112838214 A CN112838214 A CN 112838214A CN 202110100708 A CN202110100708 A CN 202110100708A CN 112838214 A CN112838214 A CN 112838214A
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mesoporous carbon
nitrogen
fep
situ modified
lithium ion
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张训海
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Chongqing Shijiufen Technology Co ltd
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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
    • H01M4/5805—Phosphides
    • 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
    • H01M4/62—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/027—Negative 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 lithium ion battery cathode material with FeP modified in situ by mesoporous carbon2+FeOOH nanorods are generated in situ in a nitrogen-doped mesoporous carbon matrix and are further phosphorized and etched by sodium hypophosphite, the generated tubular nano FeP grows uniformly in the nitrogen-doped mesoporous carbon matrix, the aggregation of the nano FeP is reduced, the tubular nano FeP has higher specific surface area and rich lithium deintercalation sites, the in-situ modification effect of the nitrogen-doped mesoporous carbon forms a three-dimensional conductive network, the electron, transmission and migration are promoted, a porous structure can provide a buffer space, the volume expansion phenomenon of the tubular nano FeP is accommodated, and the tube of the nano FeP is maintainedThe shape, appearance and structure stability of the composite material improve the capacity retention rate and the cycle stability.

Description

Mesoporous carbon in-situ modified FeP lithium ion battery cathode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a mesoporous carbon in-situ modified FeP lithium ion battery cathode material and a preparation method thereof.
Background
With the rapid development of industry, the demand for fossil energy is increasing day by day, but the excessive combustion of fossil capacity has caused serious environmental pollution and energy exhaustion, so green clean energy needs to be vigorously developed to solve the problems of environmental pollution and energy shortage, the lithium ion battery is a commercialized secondary battery, has the advantages of high energy density, stable cycle performance, environmental protection and the like, is widely applied to portable electronic equipment, electric automobiles and the like, but the negative electrode of the commercial lithium ion battery is a graphite negative electrode with lower theoretical specific capacity, and greatly limits the practical application of the lithium ion battery.
The lithium ion battery cathode material currently under hot research mainly comprises transition metalOxides, e.g. MnO2、Fe3O4、SiO2Etc.; and transition metal sulfides, e.g. MoS2FeS and the like, transition metal phosphide such as FeP, CoP and the like has higher theoretical specific capacity and wide development prospect, wherein FeP has the advantages of lower relative intercalation potential, rich reserve, low price, easy obtainment, controllable appearance and the like, and is a lithium ion battery cathode material with development prospect.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a mesoporous carbon in-situ modified FeP lithium ion battery cathode material and a preparation method thereof, and solves the problem of poor electrochemical performance of the FeP cathode material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a mesoporous carbon in-situ modified FeP lithium ion battery cathode material is as follows:
(1) adding dimethyl sulfoxide solvent, melamine and 5, 5-bis (bromomethyl) -2, 2-bipyridine in a mass ratio of 10:40-45 into a reaction bottle, heating to 160 ℃, reacting for 12-24h, placing in an ice water bath for cooling, adding methanol to separate out a precipitate, and washing by using dichloromethane and methanol to obtain the triazine ring group microporous polymer.
(2) Adding distilled water, triazine ring group microporous polymer and potassium hydroxide into a beaker, uniformly dispersing by ultrasonic, stirring for 6-12h, vacuum drying the solution to remove the solvent, putting the mixed product into a tube furnace for carbonization, and washing the carbonized product by hydrochloric acid and distilled water to obtain the nitrogen-doped mesoporous carbon.
(3) Adding distilled water solvent, nitrogen-doped mesoporous carbon, ferrous chloride, ammonium fluoride and urea into a reaction bottle, reacting for 6-12h at 70-90 ℃, centrifugally separating to remove the solvent, washing with distilled water and ethanol, and obtaining the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod.
(4) And uniformly mixing the nitrogen-doped mesoporous carbon in-situ modified FeOOH nano-rod and sodium hypophosphite, and then placing the mixture into a tubular furnace for calcining to obtain the nitrogen-doped mesoporous carbon in-situ modified FeP nano-tube.
