CN109686579B - Porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon and energy storage application thereof - Google Patents

Porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon and energy storage application thereof Download PDF

Info

Publication number
CN109686579B
CN109686579B CN201811562875.5A CN201811562875A CN109686579B CN 109686579 B CN109686579 B CN 109686579B CN 201811562875 A CN201811562875 A CN 201811562875A CN 109686579 B CN109686579 B CN 109686579B
Authority
CN
China
Prior art keywords
porous carbon
graphite
carbon hybrid
polyhalogenated
hybrid material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811562875.5A
Other languages
Chinese (zh)
Other versions
CN109686579A (en
Inventor
杨应奎
何承恩
邱胜强
刘倩
蒋玉林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South Central Minzu University
Original Assignee
South Central University for Nationalities
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South Central University for Nationalities filed Critical South Central University for Nationalities
Priority to CN201811562875.5A priority Critical patent/CN109686579B/en
Publication of CN109686579A publication Critical patent/CN109686579A/en
Application granted granted Critical
Publication of CN109686579B publication Critical patent/CN109686579B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention provides a porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon and an energy storage application thereof, and the preparation method is characterized by comprising the following steps: uniformly mixing polyhalogenated hydrocarbon, a graphite material, a dehalogenation reagent and a solvent, carrying out ball milling reaction at room temperature to convert the polyhalogenated hydrocarbon into porous carbon, assisting graphite stripping to generate graphene, and dispersing graphene sheets; and then, activating at high temperature under inert atmosphere, washing and drying to obtain the porous carbon hybrid material. The porous carbon hybrid material can be used as an electrode active material with excellent performance in the field of energy storage, such as super capacitors or metal ion batteries; the functional material can also be used as a corresponding functional material to be applied to multiple fields such as catalysis, adsorption and the like; thereby effectively relieving the environmental pollution caused by the polyhalogenated hydrocarbon and improving the added value of the white pollutant.

