CN109524244B - Nitrogen-containing two-dimensional conjugated carbon material and preparation method and application thereof - Google Patents
Nitrogen-containing two-dimensional conjugated carbon material and preparation method and application thereof Download PDFInfo
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000005580 triphenylene group Chemical group 0.000 claims abstract description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 3
- 125000003373 pyrazinyl group Chemical group 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- SKBJSCXKLGRIPF-UHFFFAOYSA-N triphenylene-1,2,3,4,5,6-hexamine Chemical group NC1=C(N)C(N)=C2C3=C(N)C(N)=CC=C3C3=CC=CC=C3C2=C1N SKBJSCXKLGRIPF-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
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- 238000000034 method Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002904 solvent Substances 0.000 claims description 6
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- PKRGYJHUXHCUCN-UHFFFAOYSA-N cyclohexanehexone Chemical compound O=C1C(=O)C(=O)C(=O)C(=O)C1=O PKRGYJHUXHCUCN-UHFFFAOYSA-N 0.000 claims description 5
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- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
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- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical group CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
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- 239000003990 capacitor Substances 0.000 abstract description 20
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- MQIMWEBORAIJPP-UHFFFAOYSA-N cyclohexane-1,2,3,4,5,6-hexone;octahydrate Chemical compound O.O.O.O.O.O.O.O.O=C1C(=O)C(=O)C(=O)C(=O)C1=O MQIMWEBORAIJPP-UHFFFAOYSA-N 0.000 description 8
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
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- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 4
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
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- SXZIXHOMFPUIRK-UHFFFAOYSA-N diphenylmethanimine Chemical compound C=1C=CC=CC=1C(=N)C1=CC=CC=C1 SXZIXHOMFPUIRK-UHFFFAOYSA-N 0.000 description 4
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- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- ZPYAXYMMXFVTQA-UHFFFAOYSA-N triphenylene-1,2,3,4,5,6-hexamine hydrochloride Chemical compound C1=CC=C2C(=C1)C3=C(C4=C2C(=C(C(=C4N)N)N)N)C(=C(C=C3)N)N.Cl ZPYAXYMMXFVTQA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
- C01P2006/37—Stability against thermal decomposition
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a nitrogen-containing two-dimensional conjugated carbon material and a preparation method and application thereof, wherein the nitrogen-containing two-dimensional conjugated carbon material is a regular and ordered two-dimensional conjugated structure formed by connecting a triphenylene unit and a cyclohexyl unit through a pyrazine ring, and comprises a conjugated structure unit shown as a formula I, a regular and ordered two-dimensional structure, a conjugated large-pi structure, a uniform microporous structure and a very high specific surface area (2000-3500 m)2Per gram), excellent thermal stability (more than or equal to 1000 ℃) and chemical stability and nitrogen-doped carbon structure. The nitrogen-containing two-dimensional conjugated carbon material prepared by the preparation method can be applied as an electrode material of a super capacitor, has a wide application range, and has various excellent performances such as high specific capacitance, high rate performance, excellent cycle stability, high energy density and high power density.
Description
Technical Field
The invention belongs to the field of electrochemical materials, and relates to a nitrogen-containing two-dimensional conjugated carbon material, and a preparation method and application thereof.
Background
The super capacitor is an electrochemical element, and the energy storage process is reversible and can be repeatedly charged and discharged for tens of thousands of times. The increasing development of portable electronic devices and wearable devices in today's society places ever-increasing demands on energy storage devices. Among many energy storage devices, super capacitors are increasingly widely concerned due to their characteristics of high charge-discharge rate, high power density, long cycle life, and the like, but compared with energy storage devices such as lithium ion batteries, the super capacitors have low energy density, which greatly hinders the application of the super capacitors. Therefore, the current research on the super capacitor mainly focuses on maintaining the advantages of long cycle life and high power density, and improving the energy density. The main means for solving the problem is to develop an electrode material with high specific capacitance, high rate performance and excellent cycling stability.