(5) Dissolving a nitrogen-doped mesoporous carbon in-situ modified FeP nanotube, conductive carbon black and polyvinylidene fluoride in an N-methyl pyrrolidone solvent in a mass ratio of 8:1:1, then coating the mixture on the surface of copper foil, drying and tabletting to obtain the mesoporous carbon in-situ modified FeP lithium ion battery cathode material.
Preferably, the mass ratio of the triazine ring group microporous polymer to the potassium hydroxide in the step (2) is 100: 150-300.
Preferably, the carbonization in the step (2) is carried out in a nitrogen atmosphere, the carbonization temperature is 700-800 ℃, and the carbonization time is 2-3 h.
Preferably, the mass ratio of the nitrogen-doped mesoporous carbon, the ferrous chloride, the ammonium fluoride and the urea in the step (3) is 5-15:100:2-2.5: 8-12.
Preferably, the mass ratio of the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod to the sodium hypophosphite in the step (4) is 10: 250-350.
Preferably, the calcination in the step (4) is performed in a nitrogen atmosphere, the calcination temperature is 300-350 ℃, and the calcination time is 2-3 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
the mesoporous carbon in-situ modified FeP lithium ion battery cathode material takes melamine and 5, 5-bis (bromomethyl) -2, 2-bipyridine as polymerization monomers, nucleophilic substitution is carried out through bromine atoms and amino groups to generate a triazine ring group microporous polymer, the triazine ring group microporous polymer contains a large number of microporous structures, a rigid aromatic ring molecular chain of the polymer is further taken as a carbon source, a triazine ring is taken as a nitrogen source, potassium hydroxide is subjected to pore-forming activation, and high-temperature carbonization is carried out to obtain nitrogen-doped mesoporous carbon.
According to the lithium ion battery cathode material with FeP modified in situ by mesoporous carbon, nitrogen-doped mesoporous carbon is used as a growth carrier, ammonium fluoride is used as a structure directing agent, and in a hydrothermal system, urea hydrothermally generates hydroxyl to enable Fe2+FeOOH nanorods are generated in situ in a nitrogen-doped mesoporous carbon matrix and are further phosphorized and etched by sodium hypophosphite, generated tubular nano FeP grows uniformly in the nitrogen-doped mesoporous carbon matrix, the agglomeration of the nano FeP is reduced, and therefore the tubular nano FeP nanorods have higher specific surface area and rich lithium desorption sites, and a three-dimensional conductive network is formed on the surface of the tubular nano FeP due to the in-situ modification effect of the nitrogen-doped mesoporous carbon, so that electrons, transmission and migration are promoted, the actual specific capacity and rate capability are improved, a buffer space can be provided by a porous structure, the volume expansion phenomenon of the tubular nano FeP is accommodated, the tubular appearance and structural stability of the nano FeP are maintained, the pulverization and decomposition of a negative electrode material matrix are reduced, and the capacity retention rate and the cycling stability of the negative electrode material are improved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a mesoporous carbon in-situ modified FeP lithium ion battery cathode material is prepared as follows:
(1) adding dimethyl sulfoxide solvent, melamine and 5, 5-bis (bromomethyl) -2, 2-bipyridine in a mass ratio of 10:40-45 into a reaction bottle, heating to 160 ℃, reacting for 12-24h, placing in an ice water bath for cooling, adding methanol to separate out a precipitate, and washing by using dichloromethane and methanol to obtain the triazine ring group microporous polymer.
(2) Adding distilled water, triazine ring group microporous polymer with the mass ratio of 100: 150-.
(3) Adding distilled water solvent, nitrogen-doped mesoporous carbon with the mass ratio of 5-15:100:2-2.5:8-12, ferrous chloride, ammonium fluoride and urea into a reaction bottle, reacting for 6-12h at 70-90 ℃, centrifugally separating to remove the solvent, washing with distilled water and ethanol to obtain the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod.
(4) Uniformly mixing the nitrogen-doped mesoporous carbon in-situ modified FeOOH nano-rod and sodium hypophosphite in a mass ratio of 10:250-350, placing the mixture in a tube furnace, calcining for 2-3h in a nitrogen atmosphere at the calcining temperature of 300-350 ℃ to obtain the nitrogen-doped mesoporous carbon in-situ modified FeP nano-tube.
