CN108565129A - A kind of preparation method of the nitrogen co-doped porous carbon composite of carbon nanotube/boron - Google Patents
A kind of preparation method of the nitrogen co-doped porous carbon composite of carbon nanotube/boron Download PDFInfo
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- CN108565129A CN108565129A CN201810319261.8A CN201810319261A CN108565129A CN 108565129 A CN108565129 A CN 108565129A CN 201810319261 A CN201810319261 A CN 201810319261A CN 108565129 A CN108565129 A CN 108565129A
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- nitrogen
- carbon nanotube
- boron
- doped porous
- porous carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 167
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 94
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 94
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 75
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 73
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 73
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007772 electrode material Substances 0.000 claims abstract description 17
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 25
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 235000013601 eggs Nutrition 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229920000767 polyaniline Polymers 0.000 claims 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000012718 coordination polymerization Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 239000011365 complex material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910019785 NBF4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
-
- 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
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation methods of the nitrogen co-doped porous carbon composite of carbon nanotube/boron, belong to Nano-manganese Dioxide Electrode Materials for Supercapacitors preparing technical field.Specific method is：1, the pretreatment of carbon nanotube；2, pretreated carbon nanotube carries out coordination polymerization with nitrogenous carbon source, metal activation agent；3, further coordination and ligand cure boron source with cooperation presoma；4, ligand is heat-treated under inert gas protection；5, acidleach processing, washing, drying are to get the nitrogen co-doped porous carbon composite of carbon nanotube/boron.Product produced by the present invention big, good conductivity, advantages such as electro-chemical activity height with specific surface, preparation flow of the present invention is simple, safe, production cost is low, product yield is high and the required equipment of reaction is simple, therefore is easily industrialized production.Prepared electrode material shows very excellent capacitance characteristic.
Description
Technical field
The invention belongs to Nano-manganese Dioxide Electrode Materials for Supercapacitors preparing technical fields, and in particular to a kind of carbon nanotube/boron
The preparation method of nitrogen co-doped porous carbon composite electrode material.
Background technology
Ultracapacitor is as novel energy storage device, with its high specific capacitance, big power density（1-10kW/kg）With
Long cycle life（More than 100000 cycles）, have in the fields such as portable instrument, power hybrid vehicle power supply, information technology
There is important commercial promise and is widely applied value.For a long time, ultracapacitor realization, which is commercially produced, is still faced with surely
Qualitative difference two hang-ups low with energy density.Therefore, under the premise of not sacrificing power density and keeping cost, design synthesis is high
Cycle life, high-energy super capacitor material be highly important.
The nitrogen co-doped porous carbon materials of boron are since it is with excellent chemism, high electrochemistry specific surface area and electrolysis
Liquid permeability is a kind of very potential electrode material for super capacitor.In the prior art, generally select nitrogenous carbon source direct
It polymerize the synthesis nitrogen co-doped porous carbon materials of boron with boron source.But in the building-up process of material, due to electron rich nitrogen and short of electricity
The coupling of sub- boron is readily formed chemically inert B-N keys, so as to get the nitrogen co-doped porous carbon of boron have very poor electricity
Hold characteristic.In addition, although the nitrogen co-doped porous carbon materials of boron can improve the electric conductivity of its own by the doping of nitrogen, it is conductive
Property can not still match in excellence or beauty with graphitic carbon.Therefore, it solves the electric conductivity of material difference and prevents chemically inert B-N keys formation to be synthesis boron
Nitrogen co-doped porous carbon materials one significantly work.
Carbon nanotube has excellent electric conductivity, porosity, carbon nanotube and boron nitrogen is co-doped with as monodimension nanometer material
Miscellaneous porous carbon materials are effectively compound, so as to inherently promote the electric conductivity of the nitrogen co-doped porous carbon materials of boron.Currently, existing
There are no the nitrogen co-doped porous carbon compound super capacitances of carbon nanotube/boron for electro-chemical activity height, good conductivity occur in technology
Device electrode material.
