CN107275116A - Nitrogen-doped ordered porous high-conductivity graphene fiber and preparation method and application thereof - Google Patents
Nitrogen-doped ordered porous high-conductivity graphene fiber and preparation method and application thereof Download PDFInfo
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- CN107275116A CN107275116A CN201710323841.XA CN201710323841A CN107275116A CN 107275116 A CN107275116 A CN 107275116A CN 201710323841 A CN201710323841 A CN 201710323841A CN 107275116 A CN107275116 A CN 107275116A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000000835 fiber Substances 0.000 title claims abstract description 155
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 150
- 238000002360 preparation method Methods 0.000 title abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 15
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
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- ZAZKKCQEYGCTGV-UHFFFAOYSA-N C(C)N1C(N(C=C1)C)S(=O)(=O)N Chemical class C(C)N1C(N(C=C1)C)S(=O)(=O)N ZAZKKCQEYGCTGV-UHFFFAOYSA-N 0.000 claims description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a nitrogen-doped ordered porous high-conductivity graphene fiber and a preparation method and application thereof; the method is characterized in that the mass doping amount of the active nitrogen is 0.7-26.3%; the diameter of the fiber is 25 to 350 microns. The preparation method comprises the following steps: taking natural graphite flakes as raw materials, and preparing high-concentration graphene oxide dispersion liquid according to a Hummers improved method; fully stirring and uniformly mixing the graphene oxide dispersion liquid and a water-soluble nitrogen-containing precursor, injecting the mixture into a cylindrical slender pipeline, sealing two ends of the cylindrical slender pipeline, and heating and pre-reducing the mixture to obtain amino functionalized graphene fibers; opening two ends, sealing and drying to obtain dehydrated amino functionalized graphene fibers; and then heating and preserving heat under the continuous gas protection to obtain the nitrogen-doped ordered porous high-conductivity graphene fiber. The invention has the advantages of low cost, simple process, environmental protection and suitability for large-scale industrial production, and the obtained capacitor has good flexibility, high specific capacitance and good cyclicity, and can be used in a plurality of fields such as energy storage, flexible wearable electronics and the like.
Description
Technical field
The present invention relates to graphene fiber field, more particularly to a kind of ordered porous highly conductive graphene fiber of N doping and
Its preparation method and application.
Background technology
Ultracapacitor, is called electrochemical capacitor, and the interface for being built upon roentgen Helmholtz proposition is double
A kind of brand-new energy-storage travelling wave tube in electric layer theoretical foundation.It can be divided into double layer capacitor and fake capacitance by energy storage principle difference
Device, the former is mainly using porous carbon materials as electrode, and the latter is mainly used as electrode material using metal oxide or conducting polymer
Material.Compared with fuel cell and lithium ion battery, it has higher power density, faster charge/discharge rates and longer followed
The ring life-span.Wherein, the one dimension fibre ultracapacitor being made up of compliant conductive fiber electrode is because the characteristics of it can weave and can
Dress the application potential in electronic device and be increasingly becoming study hotspot.
Graphene is a kind of novel planar two-dimensional nano-carbon material (Science, the 2004,306,666- that find in 2004
669), because it has high intensity, great specific surface area, excellent electric conductivity and thermal conductivity and can be by cheap change
The advantages of method is converted, and it is increasingly becoming one of optimal electrode material of electric double layer fiber type ultracapacitor.For example, Zhejiang
The superb et al. of Jiang great Xue is prepared for the graphene/carbon nano-tube composite fibre electricity that polyelectrolyte is wrapped up by coaxial wet spinning
Pole, the introducing of CNT improves filamentary conductive so that the energy-storage property of fibre supercapacitors is improved
(Nat.Commun.,2014,5,3754)；Peng Huisheng of Fudan University et al. is prepared for graphene oxide/lead by hydro-thermal assembling
Electric polymer composite fibre electrode, because conducting polymer avtive spot introduces fake capacitance in the capacitor, so as to improve
The capacitance (Adv.Mater., 2016,28,3646-3652) of ultracapacitor.
Although the research on graphene fiber super capacitor has made some progress both at home and abroad, its electrochemistry
Can be still barely satisfactory.To find out its cause, the graphene fiber being prepared by various methods at present will not excavate carbon material
Electric double layer capacitance and create that both additional fake capacitances are synchronous to be realized, thus the improvement of chemical property and room for promotion extremely have
Limit.
The content of the invention
The purpose of the present invention is that there is provided a kind of ordered porous highly conductive graphene of N doping is fine in view of the shortcomings of the prior art
Dimension, it is a further object of the present invention to provide the preparation method of the ordered porous highly conductive graphene fiber of above-mentioned N doping, this method
With low cost, technique is simple, be easy to large-scale production；It is ordered porous highly conductive that the present invention is also purposefully to provide above-mentioned N doping
The application of graphene fiber again in ultracapacitor.
