CN107240506A - A kind of nitrogen-doped carbon nano composite material and its production and use - Google Patents
A kind of nitrogen-doped carbon nano composite material and its production and use Download PDFInfo
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- CN107240506A CN107240506A CN201610182655.4A CN201610182655A CN107240506A CN 107240506 A CN107240506 A CN 107240506A CN 201610182655 A CN201610182655 A CN 201610182655A CN 107240506 A CN107240506 A CN 107240506A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 81
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 71
- -1 aromatic nitrile compounds Chemical class 0.000 claims abstract description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000002086 nanomaterial Substances 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 17
- 150000002825 nitriles Chemical class 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 31
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 30
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 29
- 239000007772 electrode material Substances 0.000 claims description 19
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
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- 125000003118 aryl group Chemical group 0.000 claims description 3
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
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- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
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- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
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- KAXYYLCSSXFXKR-UHFFFAOYSA-N 4-(4-cyanophenyl)benzonitrile Chemical group C1=CC(C#N)=CC=C1C1=CC=C(C#N)C=C1 KAXYYLCSSXFXKR-UHFFFAOYSA-N 0.000 description 3
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- 244000131316 Panax pseudoginseng Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- 235000008434 ginseng Nutrition 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- GHFGOVUYCKZOJH-UHFFFAOYSA-N pyridine-2,3-dicarbonitrile Chemical compound N#CC1=CC=CN=C1C#N GHFGOVUYCKZOJH-UHFFFAOYSA-N 0.000 description 1
- HLAGQMFURMNTLW-UHFFFAOYSA-N pyridine-2,4-dicarbonitrile Chemical compound N#CC1=CC=NC(C#N)=C1 HLAGQMFURMNTLW-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of nitrogen-doped carbon nano composite material, the composite has conductive network structure, and nitrogen participates in the formation of conductive network skeleton；The conductive network structure by aromatic nitrile compounds monomer with obtained after carbon nanomaterial in-situ polymerization, or the conductive network structure by the performed polymer of aromatic nitrile compounds monomer polymerize with carbon nanomaterial after obtain.The present invention polymerize the composite construction for obtaining fragrant nitrile polymer/carbon nanomaterial with carbon nanomaterial using aromatic nitrile compounds monomer, carbon nanomaterial provides abundant conductive network and good mechanical tenacity as basic framework, fragrant nitrile polymer has the characteristics of high nitrogen-containing doping and uniform nitrogen are distributed, while having high-specific surface area and equally distributed pore structure；The nitrogen-doped carbon nano composite material that the present invention is provided shows high specific capacitance and cyclical stability in ultracapacitor.
Description
Technical field
The invention belongs to ultracapacitor field, and in particular to a kind of nitrogen-doped carbon nano composite material and its system
Preparation Method and purposes, it is more particularly to a kind of based on fragrant nitrile polymer/electrode material of carbon nanometer, preparation method
With its ultracapacitor of use.
Background technology
Carbon-based supercapacitor forms electric double layer to store electricity by electrolyte ion on the surface of electrode material
Lotus, therefore be not as battery and equally limited by electrochemical reaction speed, so that with fast charging and discharging
Feature, and the cycle-index of circles up to a million can be kept.But the current stage, it is stored in ultracapacitor
Electric energy want order of magnitude lower than battery, so as to limit the business application scope of ultracapacitor.Therefore,
Now for the research of ultracapacitor, mainly do not weakening the premise of device cycle life and power density
Under, make great efforts to improve the energy density of device.Therefore, active material conduct of the research with high specific capacitance characteristic
The electrode material of ultracapacitor seems extremely important.
The research for solving this problem focuses primarily upon the specific surface area for improving material, but even for those
Material with very high ratio surface, their specific capacity is still relatively low.Nitrogen is introduced in carbon material
Group, can not only change the electric conductivity and wellability of material, and can increase material electrochemical activity.
The present invention can be uniformly introduced nitrogen-containing group in carbon material system, be a kind of comparatively ideal raising material ratio
The method of capacitance characteristic.
The use of capacitor electrode material is generally at present dusty material, it is necessary to adhesive is sticked together, with this
If electrode thickness prepared by method is excessive, the obstruction of electrolyte path can be caused.
This area needs to develop a kind of with three-dimensional conductive network, electrolyte circulation is smooth, and can improve super
Material, preparation method and the purposes of level capacitor overall performance.
The content of the invention
In view of the shortcomings of the prior art, present invention employs aromatic nitriles polymer and carbon nanomaterial composite square
Method, the introducing of carbon nanomaterial can not only provide effective electrolyte circulation, and understand leading for reinforcing material system
Electric network, and then improve the overall performance of ultracapacitor, obtain high specific capacitance, stable cycle performance it is super
Level capacitor electrode material.