Pretreated carbon nanotube and nitrogenous carbon source and excessive metal salt are coordinated by the method for the present invention first, in this process
In, excess metal ion is coordinated to form presoma with all nitrogen-containing groups in nitrogenous carbon source, boron source is then added, boron source is with before
Oxygen-containing group extra in body is driven to be acted on.After high temperature pyrolysis, the boron nitrogen carbon and carbon nanometer of no chemical inertness B-N keys are obtained
The composite material of pipe.The complex of synthesis not only there is excellent chemism, high electrochemistry specific surface area and electrolyte to ooze
Permeability, while there is excellent electric conductivity and electro-chemical activity, due to complex the above feature make it have it is very excellent
Capacitance characteristic.
Invention content
To make up the deficiencies in the prior art, the present invention provides a kind of nitrogen co-doped porous carbon composite of carbon nanotube/boron
Preparation method, solve in the nitrogen co-doped porous carbon composite preparation process of carbon nanotube/boron that synthetic method is complicated, electrification
Activity is low, safety is poor, low output, has the problems such as a large amount of chemical inertness B-N keys.
The present invention is achieved through the following technical solutions：
A kind of preparation method of the nitrogen co-doped porous carbon composite of carbon nanotube/boron, is characterized in that：Including following step
Suddenly：
（1）In deionized water by carbon nanotube dispersion, carbon nano tube suspension is obtained, polyethylene is added into above-mentioned suspension
Pyrrolidones after stirring evenly, is obtained by filtration solid formation, dries, pre-processed under the conditions of 60-100 DEG C again after washed
Carbon nanotube；Pretreated carbon nanotube can preferably it is evenly dispersed in a solvent, make it be not easy to reunite；
（2）Nitrogenous carbon source in pretreated carbon nanotube ultrasonic disperse to solvent, will be added into solvent and enough metals are lived
Agent, the solution for being sufficiently stirred uniformly mixed；The mass ratio of the pretreated carbon nanotube and nitrogenous carbon source and activator
It is 1:（1-5）:（4-20）, enough metal activation agent can be coordinated with nitrogen-containing functional group all in nitrogenous carbon source, to have
The formation of the prevention chemical inertness B-N keys of effect；
（3）To step（2）Boron source is added in obtained solution, solidification obtains solid complex at 80-150 DEG C after being sufficiently stirred
Body；
（4）Solid complex body is heat-treated under an inert atmosphere, obtains the nitrogen co-doped porous carbon composite wood of carbon nanotube/boron
The presoma of material, during being heat-treated carbonization, metal activation agent can carry out activation to composite material, make it have height
Specific surface area and suitable pore structure；
（5）Using acid-hatching of young eggs processing step（4）Obtained composite material precursor obtains carbon nanotube/boron nitrogen by post-processing
Codope porous carbon composite.
A kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron of the present invention, step（1）In press matter
Amount is than being 1:Carbon nanotube is distributed in deionized water by (20-400), obtains carbon nano tube suspension.
Further, step（1）The mass ratio of middle polyvinylpyrrolidone and the carbon nanotube in carbon nano tube suspension
It is 1:(0.2-5).
Further, step（1）Described in mixing speed be 200-2000rpm, mixing time be 4-30 hours.
A kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron of the present invention, step（2）In, institute
The mixing that solvent is one or both of water, ethyl alcohol, ethylene glycol and methanol is stated, the dispersibility of carbon nanotube in a solvent is to multiple
It is water that the electric conductivity of condensation material, which has great influence, preferred solvent of the invention,；The nitrogenous carbon source is melamine, polyphenyl
One kind in amine, polypyrrole, gelatin or in which several mixing；The metal activation agent is potassium hydroxide, sodium hydroxide, chlorination
One kind in zinc or in which several mixing, activator can effectively prevent the formation of B-N keys, be conducive to the independent bonding of boron nitrogen.