The technical scheme is that：Using graphene oxide and organic nitrogen source in extensible limited heating passage
Amino functional is realized in self assembly, then is aided with the uniform pyrolysis pore-forming that program control high temperature reduction realizes nitrogen source, finally gives activity
N doping, the graphene fiber that surface is ordered porous, specific surface area is big, electrical conductivity is high, toughness is good.Wherein surface is formed in order
The specific surface area for significantly improving ionic adsorption and the passage of migration are given full play to the electric double layer capacitance of carbon material by loose structure；
And active N doping will provide extra fake capacitance for carbon material；Electric conductivity, which is improved, will reduce internal resistance, advantageously be passed in electronics
It is defeated, thus the total capacitance of graphene fiber is greatly improved.
The present invention concrete technical scheme be：A kind of ordered porous highly conductive graphene fiber of N doping, it is characterised in that
The quality doping scope of active nitrogen is 0.7~26.3%；Fibre diameter is uniform, regulates and controls in 25~350 micrometer ranges；Fiber
The uniform porous network structure in surface, pore size distribution range is 1.5~200nm, and specific surface area scope is 200~805m2/ g, conductance
Rate scope is 11006~100300S/m.
Present invention also offers a kind of method for preparing the ordered porous highly conductive graphene fiber of above-mentioned N doping, its is specific
Step is as follows：
1) using natural graphite flakes as raw material, graphene oxide water solution is prepared according to Hummers improved methods, through high speed centrifugation
After concentration, 8~20mg/mL graphene oxide dispersion is obtained；
2) by step 1) in graphene oxide dispersion be thoroughly mixed uniformly with water-soluble nitrogenous precursor, with 5
~100mL/h extruded velocity into cylindrical microchannels and seals two ends above-mentioned mixed liquor by needle injection, heating
Prereduction obtains amino functional graphene fiber；
3) by step 2) in cylindrical elongate tube-cooled to two ends sealing is opened after room temperature, dried at 50~100 DEG C
It is dry to obtain dry amino functional graphene fiber；
4) dry amino functional graphene fiber is placed in tube furnace, be heated under continuous gas shield
600~1400 DEG C and it is incubated, further reduction and the pyrolysis pore-forming of nitrogenous precursor by graphene oxide obtain N doping
Ordered porous highly conductive graphene fiber.
Preferred steps 1) described in native graphite chip size be 100~500 mesh sizes；Described high speed centrifugation be
Centrifugal concentrating 30~60 minutes under 10000~13000rpm rotating speeds.
Preferred steps 2) described in water-soluble nitrogenous precursor be urea, cyanamid dimerization or melamine in one kind or
A variety of mixing compositions；Graphene oxide and the mass ratio of water-soluble nitrogenous precursor are 1:(0.1~5)；Step 2) described in
The material of cylindrical microchannels is one kind in glass or polytetrafluoroethylene (PTFE)；The pipeline interior diameter of cylindrical microchannels is 1~8 milli
Rice.
Preferred steps 2) described in heating prereduction be：1~6h is first heated at a temperature of 70~100 DEG C, then 140
1~10h of hydro-thermal reaction at a temperature of~280 DEG C.
Preferred steps 4) described in gas be one or more mixing compositions in hydrogen, argon gas or nitrogen；Gas stream
Speed is 50~300sccm.
Preferred steps 4) in heating rate be 0.5~5 DEG C/min, soaking time be 1h~20h.
Ultracapacitor is being prepared present invention also offers the ordered porous highly conductive graphene fiber of above-mentioned N doping
Using；It is comprised the following steps that：
The N doping porous graphene fiber that two length are 3.5~10.5 centimetres, thickness is basically identical is separated by 1~3
Spacing is parallel is fixed in substrate for millimeter, and it be connected by one end conductive silver glue that every fiber is protruded with plain conductor, centre
Part coating parcel gel electrolyte solution, natural air drying is treated to produce N doping after the solvent volatilization in gel electrolyte solution
Ordered porous highly conductive graphene fiber solid gel electrolyte ultracapacitor.
It is preferred that above-mentioned substrate is one kind in sheet glass or polyethylene terephthalate transparent resilient plastic film；
Described gel electrolyte is acid system or the gellike electrolyte of ion liquid system two, wherein acid system gel electrolyte institute
Acid is phosphoric acid or sulfuric acid, and gel electrolyte skeleton polymer used is polyvinyl alcohol, matter of the acid in dielectric substrate
It is 10~80% to measure percentage range；Ionic liquid used in ion liquid system gel electrolyte is 1- ethyl -3- methyl miaows
Azoles tetrafluoroborate or 1- ethyl-3-methylimidazole sulfonamides, gel electrolyte skeleton polymer used is poly-
(vinylidene-fluoride-co-hexafluoropropylene), chitosan or thermoplastic polyurethane, quality percentage of the ionic liquid in dielectric substrate
It is 10~80% than scope.