Description

Porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon and energy storage application thereof
Technical Field
The invention belongs to the field of porous carbon materials, and particularly relates to a porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon and an energy storage application thereof.
Background
The polymer plastic plays an important role in products in daily life, such as plastic packaging bags, agricultural mulching films, disposable tableware, plastic bottles and the like. However, the polymer plastic products are difficult to degrade and are discarded as solid waste, thereby causing serious environmental pollution. In particular, polyhalogenated hydrocarbons have very good chemical and thermal stability, are resistant to biological or natural degradation, may require thousands of years to completely decompose without special treatment, and burning halogen-containing polymers will release Cl2And toxic byproducts such as HCl and HCl cause great pressure on the environment. In addition, the increasing energy crisis also forces people to increase the utilization of resources. The research and development of energy storage devices such as super capacitors and metal ion batteries (such as lithium, sodium and potassium ion batteries) are one of effective ways to solve the environmental and energy crisis. The electrode active material, which is used as the core part of the energy storage device, is the key for the conversion between chemical energy and electric energy. Carbon materials are commonly used as electrode materials of energy storage devices, wherein the cost of the activated carbon is low, and the activated carbon has a high specific surface area, so that the activated carbon is most widely applied. Currently, the main raw materials of activated carbon are organic materials rich in carbon, such as coal, wood, husks, coconut shells, walnut shells, apricot shells, jujube shells and the like. These carbonaceous materials are converted into activated carbon by pyrolysis at high temperature and pressure, forming huge surface areas and complex pore structures. However, activated carbon generally has conductivity and a large resistance in an electrolyte. Graphite is a common negative electrode material of lithium ion batteries, but the process of soaking the electrode with electrolyte is slow, resulting in low power density.
Carbon nanotubes and graphene are ideal electrode active materials for supercapacitors and metal-ion batteries. Carbon nanotubes have excellent electrical conductivity and good mechanical properties, but have a relatively low specific surface area, are easily entangled, and are difficult to disperse. The graphene has excellent conductivity and ultrahigh theoretical specific surface area (2600 m)2/g) has good application prospect. Currently, methods for preparing graphene include graphite oxide reduction, SiC decomposition, Chemical Vapor Deposition (CVD), and mechanical exfoliationAnd the like. The oxidation-reduction method is the most used method at present, but the method uses strong acid such as sulfuric acid, nitric acid, potassium permanganate and the like, strong oxidant, hydrazine hydrate and other toxic reducing agents, so that environmental pollution is caused, and in addition, the obtained graphene is not easy to be completely reduced. Graphene prepared by a chemical vapor deposition method, a SiC decomposition method and the like has the characteristics of large area and high quality, but the cost is higher at the present stage, and the process conditions need to be further improved. Mechanical stripping of graphite is one of the most potential common methods for preparing graphene at low cost, but the stripping efficiency is low at present mainly because graphene sheets are easy to undergo surface-to-surface self-stacking to form aggregates, which affects the performance of the graphene sheets. How to prevent the self-stacking of graphene sheets in the process of mechanically stripping graphite is a key for improving the mechanical stripping efficiency and the graphene quality.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon, which can be used as an electrode active material for a supercapacitor and a metal ion battery, and can be used for energy storage applications, and which can obtain a porous carbon hybrid material having excellent properties.
In order to achieve the purpose, the invention adopts the following scheme:
< preparation method >
The invention provides a method for preparing a porous carbon hybrid material based on graphite and polyhalogenated hydrocarbon, which is characterized by comprising the following steps: uniformly mixing the polyhalogenated hydrocarbon, the graphite material, the dehalogenation reagent and the solvent, performing ball milling reaction at room temperature, and then performing high-temperature activation, washing and drying in an inert atmosphere to obtain the porous carbon hybrid material.
Preferably, the method for preparing the porous carbon hybrid material based on graphite and polyhalogenated hydrocarbon provided by the invention can also have the following characteristics: the polyhalogenated hydrocarbon is any one of halogen-containing polymers such as polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene and the like.
Preferably, the method for preparing the porous carbon hybrid material based on graphite and polyhalogenated hydrocarbon provided by the invention can also have the following characteristics: the graphite material is any one of natural graphite, flake graphite, graphite oxide and expanded graphite, and flake graphite is the best.
Preferably, the method for preparing the porous carbon hybrid material based on graphite and polyhalogenated hydrocarbon provided by the invention can also have the following characteristics: the dehalogenation reagent is at least one of potassium hydroxide, sodium ethoxide, zinc powder and lithium hydroxide, and preferably sodium ethoxide.
Preferably, the method for preparing the porous carbon hybrid material based on graphite and polyhalogenated hydrocarbon provided by the invention can also have the following characteristics: the solvent is at least one of water, ethanol, acetone, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, dichloromethane, tetrahydrofuran, ethylene glycol and toluene, and the detergent is at least one of deionized water, dilute hydrochloric acid, ethanol and acetone.
Preferably, the method for preparing the porous carbon hybrid material based on graphite and polyhalogenated hydrocarbon provided by the invention can also have the following characteristics: the ball milling stripping rate is 50-600 rpm, and the time is 0.5-60 h; the ball material ratio is 100-500: 1.
preferably, the method for preparing the porous carbon hybrid material based on graphite and polyhalogenated hydrocarbon provided by the invention can also have the following characteristics: the activation temperature is 400-1000 ℃, the best is 600 ℃, and the activation time is 0.5-12h, the best is 6 h.
Preferably, the method for preparing the porous carbon hybrid material based on graphite and polyhalogenated hydrocarbon provided by the invention can also have the following characteristics: the inert atmosphere is nitrogen or argon.
Preferably, the method for preparing the porous carbon hybrid material based on graphite and polyhalogenated hydrocarbon provided by the invention can also have the following characteristics: the drying temperature is 50-150 ℃, and the drying time is 6-24 h.
< porous carbon hybrid Material >
Further, the present invention also provides a porous carbon hybrid material produced by the method described in the above < production method >.
< application >
Further, the present invention also provides an application method of the porous carbon hybrid material as an energy storage material (e.g., an electrode active material).
Action and Effect of the invention
