CN112420991A - Doping method of novel carbon material and application thereof - Google Patents

Doping method of novel carbon material and application thereof Download PDF

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CN112420991A
CN112420991A CN202010848182.3A CN202010848182A CN112420991A CN 112420991 A CN112420991 A CN 112420991A CN 202010848182 A CN202010848182 A CN 202010848182A CN 112420991 A CN112420991 A CN 112420991A
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carbon material
doping
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microwave
doped carbon
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杨宇
彭粤海
杨卓鸿
刘飞
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South China Agricultural University
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 belongs to the technical field of carbon materials, and particularly relates to a novel carbon material doping method, which comprises the following steps: mixing the novel carbon material, the doping compound and the solvent, and carrying out microwave reaction for 3-8h at 60-240 ℃ in an inert gas atmosphere to obtain the novel microwave doped carbon material. The doping method based on the novel carbon material provided by the invention has the advantages of low reaction temperature, high doping rate, simple process and high yield, and is suitable for industrial production.

Description

Doping method of novel carbon material and application thereof
Technical Field
The invention belongs to the technical field of novel carbon materials, and particularly relates to a doping method of a novel carbon material and application thereof.
Background
With the rise of novel carbon materials such as graphene and carbon nanotubes, the processing technology of the carbon materials is continuously improved, and the heteroatom doping of the carbon materials becomes one of important branches. However, since the intrinsic band gap of some carbon materials is zero, the conductivity of the carbon materials cannot be completely controlled like that of conventional semiconductors, and the carbon materials are inert on the surface and not favorable for combination with other materials. Therefore, the main carriers can be changed into an electron type or a cavity type by adopting a doping method for the novel carbon material, so that the band gap of the novel carbon material is opened, the conductivity, the stability and the surface chemical activity of the carbon material are improved, the energy density of the carbon material is favorably improved, and the novel carbon material is diversified in use.
Patent CN106348277A discloses a method for preparing heteroatom doped carbon material, comprising the following steps: and placing the carbon material in a plasma reactor, introducing gas, and carrying out plasma treatment under the condition that the discharge power is 20-1000W, so that atoms in the gas are doped into the carbon material, thereby obtaining the heteroatom-doped carbon material.
Patent CN104803371A discloses a graphene doping method, which includes: preparing doping liquid containing doping elements; putting a target substrate into a closed container, atomizing the doping liquid, and introducing the atomized doping liquid into the closed container to enable the doping liquid to be fully paved on the surface of the substrate to generate a first doping layer; taking out the substrate with the doping liquid for curing treatment; a layer of graphene is grown on the first doped layer.
The doped porous carbon material prepared by the prior art has the problems of complex process, high reaction temperature, inaccurate control of heating program, low doping rate and the like.
Disclosure of Invention
The invention aims to provide a doping method of a novel carbon material and application thereof, so as to solve one or more of the problems.
According to one aspect of the present invention, there is provided a method for doping a novel carbon material, comprising the steps of:
mixing the novel carbon material, the doping compound and the solvent, and carrying out microwave reaction for 3-8h at 60-240 ℃ in an inert gas atmosphere to obtain the novel microwave doped carbon material.
In some embodiments, the mass ratio of the novel carbon material, the doping compound and the solvent is 1 (1-5) to 1-5.
In some embodiments, the steps further comprise: and (3) carrying out vacuum filtration, cleaning the reaction solvent in the novel microwave doped carbon material by using deionized water to obtain novel microwave doped carbon material slurry, and freeze-drying the novel microwave doped carbon material slurry to obtain novel microwave doped carbon material powder.
In some embodiments, the microwave reaction may be performed at a high pressure of 300-. Thereby, the doping rate can be improved.
In some embodiments, the dried novel carbon material, doping compound, solvent are placed in a microwave reactor and stirred for 0.5-2 h.
In some embodiments, the microwave reaction is carried out in a microwave reactor, the microwave reactor being one of a microwave closed reactor, a microwave atmospheric reactor, a microwave continuous reactor.
In some embodiments, the dopant compound is one of a doped nitrogen-containing compound, a doped fluorine-containing compound, a doped boron-containing compound, a doped bromine-containing compound, wherein,
the nitrogen-containing compound can be one of amino, pyrrole and pyridine structure nitrogen sources such as urea, melamine, polypyrrole, polyaniline, hydrazine, hexamethylenetetramine, dihydroamine and the like;
the fluorine-containing compound can be 10-70% of hydrofluoric acid and BF3Diethyl etherate, diethylaminosulfur trifluoride (DAST), hexafluorophosphoric acid (HPF)6) One of fluorine sources containing fluorine bonds;
the boron-containing compound may be boric acid;
the bromine-containing compound may be one of bromine chloride, bromine fluoride, bromine trifluoride, bromine pentafluoride, and bromine iodide.
In some embodiments, the solvent is absolute ethanol or acetonitrile.
In some embodiments, the inert gas may be one or more of argon, nitrogen, hydrogen.
In some embodiments, the reaction sequence for the microwave reaction is: keeping the temperature at 40-60 ℃ for 20-40min, then heating to 140 ℃ at 100-. This reduces side reactions and improves the doping rate.
The invention carries out the doping of novel carbon materials by using the microwave technology, comprises the carbon materials such as graphene, carbon nano tubes, carbon fibers and the like, reduces the occurrence of side reactions by accurately controlling the heating program, has the advantages of low reaction temperature, short reaction time, high doping rate, simple process, high yield and the like, and is suitable for mass production.
Compared with the traditional doping methods, such as a vapor phase growth method, a ball milling method, a plasma method, a hydrothermal method and the like, the microwave doping method has the following advantages:
(1) the reaction temperature is low, the reaction time is greatly shortened, because the working principle of the microwave reaction generator is that reactant molecules are enabled to move violently through microwaves, and the microwave field acts on Lorentz force of ions and polar molecules to enable relative movement among the particles to have particularity, so that less temperature and time for reaction can be used, energy consumption is greatly reduced, and production efficiency is improved.
(2) The method has the advantages that the doping rate is high, the previous doping mode is completed under atmospheric pressure, and the doped carbon material with the doping rate exceeding 15% is difficult to produce, so that the method can reduce the reaction potential barrier and greatly improve the reaction rate under the high-pressure environment, reduce the atom spacing and change the atom bonding and stacking mode and the electronic structure, thereby obtaining higher doping rate; the generation of side reactions is reduced by precise control of the reaction program.
(3) The method has the advantages that the process is simple, the yield can reach 80-95%, the vapor deposition method and the plasma method need harsh preparation conditions, the complexity of the process determines the cost and the efficiency of actual production, and the novel microwave-based doped carbon material with high doping rate can be obtained by simple operation.
According to another aspect of the present invention, there is provided a novel microwave doped carbon material obtained by the above preparation method. The novel microwave doped carbon material has rich hole structures, large specific surface area and good conductivity, provides a rapid channel for ion electron transmission, has catalytic effect on electrode reaction, and can adsorb intermediate products which are not beneficial to electrode reaction, such as lithium polysulfide and the like. An energy storage device made of the novel microwave-doped porous carbon material, such as a lithium-sulfur battery, has good cycle performance, effective capacity and rate performance, and a super capacitor has excellent performance of quick charging and quick discharging.
According to another aspect of the present invention, a method for preparing a lithium ion battery pole piece is provided, which comprises the following steps:
grinding and mixing the novel microwave-based doped carbon material obtained by the preparation method with an active substance, a conductive agent, a binder and a solvent, and then performing ultrasonic treatment to obtain uniformly dispersed pole piece slurry;
and cutting the copper-plated carbon cloth into pole pieces, soaking the pole pieces in the slurry, taking out and drying to obtain the lithium ion battery pole pieces.
In some embodiments, the post-soaking drying step of the pole piece is as follows: taking out the pole piece soaked in the slurry for 5-20min, and drying in a vacuum drying oven at 50-150 deg.C for 5-12 h.
In some embodiments, the ultrasound time period is 1-2 h.
In some embodiments, sulfur, silicon, phosphorus, graphite, and the like can be used as the active material of the lithium battery pole piece material.
In some embodiments, the binder is one or more of polyacrylic acid (PAA), polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), and other common binders for lithium ion batteries.
In some embodiments, the conductive additive is one or more of multi-walled carbon nanotubes, single-walled carbon nanotubes, Super P, ketjen black, and the like.
In some embodiments, the solvent is one of water, ethanol, N-methylpyrrolidone.
Drawings
FIG. 1 is a graph showing the distribution of fluorine in hemp bio-based fluorine microwave doped carbon material powder in example 1.
Fig. 2 is a graph of the cycle curve and coulombic efficiency of the lithium sulfur battery in example 1.
Fig. 3 is a rate performance graph of the lithium sulfur battery in example 1.
FIG. 4 is a graph showing the distribution of nitrogen in hemp bio-based nitrogen microwave doped carbon material powder in example 2.
Fig. 5 is a cyclic voltammogram of the supercapacitor in example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Unless otherwise specified, the following chemicals are commercially available.
The results of comparing the component contents of the doped carbon material obtained by the microwave doping method of the present invention with those of the doped carbon material obtained by the conventional doping method are shown in table 1, and it can be seen from the comparison in table 1 that the doping rate of the doped carbon material obtained by the microwave doping method of the present invention is higher than that of the conventional art.
TABLE 1 comparison of the component ratios of the doped products of different doping methods
Figure BDA0002643433010000041
Example 1
The preparation method of the novel fluorine microwave doped carbon material powder comprises the following steps:
(1) drying the novel carbon material in an oven to remove water;
(2) putting the dried novel carbon material and 40% hydrofluoric acid into a microwave reactor together, stirring, and introducing inert gas N2Carrying out microwave reaction for 7h at 120 ℃ to obtain a novel fluorine microwave doped carbon material solution;
(3) vacuum filtration is adopted, and deionized water is used for cleaning the solvent in the novel fluorine microwave doped carbon material solution to obtain novel fluorine microwave doped carbon material slurry;
(4) and (3) freeze-drying the novel fluorine microwave doped carbon material slurry to obtain novel fluorine microwave doped carbon material powder.
The yield of the novel fluorine microwave doped carbon material powder obtained in this example is 90%, the content of fluorine element is scanned by EDS test to determine the doping amount of fluorine, the scanning result is shown in fig. 1, and the doping amount of fluorine measured by the instrument is 15%. The novel fluorine microwave doped carbon material powder obtained in the embodiment is used for preparing a sulfur anode of a lithium-sulfur battery, and the specific steps are as follows:
1) mixing the novel fluorine microwave doped carbon material with a conductive agent and elemental sulfur in a mass ratio of 1:1:2, grinding for 1h, and filling into a polytetrafluoroethylene reaction kettle lining;
2) filling the reaction kettle liner into a glove box, locking, discharging air in the reaction kettle, and preventing the reaction of moisture and oxygen in the air;
3) heating the reaction kettle for 12 hours at 160 ℃ under a vacuum condition to obtain a sulfur-carbon compound containing the novel microwave doped carbon material;
4) grinding and mixing a sulfur-carbon compound containing the novel fluorine microwave doped carbon material with an active substance, a binder and a solvent, and performing ultrasonic treatment for 1h to obtain uniformly dispersed anode slurry;
5) and cutting the copper-plated carbon cloth into pole pieces, soaking the pole pieces in the positive electrode slurry for 5min, and then putting the pole pieces into a vacuum drying oven to dry for 8h at the temperature of 60 ℃ to obtain the positive pole pieces.