The present invention illustrates a kind of ordered porous highly conductive graphene fiber material of new N doping and preparation method
With the application example in ultracapacitor.It is combined by the assembling of nitrogenous precursor and graphene oxide and program control pyrolysis, no
The ordered porous network structure increase specific surface area of classification is only formed on graphene fiber surface and then electric double layer capacitance is improved, and
Realize graphene fiber situ Nitrogen Doping and contribute to fake capacitance for carbon material, while the introducing of nitrogen avtive spot can also improve fibre
The electric conductivity of dimension, under these three advantages, the chemical property of constructed fibre supercapacitors has been obtained significantly
Improve, its specific capacitance is about 4 times of 3 times of pure graphene fiber and the current peak in fibre supercapacitors field, and this is full
The demand of sufficient high energy storage provides sound assurance.In addition, we use new microfluidic be oriented to fiber into
Type technology provides for extensive, the continuous controllable homogeneous High-performance graphene fiber of production and then the ultracapacitor that obtains weaving
May.
Beneficial effect：
1) raw material uses graphene oxide and conventional water-soluble nitrogenous precursor, and raw material is easy to get, with low cost；
2) amino functional graphene fiber is prepared for simple and easy to applyly；
3) amino functional graphene fiber is easily very changed into the ordered porous fiber in N doping surface, it compares
Surface area is close to 805m2/ g, electrical conductivity is more than 100300S/m；
4) fibre supercapacitors, simple to operate, environmental protection, the danger of electroless matter leakage are prepared using two-wire parallel method
Evil；
5) effective length of fibre supercapacitors made from can freely be adjusted according to the fibre length used；
6) fibre supercapacitors made from have high specific capacity and stable charge-discharge characteristic；
7) fibre supercapacitors made from have excellent pliability.
Brief description of the drawings
Fig. 1 is 1 in the ordered porous highly conductive graphene fiber super capacitor schematic diagram of N doping prepared by the present invention, figure
It is gel electrolyte for the ordered porous highly conductive graphene fiber of N doping, 2,3 be conductive silver glue, and 4 be plain conductor, and 5 be base
Bottom；
Fig. 2 is the low power radial scan Electronic Speculum of the ordered porous highly conductive graphene fiber of N doping in present example 1
Figure；
Fig. 3 is the high power radial scan Electronic Speculum of the ordered porous highly conductive graphene fiber of N doping in present example 1
Figure；
Fig. 4 is the cross-sectional scans electron microscope of the ordered porous highly conductive graphene fiber of N doping in present example 1；
Fig. 5 is the X-ray photoelectricity of the ordered porous highly conductive graphene fiber Nitrogen element of N doping in present example 1
Sub- power spectrum；
Fig. 6 is the elasticity demonstration of the ordered porous highly conductive graphene fiber super capacitor of N doping in present example 1
Figure, flexible substrates used are polyethylene terephthalate transparent resilient plastic film, the wherein corresponding angle of bend of Fig. 6 a
For 45 degree, the corresponding angle of bend of Fig. 6 b is 90 degree, and the corresponding angle of bend of Fig. 6 c is 135 degree, the corresponding angle of bend of Fig. 6 d
For 180 degree.
Fig. 7 be in present example 1 the ordered porous highly conductive graphene fiber super capacitor of N doping differently curved
The specific capacitance change curve of angle, current density is 0.1mA/cm2；
Fig. 8 is that the ordered porous highly conductive graphene fiber of N doping and pure graphene fiber in present example 1 are super
Cyclic voltammetric comparison diagram of the capacitor under 5mV/s sweep speeds；
Fig. 9 is the ordered porous highly conductive graphene fiber super capacitor of N doping and pure graphite in present example 1
Alkene fibre supercapacitors are in 0.1mA/cm2Constant current charge-discharge comparison diagram under current density；
Figure 10 is that the ordered porous highly conductive graphene fiber super capacitor of N doping in present example 2 is swept in difference
Retouch the cyclic voltammogram under speed；
Figure 11 is the ordered porous highly conductive graphene fiber super capacitor of N doping in present example 2 in different electricity
Constant current charge-discharge figure under current density.
Embodiment
The purpose of the present invention is to propose to a kind of N doping ordered porous highly conductive graphene fiber and its preparation method, and
The method for preparing ultracapacitor using the ordered porous highly conductive graphene fiber of the N doping, to significantly improve the super electricity of fiber
The chemical property and energy storage characteristic of container provide new approaches.
