CN109524244A - Nitrogenous two dimension conjugation carbon material of one kind and the preparation method and application thereof - Google Patents
Nitrogenous two dimension conjugation carbon material of one kind and the preparation method and application thereof Download PDFInfo
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- CN109524244A CN109524244A CN201710847482.8A CN201710847482A CN109524244A CN 109524244 A CN109524244 A CN 109524244A CN 201710847482 A CN201710847482 A CN 201710847482A CN 109524244 A CN109524244 A CN 109524244A
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- nitrogenous
- carbon material
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- supercapacitor
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 50
- 230000021615 conjugation Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007772 electrode material Substances 0.000 claims abstract description 22
- 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- -1 amino trimethylene benzene Chemical compound 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 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
- 239000007789 gas Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 4
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 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 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 239000013310 covalent-organic framework Substances 0.000 description 64
- 239000000463 material Substances 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 8
- 150000002466 imines Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000002243 precursor Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-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
- 239000012300 argon atmosphere Substances 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 206010013786 Dry skin Diseases 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
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 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
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C01P2006/32—Thermal properties
- C01P2006/37—Stability against thermal decomposition
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of nitrogenous two dimension conjugation carbon materials and the preparation method and application thereof, the nitrogenous two dimension conjugation carbon material is that triphenylene unit and cyclohexyl unit connect the regular two-dimentional conjugated structure to be formed by pyridine ring, it includes conjugated structure unit shown in formula I, has regular two-dimensional structure, the big π structure of conjugation, uniform microcellular structure, high specific surface area (2000-3500m2/ g), the carbon structures of outstanding thermal stability (>=1000 DEG C) and chemical stability and N doping.The nitrogenous two dimension conjugation carbon material of preparation method preparation can be using the electrode material as supercapacitor through the invention, it is applied widely, there are a variety of excellent performances such as high specific capacitance, high rate capability, outstanding cyclical stability, high-energy density and high power density.
Description
Technical field
The invention belongs to electrochemical material fields, are related to nitrogenous two dimension conjugation carbon material of one kind and preparation method thereof and answer
With.
Background technique
Supercapacitor is that a kind of electrochemical element, thermal energy storage process are reversible, can be hundreds of thousands of times with repeated charge.When
The increasingly developed requirement to energy storage device of modern society's portable electronic device and wearable device is higher and higher.In numerous energy storage
In device, supercapacitor is because having the characteristics that high charge-discharge rate, high power density and long circulation life, and by increasingly wide
It pays close attention to generally, but compared to energy storage devices such as lithium ion batteries, the energy density of supercapacitor is lower, this drawback is very big
Hinder the application of supercapacitor.Therefore, currently the research of supercapacitor is concentrated mainly on and is kept for its long circulating longevity
Under the advantages that life and high power density, its energy density is promoted.The main means for solving the problems, such as this are that exploitation has high ratio electricity
Hold, the electrode material that high rate capability and cyclical stability are excellent.
In these new materials, two-dimentional conjugated material because have high-specific surface area, big conjugated structure, controllable aperture and easily
The features such as functionalization, has very big development potentiality in electrode material for super capacitor field.Therefore, one kind novel two is developed
Conjugated material is tieed up, applies in electrode of super capacitor field, has very important significance.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of nitrogenous two dimension conjugation carbon material and its preparations
Method and application.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of nitrogenous two dimension conjugation carbon material (HATP-COF), the nitrogenous two dimension conjugation
Carbon material is that triphenylene unit and cyclohexyl unit connect the regular two-dimentional conjugated structure to be formed by pyridine ring, is wrapped
Include conjugated structure unit shown in formula I:
In the present invention, nitrogenous two dimension conjugation carbon material has the big pi-conjugated knot of regular two-dimensional structure, conjugation
Structure, uniform microcellular structure, high specific surface area (2000-3500m2/ g), outstanding thermal stability (>=1000 DEG C) and change
The carbon structure of stability and N doping is learned, there is very good performance.
In the present invention, conjugated structure unit shown in Formulas I includes the small annular unit structure of at least four, and dotted line is expressed as
It can continue to extend at connection conjugate unit, form small annular unit structure.
Preferably, the specific surface area of the nitrogenous two dimension conjugation carbon material is 500~3500m2/ g, such as can be
500m2/g、700m2/g、1000m2/g、1500m2/g、2000m2/g、2500m2/g、3000m2/ g or 3500m2/g。
Preferably, it is described it is nitrogenous two dimension conjugation carbon material pore-size distribution be 0.5-1.5nm, such as can be 0.5nm,
0.7nm, 0.9nm, 1nm, 1.2nm or 1.5nm.
Second aspect, the present invention provide a kind of preparation method of nitrogenous two dimension conjugation carbon material, and the method includes following
Step:
(1) six amino trimethylene benzene (HATP) or its hydrochloride are mixed with six ketone hexamethylenes or its eight hydrate, heating is anti-
It should obtain the preceding aggressiveness of nitrogenous two dimension conjugation carbon material；
(2) the preceding aggressiveness that step (1) obtains is heat-treated, obtains the nitrogenous two dimension conjugation carbon material.
In the present invention, preparation method step as described above is few, easy to operate, and reaction efficiency is high.
Preferably, six amino trimethylene benzene described in step (1) or its hydrochloride and six ketone hexamethylenes or its eight hydrate are anti-
The molar ratio answered is 1:3~3:1, such as can be 1:3,1:2,1:1,2:1 or 3:1, preferably 1:1.
In the present invention, the structure of the six amino trimethylene benzene hydrochloride (a) and six ketone hexamethylenes, eight hydrate (b) is as follows
It is shown:
Preferably, reaction described in step (1) carries out in polar solvent.
Preferably, the polar solvent is N-methyl pyrrolidones (NMP), dimethyl sulfoxide (DMSO), dimethyl formyl
One of amine (DMF), glacial acetic acid or propionic acid or at least two combination, preferably NMP.
Preferably, it reacts described in step (1) and carries out in the presence of a catalyst.
Preferably, catalyst described in step (1) be one of the concentrated sulfuric acid, glacial acetic acid, propionic acid or p-methyl benzenesulfonic acid or
At least two combination, the further preferably concentrated sulfuric acid (concentration 98%).
Preferably, it is heated to be solvent heat heating described in step (1).
Preferably, heating described in step (1) carries out under protective gas protection.
Further, the protective gas is the group of one of argon gas, nitrogen, helium or neon or at least two
It closes, preferably nitrogen.
Preferably, the temperature of heating described in step (1) is 100~200 DEG C, such as can be 100 DEG C, 120 DEG C, 150
DEG C, 170 DEG C, 180 DEG C or 200 DEG C.
Preferably, the time of heating described in step (1) is 1~21 day, such as can be 1 day, 4 days, 8 days, 13 days, 17
It, 19 days or 21 days, preferably 3 days.
Preferably, washed after heating reaction described in step (1), it is described wash the solvent that uses for tetrahydrofuran,
Any three kinds of combination, the preferably group of tetrahydrofuran, first alcohol and water in methanol, water, ethyl alcohol, methylene chloride, chloroform or acetone
It closes.
Preferably, the time of washing described in step (1) is that every kind of solvent washs 2~24 hours respectively, such as can be 2
Hour, 5 hours, 7 hours, 10 hours, 12 hours, 15 hours, 18 hours, 21 hours or 24 hours, further preferably 4~8
Hour.
Preferably, the temperature of heat treatment described in step (2) be 400~2000 DEG C, such as can be 400 DEG C, 800 DEG C,
1200 DEG C, 1500 DEG C, 1700 DEG C, 1900 DEG C or 2000 DEG C.
Preferably, the time of heat treatment described in step (2) is 2~24 hours, for example, can be 2 hours, 5 hours, it is 8 small
When, 10 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours.
Preferably, heat treatment described in step (2) carries out under protective gas protection.
Preferably, the protective gas is the combination of one of argon gas, nitrogen, helium or neon or at least two,
Preferably argon gas.
The third aspect, the present invention provide a kind of electrode material, and the electrode material includes that nitrogenous two dimension as described above is total
Yoke carbon material.
Fourth aspect, the present invention provide a kind of supercapacitor, and the supercapacitor is with nitrogenous two dimension as described above
Carbon material is conjugated as electrode material.
In the present invention, supercapacitor of the nitrogenous two dimension conjugation carbon material prepared by the present invention as electrode material is passed to
With the property that high specific capacitance, high rate capability, outstanding cyclical stability, high-energy density and high power density etc. are very excellent
Energy.
In the present invention, the electrode material of the supercapacitor further includes adhesive and conductive agent.
Preferably, described adhesive is in Kynoar, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose or butadiene-styrene rubber
It is a kind of or at least two combination, preferably polytetrafluoroethylene (PTFE).
Preferably, mass percent of the described adhesive in electrode material is 0-30%, for example, can be 0,5%,
10%, 15%, 20%, 25% or 30%.
Preferably, the conductive material is carbon black and/or acetylene black.
Preferably, mass percent of the conductive agent in electrode material is 0-50%, for example, can be 0,10%,
20%, 30%, 40% or 50%.
In the present invention, electrode material, conductive material (can not add conductive material) and adhesive (can not be added into bonding
Agent) uniformly mixing, rolling is in blocks, slice obtains the electrode of supercapacitor.
Preferably, it is and capacitor case width phase by the electrode size that the electrode material of the supercapacitor is prepared
The electrode of adaptation.
In the present invention, the supercapacitor uses different electrolytes system.
Preferably, the solution system of the electrolyte be acid system, alkaline system or organic system, further preferably
1- ethyl-3-methylimidazole tetrafluoroborate (EMIMBF4) or sulfuric acid solution.
Compared with the existing technology, the invention has the following advantages:
(1) nitrogenous two dimension conjugation carbon material provided by the invention has the big π knot of regular two-dimensional structure, conjugation
Structure, uniform microcellular structure, high specific surface area (2000-3500m2/ g), outstanding thermal stability (>=1000 DEG C) and change
The carbon structure of stability and N doping is learned, function admirable has very wide application prospect.
(2) the nitrogenous two dimension conjugation carbon material that preparation method is prepared through the invention can be using as supercapacitor
Electrode material, suitable for a variety of systems such as acid system, alkaline system and other organic systems, property stablize, be applicable in model
It encloses wide.And the supercapacitor of nitrogenous two dimension conjugation carbon material as electrode material has high specific capacitance, height using in the present invention
The very excellent performances such as high rate performance, outstanding cyclical stability, high-energy density and high power density have boundless
Commercial application prospect.
Detailed description of the invention
Fig. 1 is nitrogenous two-dimentional conjugated material HATP-COF, HATP-COF precursor prepared by the embodiment of the present invention 1
(Pristine HATP COF), six amino trimethylene benzene hydrochlorides (HATP) and six ketone hexamethylenes, eight hydrate (HKH) Fourier are red
The comparison diagram of external spectrum figure.
Fig. 2A is nitrogenous two-dimentional conjugated material HATP-COF solid-state prepared by the embodiment of the present invention 113C nuclear magnetic spectrogram.
Fig. 2 B is nitrogenous two dimension conjugated material HATP-COF precursor (Pristine HATP prepared by the embodiment of the present invention 1
COF) solid-state13C nuclear magnetic spectrogram.
Fig. 2 C is nitrogenous two-dimentional conjugated material HATP-COF solid-state prepared by the embodiment of the present invention 115N nuclear magnetic spectrogram.
Fig. 2 D is nitrogenous two dimension conjugated material HATP-COF precursor (Pristine HATP prepared by the embodiment of the present invention 1
COF) solid-state15N nuclear magnetic spectrogram.
Fig. 3 A is nitrogenous two-dimentional conjugated material HATP-COF carbon distribution map prepared by the embodiment of the present invention 1.
Fig. 3 B is nitrogenous two-dimentional conjugated material HATP-COF nitrogen distribution map prepared by the embodiment of the present invention 1.
Fig. 3 C is nitrogenous two-dimentional conjugated material HATP-COF oxygen element distribution map prepared by the embodiment of the present invention 1.
Fig. 4 A is nitrogenous two dimension conjugated material HATP-COF scanning electron microscope (SEM) photograph (10 μ of scale prepared by the embodiment of the present invention 1
m)。
Fig. 4 B is nitrogenous two dimension conjugated material HATP-COF scanning electron microscope (SEM) photograph (5 μm of scale) prepared by the embodiment of the present invention 1.
Fig. 4 C is nitrogenous two dimension conjugated material HATP-COF scanning electron microscope (SEM) photograph (4 μm of scale) prepared by the embodiment of the present invention 1.
Fig. 4 D is nitrogenous two dimension conjugated material HATP-COF scanning electron microscope (SEM) photograph (3 μm of scale) prepared by the embodiment of the present invention 1.
Fig. 4 E is nitrogenous two dimension conjugated material HATP-COF scanning electron microscope (SEM) photograph (2 μm of scale) prepared by the embodiment of the present invention 1.
Fig. 5 is nitrogenous two-dimentional conjugated material HATP-COF transmission electron microscope picture (scale 2nm) prepared by the embodiment of the present invention 1.
Fig. 6 A is the isothermal nitrogen adsorption figure of nitrogenous two-dimentional conjugated material HATP-COF prepared by the embodiment of the present invention 1.
Fig. 6 B is the graph of pore diameter distribution of nitrogenous two-dimentional conjugated material HATP-COF prepared by the embodiment of the present invention 1.
Fig. 7 is using nitrogenous two-dimentional conjugated material prepared by the present invention as the supercapacitor of electrode material specific capacitance-electric current
Density relationship figure.
Fig. 8 is using nitrogenous two-dimentional conjugated material prepared by the present invention as the electrode of super capacitor specific capacitance-of electrode material
Cycle-index curve graph.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Instrument for testing: Fourier Transform Infrared Spectrometer: JEOL FT IR-6100；Field emission scanning electron microscope
(FESEM): JEOL JSM-6700FE-SEM (acceleration voltage 5.0kV)；Transmission electron microscope (TEM): JEOL JEM -3200；
Powder x-ray diffractometry (PXRD): Rigaku RINT Ultima III.
Embodiment 1:
The present embodiment prepares nitrogenous two dimension conjugation carbon material HATP-COF by following steps:
Step (1): (HATP) synthesis of six amino trimethylene benzene monomers: by triphenylene compound 1 and bromine, iron, nitrobenzene
(PhNO2) carried out bromination reaction 2 hours at 205 DEG C, obtain hexabromo object, compound 2；By compound 2 and 1,1'- dinaphthalene-
The bis- diphenyl phosphines of 2,2'- (rac-BINAP), benzophenone contracting imines (Ph2C=NH), tris(dibenzylideneacetone) dipalladium (Pd2
(dba)3) 110 DEG C of reaction overnights in toluene, generate group with imine moiety 3；Finally, being obtained in tetrahydrofuran (THF) by acidolysis
To six amino trimethylene benzene monomers, compound 4 (HATP), synthetic route is as follows:
Step (2): the synthesis of dimmer compound before HATP-COF: six ketone hexamethylene eight of 40.00mg monomer HATP, 23.5mg
Hydrate and the 0.1mL98% concentrated sulfuric acid are added in the NMP of 2mL.Mixed liquor is placed in reactor, by the cooling of liquid nitrogen three times-
- thaw cycles degassing is vacuumized, is heated 3 days at 120 DEG C under nitrogen protection.Reaction solution is cooled to room temperature, and centrifugation obtains black
Powder.After washing 6 hours respectively with tetrahydrofuran, methanol and water, vacuum drying obtains preceding dimmer compound (black powder in 12 hours
End, yield 95%).
Step (3): the synthesis of nitrogenous two dimension conjugation carbon material HATP-COF: aggressiveness is placed in electric tube furnace before 500mg HATP
In, deaeration in condenser is three times.Under an argon atmosphere, tube furnace is warming up to 800 DEG C with 10 DEG C/min of heating rate, and heat treatment 4 is small
When, nitrogenous two dimension conjugated material HATP-COF (nitrogen content 19.32%) is obtained, step (2), step (3) synthetic route are as follows:
The HATP-COF being prepared in embodiment 1 is characterized and tested, including infrared spectroscopy, nuclear magnetic resonance, is swept
Retouch Electronic Speculum and transmission electron microscope picture, the test in aperture and adsorption effect.
Fig. 1 show the infrared spectrogram comparison diagram of HATP-COF, HATP-COF precursor, HATP and HKH；Fig. 2A is
HATP-COF solid-state13C nuclear magnetic spectrogram, Fig. 2 B are HATP-COF precursor solid-state13C nuclear magnetic spectrogram, Fig. 2 C are HATP-COF solid-state15N
Nuclear magnetic spectrogram, Fig. 2 D are HATP-COF precursor solid-state15N nuclear magnetic spectrogram, HATP-COF is synthesized successfully from the above data, it is proved that.
By Fig. 3 A be carbon distribution map, Fig. 3 B is nitrogen distribution map and Fig. 3 C is oxygen element distribution map, from Fig. 3 B
In as can be seen that nitrogen be uniformly distributed in the material；It can by the scanning electron microscope (SEM) photograph of Fig. 4 A, Fig. 4 B, Fig. 4 C, Fig. 4 D and Fig. 4 E
To find out, HATP-COF is in laminar structured；By the transmission electron microscope picture of Fig. 5 can be seen that HATP-COF in stratiform, densification and
High crystalline substance structure, interlamellar spacing areFig. 6 A is the isothermal nitrogen adsorption figure of HATP-COF；Pass through the pore-size distribution of Fig. 6 B
Figure it can be concluded that conclusion be, HATP-COF have size uniformity micropore, wherein aperture be 1nm.It is heat-treated with 1100 DEG C
HATP-COF has high specific surface area, up to 2743m2/g。
Embodiment 2
The present embodiment prepares nitrogenous two dimension conjugation carbon material HATP-COF by following steps:
Step (1): (HATP) synthesis of six amino trimethylene benzene monomers: by triphenylene compound 1 and bromine, iron, nitrobenzene
(PhNO2) carried out bromination reaction 2 hours at 205 DEG C, obtain hexabromo object, compound 2；By compound 2 and 1,1'- dinaphthalene-
The bis- diphenyl phosphines of 2,2'- (rac-BINAP), benzophenone contracting imines (Ph2C=NH), tris(dibenzylideneacetone) dipalladium (Pd2
(dba)3) 110 DEG C of reaction overnights in toluene, generate group with imine moiety 3；Finally, being obtained in tetrahydrofuran (THF) by acidolysis
To six amino trimethylene benzene monomers, compound 4 (HATP), synthetic route is as follows:
Step (2): the synthesis of dimmer compound before HATP-COF: six ketone hexamethylene eight of 40.00mg monomer HATP, 70.5mg
Hydrate and the 0.2mL98% concentrated sulfuric acid are added in the NMP of 3mL.Mixed liquor is placed in reactor, by the cooling of liquid nitrogen three times-
- thaw cycles degassing is vacuumized, is heated 1 day at 200 DEG C under nitrogen protection.Reaction solution is cooled to room temperature, and centrifugation obtains black
Powder.After washing 2 hours respectively with tetrahydrofuran, methanol and chloroform, vacuum drying obtains preceding dimmer compound (black in 12 hours
Powder, yield 94.5%).
Step (3): electric tube furnace specifically the synthesis of nitrogenous two dimension conjugation carbon material HATP-COF: is placed in front of 490mg HATP
In, deaeration in condenser is three times.Under an argon atmosphere, tube furnace is warming up to 2000 DEG C with 10 DEG C/min of heating rate, and heat treatment 2 is small
When, nitrogenous two dimension conjugated material HATP-COF (nitrogen content 18.78%) is obtained, step (2), step (3) synthetic route are as follows:
Embodiment 3
The present embodiment prepares nitrogenous two dimension conjugation carbon material HATP-COF by following steps:
Step (1): (HATP) synthesis of six amino trimethylene benzene monomers: by triphenylene compound 1 and bromine, iron, nitrobenzene
(PhNO2) carried out bromination reaction 2 hours at 205 DEG C, obtain hexabromo object, compound 2；By compound 2 and 1,1'- dinaphthalene-
The bis- diphenyl phosphines of 2,2'- (rac-BINAP), benzophenone contracting imines (Ph2C=NH), tris(dibenzylideneacetone) dipalladium (Pd2
(dba)3) 110 DEG C of reaction overnights in toluene, generate group with imine moiety 3；Finally, being obtained in tetrahydrofuran (THF) by acidolysis
To six amino trimethylene benzene monomers, compound 4 (HATP), synthetic route is as follows:
Step (2): the synthesis of dimmer compound before HATP-COF: six ketone hexamethylene of 120.00mg monomer HATP, 23.5mg
Eight hydrates and the 0.15mL98% concentrated sulfuric acid are added in the NMP of 2.5mL.Mixed liquor is placed in reactor, by liquid nitrogen three times
- thaw cycles degassing cool down-is vacuumized, is heated 21 days at 100 DEG C under nitrogen protection.Reaction solution is cooled to room temperature, is centrifuged
To black powder.After washing 24 hours respectively with methylene chloride, ethyl alcohol and acetone, aggressiveness chemical combination before vacuum drying obtains for 12 hours
Object (black powder, yield 92.3%).
Step (3): the synthesis of nitrogenous two dimension conjugation carbon material HATP-COF: 480mg HATP is placed in electric tube furnace, very
Empty deoxygenation is three times.Under an argon atmosphere, tube furnace is warming up to 400 DEG C with 10 DEG C/min of heating rate, is heat-treated 24 hours, obtains
To nitrogenous two dimension conjugated material HATP-COF (nitrogen content 17.81%), step (2), step (3) synthetic route are as follows:
Embodiment 4
The present embodiment prepares nitrogenous two dimension conjugation carbon material HATP-COF by following steps:
Step (1): (HATP) synthesis of six amino trimethylene benzene monomers: by triphenylene compound 1 and bromine, iron, nitrobenzene
(PhNO2) carried out bromination reaction 2 hours at 205 DEG C, obtain hexabromo object, compound 2；By compound 2 and 1,1'- dinaphthalene-
The bis- diphenyl phosphines of 2,2'- (rac-BINAP), benzophenone contracting imines (Ph2C=NH), tris(dibenzylideneacetone) dipalladium (Pd2
(dba)3) 110 DEG C of reaction overnights in toluene, generate group with imine moiety 3；Finally, being obtained in tetrahydrofuran (THF) by acidolysis
To six amino trimethylene benzene monomers, compound 4 (HATP), synthetic route is as follows:
Step (2): the synthesis of dimmer compound before HATP-COF: six ketone hexamethylene of 40.00mg monomer HATP, 47mg, eight water
It closes object and the 0.12mL98% concentrated sulfuric acid is added in the NMP of 2.5mL.Mixed liquor is placed in reactor, by the cooling of liquid nitrogen three times-
- thaw cycles degassing is vacuumized, is heated 5 days at 140 DEG C under nitrogen protection.Reaction solution is cooled to room temperature, and centrifugation obtains black
Powder.After washing 7 hours respectively with tetrahydrofuran, acetone and ethyl alcohol, vacuum drying obtains preceding dimmer compound (black in 11 hours
Powder, yield 94.5%).
Step (3): the synthesis of nitrogenous two dimension conjugation carbon material HATP-COF: aggressiveness is in electric tube furnace before 490mg HATP
In, deaeration in condenser is three times.Under an argon atmosphere, tube furnace is warming up to 900 DEG C with 10 DEG C/min of heating rate, and heat treatment 5 is small
When, nitrogenous two dimension conjugated material HATP-COF (nitrogen content 18.45%) is obtained, step (2), step (3) synthetic route are as follows:
Embodiment 5
Nitrogenous two dimension conjugation carbon material HATP-COF prepared by embodiment 1 applies the electrode preparation in supercapacitor
In, the specific steps are as follows:
By nitrogenous two dimension conjugation carbon material HATP-COF, carbon black and polytetrafluoroethylene (PTFE) according to mass percent 70:10:20 into
Row mixing, is added ethyl alcohol, mixture is ground, paste is tuned into, on stainless steel by paste even spread, rolls flakiness.
Thin slice is placed in a vacuum drying oven 120 DEG C of dryings 12 hours, and in the disk for being cut into diameter 12mm, every quality is about
0.7-1mg.The thin slice of two-phase homogenous quantities is pressed on stainless steel wire mesh (316L, 400 mesh, diameter 15mm), as two electrodes.
The button-shaped supercapacitor of 2032 types is made according to the assembling mode of button cell, the diaphragm of supercapacitor uses glass fibre
1- ethyl-3-methylimidazole tetrafluoroborate and sulfuric acid solution is respectively adopted in film, electrolyte.
The electrode for the supercapacitor that embodiment 5 is prepared carries out electro-chemical test, and concrete outcome is as follows:
The specific capacitance value of HATP-COF material is 258Fg-1(current density: 0.5Ag-1, electrolyte: EMIMBF4).When
Current density reaches 100Ag-1When, still keep 174Fg-1(as shown in Figure 7).In 2Ag-1Current density under, HATP-
Electrode (the electrolyte: EMIMBF of COF material preparation4) after circulation 10000 times, still keep 89% specific capacitance (such as Fig. 8 institute
Show).
When using 1M H2SO4When solution is as electrolyte, the specific capacitance value of HATP-COF material is up to 434Fg-1(electricity
Current density: 0.5Ag-1).When current density is 100Ag-1When, still keep 287.5Fg-1(as shown in Figure 7).In 2Ag-1
Current density under, the electrode of HATP-COF material preparation still keeps 87% specific capacitance (such as Fig. 8 institute after circulation 10000 times
Show).
When using EMIMBF4When as electrolyte, HATP-COF is in 250Wkg-1Under power density, energy density is up to
110Wh·kg-1.50kWkg is up in power density-1When, still there is 73.2Whkg-1Energy density.
When using 1M H2SO4When solution is as electrolyte, HATP-COF is in 250Wkg-1Under power density, energy density
For 15.1Whkg-1.50kWkg is up in power density-1When, still there is 10Whkg-1Energy density.
Embodiment 6
Nitrogenous two dimension conjugation carbon material HATP-COF prepared by embodiment 2 applies the electrode preparation in supercapacitor
In, the specific steps are as follows:
By it is nitrogenous two dimension conjugation carbon material HATP-COF and polytetrafluoroethylene (PTFE), carbon black according to mass percent 50:10:40 into
Row mixing, is added ethyl alcohol, mixture is ground, paste is tuned into, on stainless steel by paste even spread, rolls flakiness.
Thin slice is placed in a vacuum drying oven 115 DEG C of dryings 13 hours, and in the disk for being cut into diameter 12mm, every quality is about
0.7-1mg.The thin slice of two-phase homogenous quantities is pressed on stainless steel wire mesh (316L, 400 mesh, diameter 15mm), as two electrodes.
The button-shaped supercapacitor of 2032 types is made according to the assembling mode of button cell, the diaphragm of supercapacitor uses glass fibre
1- ethyl-3-methylimidazole tetrafluoroborate and sulfuric acid solution is respectively adopted in film, electrolyte.
Embodiment 7
Nitrogenous two dimension conjugation carbon material HATP-COF prepared by embodiment 3 applies the electrode preparation in supercapacitor
In, the specific steps are as follows:
Nitrogenous two dimension conjugation carbon material HATP-COF acetylene black is mixed according to mass percent 95:5, second is added
Alcohol grinds mixture, is tuned into paste, on stainless steel by paste even spread, rolls flakiness.It is dry that thin slice is placed in vacuum
120 DEG C drying 11 hours in dry case, in the disk for being cut into diameter 12mm, every quality is about 0.7-1mg.It is identical by two
The thin slice of quality is pressed on stainless steel wire mesh (316L, 400 mesh, diameter 15mm), as two electrodes.According to the group of button cell
Dress mode makes the button-shaped supercapacitor of 2032 types, and the diaphragm of supercapacitor uses glass fibre membrane, and electrolyte is adopted respectively
With 1- ethyl-3-methylimidazole tetrafluoroborate and sulfuric acid solution.
Embodiment 8
Nitrogenous two dimension conjugation carbon material HATP-COF prepared by embodiment 4 applies the electrode preparation in supercapacitor
In, the specific steps are as follows:
Nitrogenous two dimension conjugation carbon material HATP-COF and polytetrafluoroethylene (PTFE) are mixed according to mass percent 70:30,
Ethyl alcohol is added, mixture is ground, paste is tuned into, on stainless steel by paste even spread, rolls flakiness.Thin slice is placed in
125 DEG C drying 11.5 hours in vacuum oven, in the disk for being cut into diameter 12mm, every quality is about 0.7-1mg.
The thin slice of two-phase homogenous quantities is pressed on stainless steel wire mesh (316L, 400 mesh, diameter 15mm), as two electrodes.According to button
The assembling mode of battery makes the button-shaped supercapacitor of 2032 types, and the diaphragm of supercapacitor uses glass fibre membrane, electrolysis
1- ethyl-3-methylimidazole tetrafluoroborate and sulfuric acid solution is respectively adopted in liquid.
The Applicant declares that the present invention is explained by the above embodiments the nitrogenous two dimension conjugation carbon material of of the invention one kind and
Preparation method and application, but the invention is not limited to above-mentioned processing steps, that is, it is above-mentioned not mean that the present invention must rely on
Processing step could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, to institute of the present invention
The equivalence replacement and addition, the selection of concrete mode of auxiliary element etc. for selecting raw material, all fall within protection scope of the present invention and
Within the open scope.
Claims (10)
1. a kind of nitrogenous two dimension conjugation carbon material, which is characterized in that the nitrogenous two dimension conjugation carbon material be triphenylene unit and
Cyclohexyl unit connects the regular two-dimentional conjugated structure to be formed by pyridine ring comprising conjugation knot shown in formula I
Structure unit:
2. nitrogenous two dimension conjugation carbon material according to claim 1, which is characterized in that the nitrogenous two dimension conjugation carbon material
Specific surface area be 500~3500m2/g；
Preferably, the pore-size distribution of the nitrogenous two dimension conjugation carbon material is 0.5-1.5nm.
3. the preparation method of nitrogenous two dimension conjugation carbon material according to claim 1 or 2, which is characterized in that the method
The following steps are included:
(1) six amino trimethylene benzene or its hydrochloride are mixed with six ketone hexamethylenes or its eight hydrate, heating reaction obtains nitrogenous
The preceding aggressiveness of two dimension conjugation carbon material；
(2) the preceding aggressiveness that step (1) obtains is heat-treated, obtains the nitrogenous two dimension conjugation carbon material.
4. the preparation method of nitrogenous two dimension conjugation carbon material according to claim 3, which is characterized in that institute in step (1)
The molar ratio for stating six amino trimethylene benzene or its hydrochloride and six ketone hexamethylenes or its eight hydrate reaction is 1:3~3:1, preferably 1:
1；
Preferably, reaction described in step (1) carries out in polar solvent；
Preferably, the polar solvent is N-methyl pyrrolidones, dimethyl sulfoxide, dimethylformamide, glacial acetic acid or propionic acid
One of or at least two combination, preferably N-methyl pyrrolidones；
Preferably, it reacts described in step (1) and carries out in the presence of a catalyst；
Preferably, catalyst described in step (1) is one of the concentrated sulfuric acid, glacial acetic acid, propionic acid or p-methyl benzenesulfonic acid or at least
Two kinds of combination, the preferably concentrated sulfuric acid；
Preferably, it is heated to be solvent heat heating described in step (1)；
Preferably, heating described in step (1) carries out under protective gas protection；
Further, the protective gas is the combination of one of argon gas, nitrogen, helium or neon or at least two, excellent
It is selected as nitrogen；
Preferably, the temperature of heating described in step (1) is 100~200 DEG C；
Preferably, the time of heating described in step (1) is 1~21 day, preferably 3 days；
It preferably, further include being washed after the heating is reacted in step (1), the solvent used that washs is tetrahydro furan
It mutters, any three kinds of combination in methanol, water, ethyl alcohol, methylene chloride, chloroform or acetone, preferably tetrahydrofuran, first alcohol and water
Combination；
Preferably, the time of washing described in step (1) is that every kind of solvent washs 2~24 hours respectively, further preferably 4~
8 hours.
5. the preparation method of nitrogenous two dimension conjugation carbon material according to claim 3, which is characterized in that institute in step (2)
The temperature for stating heat treatment is 400~2000 DEG C；
Preferably, the time of heat treatment described in step (2) is 2~24 hours, preferably 4 hours；
Preferably, heat treatment described in step (2) carries out under protective gas protection；
Preferably, the protective gas is the combination of one of argon gas, nitrogen, helium or neon or at least two, preferably
For argon gas.
6. a kind of electrode material, which is characterized in that the electrode material includes that nitrogenous two dimension as claimed in claim 1 or 2 is total
Yoke carbon material.
7. a kind of supercapacitor, which is characterized in that the supercapacitor is total with nitrogenous two dimension of any of claims 1 or 2
Yoke carbon material is as electrode material.
8. supercapacitor according to claim 7, which is characterized in that the electrode material of the supercapacitor further includes
Adhesive and conductive agent.
9. supercapacitor according to claim 8, which is characterized in that described adhesive is Kynoar, polytetrafluoro
One of ethylene, sodium carboxymethylcellulose or butadiene-styrene rubber or at least two combination, preferably polytetrafluoroethylene (PTFE)；
Preferably, mass percent of the described adhesive in electrode material is 0-30%；
Preferably, the conductive agent is carbon black and/or acetylene black；
Preferably, mass percent of the conductive agent in electrode material is 0-50%.
10. according to the described in any item supercapacitors of claim 7-9, which is characterized in that the supercapacitor used
The solution system of electrolyte is acid system, alkaline system or organic system, further preferably 1- ethyl-3-methylimidazole four
Borofluoride or sulfuric acid solution.
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| CN112812300A (en) * | 2021-01-27 | 2021-05-18 | 中国科学院重庆绿色智能技术研究院 | Novel common-frame organic framework material and preparation method and application thereof |
| CN112920405A (en) * | 2021-01-27 | 2021-06-08 | 中国科学院重庆绿色智能技术研究院 | Thin-layer covalent organic framework material with irreversible bond connection and preparation method and application thereof |
| CN112920405B (en) * | 2021-01-27 | 2022-08-26 | 中国科学院重庆绿色智能技术研究院 | Thin-layer covalent organic framework material with irreversible bond connection and preparation method and application thereof |
| CN113036144A (en) * | 2021-03-10 | 2021-06-25 | 山东大学 | High-stability zinc-iodine battery positive electrode composite material and preparation method and application thereof |
| CN116496495A (en) * | 2022-01-18 | 2023-07-28 | 闽都创新实验室 | Crown ether group covalent organic polymer and light-assisted lithium battery cell device thereof |
| CN116496495B (en) * | 2022-01-18 | 2024-05-28 | 闽都创新实验室 | Crown ether group covalent organic polymer and light-assisted lithium battery cell device thereof |
| CN116102561A (en) * | 2023-02-21 | 2023-05-12 | 天津大学 | Amino coordination-based tricyclic quinazolinyl two-dimensional conductive metal organic framework material |
| CN116313540A (en) * | 2023-03-29 | 2023-06-23 | 重庆中科超容科技有限公司 | Electrode material for capacitor and preparation method thereof |
| CN116313540B (en) * | 2023-03-29 | 2024-05-07 | 重庆中科超容科技有限公司 | Electrode material for capacitor and preparation method thereof |
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