The positive electrode plate prepared in example 1 was used in a lithium sulfur battery, and the cycle test and the rate test were performed on the lithium sulfur battery, and the test results are shown in fig. 2 and 3.
It can be seen from the figure that the novel fluorine microwave doped carbon material used as the sulfur positive electrode of the lithium sulfur battery has good reversible capacity and rate performance, because fluorine atoms with extremely high electronegativity are introduced, defects can be formed on the surface, so that the conductivity and the energy density are improved, the chemical reaction activity is increased, and the wettability is also improved.
Example 2
The preparation method of the novel nitrogen microwave doped carbon material powder comprises the following preparation methods:
(1) drying the novel carbon material in an oven to remove water;
(2) mixing the dried novel carbon material and urea according to the mass ratio of 4:1, putting the mixture into a microwave reactor, stirring, introducing inert gas, and carrying out microwave reaction for 7 hours at 120 ℃ to obtain a novel nitrogen microwave doped carbon material solution;
(3) vacuum filtration is adopted, and deionized water is used for cleaning a solvent in the novel nitrogen microwave doped carbon material solution to obtain novel nitrogen microwave doped carbon material slurry;
(4) and (3) freeze-drying the novel nitrogen microwave doped carbon material slurry to obtain the novel nitrogen microwave doped carbon material powder.
The yield of the novel nitrogen microwave doped carbon material powder obtained in this example was 92%, the content of nitrogen element was scanned by EDS test to determine the doping amount of nitrogen, the scanning result is shown in fig. 4, and the doping amount of nitrogen measured by the instrument was 11%. The novel nitrogen microwave doped carbon material powder prepared in the embodiment 2 is used for preparing a sulfur positive electrode of a lithium-sulfur battery, and the specific steps are as follows:
1) mixing the novel microwave doped carbon material, a conductive agent and elemental sulfur in a mass ratio of 1:1:2, grinding for 1h, and filling into a polytetrafluoroethylene reaction kettle lining;
2) filling the reaction kettle liner into a glove box, locking, discharging air in the reaction kettle, and preventing the reaction of moisture and oxygen in the air;
3) heating the reaction kettle at 160 ℃ for 12h under a vacuum condition to obtain a sulfur-carbon compound containing the novel doped carbon material;
4) grinding and mixing a sulfur-carbon composite containing the novel microwave doped carbon material with an active substance, a binder and a solvent, and performing ultrasonic treatment for 1h to obtain uniformly dispersed anode slurry;
5) and cutting the copper-plated carbon cloth into pole pieces, soaking the pole pieces in the positive electrode slurry for 5min, and then putting the pole pieces into a vacuum drying oven to dry for 8h at the temperature of 60 ℃ to obtain the positive pole pieces.
The positive electrode plate obtained in example 2 was used for a supercapacitor cell, and cyclic voltammetry tests were performed, and the test results are shown in fig. 5.
As can be seen from the figure, the ultra-large specific surface area provides a high electric double layer capacitance capacity for the supercapacitor using the novel nitrogen microwave doped carbon material. The doping can generate pseudo-capacitance capacity on one hand, and can promote electron transfer on the other hand, and the transfer resistance of charges in the electrode under high current density is reduced, so that the capacitance performance is improved, and the super capacitor has great application potential.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

Claims (10)

1. The doping method of the novel carbon material is characterized by comprising the following steps of:
mixing the novel carbon material, the doping compound and the solvent, and carrying out microwave reaction for 3-8h at 60-240 ℃ in an inert gas atmosphere to obtain the novel microwave doped carbon material.
2. The doping method according to claim 1, characterized by further comprising the steps of:
and (3) carrying out vacuum filtration, cleaning the reaction solvent in the novel microwave doped carbon material by using deionized water to obtain novel microwave doped carbon material slurry, and freeze-drying the novel microwave doped carbon material slurry to obtain novel microwave doped carbon material powder.