Among the new materials, the two-dimensional conjugated material has great development potential in the field of electrode materials of super capacitors due to the characteristics of high specific surface area, large conjugated structure, adjustable pore diameter, easy functionalization and the like. Therefore, a novel two-dimensional conjugated material is developed, and has very important significance when being applied to the field of super capacitor electrodes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a nitrogen-containing two-dimensional conjugated carbon material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a nitrogen-containing two-dimensional conjugated carbon material (HATP-COF) which is a regularly ordered two-dimensional conjugated structure formed by connecting a triphenylene unit and a cyclohexyl unit via a pyrazine ring, and which includes a conjugated structural unit represented by formula I:
in the invention, the nitrogen-containing two-dimensional conjugated carbon material has a regular ordered two-dimensional structure, a conjugated large-pi conjugated structure, a uniform microporous structure and an extremely high specific surface area (2000-3500 m)2Perg), excellent thermal stability (not less than 1000 ℃) and chemical stability, and nitrogen-doped carbon structure, and has very excellent performance.
In the invention, the conjugated structural unit shown in formula I comprises at least 4 small cyclic unit structures, and the dotted line indicates that the conjugated unit can be continuously extended to form the small cyclic unit structure.
Preferably, the specific surface area of the nitrogen-containing two-dimensional conjugated carbon material is 500-3500 m2G, may be, for example, 500m2/g、700m2/g、1000m2/g、1500m2/g、2000m2/g、2500m2/g、3000m2/g or 3500m2/g。
Preferably, the nitrogen-containing two-dimensional conjugated carbon material has a pore size distribution of 0.5 to 1.5nm, and may be, for example, 0.5nm, 0.7nm, 0.9nm, 1nm, 1.2nm, or 1.5 nm.
In a second aspect, the present invention provides a method for preparing a nitrogen-containing two-dimensional conjugated carbon material, comprising the steps of:
(1) mixing Hexaaminotriphenylene (HATP) or hydrochloride thereof with hexaketocyclohexane or octahydrate, and heating for reaction to obtain a precursor of the nitrogen-containing two-dimensional conjugated carbon material;
(2) and (2) carrying out heat treatment on the prepolymer obtained in the step (1) to obtain the nitrogen-containing two-dimensional conjugated carbon material.
In the invention, the preparation method has the advantages of few steps, simple operation and high reaction efficiency.
Preferably, the molar ratio of the hexaaminotriphenylene or hydrochloride thereof to the hexaketocyclohexane or octahydrate in step (1) is 1:3 to 3:1, for example 1:3, 1:2, 1:1, 2:1 or 3:1, preferably 1: 1.
In the present invention, the structures of the hexaaminotriphenylene hydrochloride (a) and the hexaketocyclohexane octahydrate (b) are as follows:
preferably, the reaction in step (1) is carried out in a polar solvent.
Preferably, the polar solvent is one or a combination of at least two of Nitrogen Methyl Pyrrolidone (NMP), dimethyl sulfoxide (DMSO), Dimethylformamide (DMF), glacial acetic acid or propionic acid, preferably NMP.
Preferably, the reaction in step (1) is carried out in the presence of a catalyst.
Preferably, the catalyst in step (1) is one or a combination of at least two of concentrated sulfuric acid, glacial acetic acid, propionic acid and p-toluenesulfonic acid, and further preferably concentrated sulfuric acid (with a concentration of 98%).
Preferably, the heating in step (1) is a solvothermal heating method.
Preferably, the heating in step (1) is carried out under the protection of a protective gas.
Further, the protective gas is one or a combination of at least two of argon, nitrogen, helium or neon, preferably nitrogen.
Preferably, the heating temperature in step (1) is 100 to 200 ℃, for example, 100 ℃, 120 ℃, 150 ℃, 170 ℃, 180 ℃ or 200 ℃.
Preferably, the heating time in step (1) is 1 to 21 days, for example, 1 day, 4 days, 8 days, 13 days, 17 days, 19 days or 21 days, preferably 3 days.
Preferably, the heating reaction in step (1) is followed by washing, and the solvent used for washing is a combination of any three of tetrahydrofuran, methanol, water, ethanol, dichloromethane, chloroform or acetone, preferably a combination of tetrahydrofuran, methanol and water.
Preferably, the washing time in step (1) is 2 to 24 hours for each solvent, and may be, for example, 2 hours, 5 hours, 7 hours, 10 hours, 12 hours, 15 hours, 18 hours, 21 hours, or 24 hours, and further preferably 4 to 8 hours.
Preferably, the temperature of the heat treatment in the step (2) is 400 to 2000 ℃, and may be, for example, 400 ℃, 800 ℃, 1200 ℃, 1500 ℃, 1700 ℃, 1900 ℃ or 2000 ℃.
Preferably, the time of the heat treatment in the step (2) is 2 to 24 hours, and for example, may be 2 hours, 5 hours, 8 hours, 10 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours.