The method that the present invention prepares the ordered porous highly conductive graphene fiber of N doping comprises the following steps：
Natural graphite flakes using 100~500 mesh sizes prepare graphene oxide water as raw material according to Hummers improved methods
Solution, after more than 10000~13000 rpms rotating speed centrifugal concentratings 30~60 minutes, obtains 8~20mg/mL oxygen
Graphite alkene dispersion liquid；By graphene oxide dispersion and water-soluble nitrogenous precursor (before graphene oxide and water solubility are nitrogenous
The mass ratio for driving body is 1:0.1~1:5) be thoroughly mixed it is uniform, with 5~100mL/h extruded velocity by above-mentioned mixed liquor
Into cylindrical microchannels and two ends are sealed by needle injection, be placed in baking oven and heat prereduction and obtain amino functional fossil
Black alkene fiber；Then two ends sealing will be opened after cylindrical elongate tube-cooled to room temperature, dries and taken off at 50~100 DEG C
Water amino functional graphene fiber；Dry amino functional graphene fiber is placed in tube furnace, in continuous gas
600~1400 DEG C are heated under protection, further reduction and the pyrolysis pore-forming of nitrogenous precursor by graphene oxide are obtained
The ordered porous highly conductive graphene fiber of N doping.Described water-soluble nitrogenous precursor is urea, cyanamid dimerization, melamine
In one or more mixing compositions.The material of described cylindrical elongate pipeline is one kind in glass, polytetrafluoroethylene (PTFE), pipe
Road interior diameter is 1~8 millimeter.Described pre-reduction procedure includes：1~6h, Ran Hou are first heated at a temperature of 70~100 DEG C
1~10h of hydro-thermal reaction at a temperature of 140~280 DEG C.Described continuous gas is that the one or more in hydrogen, argon gas, nitrogen are mixed
It is combined into, gas flow rate is 50~300sccm.Described includes the step of fiber to be heated to 600~1400 DEG C：With 0.5~5
DEG C/fiber is heated to 600~1400 DEG C and is incubated 1h~20h by min heating rate.
The diameter of the ordered porous highly conductive graphene fiber of N doping prepared according to the above method is in 25~350 microns of models
In enclosing, N doping amount scope is 0.7~26.3wt%, and pore size distribution range is 1.5~200nm, specific surface area scope is 200~
805m2/ g, conductivity range is 11006~100300S/m.
The method that the present invention prepares ultracapacitor using the ordered porous highly conductive graphene fiber of N doping includes following
Step：
The N doping porous graphene fiber that two length are 3.5~10.5 centimetres, thickness is basically identical is separated by 1~3
Spacing is parallel is fixed in substrate for millimeter, and it be connected by one end conductive silver glue that every fiber is protruded with plain conductor, centre
Part coating parcel gel electrolyte solution, natural air drying is treated to produce N doping after the solvent volatilization in gel electrolyte solution
Ordered porous highly conductive graphene fiber solid gel electrolyte ultracapacitor (as shown in Figure 1).Described substrate is glass
Piece or polyethylene terephthalate transparent resilient plastic film.Described gel electrolyte includes acid system or ion
The gellike electrolyte of liquid system two.Acid wherein used in acid system gel electrolyte includes phosphoric acid or sulfuric acid, and used is solidifying
Glue electrolyte skeleton polymer is polyvinyl alcohol, and mass percent scope of the acid in dielectric substrate is 10~80%；Ionic liquid
Ionic liquid used in body system gel electrolyte includes 1- ethyl-3-methylimidazoles tetrafluoroborate (EMIBF4) or 1- second
Base -3- methylimidazoles sulfonamide (EMITFSI), gel electrolyte skeleton polymer used include it is poly- (vinylidene -
Co- hexafluoropropene) (PVDF-HFP), chitosan or thermoplastic polyurethane, quality percentage of the ionic liquid in dielectric substrate
It is 10~80% than scope.
The present invention is specifically described below by embodiment, the present embodiment is served only for doing further the present invention
Bright, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art makes one according to the content of foregoing invention
A little nonessential changes and adjustment belong to protection scope of the present invention.
Embodiment 1
Using the natural graphite flakes of 160 mesh as raw material, graphene oxide water solution, warp are prepared according to Hummers improved methods
More than 12000 rpms rotating speed centrifugal concentratings obtain 14mg/mL graphene oxide dispersion after 50 minutes；Take 30mL should
(mass ratio of graphene oxide and urea is 1 to graphene oxide dispersion with 210mg urea:0.5) it is thoroughly mixed uniformly,
It is using 20mL/h extruded velocity that above-mentioned mixed liquor is micro- as 3 millimeters of polytetrafluoroethylene (PTFE) cylinder by needle injection to interior diameter
Sealed in passage and by two ends, be placed in baking oven and 4h is first heated at a temperature of 90 DEG C, then the hydro-thermal reaction 5h at a temperature of 160 DEG C
Obtain amino functional graphene fiber；Then cylindrical microchannels are cooled to after room temperature and open two ends sealing, at 90 DEG C
Drying obtains being dehydrated amino functional graphene fiber；Dry amino functional graphene fiber is placed in tube furnace,
Under gas flow rate is protected for 200sccm continuous argon gas, fiber is heated to 900 DEG C with 2.5 DEG C/min heating rate and protected
Warm 2h, natural cooling obtains the ordered porous highly conductive graphene fiber of N doping.