(5) Dissolving a nitrogen-doped mesoporous carbon in-situ modified FeP nanotube, conductive carbon black and polyvinylidene fluoride in an N-methyl pyrrolidone solvent in a mass ratio of 8:1:1, then coating the mixture on the surface of copper foil, drying and tabletting to obtain the mesoporous carbon in-situ modified FeP lithium ion battery cathode material.
Example 1
(1) Adding dimethyl sulfoxide solvent, melamine and 5, 5-bis (bromomethyl) -2, 2-bipyridine in a mass ratio of 10:40 into a reaction bottle, heating to 140 ℃, reacting for 12h, cooling in an ice water bath, adding methanol to separate out a precipitate, and washing with dichloromethane and methanol to obtain the triazine ring group microporous polymer.
(2) Adding distilled water, triazine ring group microporous polymer and potassium hydroxide in a mass ratio of 100:150 into a beaker, uniformly dispersing by ultrasonic, stirring for 6 hours, carrying out vacuum drying on the solution to remove the solvent, putting the mixed product into a tubular furnace, carbonizing for 2 hours in a nitrogen atmosphere at the temperature of 700 ℃, and washing the carbonized product by hydrochloric acid and distilled water to obtain the nitrogen-doped mesoporous carbon.
(3) Adding a distilled water solvent, nitrogen-doped mesoporous carbon with the mass ratio of 5:100:2:8, ferrous chloride, ammonium fluoride and urea into a reaction bottle, reacting for 6 hours at 70 ℃, centrifugally separating to remove the solvent, washing with distilled water and ethanol to obtain the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod.
(4) Uniformly mixing the nitrogen-doped mesoporous carbon in-situ modified FeOOH nano-rod and sodium hypophosphite in a mass ratio of 10:250, placing the mixture in a tube furnace, and calcining for 2 hours in a nitrogen atmosphere at the calcining temperature of 300 ℃ to obtain the nitrogen-doped mesoporous carbon in-situ modified FeP nano-tube.
(5) Dissolving a nitrogen-doped mesoporous carbon in-situ modified FeP nanotube, conductive carbon black and polyvinylidene fluoride in an N-methyl pyrrolidone solvent in a mass ratio of 8:1:1, then coating the mixture on the surface of copper foil, drying and tabletting to obtain the mesoporous carbon in-situ modified FeP lithium ion battery cathode material.
Example 2
(1) Adding dimethyl sulfoxide solvent, melamine and 5, 5-bis (bromomethyl) -2, 2-bipyridine in a mass ratio of 10:42 into a reaction bottle, heating to 160 ℃, reacting for 24 hours, placing in an ice water bath for cooling, adding methanol to separate out a precipitate, and washing with dichloromethane and methanol to obtain the triazine ring group microporous polymer.
(2) Adding distilled water, triazine ring group microporous polymer and potassium hydroxide in a mass ratio of 100:200 into a beaker, uniformly dispersing by ultrasonic, stirring for 10 hours, carrying out vacuum drying on the solution to remove the solvent, putting the mixed product into a tubular furnace, carbonizing for 3 hours in a nitrogen atmosphere at the temperature of 700 ℃, and washing the carbonized product by hydrochloric acid and distilled water to obtain the nitrogen-doped mesoporous carbon.
(3) Adding distilled water solvent, nitrogen-doped mesoporous carbon with the mass ratio of 8:100:2.1:9, ferrous chloride, ammonium fluoride and urea into a reaction bottle, reacting for 8 hours at 90 ℃, centrifugally separating to remove the solvent, washing with distilled water and ethanol to obtain the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod.
(4) Uniformly mixing the nitrogen-doped mesoporous carbon in-situ modified FeOOH nano-rod and sodium hypophosphite in a mass ratio of 10:280, placing the mixture in a tube furnace, calcining for 3 hours in a nitrogen atmosphere at the calcining temperature of 320 ℃, and obtaining the nitrogen-doped mesoporous carbon in-situ modified FeP nano-tube.
(5) Dissolving a nitrogen-doped mesoporous carbon in-situ modified FeP nanotube, conductive carbon black and polyvinylidene fluoride in an N-methyl pyrrolidone solvent in a mass ratio of 8:1:1, then coating the mixture on the surface of copper foil, drying and tabletting to obtain the mesoporous carbon in-situ modified FeP lithium ion battery cathode material.
Example 3
(1) Adding dimethyl sulfoxide solvent, melamine and 5, 5-bis (bromomethyl) -2, 2-bipyridine in a mass ratio of 10:43 into a reaction bottle, heating to 150 ℃, reacting for 18h, cooling in an ice water bath, adding methanol to separate out a precipitate, and washing with dichloromethane and methanol to obtain the triazine ring group microporous polymer.
(2) Adding distilled water, triazine ring group microporous polymer and potassium hydroxide in a mass ratio of 100:250 into a beaker, uniformly dispersing by ultrasonic, stirring for 10 hours, carrying out vacuum drying on the solution to remove the solvent, putting the mixed product into a tubular furnace, carbonizing for 2.5 hours in a nitrogen atmosphere at the temperature of 750 ℃, and washing the carbonized product by hydrochloric acid and distilled water to obtain the nitrogen-doped mesoporous carbon.
(3) Adding a distilled water solvent, nitrogen-doped mesoporous carbon with the mass ratio of 12:100:2.4:10, ferrous chloride, ammonium fluoride and urea into a reaction bottle, reacting for 10 hours at 80 ℃, centrifugally separating to remove the solvent, washing with distilled water and ethanol to obtain the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod.
(4) Uniformly mixing the nitrogen-doped mesoporous carbon in-situ modified FeOOH nano-rod and sodium hypophosphite in a mass ratio of 10:320, placing the mixture in a tube furnace, and calcining for 2.5 hours in a nitrogen atmosphere at the calcining temperature of 320 ℃ to obtain the nitrogen-doped mesoporous carbon in-situ modified FeP nano-tube.
(5) Dissolving a nitrogen-doped mesoporous carbon in-situ modified FeP nanotube, conductive carbon black and polyvinylidene fluoride in an N-methyl pyrrolidone solvent in a mass ratio of 8:1:1, then coating the mixture on the surface of copper foil, drying and tabletting to obtain the mesoporous carbon in-situ modified FeP lithium ion battery cathode material.
Example 4
(1) Adding dimethyl sulfoxide solvent, melamine and 5, 5-bis (bromomethyl) -2, 2-bipyridine in a mass ratio of 10:45 into a reaction bottle, heating to 160 ℃, reacting for 24 hours, placing in an ice water bath for cooling, adding methanol to separate out a precipitate, and washing with dichloromethane and methanol to obtain the triazine ring group microporous polymer.
(2) Adding distilled water, triazine ring group microporous polymer and potassium hydroxide in a mass ratio of 100:300 into a beaker, uniformly dispersing by ultrasonic, stirring for 12 hours, carrying out vacuum drying on the solution to remove the solvent, putting the mixed product into a tubular furnace, carbonizing for 3 hours in a nitrogen atmosphere at the temperature of 800 ℃, and washing the carbonized product by hydrochloric acid and distilled water to obtain the nitrogen-doped mesoporous carbon.
(3) Adding distilled water solvent, nitrogen-doped mesoporous carbon with the mass ratio of 15:100:2.5:12, ferrous chloride, ammonium fluoride and urea into a reaction bottle, reacting for 12 hours at 90 ℃, centrifugally separating to remove the solvent, washing with distilled water and ethanol to obtain the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod.
(4) Uniformly mixing the nitrogen-doped mesoporous carbon in-situ modified FeOOH nano-rod and sodium hypophosphite in a mass ratio of 10:350, placing the mixture in a tube furnace, calcining for 3 hours in a nitrogen atmosphere at the calcining temperature of 350 ℃, and obtaining the nitrogen-doped mesoporous carbon in-situ modified FeP nano-tube.
(5) Dissolving a nitrogen-doped mesoporous carbon in-situ modified FeP nanotube, conductive carbon black and polyvinylidene fluoride in an N-methyl pyrrolidone solvent in a mass ratio of 8:1:1, then coating the mixture on the surface of copper foil, drying and tabletting to obtain the mesoporous carbon in-situ modified FeP lithium ion battery cathode material.