Preferably, the heat treatment in step (2) is performed under the protection of a protective gas.
Preferably, the protective gas is one or a combination of at least two of argon, nitrogen, helium or neon, preferably argon.
In a third aspect, the present invention provides an electrode material comprising the nitrogen-containing two-dimensional conjugated carbon material as described above.
In a fourth aspect, the present invention provides a supercapacitor using the nitrogen-containing two-dimensional conjugated carbon material as described above as an electrode material.
In the invention, the supercapacitor using the nitrogen-containing two-dimensional conjugated carbon material prepared by the method as an electrode material has very excellent performances such as high specific capacitance, high rate performance, excellent cycle stability, high energy density and high power density.
In the invention, the electrode material of the supercapacitor further comprises a binder and a conductive agent.
Preferably, the binder is one or a combination of at least two of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose or styrene butadiene rubber, and is preferably polytetrafluoroethylene.
Preferably, the binder is present in the electrode material in an amount of 0-30% by mass, for example 0, 5%, 10%, 15%, 20%, 25% or 30%.
Preferably, the conductive material is carbon black and/or acetylene black.
Preferably, the mass percentage of the conductive agent in the electrode material is 0-50%, and may be, for example, 0, 10%, 20%, 30%, 40%, or 50%.
In the invention, the electrode material, the conductive material (with or without the addition of the conductive material) and the adhesive (with or without the addition of the adhesive) are uniformly mixed, and the electrode of the supercapacitor is obtained by rolling and slicing.
Preferably, the size of the electrode prepared from the electrode material of the supercapacitor is an electrode which is adaptive to the width of a capacitor shell.
In the invention, the super capacitor adopts different electrolyte systems.
Preferably, the solution system of the electrolyte is an acidic system, an alkaline system or an organic system, and more preferably 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF)4) Or a sulfuric acid solution.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nitrogen-containing two-dimensional conjugated carbon material provided by the invention has a regular and ordered two-dimensional structure, a conjugated large-pi structure, a uniform microporous structure and a very high specific surface area (2000-3500 m)2The carbon material has the advantages of high thermal stability (more than or equal to 1000 ℃) and chemical stability, nitrogen-doped carbon structure, excellent performance and wide application prospect.
(2) The nitrogen-containing two-dimensional conjugated carbon material prepared by the preparation method can be applied as an electrode material of a super capacitor, is suitable for various systems such as an acidic system, an alkaline system and other organic systems, and has stable property and wide application range. And the super capacitor using the nitrogen-containing two-dimensional conjugated carbon material as the electrode material has excellent performances such as high specific capacitance, high rate performance, excellent cycle stability, high energy density and high power density, and has very wide commercial application prospect.
Drawings
FIG. 1 is a comparison of Fourier infrared spectra of nitrogen-containing two-dimensional conjugated materials HATP-COF, HATP-COF precursor (Pristine HATP COF), hexaaminotriphenylene Hydrochloride (HATP), and hexaketocyclohexane octahydrate (HKH) prepared in example 1 of the present invention.
FIG. 2A shows HATP-COF solid-state nitrogen-containing two-dimensional conjugated material prepared in example 1 of the present invention13C nuclear magnetic spectrum.
FIG. 2B is a HATP-COF precursor (Pristine HATPCOF) solid state of a nitrogen-containing two-dimensional conjugated material prepared in example 1 of the present invention13C nuclear magnetic spectrum.
FIG. 2C is a HATP-COF solid state of the nitrogen-containing two-dimensional conjugated material prepared in example 1 of the present invention15N nuclear magnetic spectrum.
FIG. 2D is a HATP-COF precursor (Pristine HATPCOF) solid state nitrogen-containing two-dimensional conjugated material prepared in example 1 of the present invention15N nuclear magnetic spectrum.
FIG. 3A is a distribution diagram of carbon elements in HATP-COF of the two-dimensional nitrogen-containing conjugated material prepared in example 1 of the present invention.
FIG. 3B is a nitrogen distribution diagram of HATP-COF of the nitrogen-containing two-dimensional conjugated material prepared in example 1 of the present invention.
FIG. 3C is the oxygen distribution diagram of HATP-COF of the two-dimensional nitrogen-containing conjugated material prepared in example 1 of the present invention.
FIG. 4A is a scanning electron micrograph (10 μm on a scale) of a nitrogen-containing two-dimensional conjugated material HATP-COF prepared in example 1 of the present invention.