According to the preparation method, the polyhalogenated hydrocarbon, the graphite material, the dehalogenation reagent and the solvent are uniformly mixed, the ball milling reaction is carried out at room temperature, the efficient conversion of the polyhalogenated hydrocarbon to porous carbon is synchronously realized (dehalogenation generates a porous carbon precursor), the graphite is assisted to be stripped to generate graphene, meanwhile, graphene sheet layers are dispersed, and finally, the porous carbon hybrid material with large specific surface area and high conductivity is obtained. The porous carbon hybrid material can be used as an electrode active material with excellent performance in the field of energy storage, such as super capacitors or metal ion batteries; the functional material can also be used as a corresponding functional material to be applied to multiple fields such as catalysis, adsorption and the like; thereby effectively relieving the environmental pollution caused by the polyhalogenated hydrocarbon and improving the added value of the white pollutant.
Drawings
FIG. 1 is a transmission electron micrograph of a porous carbon hybrid material prepared in example one;
FIG. 2 is a cyclic voltammogram of the porous carbon hybrid supercapacitor prepared in the first example;
FIG. 3 is a constant current charging and discharging curve diagram of the porous carbon hybrid material supercapacitor prepared in the first embodiment;
FIG. 4 is a cycle life curve of the porous carbon hybrid supercapacitor prepared in the first example;
FIG. 5 is a graph of rate performance of the porous carbon hybrid material lithium ion battery prepared in example II;
fig. 6 is a cycle life graph of the porous carbon hybrid material lithium ion battery prepared in example two.
Detailed Description
The following detailed description of specific embodiments of the present invention for preparing porous carbon hybrid materials based on graphite and polyhalogenated hydrocarbons and energy storage applications thereof will be described in detail with reference to the accompanying drawings.
< example one >
The preparation method comprises the following steps:
10g of polyvinyl chloride powder is uniformly mixed with 20ml of NMP, 30g of sodium hydroxide and 0.5g of expanded graphite are added, the mixture is uniformly mixed and then transferred into a ball milling tank, and the ball milling reaction is carried out for 6 hours at the rotating speed of 200rpm and the ball-material ratio (100: 1). And after the reaction is finished, taking out the mixture, drying, transferring the mixture to a tubular furnace, carbonizing the mixture for 2h at 500 ℃ under argon atmosphere, washing the mixture with 1M dilute hydrochloric acid, repeatedly carrying out suction filtration and washing with water and ethanol, and drying the product for 16h at 80 ℃ in vacuum to obtain the porous carbon hybrid material.
And (3) performance characterization:
the obtained porous carbon hybrid material is shot by a transmission electron microscope, the appearance of the porous carbon hybrid material is shown in figure 1, the porous carbon hybrid material is in a porous state, the porous carbon derived from polyvinyl chloride is coated on a graphene sheet layer, and the graphene can be judged to be a single layer or a few layers, so that the polyvinyl chloride can effectively promote graphite stripping and prevent the graphene sheet layer from being re-aggregated.
The obtained porous carbon hybrid material is further used as an electrode and assembled into a super capacitor for testing, as shown in fig. 2, CV curves of the material under a scanning speed of 5-100 mV/s are approximate to rectangles, and typical double-layer capacitance characteristics are reflected. And the specific capacitance at 5mV/s reaches 230F/g, and the specific capacity when the scanning speed is increased to 100mV/s still keeps 126F/g; as shown in fig. 3, the specific capacitance of the porous carbon hybrid material electrode at 0.5A/g reaches 236F/g, and the specific capacity is still maintained at 144F/g when the charge-discharge current density is increased to 20A/g, i.e., the capacity retention rate is 54% after the current density is increased by 40 times, and the capacity retention rate is 61% after the scanning rate is increased by 20 times. In addition, as shown in fig. 4, the specific capacity of the porous carbon hybrid material is basically stable and unchanged after 10000 cycles of continuous charging and discharging, and excellent cycle performance is embodied.
< example two >
The preparation method comprises the following steps:
taking 10g of polyvinylidene chloride powder and 20ml of NMP, uniformly mixing, adding 40g of potassium hydroxide and 1.0g of crystalline flake graphite, uniformly mixing, transferring into a ball milling tank, carrying out ball milling reaction for 2 hours at the rotating speed of 300rpm, and carrying out ball-to-material ratio (50: 1). And after the reaction is finished, taking out the mixture, drying, transferring the mixture to a tubular furnace, carbonizing the mixture for 3h at 600 ℃ under argon atmosphere, washing the mixture with 1M dilute hydrochloric acid, performing suction filtration and washing on the product with deionized water and ethanol repeatedly, and drying the product for 12h in vacuum at 100 ℃ to obtain the porous carbon hybrid material.
And (3) performance characterization:
uniformly mixing and grinding the porous carbon hybrid material prepared in the step, a conductive agent (SP) and polyvinylidene fluoride (PVDF) according to the mass ratio of 6:3:1, dripping a proper amount of N-methyl-2-pyrrolidone (NMP) according to the condition, grinding and stirring to form stable slurry. The coating is coated on a carbon-coated aluminum foil, and the thickness is 0.06 mm. After drying, a slicing machine is used for manufacturing a pole piece with the diameter of 10mm, and the pole piece is assembled into a lithium ion battery half cell for testing, wherein the electrolyte is 1M LiPF6The electrolyte is prepared by mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC) according to the volume ratio of 1: 1.
As seen from the rate capability test of FIG. 5, the charging specific capacity reaches 282.6mA h/g when the current density is 25 mA/g; the charging specific capacity is slowly reduced when the current density is gradually increased, and the charging specific capacity is still more than 105.5mAh/g when the current density is up to 2000 mA/g; namely, the capacity retention rate is 37.3 percent after the current density is improved by 80 times, which shows that the porous carbon hybrid material has excellent specific capacity and good rate performance.
As can be seen from the cyclical stability curve of fig. 6: the charging specific capacity is still 123.6mAh/g after the battery is cycled for 170 circles under the current density of 500mA/g, the retention rate reaches 57.7 percent, and the excellent cycling stability performance is reflected.
< example three >
Taking 10g of polyvinylidene fluoride powder and 20ml of toluene, uniformly mixing, adding 20g of sodium ethoxide and 0.5g of graphite oxide, uniformly mixing, transferring to a ball milling tank, carrying out ball milling for 1.5h at the rotation speed of 400rpm, taking out and drying the mixture with the ball-material ratio (50:1), carbonizing at 800 ℃ for 5h under nitrogen atmosphere, washing with 1M HCl, repeatedly washing with water and ethanol, and vacuum drying at 60 ℃ for 24h to obtain the porous carbon hybrid material.
< example four >
10g of polyhexafluoropropylene and 20ml of NMP are uniformly mixed, 30g of sodium ethoxide and 0.8g of crystalline flake graphite are added, the mixture is uniformly mixed and then transferred into a ball milling tank, and the ball milling reaction is carried out for 6 hours at the rotating speed of 300rpm and the ball-to-material ratio (200: 1). And after the reaction is finished, taking out and drying the mixture, carbonizing the mixture for 4h at 1000 ℃ in nitrogen atmosphere, washing the mixture with 1M HCl, repeatedly washing the mixture with water and ethanol, and drying the mixture for 12h in vacuum at 120 ℃ to obtain the porous carbon hybrid material.
The above embodiments are merely illustrative of the technical solutions of the present invention. The preparation of porous carbon hybrid materials based on graphite and polyhalogenated hydrocarbons and the energy storage application thereof according to the present invention are not limited to the contents described in the above examples, but are subject to the scope defined by the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.