The morphology characterization of highly conductive graphene fiber ordered porous to N doping is as shown in Figure 2, Figure 3 and Figure 4.Fig. 2 is low
Times radial scan electron microscope, shows that the fiber to be formed is very regular homogeneous, even thickness；Fig. 3 is high power radial scan electron microscope,
Show the densely covered porous network structure uniform in order of fiber surface.Fig. 4 is cross-sectional scans electron microscope, shows that fibrous inside is accumulated
Consolidation, diameter is about 200 microns.Its electrical conductivity is up to 30785S/m, and specific surface area is up to 388.6m2/ g, pore size distribution range
For 2.4~190.5nm, and it is concentrated mainly on mesoporous region.The program control uniform pyrolysis of this explanation nitrogen presoma at high temperature is not only
Active N doping can be realized, and can substantially increase the porosity of fiber, and then improves its specific surface area；Meanwhile, graphene is fine
Dimension still can keep very high electric conductivity.
In addition, in the ordered porous highly conductive graphene fiber of N doping nitrogen x-ray photoelectron power spectrum such as Fig. 5 institutes
Show.It can be seen that there are four peaks at 398.4,400,401.2 and 402.5eV, pyridine nitrogen, pyrroles are corresponded to respectively
The existence form of nitrogen, graphite nitrogen and nitrogen oxide these four nitrogens, this explanation is successfully realized active N doping, and N doping amount
For 5.62wt%.
Two length are separated by 2 millimeters of spacing are parallel to be fixed on for 5.5 centimetres of above-mentioned N doping porous graphene fiber
On polyethylene terephthalate transparent resilient plastic film, one end conductive silver glue that every fiber is protruded is by itself and metal
Wire is connected, center section coating parcel phosphoric acid/polyvinyl alcohol gel electrolyte aqueous solution, and N doping is produced after natural air drying
Ordered porous highly conductive graphene fiber solid gel electrolyte ultracapacitor (mass percent of the phosphoric acid in dielectric substrate
For 50%).
Fibre supercapacitors prepared by this method have good flexibility, as shown in fig. 6, can will be many in order by N doping
The highly conductive graphene fiber super capacitor in hole bends to 180 degree always from 45 degree.Fig. 7 is the constant current under differently curved angle
The variation diagram of specific capacitance obtained by discharge and recharge, it can be seen that prepared ultracapacitor is under different case of bendings
Capacitance does not change substantially, illustrates that performance is highly stable.
To the ordered porous highly conductive graphene fiber (NGFs) of N doping prepared under the same terms and pure graphene fiber
(GFs) electrochemical Characterization of ultracapacitor is as shown in Figure 8 and Figure 9.Fig. 8 is both circulation volts under 5mV/s sweep speeds
Pacify curve, it can be seen that the intimate square of cyclic voltammetry curve of the ordered porous highly conductive graphene fiber super capacitor of N doping
Shape, and area is much larger than pure graphene fiber super capacitor, shows fabulous chemical property.Fig. 9 for both
0.1mA/cm2Constant current charge-discharge curve under current density, it can be seen that the ordered porous highly conductive graphene fiber of N doping
The discharge and recharge time of ultracapacitor is obviously prolonged, the specific capacitance value up to 1132mF/cm thus calculated2, it is not only pure graphite
Alkene fibre supercapacitors (415.3mF/cm2) nearly 3 times, be also the current peak in fibre supercapacitors field
(304.5mF/cm2) nearly 4 times, it was demonstrated that the preparation method of the ordered porous highly conductive graphene fiber of N doping proposed by the present invention
With great superiority.
Embodiment 2
Using the natural graphite flakes of 100 mesh as raw material, graphene oxide water solution, warp are prepared according to Hummers improved methods
More than 13000 rpms rotating speed centrifugal concentratings obtain 20mg/mL graphene oxide dispersion after 60 minutes；Take 30mL should
(mass ratio of graphene oxide and urea is 1 to graphene oxide dispersion with 150mg urea:0.25) it is thoroughly mixed
It is even, using 10mL/h extruded velocity by above-mentioned mixed liquor by needle injection to interior diameter as 4 millimeters of polytetrafluoroethylene (PTFE) cylinder
Sealed in shape microchannel and by two ends, be placed in baking oven and 1h is first heated at a temperature of 100 DEG C, then the hydro-thermal at a temperature of 180 DEG C
Reaction 4h obtains amino functional graphene fiber；Then cylindrical microchannels are cooled to after room temperature and open two ends sealing,
Drying obtains being dehydrated amino functional graphene fiber at 80 DEG C；Dry amino functional graphene fiber is placed in tube furnace
In, in the case where gas flow rate is protected for 50sccm continuous nitrogen, fiber is heated to 1200 DEG C with 0.5 DEG C/min heating rate
And 2h is incubated, natural cooling obtains the ordered porous highly conductive graphene fiber of N doping.Its diameter is about 350 microns, electrical conductivity
Up to 61350S/m, specific surface area is up to 450m2/ g, pore size distribution range is 1.5~160.2nm, and N doping amount is
1.71wt%.
Two length are separated by 3 millimeters of spacing are parallel to be fixed on for 10.5 centimetres of above-mentioned N doping porous graphene fiber
On polyethylene terephthalate transparent resilient plastic film, one end conductive silver glue that every fiber is protruded is by itself and metal
Wire is connected, center section coating parcel EMIBF4/PVDF-HFP gel electrolyte organic solutions, and nitrogen is produced after natural air drying
Adulterate ordered porous highly conductive graphene fiber solid gel electrolyte ultracapacitor (quality of the EMIBF4 in dielectric substrate
80%) percentage be.
To the electrochemical Characterizations of the fibre supercapacitors as shown in Figure 10,11.Figure 10 is that ultracapacitor is swept in difference
The cyclic voltammogram under speed is retouched, shows that it remains to keep almost rectangular curve under high sweep speed, shows super capacitor
The excellent chemical property of device.Figure 11 is constant current charge-discharge curve of the ultracapacitor under different current densities, in 1mA/
cm2It has up to 306.3mF/cm during current density2Specific capacitance, while its power density be 1.5~15W/cm2, energy is close
Spend for 46.9~95.7 μ Wh/cm2, it is the peak in current fibre supercapacitors field.
Embodiment 3
Using the natural graphite flakes of 500 mesh as raw material, graphene oxide water solution, warp are prepared according to Hummers improved methods
More than 10000 rpms rotating speed centrifugal concentratings obtain 8mg/mL graphene oxide dispersion after 30 minutes；Take the 30mL oxygen
(mass ratio of graphene oxide and cyanamid dimerization is 1 to graphite alkene dispersion liquid with 1200mg cyanamid dimerizations:5) it is thoroughly mixed
Uniformly, it is using 100mL/h extruded velocity that above-mentioned mixed liquor is micro- as 8 millimeters of glass cylinder shape by needle injection to interior diameter
Sealed in passage and by two ends, be placed in baking oven and 6h is first heated at a temperature of 70 DEG C, then the hydro-thermal reaction at a temperature of 140 DEG C
10h obtains amino functional graphene fiber；Then two ends sealing will be opened after cylindrical elongate tube-cooled to room temperature,
Drying obtains the dehydration amino functional graphene fiber that volume is further shunk at 100 DEG C；By dry amino functional fossil
Black alkene fiber is placed in tube furnace, in the hydrogen and the argon gas gaseous mixture (volume flow of hydrogen and argon gas that gas flow rate is 300sccm
Amount is than being 5%：95%) under protection, fiber is heated to 600 DEG C with 5 DEG C/min heating rate and 20h is incubated, it is naturally cold
But the ordered porous highly conductive graphene fiber of N doping is obtained.Its diameter is about 300 microns, and electrical conductivity is up to 11006S/m, than
Surface area is up to 200m2/ g, pore size distribution range is 2.1~200nm, and N doping amount is 26.3wt%.
Two length are separated by 1 millimeter of spacing is parallel to be fixed on for 3.5 centimetres of above-mentioned N doping porous graphene fiber
On sheet glass, it is connected by one end conductive silver glue that every fiber is protruded with plain conductor, and center section coating parcel sulfuric acid/
The ordered porous highly conductive graphene fiber solid gel of N doping is produced after polyvinyl alcohol gel electrolyte solution, natural air drying
Electrolyte ultracapacitor (mass percent of the sulfuric acid in dielectric substrate is 80%).Measure in 0.1mA/cm2Current density
When its have up to 389.3mF/cm2Specific capacitance.
Embodiment 4
Using the natural graphite flakes of 200 mesh as raw material, graphene oxide water solution, warp are prepared according to Hummers improved methods
More than 11000 rpms rotating speed centrifugal concentratings obtain 18mg/mL graphene oxide dispersion after 55 minutes；Take 30mL should
(mass ratio of graphene oxide and melamine is 1 to graphene oxide dispersion with 54mg melamines:0.1) it is sufficiently stirred for mixing
Close uniform, it is using 5mL/h extruded velocity that above-mentioned mixed liquor is micro- as 2 millimeters of glass cylinder shape by needle injection to interior diameter
Sealed in passage and by two ends, be placed in baking oven and 2h is first heated at a temperature of 90 DEG C, then the hydro-thermal reaction 1h at a temperature of 280 DEG C
Obtain amino functional graphene fiber；Then cylindrical microchannels are cooled to after room temperature and open two ends sealing, at 50 DEG C
Drying obtains being dehydrated amino functional graphene fiber；Dry amino functional graphene fiber is placed in tube furnace,
(volume flow ratio of hydrogen and nitrogen is 5% to the hydrogen and nitrogen mixture that gas flow rate is 250sccm：95%) protection
Under, fiber is heated to 1400 DEG C with 1.5 DEG C/min heating rate and 1h is incubated, it is ordered porous that natural cooling obtains N doping
Highly conductive graphene fiber.Its diameter is about 150 microns, and electrical conductivity is up to 100300S/m, and specific surface area is up to 805m2/ g holes
Footpath distribution is 1.7~181.3nm, and N doping amount is 0.7wt%.