FIG. 4B is a scanning electron micrograph (5 μm on a scale) of a nitrogen-containing two-dimensional conjugated material HATP-COF prepared in example 1 of the present invention.
FIG. 4C is a scanning electron micrograph (scale 4 μm) of a nitrogen-containing two-dimensional conjugated material HATP-COF prepared in example 1 of the present invention.
FIG. 4D is a scanning electron micrograph (3 μm on a scale) of a nitrogen-containing two-dimensional conjugated material HATP-COF prepared in example 1 of the present invention.
FIG. 4E is a scanning electron micrograph (2 μm on a scale) of a nitrogen-containing two-dimensional conjugated material HATP-COF prepared in example 1 of the present invention.
FIG. 5 is a transmission electron micrograph (scale 2nm) of a nitrogen-containing two-dimensional conjugated material HATP-COF prepared in example 1 of the present invention.
FIG. 6A is the isothermal nitrogen sorption drawing of the nitrogen-containing two-dimensional conjugated material HATP-COF prepared in example 1 of the present invention.
FIG. 6B is a diagram showing the distribution of pore diameters of the nitrogen-containing two-dimensional conjugated material HATP-COF prepared in example 1 of the present invention.
FIG. 7 is a graph showing the relationship between specific capacitance and current density of a supercapacitor using a nitrogen-containing two-dimensional conjugated material prepared according to the present invention as an electrode material.
FIG. 8 is a graph of specific capacitance versus cycle number of a supercapacitor electrode using the nitrogen-containing two-dimensional conjugated material prepared by the present invention as an electrode material.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The test instruments are a Fourier transform infrared spectrometer JEO L FT IR-6100, a Field Emission Scanning Electron Microscope (FESEM) JEO L JSM-6700FE-SEM (acceleration voltage 5.0kV), a Transmission Electron Microscope (TEM) JEO L JEM-3200, and a powder x-ray diffractometer (PXRD) Rigaku RINT Ultima III.
Example 1:
this example prepares a nitrogen-containing two-dimensional conjugated carbon material, HATP-COF, by the following steps:
step (1): synthesis of hexaaminotriphenylene monomer (HATP): mixing triphenylene compound 1 with liquid bromine, iron, nitrobenzene (PhNO)2) Carrying out bromination reaction for 2 hours at 205 ℃ to obtain hexabromide and a compound 2; compound 2 was reacted with 1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine (rac-BINAP), benzophenone imine (Ph)2C ═ NH), tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) In toluene at 110 deg.CReacting overnight to generate an imine compound 3; finally, the hexaaminotriphenylene monomer, compound 4(HATP), is obtained by acid hydrolysis in Tetrahydrofuran (THF) via the following synthetic route:
step (2) Synthesis of HATP-COF Pre-Polymer Compound 40.00mg of monomeric HATP, 23.5mg of hexaketocyclohexane octahydrate and 0.1m L98% concentrated sulfuric acid were added to 2m L of NMP, the mixture was placed in a reactor, degassed by three liquid nitrogen cooling-evacuation-thawing cycles, heated at 120 ℃ for 3 days under nitrogen protection, the reaction solution was cooled to room temperature, centrifuged to obtain a black powder, washed with tetrahydrofuran, methanol and water for 6 hours, respectively, and dried under vacuum for 12 hours to obtain a Pre-Polymer Compound (black powder, yield 95%).
And (3): synthesis of nitrogen-containing two-dimensional conjugated carbon material HATP-COF: 500mg of HATP precursor was placed in an electric tube furnace and deoxygenated under vacuum three times. Under the argon atmosphere, a tube furnace is heated to 800 ℃ at the heating rate of 10 ℃/min, the heat treatment is carried out for 4 hours, the nitrogen-containing two-dimensional conjugated material HATP-COF (the nitrogen content is 19.32%) is obtained, and the synthetic routes of the step (2) and the step (3) are as follows:
characterization and test are carried out on the HATP-COF prepared in the example 1, wherein the characterization and test comprise infrared spectroscopy, nuclear magnetic resonance, scanning electron microscopy, transmission electron microscopy, pore diameter test and adsorption effect test.
FIG. 1 is a graph showing a comparison of infrared spectra of HATP-COF, HATP-COF precursor, HATP and HKH; FIG. 2A is a HATP-COF solid state13C NMR spectrum, FIG. 2B solid state of HATP-COF precursor13C nuclear magnetic spectrum, FIG. 2C is HATP-COF solid state15N NMR spectrum, FIG. 2D shows the HATP-COF precursor in solid state15N nuclear magnetic spectrum, and the success of HATP-COF synthesis is proved by the data.
By using FIG. 3A as a distribution diagram of carbon element, FIG. 3B as a distribution diagram of nitrogen element and FIG. 3C as a distribution diagram of oxygen element,as can be seen from fig. 3B, the nitrogen element is uniformly distributed in the material; as can be seen from the scanning electron micrographs of fig. 4A, 4B, 4C, 4D and 4E, the HATP-COF has a lamellar structure; as can be seen from the transmission electron micrograph of FIG. 5, HATP-COF is a layered, dense and highly crystalline structure with a layer-to-layer spacing of
FIG. 6A is the isothermal nitrogen sorption of HATP-COF; as can be concluded from the pore size distribution diagram of FIG. 6B, HATP-COF has micropores of uniform size, in which the pore size is 1 nm. The HATP-COF heat treated at 1100 ℃ has extremely high specific surface area which can reach 2743m2/g。
Example 2
This example prepares a nitrogen-containing two-dimensional conjugated carbon material, HATP-COF, by the following steps:
step (1): synthesis of hexaaminotriphenylene monomer (HATP): mixing triphenylene compound 1 with liquid bromine, iron, nitrobenzene (PhNO)2) Carrying out bromination reaction for 2 hours at 205 ℃ to obtain hexabromide and a compound 2; compound 2 was reacted with 1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine (rac-BINAP), benzophenone imine (Ph)2C ═ NH), tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) Reacting at 110 ℃ overnight in toluene to generate an imine compound 3; finally, the hexaaminotriphenylene monomer, compound 4(HATP), is obtained by acid hydrolysis in Tetrahydrofuran (THF) via the following synthetic route:
step (2) Synthesis of HATP-COF Pre-Polymer Compound 40.00mg of monomeric HATP, 70.5mg of hexaketocyclohexane octahydrate and 0.2m L98% concentrated sulfuric acid were added to 3m L of NMP, the mixture was placed in a reactor, degassed by three liquid nitrogen cooling-evacuation-thawing cycles, heated at 200 ℃ for 1 day under nitrogen protection, the reaction solution was cooled to room temperature, centrifuged to obtain a black powder, washed with tetrahydrofuran, methanol and chloroform, respectively, for 2 hours, and vacuum-dried for 12 hours to obtain a pre-polymer compound (black powder, yield 94.5%).
And (3): synthesis of nitrogen-containing two-dimensional conjugated carbon material HATP-COF: 490mg HATP was specifically placed in a tube electric furnace and deoxygenated in vacuo three times. Under the argon atmosphere, a tube furnace is heated to 2000 ℃ at the heating rate of 10 ℃/min, the heat treatment is carried out for 2 hours, the nitrogen-containing two-dimensional conjugated material HATP-COF (nitrogen content is 18.78%) is obtained, and the synthetic route of the step (2) and the step (3) is as follows:
example 3
This example prepares a nitrogen-containing two-dimensional conjugated carbon material, HATP-COF, by the following steps:
step (1): synthesis of hexaaminotriphenylene monomer (HATP): mixing triphenylene compound 1 with liquid bromine, iron, nitrobenzene (PhNO)2) Carrying out bromination reaction for 2 hours at 205 ℃ to obtain hexabromide and a compound 2; compound 2 was reacted with 1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine (rac-BINAP), benzophenone imine (Ph)2C ═ NH), tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) Reacting at 110 ℃ overnight in toluene to generate an imine compound 3; finally, the hexaaminotriphenylene monomer, compound 4(HATP), is obtained by acid hydrolysis in Tetrahydrofuran (THF) via the following synthetic route:
step (2) Synthesis of HATP-COF Pre-Polymer Compound 120.00mg of monomeric HATP, 23.5mg of hexaketocyclohexane octahydrate and 0.15m L98% concentrated sulfuric acid were added to 2.5m L of NMP, the mixture was placed in a reactor, degassed by three liquid nitrogen cooling-evacuation-thawing cycles, heated at 100 ℃ for 21 days under nitrogen protection, the reaction solution was cooled to room temperature, centrifuged to obtain a black powder, washed with dichloromethane, ethanol and acetone for 24 hours, respectively, and dried under vacuum for 12 hours to obtain a pre-polymer compound (black powder, yield 92.3%).
And (3): synthesis of nitrogen-containing two-dimensional conjugated carbon material HATP-COF: 480mg of HATP were placed in a tube electric furnace and deoxygenated under vacuum three times. Under the argon atmosphere, a tube furnace is heated to 400 ℃ at the heating rate of 10 ℃/min, the heat treatment is carried out for 24 hours, the nitrogen-containing two-dimensional conjugated material HATP-COF (nitrogen content is 17.81%) is obtained, and the synthetic routes of the step (2) and the step (3) are as follows:
example 4
This example prepares a nitrogen-containing two-dimensional conjugated carbon material, HATP-COF, by the following steps:
step (1): synthesis of hexaaminotriphenylene monomer (HATP): mixing triphenylene compound 1 with liquid bromine, iron, nitrobenzene (PhNO)2) Carrying out bromination reaction for 2 hours at 205 ℃ to obtain hexabromide and a compound 2; compound 2 was reacted with 1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine (rac-BINAP), benzophenone imine (Ph)2C ═ NH), tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) Reacting at 110 ℃ overnight in toluene to generate an imine compound 3; finally, the hexaaminotriphenylene monomer, compound 4(HATP), is obtained by acid hydrolysis in Tetrahydrofuran (THF) via the following synthetic route:
step (2) Synthesis of HATP-COF Pre-Polymer Compound 40.00mg of monomeric HATP, 47mg of hexaketocyclohexane octahydrate and 0.12m L98% concentrated sulfuric acid were added to 2.5m L of NMP, the mixture was placed in a reactor, degassed by three liquid nitrogen cooling-evacuation-thawing cycles, heated at 140 ℃ for 5 days under nitrogen protection, the reaction solution was cooled to room temperature, centrifuged to obtain a black powder, washed with tetrahydrofuran, acetone and ethanol for 7 hours, respectively, and vacuum-dried for 11 hours to obtain a pre-polymer compound (black powder, yield 94.5%).
And (3): synthesis of nitrogen-containing two-dimensional conjugated carbon material HATP-COF: 490mg of HATP prepolymer were deoxygenated in a tubular electric furnace under vacuum three times. Under the argon atmosphere, a tube furnace is heated to 900 ℃ at the heating rate of 10 ℃/min, the heat treatment is carried out for 5 hours, the nitrogen-containing two-dimensional conjugated material HATP-COF (nitrogen content is 18.45%) is obtained, and the synthetic route of the step (2) and the step (3) is as follows:
example 5
The nitrogen-containing two-dimensional conjugated carbon material HATP-COF prepared in the example 1 is applied to the preparation of the electrode of the supercapacitor, and the specific steps are as follows:
mixing a nitrogen-containing two-dimensional conjugated carbon material HATP-COF, carbon black and polytetrafluoroethylene according to the mass percentage of 70:10:20, adding ethanol, grinding the mixture into paste, uniformly coating the paste on a stainless steel plate, rolling into sheets, drying the sheets in a vacuum drying oven at 120 ℃ for 12 hours, cutting into round sheets with the diameter of 12mm, wherein the mass of each sheet is 0.7-1mg, pressing the two sheets with the same mass onto a stainless steel metal net (316L, 400 meshes and the diameter of 15mm), using the round sheets as two electrodes, manufacturing a 2032 type button super capacitor according to the assembly mode of a button cell, wherein a diaphragm of the super capacitor adopts a glass fiber film, and electrolyte respectively adopts 1-ethyl-3-methylimidazole tetrafluoroborate and sulfuric acid solution.
Electrochemical tests were performed on the supercapacitor electrode prepared in example 5, and the specific results were as follows:
the specific capacitance value of the HATP-COF material is 258F g-1(Current Density: 0.5A. g)-1Electrolyte solution: EMIMBF4). When the current density reaches 100 A.g-1When the reaction time is long, 174 F.g is maintained-1(as shown in fig. 7). At 2 A.g-1At a current density of (2), an electrode (electrolyte: EMIMBF) made of the HATP-COF material4) After 10000 cycles, 89% of the specific capacitance was still maintained (as shown in fig. 8).
When using 1M H2SO4When the solution is used as an electrolyte, the specific capacitance value of the HATP-COF material is as high as 434F g-1(Current Density: 0.5A. g)-1). When the current density is 100 A.g-1When the reaction solution was used, 287.5 Fg was maintained-1(as shown in fig. 7). At 2 A.g-1At a current density of (2), HATP-COF materialThe prepared electrode still maintained 87% of specific capacitance after 10000 cycles (as shown in fig. 8).