Further, step（2）Middle whipping temp is 50-70 DEG C, mixing speed 100-200r/min, mixing time are
2-3h。
A kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron of the present invention, step（3）Described in
Boron source is boric acid.
Further, step（3）Middle whipping temp is 50-70 DEG C, mixing speed 100-200r/min, mixing time are
3-4h。
A kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron of the present invention, step（4）At middle heat
Reason operates：Solid complex body rises to 600-1000 DEG C with 5-15 DEG C/min speed by room temperature, carries out under inert gas protection
It is heat-treated 1-5h.
Further, step（4）Described in inert gas be nitrogen, argon gas, one kind in helium；Inert gas flow is
60-1000mL/min。
A kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron of the present invention, step（5）In, acid
Leaching method handle presoma the specific steps are：In the acid solution that mass concentration is 20-40%, stir 2-5h at ambient temperature, i.e., it is complete
At acidleach processing；The wherein described acid solution is one kind in hydrochloric acid, nitric acid, phosphoric acid or acetum or in which several mixed
It closes.
Further, step（5）In, post-processing the specific steps are：PH=7 of solution are washed with distilled water to, are centrifuged
Afterwards, sample is dry under conditions of temperature is 80-120 DEG C, obtain the nitrogen co-doped porous carbon composite of carbon nanotube/boron.
A kind of ultracapacitor high performance electrode material of the present invention, is prepared by method described above.
The beneficial effects of the invention are as follows：
（1）The present invention is coordinated method using two steps, first matches pretreated carbon nanotube and nitrogenous carbon source, metal activation agent
Position polymerization forms cooperation presoma, and then further coordination and ligand cure boron source with cooperation presoma, and two steps are coordinated not only
The formation for effectively preventing B-N keys, is conducive to the independent bonding of boron nitrogen, and ensure that the nitrogen content and boracic of composite material
Amount, meanwhile, the introducing of carbon nanotube greatly improves the electric conductivity of combination electrode material.
（2）The method of the present invention prepare the nitrogen co-doped porous carbon joint product of carbon nanotube/boron have high specific surface area and
Suitable pore structure, specific surface area is up to 1300m2g-1More than, pore volume is 0.3-0.4 cm3g-1, average pore size 2.5-3
Nm is conducive to the transmission of electrolyte, can effectively improve the intrinsic capacity of material.
（3）The method of the present invention prepares the nitrogen co-doped porous carbon joint product of carbon nanotube/boron, and good conductivity, electrochemistry are lived
Property high and carbon nanotube mesh support construction be conducive to the transmission of electronics, therefore be conducive to answering in terms of super-capacitor
With.Using it as electrode material for super capacitor, which show excellent energy storage characteristics.In current density 1A/g, electricity
Hold and be up to 308F/g, to be significantly larger than the nitrogen co-doped porous carbon composite of carbon nanotube/boron of step mixing method synthesis（244
F/g）With pure carbon nanotube（106 F/g）The specific capacitance of sum.The nitrogen co-doped porous carbon joint product of carbon nanotube/boron passes through
After 5000 constant current charge-discharge cycles, specific capacitance is still the 99.97% of initial capacitance.When being electrode assembling into electricity using this material
When capacitor devices, water system capacitor is in the case where power density is 500W/kg, energy density 9.89Wh/kg.Organic system capacitor exists
Power density is under 10500W/kg, and energy density is still 57.47Wh/kg.Such performance will be much better than commercial capacitor.
It lays the foundation for the commercialization of ultracapacitor battery from now on.
（4）Preparation flow of the present invention is simple, safe, production cost is low, product yield is high and reacts required equipment
Simply, therefore it is easily industrialized production.
Description of the drawings
Attached drawing 1 is the transmission electron microscope of the nitrogen co-doped porous carbon composite of carbon nanotube/boron of 1 gained of embodiment
Figure；
Attached drawing 2 is nitrogen adsorption-desorption isothermal of the nitrogen co-doped porous carbon composite of carbon nanotube/boron of 1 gained of embodiment
Curve and corresponding NLDFT pore size distribution curves；
Attached drawing 3 is the x-ray photoelectron spectroscopy of the nitrogen co-doped porous carbon composite of carbon nanotube/boron of 1 gained of embodiment
（XPS）Full figure；
Attached drawing 4 is the N 1s XPS spectrum figures of the nitrogen co-doped porous carbon composite of carbon nanotube/boron of 1 gained of embodiment；
Attached drawing 5 is the B 1s XPS spectrum figures of the nitrogen co-doped porous carbon composite of carbon nanotube/boron of 1 gained of embodiment；
Attached drawing 6 is the constant current charge-discharge curve of three kinds of Different electrodes materials, wherein 1-embodiment, 1 gained（Two coordination methods）
The constant current charge-discharge curve of the nitrogen co-doped porous carbon composite of carbon nanotube/boron, the carbon nanometer of 2-one step mixing method synthesis
The constant current charge-discharge curve of the nitrogen co-doped porous carbon composite of pipe/boron, the constant current charge-discharge curve of 3-pure carbon nanotubes；
Attached drawing 7 is following for the complex electrode material of the nitrogen co-doped porous carbon composite of carbon nanotube/boron of 1 gained of embodiment
The curve that ring service life and coulombic efficiency change with cycle-index；
Attached drawing 8 is that two electrodes of the nitrogen co-doped porous carbon composite electrode material assembling of 1 gained carbon nanotube of embodiment/boron are symmetrically electric
Container is in 6M KOH aqueous electrolytes and 1M Et4NBF4Energy density in-PC organic system electrolyte with power density variation
Figure.
Specific implementation mode
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, to help the skill of this field
Art personnel have more complete, accurate and deep understanding, protection scope of the present invention packet to the inventive concept of the present invention, technical solution
Following embodiment is included but is not limited to, it is any to technical scheme of the present invention under the premise of without departing from spirit and scope
Details and the modification made of form each fall in protection scope of the present invention.
Embodiment 1
The preparation method of the nitrogen co-doped porous carbon composite of carbon nanotube/boron of the present embodiment, includes the following steps：
（1）0.2g carbon nanotubes are dispersed in 50mL deionized waters, carbon nano tube suspension is obtained, are added into above-mentioned suspension
Enter to 1g polyvinylpyrrolidones.Low whipping speed is that after being stirred 4 hours under 1000 rpm, solid formation is obtained by filtration, washed
It is dried under the conditions of 60 DEG C again afterwards, obtains pretreated carbon nanotube；
（2）By in the pretreated carbon nanotube ultrasonic disperses to the aqueous solution of 50mL of 0.2g, a certain amount of trimerization is added into solution
Cyanamide and sodium hydroxide activator, under the conditions of temperature is 50 DEG C, mixing speed is 100r/min, stir 2h, wherein pre-processing
Carbon nanotube and nitrogenous carbon source and the mass ratio of activator be 1：4：8.
（3）In the solution obtained to step 2 be added 0.8g boric acid, continue temperature be 70 DEG C, mixing speed 100
4h is stirred under the conditions of r/min, then solidification obtains solid complex body under the conditions of temperature is 150 DEG C.
（4）Solid complex body that step 3 obtains with 15 DEG C/min speed is risen to 1000 DEG C by room temperature and in nitrogen protection
Under carry out heat treatment 1h, wherein inert atmosphere flow is 100mL/min.
（5）The presoma for the compound that step 4 is obtained stirs at ambient temperature in the hydrochloric acid that mass concentration is 40%
2h is mixed, that is, completes acidleach processing.Then, pH=7 of solution are washed with distilled water to, after centrifugation, are in temperature by sample
It is dried to get to the nitrogen co-doped porous carbon composite of carbon nanotube/boron under conditions of 80 DEG C.
The transmission electron microscope figure of the nitrogen co-doped porous carbon composite of carbon nanotube/boron manufactured in the present embodiment is for example attached
Shown in Fig. 1, it can be seen from the figure that carbon nanotube is well combined with the nitrogen co-doped porous carbon of boron, and carbon nanotube height point
It is dispersed in the nitrogen co-doped porous carbon of boron, the high dispersion of carbon nanotube improves the electric conductivity of complex.
The nitrogen adsorption of the nitrogen co-doped porous carbon composite of carbon nanotube/boron manufactured in the present embodiment-desorption isothermal is bent
Line and corresponding NLDFT pore size distribution curves are as shown in Fig. 2, and the thermoisopleth of composite material is IV type adsorption-desorption isothermals
Line has apparent rising in low-pressure area curve, and in higher-pressure region, curve is there are H2 hysteresis loops, illustrate composite material be have simultaneously micropore and
Mesoporous presence, it was demonstrated that composite material has hierarchical porous structure, is conducive to deposit and the transmission of electrolyte.It is de- according to nitrogen adsorption-
Attached isothermal curve calculates, and the specific surface area of complex is 1377 m2g-1, pore volume is 0.34 cm3g-1, average pore size 2.8
Nm, high specific surface area are conducive to the absorption of electrolyte, to promote the electric double layer capacitance of composite material.
The x-ray photoelectron spectroscopy of the nitrogen co-doped porous carbon composite of carbon nanotube/boron manufactured in the present embodiment（XPS）
Full figure is as shown in Fig. 3, and complex material is only containing carbon, nitrogen, boron and oxygen element and without other impurities as we can see from the figure, and
And from will also realize that boron and nitrogen has successfully been doped in complex in figure.The content of each element can be counted by XPS spectrum figure
It calculates.Understand that complex material nitrogen content is 4.72 at.%, boron content is 3.03 at.%, oxygen content is 8.10 at.%.Wherein,
Oxygen in complex material mostlys come from the oxygen in absorption oxygen and high stable group.Attached drawing 4 is the peaks N1s of composite material, can
To find out N1s points for four characteristic peaks, it is located at 398.7eV, 400.3eV, 401.8eV and 403eV, these peak values difference
With pyridine nitrogen（N-1）, pyrroles's nitrogen（N-2）, quaternary nitrogen（N-3）With oxygen-containing nitrogen（N-4）Combination can be corresponding.In addition, composite wood
The peaks B1s of material are as shown in Figure 5, it can be seen that it is respectively BC3 that it, which is divided into two characteristic peaks,（B-1：191.3eV）And BC2O（B-
2：192.9eV）.It can be analyzed from data above, for nitrogen-atoms there is no directly being combined with nitrogen-atoms, this is primarily due to gold
Belong to activator and introduces the formation that can effectively prevent B-N keys in advance.The independent bonding of boron nitrogen greatly improves combination electrode material
Capacitance characteristic, because heteroatomic addition can increase the fake capacitance of electrode material.
In order to verify the capacitance characteristic of composite material, we have carried out three-electrode system and two electrodes to composite electrode
The test of system.First, by the composite material of preparation and polytetrafluoroethylene (PTFE)（PTFE）It is 90 according to mass ratio：5 mixing are added suitable
Pasty mixture is obtained after amount ethyl alcohol.Using nickel foam as collector, pasty mixture is equably smeared on it with glass bar,
Application area is 1cm × 1cm.Then, the nickel foam for being coated with active material is placed in 70 DEG C of dry 6h in drying box.Again will
The dried nickel foam for being coated with active material depresses to pellet electrode in 20 MPa pressure.With saturated calomel electrode（SCE）For
Reference electrode, platinized platinum are auxiliary electrode, and the electrode of preparation is working electrode, and 6 mol/L KOH are electrolyte, form three electrodes
System.In three-electrode system, Fig. 6 shows constant current of the different electrode material for super capacitor in the case where current density is 1A/g
Charging and discharging curve.Curve 1 is that the present embodiment is multiple by the nitrogen co-doped porous carbon of carbon nanotube/boron of two steps coordination method synthesis in figure
The constant current charge-discharge curve of condensation material, curve 2 and curve 3 are control sample.Wherein being shown in curve 2 directly will pretreatment
The nitrogen co-doped porous carbon composite wood of carbon nanotube/boron that is mixed to get of carbon nanotube, nitrogen source, boron source and one step of metal activation agent
The constant current charge-discharge curve of material, curve 3 are the constant current charge-discharge curve of pure carbon nanotube.It is calculated it is found that two steps by figure
The specific capacitance of the nitrogen co-doped porous carbon composite of carbon nanotube/boron of coordination method synthesis is 308F/g, to be significantly larger than a step
The nitrogen co-doped porous carbon composite of carbon nanotube/boron of mixing method synthesis（244 F/g）With pure carbon nanotube（106 F/g）
The specific capacitance of sum.Further illustrate metal activation agent introduces the formation that can effectively prevent chemical inertness B-N keys in advance, to
Promote the capacitance characteristic of composite material.Therefore it says, the nitrogen co-doped porous carbon composite of carbon nanotube/boron manufactured in the present embodiment
It is a kind of electrode material with excellent energy storage characteristic.
Cycle life figure of Fig. 7 composite materials manufactured in the present embodiment through 5000 constant current charge-discharges.As shown, multiple
Condensation material electrode is after 5000 cycles, and specific capacitance is still the 99.97% of initial capacitance, and coulombic efficiency remains
99.65%。
To verify the practicability of electrode material, the ultracapacitor of two electrode systems is assembled.With manufactured in the present embodiment
Composite material is positive and negative electrode, and 6mol/L KOH solutions are aqueous electrolyte or 1mol/L Et4NBF4- PC is electrolysed for organic system
Liquid, polypropylene are assembled into 2032 button cells as diaphragm.And the energy storage characteristic of ultracapacitor is tested.For storage
Can energy device, energy and power density be to determine its one of determinant that commercially produce.Fig. 8 is two electrode systems electricity
The energy density that container is tested in water system and organic system electrolyte with power density variation diagram.It is found that water system capacitor exists
Power density is energy density 9.89Wh/kg under 500W/kg.Organic system capacitor power density be 10500 W/kg under,
Its energy density is still 56.77Wh/kg.Such performance will be much better than commercial capacitor.
Embodiment 2
（1）0.2g carbon nanotubes are dispersed in 100mL deionized waters, carbon nano tube suspension is obtained, into above-mentioned suspension
It is added to 1.8g polyvinylpyrrolidones.Low whipping speed is after being stirred 7 hours under 500 rpm, solid formation to be obtained by filtration, through washing
It is dried under the conditions of 80 DEG C again after washing, obtains pretreated carbon nanotube；
（2）By in the pretreated carbon nanotube ultrasonic disperses to the aqueous solution of 60mL of 0.2g, a certain amount of trimerization is added into solution
Cyanamide and sodium hydroxide activator, under the conditions of temperature is 30 DEG C, mixing speed is 200r/min, stir 5h, wherein pre-processing
Carbon nanotube and nitrogenous carbon source and the mass ratio of activator be 1：5：12.
（3）The boric acid of 1.0g is added in the suspension obtained to step 2, continues temperature is 80 DEG C, mixing speed is
7h is stirred under the conditions of 200r/min, then solidification obtains solid complex body under the conditions of temperature is 120 DEG C.
（4）Solid complex body that step 3 obtains is risen to 900 DEG C and under protection of argon gas with 5 DEG C/min speed by room temperature
Heat treatment 2h is carried out, wherein inert atmosphere flow is 100mL/min.