Two length are separated by 2 millimeters of spacing are parallel to be fixed on for 6.5 centimetres of above-mentioned N doping porous graphene fiber
On sheet glass, it is connected by one end conductive silver glue that every fiber is protruded with plain conductor, center section coating parcel
The ordered porous highly conductive graphene fiber of N doping is produced after EMITFSI/ chitosan gel rubber electrolyte solutions, natural air drying to consolidate
State gel electrolyte ultracapacitor (mass percents of the EMITFSI in dielectric substrate is 10%).Measure in 1mA/cm2Electricity
It has up to 180.7mF/cm during current density2Specific capacitance.
Embodiment 5
Using the natural graphite flakes of 300 mesh as raw material, graphene oxide water solution, warp are prepared according to Hummers improved methods
More than 12000 rpms rotating speed centrifugal concentratings obtain 8mg/mL graphene oxide dispersion after 40 minutes；Take the 30mL oxygen
Graphite alkene dispersion liquid and 240mg cyanamid dimerizations and 240mg melamines be (graphene oxide and cyanamid dimerization and melamine
Mass ratio is 1:1:1) be thoroughly mixed it is uniform, with 60mL/h extruded velocity by above-mentioned mixed liquor by needle injection to interior
In a diameter of 1 millimeter of glass cylinder shape microchannel and two ends are sealed, be placed in baking oven and 4h is first heated at a temperature of 90 DEG C, so
Hydro-thermal reaction 3h obtains amino functional graphene fiber at a temperature of 150 DEG C afterwards；Then cylindrical microchannels are cooled to room
Two ends sealing is opened after temperature, drying obtains being dehydrated amino functional graphene fiber at 70 DEG C；By dry amino functional
Graphene fiber is placed in tube furnace, under protection of the gas flow rate for 150sccm continuous helium, with 3.5 DEG C/min liter
Fiber is heated to 1000 DEG C and is incubated 5h by warm speed, and natural cooling obtains the ordered porous highly conductive graphene fiber of N doping.
Its diameter is about 25 microns, and electrical conductivity is up to 40568S/m, and specific surface area is up to 380m2/ g, pore size distribution range be 1.8~
192.3nm, N doping amount is 12.4wt%.
Two length are separated by 2 millimeters of spacing are parallel to be fixed on for 5.5 centimetres of above-mentioned N doping porous graphene fiber
On polyethylene terephthalate transparent resilient plastic film, one end conductive silver glue that every fiber is protruded is by itself and metal
Wire is connected, center section coating parcel EMIBF4/ thermoplastic polyurethane gel electrolyte solutions, and nitrogen is produced after natural air drying
Adulterate ordered porous highly conductive graphene fiber solid gel electrolyte ultracapacitor (quality of the EMIBF4 in dielectric substrate
40%) percentage be.Measure in 1mA/cm2It has up to 168.9mF/cm during current density2Specific capacitance.
Embodiment 6
Using the natural graphite flakes of 400 mesh as raw material, graphene oxide water solution, warp are prepared according to Hummers improved methods
More than 12000 rpms rotating speed centrifugal concentratings obtain 12mg/mL graphene oxide dispersion after 45 minutes；Take 30mL should
(mass ratio of graphene oxide and melamine is 1 to graphene oxide dispersion with 1080mg melamines:3) it is sufficiently stirred for mixing
Close uniform, using 30mL/h extruded velocity by above-mentioned mixed liquor by needle injection to interior diameter as 5 millimeters of glass cylinder shape
Sealed in microchannel and by two ends, be placed in baking oven and 5h is first heated at a temperature of 80 DEG C, then the hydro-thermal reaction at a temperature of 200 DEG C
2h obtains amino functional graphene fiber；Then cylindrical microchannels are cooled to after room temperature and open two ends sealing, at 90 DEG C
Lower drying obtains being dehydrated amino functional graphene fiber；Dry amino functional graphene fiber is placed in tube furnace,
Under protection of the gas flow rate for 100sccm continuous nitrogen, fiber is heated to 800 DEG C with 4.5 DEG C/min heating rate
And 6h is incubated, natural cooling obtains the ordered porous highly conductive graphene fiber of N doping.Its diameter is about 250 microns, electrical conductivity
Up to 22307S/m, specific surface area is up to 520m2/ g, pore size distribution range is 1.6~176.5nm, and N doping amount is
18.5wt%.
Two length are separated by 3 millimeters of spacing are parallel to be fixed on for 7.5 centimetres of above-mentioned N doping porous graphene fiber
On polyethylene terephthalate transparent resilient plastic film, one end conductive silver glue that every fiber is protruded is by itself and metal
Wire is connected, center section coating parcel phosphoric acid/polyvinyl alcohol gel electrolyte solution, and producing N doping after natural air drying has
(mass percent of the phosphoric acid in dielectric substrate be the porous highly conductive graphene fiber solid gel electrolyte ultracapacitor of sequence
10%).Measure in 0.1mA/cm2It has up to 568.2mF/cm during current density2Specific capacitance.
Claims (10)
1. a kind of ordered porous highly conductive graphene fiber of N doping, it is characterised in that the quality doping scope of active nitrogen is
0.7~26.3%；Fibre diameter is uniform, regulates and controls in 25~350 micrometer ranges；The uniform porous network structure of fiber surface, hole
Footpath distribution is 1.5~200nm, and specific surface area scope is 200~805m2/ g, conductivity range is 11006~100300S/
m。
2. a kind of method of the ordered porous highly conductive graphene fiber of the N doping prepared as described in requiring 1, its specific steps is such as
Under：
1) using natural graphite flakes as raw material, graphene oxide water solution is prepared according to Hummers improved methods, is concentrated through high speed centrifugation
Afterwards, 8~20mg/mL graphene oxide dispersion is obtained；
2) by step 1) in graphene oxide dispersion and water-soluble nitrogenous precursor be thoroughly mixed uniformly, with 5~
100mL/h extruded velocity into cylindrical microchannels and seals two ends above-mentioned mixed liquor by needle injection, and heating is pre-
Reduction obtains amino functional graphene fiber；
3) by step 2) in cylindrical elongate tube-cooled after open two ends sealing, at 50~100 DEG C drying obtain drying
Amino functional graphene fiber；
4) dry amino functional graphene fiber is placed in tube furnace, it is heated to 600 under continuous gas shield~
1400 DEG C and it is incubated, obtains the ordered porous highly conductive graphene fiber of N doping.
3. method according to claim 2, it is characterised in that step 1) described in native graphite chip size for 100~
500 mesh sizes；Described high speed centrifugation is centrifugal concentrating 30~60 minutes under 10000~13000rpm rotating speeds.
4. method according to claim 2, it is characterised in that step 2) described in water-soluble nitrogenous precursor be urea,
One or more mixing compositions in cyanamid dimerization or melamine；Graphene oxide and the mass ratio of water-soluble nitrogenous precursor
For 1:(0.1~5)；Step 2) described in the materials of cylindrical microchannels be one kind in glass or polytetrafluoroethylene (PTFE)；Cylinder
The pipeline interior diameter of shape microchannel is 1~8 millimeter.
5. method according to claim 2, it is characterised in that step 2) described in heating prereduction be：First 70~
1~6h is heated at a temperature of 100 DEG C, then 1~10h of hydro-thermal reaction at a temperature of 140~280 DEG C.
6. method according to claim 2, it is characterised in that step 4) described in gas be hydrogen, argon gas or nitrogen
One or more mixing compositions；Gas flow rate is 50~300sccm.
7. method according to claim 2, it is characterised in that step 4) in heating rate be 0.5~5 DEG C/min, insulation
Time is 1h~20h.
8. a kind of ordered porous highly conductive graphene fiber of N doping as claimed in claim 1 is preparing answering for ultracapacitor
With.
9. application according to claim 8, it is comprised the following steps that：
Two length are separated by 1~3 millimeter of spacing is parallel to be fixed on for 3.5~10.5 centimetres of N doping porous graphene fiber
In substrate, it is connected by one end conductive silver glue that every fiber is protruded with plain conductor, center section coating parcel gel electricity
Electrolyte solution, natural air drying is treated to produce the ordered porous highly conductive graphite of N doping after the solvent volatilization in gel electrolyte solution
Alkene fiber solid gel electrolyte ultracapacitor.
10. application according to claim 9, it is characterised in that described substrate is sheet glass or poly terephthalic acid second two
One kind in alcohol ester transparent resilient plastic film；Described gel electrolyte is acid system or the gellike of ion liquid system two
Electrolyte, the wherein acid used in acid system gel electrolyte are phosphoric acid or sulfuric acid, gel electrolyte skeleton polymer used
For polyvinyl alcohol, mass percent scope of the acid in dielectric substrate is 10~80%；Ion liquid system gel electrolyte institute
Ionic liquid is 1- ethyl-3-methylimidazoles tetrafluoroborate or 1- ethyl-3-methylimidazole sulfonamides, institute
Gel electrolyte skeleton polymer is poly- (vinylidene-fluoride-co-hexafluoropropylene), chitosan or thermoplastic polyurethane, from
Mass percent scope of the sub- liquid in dielectric substrate is 10~80%.
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