3. The doping method according to claim 1 or 2, wherein the reaction procedure of the microwave reaction is as follows: keeping the temperature at 40-60 ℃ for 20-40min, then heating to 140 ℃ at 100-.
4. The doping method according to claim 3, wherein the doping compound is one of a nitrogen-containing doping compound, a fluorine-containing doping compound, a boron-containing doping compound, and a bromine-containing doping compound.
5. The doping method according to claim 4, wherein the nitrogen-containing compound is one of urea, melamine, polypyrrole, polyaniline, hydrazine, hexamethylenetetramine, and diamine;
the fluorine-containing compound is 10-70% of one of hydrofluoric acid, BF3 diethyl ether, diethylaminosulfur trifluoride and hexafluorophosphoric acid;
the boron-containing compound is boric acid;
the bromine-containing compound is one of bromine chloride, bromine fluoride, bromine trifluoride, bromine pentafluoride and bromine iodide.
6. A novel microwave doped carbon material obtained by the doping method of claim 5.
7. A preparation method of a lithium battery pole piece comprises the following steps:
grinding and mixing the novel microwave doped carbon material as claimed in claim 6 with an active substance, a conductive agent, a binder and a solvent, and then performing ultrasonic treatment to obtain uniformly dispersed slurry;
and cutting the copper-plated carbon cloth into pole pieces, soaking the pole pieces in the slurry, taking out and drying to obtain the pole pieces.
8. A pole piece obtained by the preparation method of claim 7.
9. Use of the pole piece of claim 8 in an energy storage device.
10. Use according to claim 9, wherein the energy storage device is a lithium battery or a super capacitor battery.
CN202010848182.3A 2020-08-21 2020-08-21 Doping method of novel carbon material and application thereof Pending CN112420991A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103288069A (en) * 2013-05-10 2013-09-11 西北工业大学 Method for preparing fluorinated graphene through microwave hydrothermal method
WO2015050353A1 (en) * 2013-10-01 2015-04-09 코닝정밀소재 주식회사 Method for fabricating graphene flake for electrode material of electric double-layer capacitor, graphene flake fabricated by same, and electric double-layer capacitor comprising same as electrode material
CN106024413A (en) * 2016-07-20 2016-10-12 扬州大学 Super capacitor device made of graphitized nitrogen doped porous nanometer sheet carbon material
CN109251031A (en) * 2018-11-23 2019-01-22 福建农林大学 A kind of method of microwave assisted aqueous extraction hot preparation for the nitrogen co-doped porous carbon material of boron of supercapacitor
CN110136990A (en) * 2019-05-29 2019-08-16 信阳学院 A kind of N doping carbon-based electrode material and preparation method thereof
CN111007118A (en) * 2018-02-06 2020-04-14 红河学院 Boron-sulfur co-doped graphene, preparation method and application thereof in preparing AFB1Electrochemical sensor of

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103288069A (en) * 2013-05-10 2013-09-11 西北工业大学 Method for preparing fluorinated graphene through microwave hydrothermal method
WO2015050353A1 (en) * 2013-10-01 2015-04-09 코닝정밀소재 주식회사 Method for fabricating graphene flake for electrode material of electric double-layer capacitor, graphene flake fabricated by same, and electric double-layer capacitor comprising same as electrode material
CN106024413A (en) * 2016-07-20 2016-10-12 扬州大学 Super capacitor device made of graphitized nitrogen doped porous nanometer sheet carbon material
CN111007118A (en) * 2018-02-06 2020-04-14 红河学院 Boron-sulfur co-doped graphene, preparation method and application thereof in preparing AFB1Electrochemical sensor of
CN109251031A (en) * 2018-11-23 2019-01-22 福建农林大学 A kind of method of microwave assisted aqueous extraction hot preparation for the nitrogen co-doped porous carbon material of boron of supercapacitor
CN110136990A (en) * 2019-05-29 2019-08-16 信阳学院 A kind of N doping carbon-based electrode material and preparation method thereof

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Application publication date: 20210226