Claims (9)

1. The method for preparing the porous carbon hybrid material based on graphite and polyhalogenated hydrocarbon is characterized by comprising the following steps:
uniformly mixing polyhalogenated hydrocarbon, a graphite material, a dehalogenation reagent and a solvent, performing ball milling reaction at room temperature, then activating at high temperature in an inert atmosphere, synchronously realizing high-efficiency conversion of the polyhalogenated hydrocarbon to porous carbon, assisting graphite to strip to generate graphene, dispersing graphene sheet layers, washing and drying to obtain the porous carbon hybrid material formed by coating the porous carbon on the graphene sheet layers,
wherein the ball milling stripping rate is 50-600 rpm, and the time is 0.5-60 h; the ball material ratio is 100-500: 1.
2. the method for preparing porous carbon hybrid materials based on graphite and polyhalogenated hydrocarbons according to claim 1, characterized in that:
wherein the polyhalogenated hydrocarbon is any one of polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene and polyhexafluoropropylene.
3. The method for preparing porous carbon hybrid materials based on graphite and polyhalogenated hydrocarbons according to claim 1, characterized in that:
wherein the graphite material is any one of natural graphite, crystalline flake graphite, graphite oxide and expanded graphite.
4. The method for preparing porous carbon hybrid materials based on graphite and polyhalogenated hydrocarbons according to claim 1, characterized in that:
wherein, the dehalogenation reagent is at least one of potassium hydroxide, sodium ethoxide, zinc powder and lithium hydroxide.
5. The method for preparing porous carbon hybrid materials based on graphite and polyhalogenated hydrocarbons according to claim 1, characterized in that:
wherein the solvent is at least one of water, ethanol, acetone, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, dichloromethane, tetrahydrofuran, glycol and toluene,
the detergent is at least one of deionized water, dilute hydrochloric acid, ethanol and acetone.
6. The method for preparing porous carbon hybrid materials based on graphite and polyhalogenated hydrocarbons according to claim 1, characterized in that:
wherein the activation temperature is 400-1000 ℃, and the activation time is 0.5-12 h.
7. The method for preparing porous carbon hybrid materials based on graphite and polyhalogenated hydrocarbons according to claim 1, characterized in that:
wherein the drying temperature is 50-150 ℃, and the drying time is 6-24 h.
8. Porous carbon hybrid material, characterized in that:
prepared by the method of any one of the preceding claims 1 to 7.
9. Use of a porous carbon hybrid material according to claim 8, characterized in that:
the porous carbon hybrid material is used as an energy storage material.
CN201811562875.5A 2018-12-20 2018-12-20 Porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon and energy storage application thereof Active CN109686579B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811562875.5A CN109686579B (en) 2018-12-20 2018-12-20 Porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon and energy storage application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811562875.5A CN109686579B (en) 2018-12-20 2018-12-20 Porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon and energy storage application thereof