To achieve these goals, the invention provides a kind of carbon based on aromatic nitriles polymer is nano combined
Material as ultracapacitor electrode material.The carbon nano-composite material that the present invention is provided has abundant shape
Looks structure, high-specific surface area, uniform electric transmission network structure and abundant nitrogen content.
The present invention is realized by following concrete scheme：
A kind of nitrogen-doped carbon nano composite material, the composite has conductive network structure, nitrogen ginseng
With the formation of conductive network skeleton；
The conductive network structure by aromatic nitrile compounds monomer with obtained after carbon nanomaterial in-situ polymerization, or
Conductive network structure described in person by the performed polymer of aromatic nitrile compounds monomer polymerize with carbon nanomaterial after obtain.
It is that the fragrant nitrile polymer that elementary cell synthesis is obtained has high nitrogen by using aromatic nitrile compounds monomer
The excellent specific property of constituent content and uniform nitrogen-doping, while using carbon nanomaterial as basic framework,
Make it have abundant conductive network, good mechanical performance, high-specific surface area and equally distributed hole knot
The characteristics of structure, further high temperature pyrolysis greatly improves its electric conductivity, and obtained nitrogen-doped carbon is nano combined
Material is used as the electrode material of super capacitor, shows good cyclical stability and high rate performance.
In the nitrogen-doped carbon nano composite material that the present invention is provided, nitrogen participates in the formation of network skeleton, makes
The composite have higher fake capacitance, good hydrophilic property, when preparing electrode material for super capacitor,
So that the electrolyte circulation of electrode material is good.
In the nitrogen-doped carbon nano composite material that the present invention is provided, network structure can increase the composite
Electric conductivity, while improve its specific surface area, improve the specific capacitance of the composite.
In-situ polymerization of the present invention refers to using aromatic nitrile compounds monomer as polymerized monomer, carbon nanomaterial from
Polymerization mixes progress polymerisation with aromatic nitrile compounds monomer at the very start；And those skilled in the art also may be used
So that aromatic nitrile compounds monomer is first polymerized into performed polymer, carbon nanomaterial is added afterwards, with fragrant nitrilation
The prepolymer reaction of monomer adduct, is polymerize, and obtains object.
Aromatic nitrile compounds monomer of the present invention be cyano group replace aromatic compound preferably, it is described
Aromatic nitrile compounds monomer is the heteroaromatic compound of the aromatic cycle compound that cyano group replaces or cyano group substitution.
Preferably, the aromatic compound of the cyano group substitution is benzonitrile, para-Phthalonitrile (p-DCB), neighbour
Appointing in benzene dicarbonitrile (o-DCB), isophthalodinitrile (m-DCB) and 1,3,5- tricyanos benzene (TCB)
The combination of a kind or at least two kinds of of meaning.
Preferably, the heteroaromatic compound of the cyano group substitution, hetero atom is preferably nitrogen-atoms, is preferably
The pyridine of cyano group substitution, the number of cyano substituent is at least 2, preferably 2-4.
It is typical but non-limiting to be：2- cyanopyridines, nicotinonitrile, 4- cyanopyridines, 2,4- dicyanos
In pyridine (2,4-DCP), 4,4 '-dicyanobiphenyl (DCBP) and 2,6- dicyanopyridines (2,6-DCP)
Any a kind or at least two kinds of of combination, more preferably 4- cyanopyridines.
Composite of the present invention uses aromatic nitrile compounds monomer as the monomeric substance for preparing polymer,
Because containing cyano group so that polymerization and rearrangement reaction easily occur for the aromatic nitrile compounds；Again because containing
Aromatic rings or aromatic heterocycle so that the product after occurring polymerization and retaking is continuous big π architectures, profit
In the transmission of electronics.
Preferably, the carbon nanomaterial is selected from graphene, grapheme foam, CNT, carbon Nanowire
Any a kind or at least two kinds of of mixing in dimension, carbon nano rod, Nano carbon balls, carbon black, porous activated carbon,
Preferably CNT and graphene.
Preferably, in the composite, nitrogen content be 1~30wt%, such as 3wt%, 8wt%, 12wt%,
17wt%, 21wt%, 25wt%, 28wt% etc., preferably 2~20wt%.
Preferably, the specific surface area of the composite is 100~3000m2/ g, such as 105m2/g、185m2/g、
246m2/g、378m2/g、845m2/g、956m2/g、1087m2/g、1152m2/g、1288m2/g、1235m2/g、
1320m2/g、1454m2/g、1488m2/g、1800m2/g、2400m2/g、2600m2/g、2900m2/ g etc.,
Pore-size distribution is 0.1~100nm.
The specific surface area and pore-size distribution of composite of the present invention use the isothermal adsorption of nitrogen under 77K
Desorption method is determined, and calculates its specific surface area by BET methods, its pore-size distribution is calculated by DFT method.
The second object of the present invention is to provide a kind of nitrogen-doped carbon nano composite material as described in the first purpose
Preparation method, methods described is that aromatic nitrile compounds monomer and carbon nanomaterial are carried out into in-situ polymerization, is obtained
Nitrogen-doped carbon nano composite material；
Preferably, the reaction dissolvent of the in-situ polymerization is molten metal salt or lewis acid.
The third object of the present invention is to provide a kind of a kind of nitrogen as described in the first purpose as described in the first purpose
Adulterate carbon nano-composite material preparation method, methods described be by the performed polymer of aromatic nitrile compounds monomer with
Carbon nanomaterial carries out polymerisation, obtains nitrogen-doped carbon nano composite material；
Preferably, the reaction dissolvent of the polymerisation is molten metal salt or lewis acid；
Preferably for the degree of the performed polymer of the aromatic nitrile compounds monomer, the present invention is defined to pass through
Carbon-13 nmr spectra (13C CP-MAS NMR spectrum) detection, the integral area of 111~112 peak positions
It is the 10%-30% of the integral area of 127~128 peak positions.
In the preparation method of nitrogen-doped carbon nano composite material of the present invention, complete final polymerization it
Before, any opportunity can add carbon nanomaterial and polymer is modified.
Preferably, what the aromatic compound or cyano group that the aromatic nitrile compounds monomer replaces selected from cyano group replaced
Any a kind or at least two kinds of of combination in heteroaromatic compound；Typical but non-limiting fragrant nitrilation
Monomer adduct be selected from cyano group benzene, cyanobiphenyl, cyanofuran, cyanopyridine, cyanopyrrole, cyano thiophene,
Any a kind or at least two kinds of of combination in cyano thiazole, cyanoimidazole；The number of the cyano group substitution is 1
More than individual, preferably 2~4.
Preferably, the aromatic compound of the cyano group substitution is selected from benzonitrile, para-Phthalonitrile, O-phthalic
Any a kind or at least two kinds of of combination in nitrile, isophthalodinitrile and 1,3,5- tricyano benzene.
Preferably, the heteroaromatic compound of the cyano group substitution, hetero atom is preferably nitrogen-atoms, is preferably
The pyridine of cyano group substitution, the number of cyano substituent is at least 2, preferably 2-4；It is typical but unrestricted
Property cyano group substitution heteroaromatic compound be selected from 2- cyanopyridines, nicotinonitrile, 4- cyanopyridines, 2,4-
Any a kind or at least two kinds of of combination in dicyanopyridine, 4,4 '-dicyanobiphenyl and 2,6- dicyanopyridine,
More preferably 4- cyanopyridines.
Preferably, the carbon nanomaterial is selected from graphene, grapheme foam, CNT, carbon Nanowire
Any a kind or at least two kinds of of mixing in dimension, carbon nano rod, Nano carbon balls, carbon black and porous activated carbon,
Any a kind or at least two kinds of of combination preferably in CNT and graphene, and/or carbon nanometer material
Material it is material modified in any a kind or at least two kinds of of combination.
Molten metal salt of the present invention plays a part of solvent and catalyst, as long as can be in the molten state
Holding stablizes Undec fuse salt and is used equally for the present invention.
Preferably, the molten metal salt is selected from metal chloride, preferably copper chloride, stannous chloride, chlorine
Change any a kind or at least two kinds of of combination in zinc, iron chloride, stannic chloride, preferably zinc chloride.
Graphene, grapheme foam, CNT, carbon nano-fiber, carbon nano rod, Nano carbon balls, charcoal
Any a kind or at least two kinds of of mixing in black, porous activated carbon, preferably CNT and graphene.
Preferably, the mass ratio of step (1) the aromatic nitrile compounds monomer and molten metal salt is 1:10~1:1,
Such as 1:9、1:8、1:7、1:6、1:5、1:4、1:3、1:2 etc., preferably 1:8~1:2.
Preferably, the mass ratio of the carbon nanomaterial and aromatic nitrile compounds monomer be 0.1~5, such as 0.3,
1st, 2,3,4 etc., preferably 0.1~1.
The temperature of contact of the present invention is that can keep temperature of the metal salt in molten condition, therefore described
Contact Temperature should select the fusing point in the metal salt between boiling point.
Preferably, the temperature of the in-situ polymerization and polymerisation be selected from the reaction dissolvent fusing point to boiling point,
Preferably be selected from 300~700 DEG C, such as 320 DEG C, 370 DEG C, 430 DEG C, 470 DEG C, 540 DEG C, 580 DEG C, 630 DEG C,
680 DEG C etc., preferably 300~600 DEG C.
Preferably, it is preferable that the time of the in-situ polymerization and polymerisation is 2~100 hours, such as 2
It is hour, 8 hours, 18 hours, 32 hours, 56 hours, 70 hours, 80 hours, 95 hours etc., excellent
Elect as 10~20 hours.
Preferably, the in-situ polymerization and polymerisation are carried out in an inert atmosphere, and the inert atmosphere is argon
Any a kind or at least two kinds of of combination in gas, nitrogen, helium or neon, preferably argon gas and nitrogen
Combination.
Polymer is polymerized to by step (1) aromatic nitrile compounds monomer.
The present invention is by carbon nanomaterial and aromatic nitrile compounds monomer in situ polymerization or and aromatic nitrile compounds
The performed polymer of monomer polymerize obtaining nitrogen-doped carbon nano composite material, higher in order to obtain purity,
The less material of impurity, those skilled in the art can such as be washed after in-situ polymerization or polymerisation is completed
The step of purifying such as washing, dry, the purifying (washing, dry) step is as well known to those skilled in the art
Operation, the present invention is not specifically limited.
Typical but non-limiting washing is included using " 5wt% hydrochloric acid, pure water, tetrahydrofuran washing ", allusion quotation
Type but nonrestrictive drying include " in baking oven, being dried 10 hours at 120 DEG C ".
The three of the object of the invention are to provide a kind of such as the purposes of first purpose nitrogen-doped carbon nano composite material, institute
Stating nitrogen-doped carbon nano composite material is used for the electrode material of ultracapacitor.
The nitrogen-doped carbon nano composite material that the present invention is provided is applicable to acid system, alkali systems and organic solution
It is widely applicable in various types of ultracapacitors such as system.
The four of the object of the invention are to provide a kind of ultracapacitor, and the ultracapacitor is with claims 1 to 3
One of the nitrogen-doped carbon nano composite material be electrode material.
Preferably, the electrode of the ultracapacitor is uniformly mixed by electrode material with binding agent, passes through roll
Machine rolling is in blocks, and diameter 1.1cm disk is cut into slicer..
Preferably, the mass ratio of the electrode material and binding agent is 9:1.
Preferably, the binding agent is selected from Kynoar, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose or fourth
Any a kind or at least two kinds of of combination in benzene rubber, preferably Kynoar.
Compared with prior art, the present invention has the advantages that：
The present invention is using aromatic nitrile compounds monomer and carbon nanomaterial in-situ polymerization or polymerize that to obtain aromatic nitriles poly-
The composite construction of compound/carbon nanomaterial, carbon nanomaterial provides abundant conductive network as basic framework
With good mechanical tenacity, fragrant nitrile polymer has the characteristics of high nitrogen-containing doping and uniform nitrogen are distributed,
There is high-specific surface area and equally distributed pore structure simultaneously；
The nitrogen-doped carbon nano composite material that the present invention is provided shows high specific capacitance in ultracapacitor, followed
Ring stability energy, under 0.5A/g current density, specific capacitance is 336F/g；In 10A/g electric current
Under density, specific capacitance is 265F/g；Circulation 10000 is enclosed under 10A/g current density, and specific capacity does not decline
Subtract.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of nitrogen-doped carbon nano composite material prepared by embodiment 1；
Fig. 2 is isothermal adsorption desorption curve and the aperture of nitrogen-doped carbon nano composite material prepared by embodiment 1
Distribution map；
Fig. 3 is electrode material institute group prepared by the method by embodiment 1 determined by constant current charge-discharge test
The specific capacitance of the alkaline ultracapacitor of dress-current density plot figure；
Fig. 4 is electrode material institute prepared by the method by embodiment 1 measured when current density is 10A/g
The specific capacitance of the alkaline ultracapacitor of assembling-cycle-index curve map.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art it will be clearly understood that
The embodiment is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
Para-Phthalonitrile (p-DCB) 1g and multi-walled carbon nanotube 0.2g are added in 100mL ethanol,
The lower ethanol evaporation solvents of 78 DEG C of stirrings, obtain both compounds, then by this compound and anhydrous zinc chloride 5.32g
It is well mixed, and be transferred in tube furnace, react 10 hours, naturally cooled to after room temperature at 600 DEG C,
Obtained carbon nano-composite material is washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, is then placed in
In baking oven, dried 10 hours at 120 DEG C, obtain nitrogen-doped carbon nano composite material.
Performance characterization：
The ratio surface of the nitrogen-doped carbon nano composite material and pore-size distribution use the isothermal of nitrogen under 77K
Adsorption-desorption method is determined, and its specific surface area is calculated by BET methods, and its aperture point is calculated by DFT method
Cloth.Specific surface area is 2300m2/ g, average pore size 1.126nm.Nitrogen content passes through x-ray photoelectron power spectrum
Analysis (XPS) is obtained, and nitrogen content is 10%；
Fig. 1 is the transmission electron microscope photo of nitrogen-doped carbon nano composite material prepared by embodiment 1；Fig. 2 is real
Apply the isothermal adsorption desorption curve and graph of pore diameter distribution of the nitrogen-doped carbon nano composite material of the preparation of example 1；
Performance test：
The composite of preparation is mixed with binding agent and rolls and cut into 1.1cm electrode slices, quality phase is weighed
Same two panels is respectively as the two poles of the earth, and using stainless (steel) wire as collector, 6mol/L potassium hydroxide aqueous solutions are used as electricity
Liquid is solved, being assembled into two electrode super capacitors from CR2032 size batteries shell and Celgard barrier films carries out perseverance
Current charge-discharge electrical testing, test voltage scope is 0~0.9V.Under 0.5A/g current density, specific capacitance is
336F/g；Under 10A/g current density, specific capacitance is 265F/g；Followed under 10A/g current density
Ring 10000 is enclosed, and specific capacity does not decay.
Fig. 3 is electrode material institute group prepared by the method by embodiment 1 determined by constant current charge-discharge test
The specific capacitance of the alkaline ultracapacitor of dress-current density plot figure；
Fig. 4 is electrode material institute prepared by the method by embodiment 1 measured when current density is 10A/g
The specific capacitance of the alkaline ultracapacitor of assembling-cycle-index curve map.
Embodiment 2
Isophthalodinitrile (m-DCB) 1g and multi-walled carbon nanotube 0.2g are added in 100mL ethanol,
Ethanol evaporation solvent under being stirred at 78 DEG C, obtains both compounds, then by this compound and anhydrous zinc chloride
5.32g is well mixed, and is transferred in tube furnace, is reacted 10 hours at 600 DEG C, is naturally cooled to room temperature
Afterwards, obtained carbon nano-composite material is washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, then
It is put into baking oven, is dried 10 hours at 120 DEG C, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 10%, and under 0.5A/g current density, specific capacitance is 332F/g；
Under 10A/g current density, specific capacitance is 267F/g；10000 are circulated under 10A/g current density
Circle, specific capacity does not decay.
Embodiment 3
Phthalonitrile (o-DCB) 1g and multi-walled carbon nanotube 0.2g are added in 100mL ethanol,
The lower ethanol evaporation solvents of 78 DEG C of stirrings, obtain both compounds, then by this compound and anhydrous zinc chloride 5.32g
It is well mixed, and be transferred in tube furnace, react 10 hours, naturally cooled to after room temperature at 600 DEG C,
Obtained carbon nano-composite material is washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, Ran Houfang
Enter in baking oven, dried 10 hours at 120 DEG C, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 10%, and under 0.5A/g current density, specific capacitance is 335F/g；
Under 10A/g current density, specific capacitance is 263F/g；10000 are circulated under 10A/g current density
Circle, specific capacity does not decay.
Embodiment 4
Para-Phthalonitrile (p-DCB) 1g and graphene 0.2g are added in 100mL ethanol, at 78 DEG C
The lower ethanol evaporation solvent of stirring, obtains both compounds, then this compound is mixed with anhydrous zinc chloride 5.32g
Close uniform, and be transferred in tube furnace, react 10 hours, naturally cooled to after room temperature at 600 DEG C, will
Obtained carbon nano-composite material is washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, is then placed in baking
In case, dried 10 hours at 120 DEG C, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 9.5%, and under 0.5A/g current density, specific capacitance is 342F/g；
Under 10A/g current density, specific capacitance is 276F/g；10000 are circulated under 10A/g current density
Circle, specific capacity does not decay.
Embodiment 5
Isophthalodinitrile (m-DCB) 1g and graphene 0.2g are added in 100mL ethanol, at 78 DEG C
The lower ethanol evaporation solvent of stirring, obtains both compounds, then this compound is mixed with anhydrous zinc chloride 5.32g
Close uniform, and be transferred in tube furnace, react 10 hours, naturally cooled to after room temperature at 600 DEG C, will
Obtained carbon nano-composite material is washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, is then placed in
In baking oven, dried 10 hours at 120 DEG C, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 9%, and under 0.5A/g current density, specific capacitance is 345F/g；
Under 10A/g current density, specific capacitance is 273F/g；Circulation 10000 is enclosed under 10A/g current density,
Specific capacity does not decay.
Embodiment 6
Phthalonitrile (o-DCB) 1g and graphene 0.2g are added in 100mL ethanol, at 78 DEG C
The lower ethanol evaporation solvent of stirring, obtains both compounds, then this compound is mixed with anhydrous zinc chloride 5.32g
Close uniform, and be transferred in tube furnace, react 10 hours, naturally cooled to after room temperature at 600 DEG C, will
Obtained carbon nano-composite material is washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, is then placed in baking
In case, dried 10 hours at 120 DEG C, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 9.5%, and under 0.5A/g current density, specific capacitance is 343F/g；
Under 10A/g current density, specific capacitance is 278F/g；10000 are circulated under 10A/g current density
Circle, specific capacity does not decay.
Embodiment 7
After bacteria cellulose is freezed, 800 DEG C of carbonization 1h in tube furnace are placed in, by obtained carbon fibre material
0.2g and 1,3,5- tricyano benzene (TCB) 1g are immersed in 100mL tetrahydrofurans, and four are evaporated at 70 DEG C
Hydrogen THF solvent, obtains both compounds, then this compound is well mixed with anhydrous zinc chloride 4.45g,
And be transferred in tube furnace, react 10 hours, naturally cool to after room temperature, by obtained carbon at 600 DEG C
Nano composite material is washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, is then placed in baking oven,
Dried 10 hours at 120 DEG C, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 7%, and under 0.5A/g current density, specific capacitance is 329F/g；
Under 10A/g current density, specific capacitance is 266F/g；Circulation 10000 is enclosed under 10A/g current density,
Specific capacity does not decay.
Embodiment 8
After bacteria cellulose is freezed, 800 DEG C of carbonization 1h in tube furnace are placed in, by obtained carbon fibre material
0.2g and 2,4- dicyanopyridine (2,4-DCP) 1g are immersed in 100mL tetrahydrofurans, are steamed at 70 DEG C
Tetrahydrofuran solvent is sent out, both compounds are obtained, then this compound is mixed with anhydrous zinc chloride 5.28g
It is even, and be transferred in tube furnace, reacted 10 hours at 600 DEG C, naturally cool to after room temperature, will obtain
Carbon nano-composite material washed successively with 5wt% hydrochloric acid, pure water, tetrahydrofuran, be then placed in baking oven,
Dried 10 hours at 120 DEG C, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 11%, and under 0.5A/g current density, specific capacitance is 344F/g；
Under 10A/g current density, specific capacitance is 272F/g；10000 are circulated under 10A/g current density
Circle, specific capacity does not decay.
Embodiment 9
After bacteria cellulose is freezed, 800 DEG C of carbonization 1h in tube furnace are placed in, by obtained carbon fibre material
0.2g and 4,4 '-dicyanobiphenyl 1g is immersed in 100mL tetrahydrofurans, and tetrahydrofuran is evaporated at 70 DEG C
Solvent, obtains both compounds, then this compound is well mixed with anhydrous zinc chloride 3.34g, and shifts
Into tube furnace, react 10 hours, naturally cooled to after room temperature at 600 DEG C, obtained carbon nanometer is multiple
Condensation material is washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, is then placed in baking oven, at 120 DEG C
Lower drying 10 hours, obtains nitrogen-doped carbon nano composite material.The composite nitrogen content is 8%,
Under 0.5A/g current density, specific capacitance is 331F/g；Under 10A/g current density, specific capacitance is
270F/g；Circulation 10000 is enclosed under 10A/g current density, and specific capacity does not decay.
Embodiment 10
After bacteria cellulose is freezed, 800 DEG C of carbonization 1h in tube furnace are placed in, by obtained carbon fibre material
0.2g and para-Phthalonitrile (p-DCB) 1g is immersed in 100mL ethanol, the ethanol evaporation solvent at 78 DEG C,
Both compounds are obtained, then this compound is well mixed with anhydrous ferric chloride 6.93g, and are transferred to tubular type
In stove, react 10 hours, naturally cool to after room temperature, by obtained carbon nano-composite material at 600 DEG C
Washed, be then placed in baking oven with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, dried at 120 DEG C
10 hours, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 9%, and under 0.5A/g current density, specific capacitance is 328F/g；
Under 10A/g current density, specific capacitance is 264F/g；10000 are circulated under 10A/g current density
Circle, specific capacity does not decay.
Embodiment 11
Para-Phthalonitrile (p-DCB) 1g and multi-walled carbon nanotube 0.1g are added in 100mL ethanol,
The lower ethanol evaporation solvents of 78 DEG C of stirrings, obtain both compounds, then by this compound and anhydrous zinc chloride 10g
It is well mixed, and be transferred in tube furnace, react 100 hours, naturally cooled to after room temperature at 700 DEG C,
Obtained carbon nano-composite material is washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, is then placed in
In baking oven, dried 10 hours at 120 DEG C, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 11%, and under 0.5A/g current density, specific capacitance is 330F/g；
Under 10A/g current density, specific capacitance is 259F/g；10000 are circulated under 10A/g current density
Circle, specific capacity does not decay.
Embodiment 12
Para-Phthalonitrile (p-DCB) 1g and multi-walled carbon nanotube 5g are added in 100mL ethanol,
The lower ethanol evaporation solvents of 78 DEG C of stirrings, obtain both compounds, then by this compound and anhydrous zinc chloride 1g
It is well mixed, and be transferred in tube furnace, react 2 hours, naturally cooled to after room temperature at 300 DEG C, will
Obtained carbon nano-composite material is washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran successively, is then placed in baking
In case, dried 10 hours at 120 DEG C, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 4%, and under 0.5A/g current density, specific capacitance is 296F/g；
Under 10A/g current density, specific capacitance is 207F/g；Circulation 10000 is enclosed under 10A/g current density,
Specific capacity conservation rate is 82%.
Embodiment 13
Para-Phthalonitrile 1g is placed in flask, vacuum nitrogen gas three times is placed in 0 DEG C of water-bath, injected
Trifluoromethanesulfonic acid 5mL, stir 4h, reaction product is placed in 80 DEG C of baking ovens and is evaporated, by obtained product with
Multi-walled carbon nanotube 0.2g is added in 100mL ethanol, the lower ethanol evaporation solvent of 78 DEG C of stirrings, obtains both
Compound, then this compound is well mixed with anhydrous zinc chloride 5g, and be transferred in tube furnace, at 600 DEG C
Lower reaction 10 hours, naturally cools to after room temperature, obtained carbon nano-composite material is used into 5wt% salt successively
Acid, pure water, tetrahydrofuran washing, are then placed in baking oven, dry 10 hours, obtain at 120 DEG C
Nitrogen-doped carbon nano composite material.
The composite nitrogen content is 10%, and under 0.5A/g current density, specific capacitance is 328F/g；
Under 10A/g current density, specific capacitance is 257F/g；10000 are circulated under 10A/g current density
Circle, specific capacity conservation rate is 95%.
Comparative example 1
Para-Phthalonitrile (p-DCB) 1g and multi-walled carbon nanotube 0.2g are added in 100mL ethanol,
The lower ethanol evaporation solvent of 78 DEG C of stirrings, obtains both compounds, and is transferred in tube furnace, at 600 DEG C
Reaction 10 hours, naturally cool to after room temperature, by obtained carbon nano-composite material successively with 5wt% hydrochloric acid,
Pure water, tetrahydrofuran washing, are then placed in baking oven, are dried 10 hours at 120 DEG C, obtain nitrogen and mix
Miscellaneous carbon nano-composite material.
The composite nitrogen content is 5%, and under 0.5A/g current density, specific capacitance is 284F/g；
Under 10A/g current density, specific capacitance is 198F/g；10000 are circulated under 10A/g current density
Circle, specific capacity conservation rate is 86%.
Comparative example 2
Para-Phthalonitrile (p-DCB) 1g is well mixed with anhydrous zinc chloride 5.32g, and is transferred to tube furnace
In, at 600 DEG C react 10 hours, naturally cool to after room temperature, by obtained carbon nano-composite material according to
It is secondary to be washed with 5wt% hydrochloric acid, pure water, tetrahydrofuran, it is then placed in baking oven, 10 is dried at 120 DEG C
Hour, obtain nitrogen-doped carbon nano composite material.
The composite nitrogen content is 12%, and under 0.5A/g current density, specific capacitance is 306F/g；
Under 10A/g current density, specific capacitance is 224F/g；10000 are circulated under 10A/g current density
Circle, specific capacity conservation rate is 78%.
Applicant states that the present invention illustrates the detailed process equipment and technique of the present invention by above-described embodiment
Flow, but the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention
Having to rely on above-mentioned detailed process equipment and technological process could implement.Person of ordinary skill in the field should
This is clear, any improvement in the present invention, the equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (9)
1. a kind of nitrogen-doped carbon nano composite material, it is characterised in that the composite has conductive network
Structure, nitrogen participates in the formation of conductive network skeleton；
The conductive network structure by aromatic nitrile compounds monomer with obtained after carbon nanomaterial in-situ polymerization, or
Conductive network structure described in person by the performed polymer of aromatic nitrile compounds monomer polymerize with carbon nanomaterial after obtain.
2. composite as claimed in claim 1, it is characterised in that the aromatic nitrile compounds monomer is
The aromatic cycle compound of cyano group substitution or the heteroaromatic compound of cyano group substitution
Preferably, the aromatic compound of cyano group substitution be benzonitrile, para-Phthalonitrile, phthalonitrile,
Any a kind or at least two kinds of of combination in isophthalodinitrile and 1,3,5- tricyano benzene；
Preferably, the heteroaromatic compound of the cyano group substitution, hetero atom is preferably nitrogen-atoms, is preferably
The pyridine of cyano group substitution, the number of cyano substituent is at least 2, preferably 2-4；
Preferably, the carbon nanomaterial is selected from graphene, grapheme foam, CNT, carbon Nanowire
Any a kind or at least two kinds of of mixing in dimension, carbon nano rod, Nano carbon balls, carbon black, porous activated carbon.
3. composite as claimed in claim 1 or 2, it is characterised in that in the composite, nitrogen
Content is 1~30wt%, preferably 2~20wt%；
Preferably, the specific surface area of the composite is 100~3000m2/ g, pore-size distribution is 0.5~100nm.
4. a kind of preparation method of nitrogen-doped carbon nano composite material as described in one of claims 1 to 3, its
It is characterised by, methods described is that aromatic nitrile compounds monomer and carbon nanomaterial are carried out into in-situ polymerization, is obtained
Nitrogen-doped carbon nano composite material；
Preferably, the reaction dissolvent of the in-situ polymerization is molten metal salt or lewis acid.
5. a kind of preparation method of nitrogen-doped carbon nano composite material as described in one of claims 1 to 3, its
It is characterised by, methods described is by the performed polymer of aromatic nitrile compounds monomer and carbon nanomaterial polymerize instead
Should, obtain nitrogen-doped carbon nano composite material；
Preferably, the reaction dissolvent of the polymerisation is molten metal salt or lewis acid.
6. the preparation method of the nitrogen-doped carbon nano composite material as described in claim 4 or 5, its feature exists
In the aromatic nitrile compounds monomer is selected from the aromatic compound of cyano group substitution or the aromatic heterocycle of cyano group substitution
Any a kind or at least two kinds of of combination in compound,
Preferably, the aromatic compound of the cyano group substitution is selected from benzonitrile, para-Phthalonitrile, O-phthalic
Any a kind or at least two kinds of of combination in nitrile, isophthalodinitrile and 1,3,5- tricyano benzene；
Preferably, the heteroaromatic compound of the cyano group substitution, hetero atom is preferably nitrogen-atoms, is preferably
The pyridine of cyano group substitution, the number of cyano substituent is at least 2, preferably 2-4.
Preferably, the carbon nanomaterial is selected from graphene, grapheme foam, CNT, carbon Nanowire
Any a kind or at least two kinds of of mixing in dimension, carbon nano rod, Nano carbon balls, carbon black and porous activated carbon,
Preferably CNT and graphene；
Preferably, the molten metal salt is selected from metal chloride, preferably copper chloride, stannous chloride, chlorine
Change any a kind or at least two kinds of of combination in zinc, iron chloride, stannic chloride, preferably zinc chloride；
Preferably, the lewis acid is selected from trifluoromethanesulfonic acid or/and sulphur；
The mass ratio of the aromatic nitrile compounds monomer and molten metal salt is 1:10~1:1, preferably 1:8~1:2；
The mass ratio of the carbon nanomaterial and aromatic nitrile compounds monomer is 0.1~5, preferably 0.1~1.
7. the preparation method as described in one of claim 4~6, it is characterised in that the in-situ polymerization and polymerization
The temperature of reaction is selected from the fusing point of the reaction dissolvent to boiling point, preferably is selected from 300~700 DEG C, preferably
300~600 DEG C；
Preferably, the time of the in-situ polymerization and polymerisation is 2~100 hours, and preferably 10~20 is small
When；
Preferably, the in-situ polymerization and polymerisation are carried out in an inert atmosphere, and the inert atmosphere is argon
Any a kind or at least two kinds of of combination in gas, nitrogen, helium or neon, preferably argon gas and nitrogen
Combination.
8. a kind of purposes of the nitrogen-doped carbon nano composite material as described in one of claims 1 to 3, its feature exists
In the nitrogen-doped carbon nano composite material is used for the electrode material of ultracapacitor.
9. a kind of ultracapacitor, it is characterised in that the ultracapacitor is with one of claims 1 to 3 institute
Nitrogen-doped carbon nano composite material is stated for electrode material.
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