When EMIMBF is adopted4When used as an electrolyte, HATP-COF is 250 W.kg-1At power density, the energy density is as high as 110 Wh.kg-1. The power density is up to 50 kW.kg-1Then, it still had 73.2 Wh.kg-1The energy density of (1).
When using 1M H2SO4When the solution is used as an electrolyte, the HATP-COF is 250 W.kg-1At a power density, the energy density was 15.1 Wh.kg-1. The power density is up to 50 kW.kg-1Then, it still has 10 Wh.kg-1The energy density of (1).
Example 6
The nitrogen-containing two-dimensional conjugated carbon material HATP-COF prepared in the example 2 is applied to the preparation of the electrode of the supercapacitor, and the specific steps are as follows:
mixing a nitrogen-containing two-dimensional conjugated carbon material HATP-COF, polytetrafluoroethylene and carbon black according to the mass percentage of 50:10:40, adding ethanol, grinding the mixture into paste, uniformly coating the paste on a stainless steel plate, rolling into sheets, drying the sheets in a vacuum drying oven at the temperature of 115 ℃ for 13 hours, cutting into circular sheets with the diameter of 12mm, wherein the mass of each sheet is about 0.7-1mg, pressing the two sheets with the same mass onto a stainless steel metal net (316L, 400 meshes and the diameter of 15mm), using the sheets as two electrodes, manufacturing a 2032 type button super capacitor according to the assembly mode of a button cell, wherein a diaphragm of the super capacitor adopts a glass fiber film, and electrolyte respectively adopts 1-ethyl-3-methylimidazole tetrafluoroborate and sulfuric acid solution.
Example 7
The nitrogen-containing two-dimensional conjugated carbon material HATP-COF prepared in the example 3 is applied to the preparation of the electrode of the supercapacitor, and the specific steps are as follows:
mixing nitrogen-containing two-dimensional conjugated carbon material HATP-COF acetylene black according to the mass percentage of 95:5, adding ethanol, grinding the mixture, mixing into paste, uniformly coating the paste on a stainless steel plate, rolling into slices, drying the slices in a vacuum drying oven at 120 ℃ for 11 hours, cutting into circular slices with the diameter of 12mm, wherein the mass of each slice is about 0.7-1mg, pressing the two-phase slices with the same mass onto a stainless steel metal net (316L, 400 meshes and 15mm in diameter) to serve as two electrodes, manufacturing a 2032 type button type super capacitor in an assembly mode of a button cell, wherein a diaphragm of the super capacitor adopts a glass fiber film, and electrolytes respectively adopt 1-ethyl-3-methylimidazolium tetrafluoroborate and a sulfuric acid solution.
Example 8
The nitrogen-containing two-dimensional conjugated carbon material HATP-COF prepared in the example 4 is applied to the preparation of the electrode of the supercapacitor, and the specific steps are as follows:
mixing nitrogen-containing two-dimensional conjugated carbon materials HATP-COF and polytetrafluoroethylene according to the mass percentage of 70:30, adding ethanol, grinding the mixture, mixing into paste, uniformly coating the paste on a stainless steel plate, rolling into sheets, drying the sheets in a vacuum drying oven at 125 ℃ for 11.5 hours, cutting into round sheets with the diameter of 12mm, wherein the mass of each sheet is about 0.7-1mg, pressing the two sheets with the same mass onto a stainless steel metal net (316L, 400 meshes and the diameter of 15mm) to be used as two electrodes, manufacturing a 2032 type button super capacitor according to the assembly mode of a button cell, wherein the diaphragm of the super capacitor adopts a glass fiber film, and the electrolyte respectively adopts 1-ethyl-3-methylimidazolium tetrafluoroborate and sulfuric acid solution.
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must be implemented by the above process steps. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (39)
1. The nitrogen-containing two-dimensional conjugated carbon material is a regular and ordered two-dimensional conjugated structure formed by connecting a triphenylene unit and a cyclohexyl unit through a pyrazine ring, and comprises a conjugated structural unit shown as a formula I:
2. the nitrogen-containing two-dimensional conjugated carbon material according to claim 1, wherein the specific surface area of the nitrogen-containing two-dimensional conjugated carbon material is 500 to 3500m2/g。
3. The nitrogen-containing two-dimensional conjugated carbon material according to claim 1, wherein the pore size distribution of the nitrogen-containing two-dimensional conjugated carbon material is 0.5 to 1.5 nm.
4. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to any one of claims 1 to 3, comprising the steps of:
(1) mixing hexaaminotriphenylene or hydrochloride thereof with hexaketocyclohexane or octahydrate, and heating for reaction to obtain a precursor of the nitrogen-containing two-dimensional conjugated carbon material;
(2) and (2) carrying out heat treatment on the prepolymer obtained in the step (1) to obtain the nitrogen-containing two-dimensional conjugated carbon material.
5. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the molar ratio of the hexaaminotriphenylene or the hydrochloride thereof to the hexaketocyclohexane or the octahydrate thereof in the step (1) is 1:3 to 3: 1.
6. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 5, wherein the molar ratio of the hexaaminotriphenylene or the hydrochloride thereof to the hexaketocyclohexane or the octahydrate thereof in the step (1) is 1: 1.
7. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the reaction in step (1) is carried out in a polar solvent.
8. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 7, wherein the polar solvent is one or a combination of at least two of azomethylpyrrolidone, dimethyl sulfoxide, dimethylformamide, glacial acetic acid, and propionic acid.
9. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 8, wherein the polar solvent is nitrogen methyl pyrrolidone.
10. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the reaction in step (1) is carried out in the presence of a catalyst.
11. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 10, wherein the catalyst in step (1) is one or a combination of at least two of concentrated sulfuric acid, glacial acetic acid, propionic acid, and p-toluenesulfonic acid.
12. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 11, wherein the catalyst in step (1) is concentrated sulfuric acid.
13. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the heating in step (1) is a solvothermal heating method.
14. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the heating in step (1) is performed under a protective gas atmosphere.
15. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 14, wherein the protective gas is one or a combination of at least two of argon, nitrogen, helium, and neon.
16. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 15, wherein the protective gas is nitrogen.
17. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the heating temperature in step (1) is 100 to 200 ℃.
18. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the heating time in step (1) is 1 to 21 days.
19. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 18, wherein the heating in step (1) is performed for 3 days.
20. The method for preparing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the step (1) further comprises washing after the heating reaction, wherein a solvent used for washing is a combination of any three of tetrahydrofuran, methanol, water, ethanol, dichloromethane, chloroform, and acetone.
21. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 20, wherein the solvent used for washing is a combination of tetrahydrofuran, methanol and water.
22. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 20, wherein the washing in step (1) is carried out for 2 to 24 hours for each solvent.
23. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 22, wherein the washing in step (1) is carried out for 4 to 8 hours for each solvent.
24. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the temperature of the heat treatment in the step (2) is 400 to 2000 ℃.
25. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the heat treatment time in step (2) is 2 to 24 hours.
26. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 25, wherein the heat treatment time in step (2) is 4 hours.
27. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 4, wherein the heat treatment in step (2) is performed under a protective gas atmosphere.
28. The method according to claim 27, wherein the protective gas is one or a combination of at least two of argon, nitrogen, helium, and neon.
29. The method for producing a nitrogen-containing two-dimensional conjugated carbon material according to claim 28, wherein the protective gas is argon gas.
30. An electrode material comprising the nitrogen-containing two-dimensional conjugated carbon material according to any one of claims 1 to 3.
31. A supercapacitor, characterized in that the supercapacitor uses the nitrogen-containing two-dimensional conjugated carbon material according to any one of claims 1 to 3 as an electrode material.
32. The supercapacitor of claim 31, wherein the electrode material of the supercapacitor further comprises a binder and a conductive agent.
33. The supercapacitor of claim 32, wherein the binder is one or a combination of at least two of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, or styrene butadiene rubber.
34. The ultracapacitor of claim 33, wherein the binder is polytetrafluoroethylene.
35. The supercapacitor according to claim 32, wherein the binder is present in the electrode material in an amount of 0-30% by mass.
36. The supercapacitor according to claim 32, wherein the conductive agent is carbon black and/or acetylene black.
37. The supercapacitor according to claim 32, wherein the conductive agent is present in the electrode material in an amount of 0-50% by mass.
38. The supercapacitor according to claim 31, wherein the solution system of the electrolyte used in the supercapacitor is an acidic system, an alkaline system or an organic system.
39. The supercapacitor according to claim 38, wherein the electrolyte used in the supercapacitor is 1-ethyl-3-methylimidazolium tetrafluoroborate or sulfuric acid solution.
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