（5）The presoma for the compound that step 4 is obtained stirs at ambient temperature in the nitric acid that mass concentration is 30%
5h is mixed, that is, completes acidleach processing.Then, pH=7 of solution are washed with distilled water to, after centrifugation, are in temperature by sample
It is dried to get to the nitrogen co-doped porous carbon composite of carbon nanotube/boron under conditions of 60 DEG C.
Claims (10)
1. a kind of preparation method of the nitrogen co-doped porous carbon composite of carbon nanotube/boron, it is characterised in that：Including following step
Suddenly：
（1）In deionized water by carbon nanotube dispersion, carbon nano tube suspension is obtained, polyethylene is added into above-mentioned suspension
Pyrrolidones after stirring evenly, is obtained by filtration solid formation, dries, pre-processed under the conditions of 60-100 DEG C again after washed
Carbon nanotube；
（2）By in pretreated carbon nanotube ultrasonic disperse to solvent, nitrogenous carbon source and metal activation agent are added into solvent, fills
Divide the solution for stirring uniformly mixed；The pretreated carbon nanotube is 1 with the mass ratio of nitrogenous carbon source and activator:（1-
5）:（4-20）；
（3）To step（2）Boric acid is added in obtained solution, solidification obtains solid complex at 80-150 DEG C after being sufficiently stirred
Body；
（4）Solid complex body is heat-treated under an inert atmosphere, obtains the nitrogen co-doped porous carbon composite wood of carbon nanotube/boron
The presoma of material；
（5）Using acid-hatching of young eggs processing step（4）Obtained composite material precursor obtains carbon nanotube/boron nitrogen by post-processing
Codope porous carbon composite.
2. a kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron according to claim 1, special
Sign is：Step（2）In, the solvent is the mixing of one or both of water, ethyl alcohol, ethylene glycol and methanol；It is described nitrogenous
Carbon source is melamine, polyaniline, polypyrrole, one kind in gelatin or in which several mixing；The metal activation agent is hydrogen
One kind in potassium oxide, sodium hydroxide, zinc chloride or in which several mixing.
3. a kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron according to claim 3, special
Sign is：Step（2）Middle whipping temp is 50-70 DEG C, mixing speed 100-200r/min, mixing time 2-3h.
4. a kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron according to claim 1, special
Sign is：Step（3）Described in boron source be boric acid.
5. a kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron according to claim 4, special
Sign is：Step（3）Middle whipping temp is 50-70 DEG C, mixing speed 100-200r/min, mixing time 3-4h.
6. a kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron according to claim 1, special
Sign is：Step（4）Middle heat treatment operation is：Solid complex body rises to 600-1000 DEG C with 5-15 DEG C/min speed by room temperature,
Heat treatment 1-5 h are carried out under inert gas protection.
7. a kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron according to claim 7, special
Sign is：Step（4）Described in inert gas be nitrogen, argon gas, one kind in helium；Inert gas flow is 60-1000
mL/min。
8. a kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron according to claim 1, special
Sign is：Step（5）In, the acid-hatching of young eggs handle composite material precursor the specific steps are：In the acid solution that mass concentration is 20-40%
In, 2-5h is stirred at ambient temperature, that is, completes acidleach processing；The wherein described acid solution is hydrochloric acid, nitric acid, phosphoric acid or acetic acid
One kind in solution or in which several mixing.
9. a kind of preparation method of nitrogen co-doped porous carbon composite of carbon nanotube/boron according to claim 8, special
Sign is：Step（5）In, post-processing the specific steps are：PH=7 of solution are washed with distilled water to, after centrifugation, by sample
It is dry under conditions of temperature is 80-120 DEG C, obtain the nitrogen co-doped porous carbon composite of carbon nanotube/boron.
10. a kind of ultracapacitor high performance electrode material, it is characterised in that be by the arbitrary method in claim 1-9
It is prepared.
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