Comparative example 1
(1) Adding dimethyl sulfoxide solvent, melamine and 5, 5-bis (bromomethyl) -2, 2-bipyridine in a mass ratio of 10:42 into a reaction bottle, heating to 150 ℃, reacting for 24 hours, placing in an ice water bath for cooling, adding methanol to separate out a precipitate, and washing with dichloromethane and methanol to obtain the triazine ring group microporous polymer.
(2) Adding distilled water, triazine ring group microporous polymer and potassium hydroxide in a mass ratio of 1:1 into a beaker, uniformly dispersing by ultrasonic, stirring for 6 hours, carrying out vacuum drying on the solution to remove the solvent, putting the mixed product into a tubular furnace, carbonizing for 3 hours in a nitrogen atmosphere at the temperature of 750 ℃, and washing the carbonized product by hydrochloric acid and distilled water to obtain the nitrogen-doped mesoporous carbon.
(3) Adding distilled water solvent, nitrogen-doped mesoporous carbon with the mass ratio of 2:100:1.8:6, ferrous chloride, ammonium fluoride and urea into a reaction bottle, reacting for 12 hours at 80 ℃, centrifugally separating to remove the solvent, washing with distilled water and ethanol to obtain the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod.
(4) Uniformly mixing the nitrogen-doped mesoporous carbon in-situ modified FeOOH nano-rod and sodium hypophosphite in a mass ratio of 10:220, placing the mixture in a tube furnace, and calcining for 2.5 hours in a nitrogen atmosphere at the calcining temperature of 320 ℃ to obtain the nitrogen-doped mesoporous carbon in-situ modified FeP nano-tube.
(5) Dissolving a nitrogen-doped mesoporous carbon in-situ modified FeP nanotube, conductive carbon black and polyvinylidene fluoride in an N-methyl pyrrolidone solvent in a mass ratio of 8:1:1, then coating the mixture on the surface of copper foil, drying and tabletting to obtain the mesoporous carbon in-situ modified FeP lithium ion battery cathode material.
Comparative example 2
(1) Adding dimethyl sulfoxide solvent, melamine and 5, 5-bis (bromomethyl) -2, 2-bipyridine in a mass ratio of 10:47 into a reaction bottle, heating to 150 ℃, reacting for 18h, cooling in an ice water bath, adding methanol to separate out a precipitate, and washing with dichloromethane and methanol to obtain the triazine ring group microporous polymer.
(2) Adding distilled water, triazine ring group microporous polymer and potassium hydroxide in a mass ratio of 100:350 into a beaker, uniformly dispersing by ultrasonic, stirring for 8 hours, carrying out vacuum drying on the solution to remove the solvent, putting the mixed product into a tubular furnace, carbonizing for 2.5 hours in a nitrogen atmosphere at the temperature of 750 ℃, and washing the carbonized product by hydrochloric acid and distilled water to obtain the nitrogen-doped mesoporous carbon.
(3) Adding distilled water solvent, nitrogen-doped mesoporous carbon with the mass ratio of 18:100:2.7:14, ferrous chloride, ammonium fluoride and urea into a reaction bottle, reacting for 12 hours at 70 ℃, centrifugally separating to remove the solvent, washing with distilled water and ethanol to obtain the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod.
(4) Uniformly mixing the nitrogen-doped mesoporous carbon in-situ modified FeOOH nano-rod and sodium hypophosphite in a mass ratio of 10:280, placing the mixture in a tube furnace, and calcining for 3 hours in a nitrogen atmosphere at the calcining temperature of 300 ℃ to obtain the nitrogen-doped mesoporous carbon in-situ modified FeP nano-tube.
(5) Dissolving a nitrogen-doped mesoporous carbon in-situ modified FeP nanotube, conductive carbon black and polyvinylidene fluoride in an N-methyl pyrrolidone solvent in a mass ratio of 8:1:1, then coating the mixture on the surface of copper foil, drying and tabletting to obtain the mesoporous carbon in-situ modified FeP lithium ion battery cathode material.
In-situ modification of FeP by mesoporous carbon, lithium ion battery cathode material, lithium sheet anode, polypropylene porous diaphragm and 1mol/L LiPF6The electrolyte of the ethylene carbonate and the dimethyl carbonate is assembled into a button cell, and the electrochemical performance is tested in a NanoCycler cell testing system.
Figure BDA0002915775630000081
Figure BDA0002915775630000091

Claims (6)

1. A mesoporous carbon in-situ modified FeP lithium ion battery cathode material is characterized in that: the preparation method of the mesoporous carbon in-situ modified FeP lithium ion battery cathode material is as follows:
(1) adding dimethyl sulfoxide solvent, melamine and 5, 5-bis (bromomethyl) -2, 2-bipyridine in a mass ratio of 10:40-45 into a reaction bottle, heating to 160 ℃, reacting for 12-24h, placing in an ice water bath for cooling, adding methanol to separate out a precipitate, and washing by using dichloromethane and methanol to obtain the triazine ring group microporous polymer.
(2) Adding distilled water, triazine ring group microporous polymer and potassium hydroxide into a beaker, uniformly dispersing by ultrasonic, stirring for 6-12h, vacuum drying the solution to remove the solvent, putting the mixed product into a tube furnace for carbonization, and washing the carbonized product by hydrochloric acid and distilled water to obtain the nitrogen-doped mesoporous carbon.
(3) Adding distilled water solvent, nitrogen-doped mesoporous carbon, ferrous chloride, ammonium fluoride and urea into a reaction bottle, reacting for 6-12h at 70-90 ℃, centrifugally separating to remove the solvent, washing with distilled water and ethanol, and obtaining the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod.
(4) And uniformly mixing the nitrogen-doped mesoporous carbon in-situ modified FeOOH nano-rod and sodium hypophosphite, and then placing the mixture into a tubular furnace for calcining to obtain the nitrogen-doped mesoporous carbon in-situ modified FeP nano-tube.
(5) Dissolving a nitrogen-doped mesoporous carbon in-situ modified FeP nanotube, conductive carbon black and polyvinylidene fluoride in an N-methyl pyrrolidone solvent in a mass ratio of 8:1:1, then coating the mixture on the surface of copper foil, drying and tabletting to obtain the mesoporous carbon in-situ modified FeP lithium ion battery cathode material.
2. The mesoporous carbon in-situ modified FeP lithium ion battery anode material of claim 1, which is characterized in that: the mass ratio of the triazine ring group microporous polymer to the potassium hydroxide in the step (2) is 100: 150-300.
3. The mesoporous carbon in-situ modified FeP lithium ion battery anode material of claim 1, which is characterized in that: and (3) in the step (2), the carbonization is carried out in a nitrogen atmosphere, the carbonization temperature is 700-800 ℃, and the carbonization time is 2-3 h.
4. The mesoporous carbon in-situ modified FeP lithium ion battery anode material of claim 1, which is characterized in that: in the step (3), the mass ratio of the nitrogen-doped mesoporous carbon to the ferrous chloride to the ammonium fluoride to the urea is 5-15:100:2-2.5: 8-12.
5. The mesoporous carbon in-situ modified FeP lithium ion battery anode material of claim 1, which is characterized in that: the mass ratio of the nitrogen-doped mesoporous carbon in-situ modified FeOOH nanorod to the sodium hypophosphite in the step (4) is 10: 250-350.
6. The mesoporous carbon in-situ modified FeP lithium ion battery anode material of claim 1, which is characterized in that: the calcination in the step (4) is carried out in a nitrogen atmosphere, the calcination temperature is 300-350 ℃, and the calcination time is 2-3 h.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115512977A (en) * 2022-10-14 2022-12-23 重庆文理学院 FeP hollow nanorod for supercapacitor and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115512977A (en) * 2022-10-14 2022-12-23 重庆文理学院 FeP hollow nanorod for supercapacitor and preparation method thereof
CN115512977B (en) * 2022-10-14 2023-06-02 重庆文理学院 FeP hollow nanorod for super capacitor and preparation method thereof

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