Publications (2)

Publication Number Publication Date
CN109686579A CN109686579A (en) 2019-04-26
CN109686579B true CN109686579B (en) 2021-05-04

Family

ID=66188046

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811562875.5A Active CN109686579B (en) 2018-12-20 2018-12-20 Porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon and energy storage application thereof

Country Status (1)

Country Link
CN (1) CN109686579B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103482597A (en) * 2012-06-14 2014-01-01 中国人民解放军63971部队 Mesoporous-macroporous carbon production method
CN104944419A (en) * 2015-06-29 2015-09-30 中国科学院宁波材料技术与工程研究所 Graphitized carbon material and preparation method thereof, and supercapacitor
CN107840318A (en) * 2016-09-18 2018-03-27 北京化工大学 A kind of preparation method with regular pore structure carbon material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103482597A (en) * 2012-06-14 2014-01-01 中国人民解放军63971部队 Mesoporous-macroporous carbon production method
CN104944419A (en) * 2015-06-29 2015-09-30 中国科学院宁波材料技术与工程研究所 Graphitized carbon material and preparation method thereof, and supercapacitor
CN107840318A (en) * 2016-09-18 2018-03-27 北京化工大学 A kind of preparation method with regular pore structure carbon material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Activated Flake Graphite Coated with Pyrolysis Carbon as Promising Anode for Lithium Storage";Jun Chen,et al.;《Electrochimica Acta》;20160304;第196卷;第405-412页 *

Also Published As

Publication number Publication date
CN109686579A (en) 2019-04-26

Similar Documents

Publication Publication Date Title
CN107959006B (en) Lignin-based hard carbon/carbon nanotube composite material, preparation method thereof and application thereof in lithium ion battery cathode material
US9437870B2 (en) Nano-silicon composite lithium ion battery anode material coated with poly (3,4-ethylenedioxythiophene) as carbon source and preparation method thereof
CN108807808B (en) Preparation method of biomass carbon aerogel modified lithium-sulfur battery diaphragm
JP2014517507A (en) Polyimide capacitor battery and manufacturing method thereof
CN111517306B (en) Graphene-like/biomass carbon fiber aerogel and preparation method and application thereof
CN110335758B (en) Cobalt manganate-nitrogen-doped hollow carbon sphere composite material with core-shell structure and preparation method and application thereof
CN107994222B (en) Sandwich-structure carbon-based composite material and preparation method and application thereof
Zhang et al. Flexible quasi-solid-state zinc-ion hybrid supercapacitor based on carbon cloths displays ultrahigh areal capacitance
CN113363465A (en) Preparation method of lithium/potassium ion battery negative electrode material
CN112079352B (en) Preparation method and application of biomass-based porous nitrogen-doped carbon material
CN111370656B (en) Silicon-carbon composite material and preparation method and application thereof
CN113540419B (en) Co-LDH/MXene composite material and preparation method and application thereof
CN114400307A (en) Tin-carbon composite material and preparation method and application thereof
CN111986931B (en) Manganese oxide nano-structure electrode material and preparation method and application thereof
CN109087820B (en) Graphene composite electrode material prepared in situ by ultrasonic chemical method
CN109449440B (en) Microporous ultrathin soft carbon nanosheet and preparation method and application thereof
CN109686579B (en) Porous carbon hybrid material prepared based on graphite and polyhalogenated hydrocarbon and energy storage application thereof
Shi et al. Nitrogen and oxygen co-doped broccoli-like porous carbon nanosheets derived from sericin for high-performance supercapacitors
CN104091916A (en) MoS2 hole nano sheet/graphene electrochemical sodium storage composite electrode and preparation method
CN110648856B (en) Graphene material, preparation method thereof and supercapacitor
CN110589818B (en) Preparation method and application of nitrogen-doped mesoporous carbon material
CN107895797B (en) Preparation method of carbon nanosheet material and application of carbon nanosheet material in sodium ion battery
CN107651663B (en) Surface functionalized carbon material and preparation method and application thereof
CN112885613A (en) Nano material and preparation method and application thereof
Mohamed et al. Catalytic Graphitization of Amorphous Coal at Low Temperature and its Application in Lithium-ion Batteries

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant