CN107993854A - Core-sheath-type Flexible graphene fibre supercapacitors, its preparation method and system - Google Patents
Core-sheath-type Flexible graphene fibre supercapacitors, its preparation method and system Download PDFInfo
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- CN107993854A CN107993854A CN201711307570.5A CN201711307570A CN107993854A CN 107993854 A CN107993854 A CN 107993854A CN 201711307570 A CN201711307570 A CN 201711307570A CN 107993854 A CN107993854 A CN 107993854A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of core-sheath-type Flexible graphene fibre supercapacitors, it includes graphene fiber sandwich layer, around the polymer dielectric intermediate layer that the sandwich layer is set and the graphene fiber sheaths set around the intermediate layer etc..The invention also discloses the direct wet spinning preparation method and preparation system of the ultracapacitor.The present invention can prepare the ultracapacitor with core sheath structure fiber with a step wet spinning, it is simple for process, it is efficient, it is of low cost, the specific capacitance of ultracapacitor of the present invention and energy density are high at the same time, and pliability is good, can weave, it is easy to amplificationization, can be widely used for the fields such as energy storage, flexible material.
Description
Technical field
The present invention relates to fibrous type ultracapacitor, more particularly to a kind of core-sheath-type Flexible graphene fiber super capacitor
Device, its direct wet spinning preparation method and system.
Background technology
Fibrous type ultracapacitor has small, and pliability is good, can weave and be readily integrated into variously-shaped micro-
The advantages that in type device, triggered people's extensive concern.Graphene fiber is a kind of macroscopic view assembled by graphene platelet
Material, because it with good mechanical strength, electrical conductance, flexibility the excellent properties such as can weave, this make its develop it is unconventional, light
There is prominent advantage in terms of amount and flexible super capacitor.At present, existing some scholars twine graphene fiber for structure
Wound, parallel and coaxial configuration fibrous type ultracapacitor.As T.W.Chou (J.L.Yu, et al.Carbon, 2017,
119,332) H will be coated with2SO4Two graphene fibers of-polyvinyl alcohol gel electrolyte form wound form graphite by twisting
Alkene fibre supercapacitors；H.S.Peng (G.X.Qu, et al.AdvancedMaterials, 2016,28,3646) will coating
Polyvinyl alcohol/H3PO4Two hollow plumbago alkene fibers parallels of gel electrolyte connect to obtain the graphene fiber of parallel construction
Ultracapacitor；CN104916453A discloses a kind of coaxial graphene fiber super capacitor and preparation method thereof, and use is wet
Method spining technology prepares graphene oxide fiber, and graphene fiber is obtained after reduction, the then dip-coating successively on graphene fiber
Modified polymer gel intermediate layer and graphene oxide sheaths, reduce and coaxial graphene fibre are obtained after dip-coating polymer dielectric
Tie up ultracapacitor.These graphene fiber super capacitors have good mechanical strength, pliability and stitchability, can
Wearing field of electronic devices has broad application prospects.But its preparation process is complicated, gel electrolyte layer is thicker and with
Electrode contact surface product is smaller, causes specific capacitance and energy density relatively low, so as to limit its extensive potential application.
The content of the invention
It is fine it is a primary object of the present invention to provide a kind of core-sheath-type Flexible graphene with improved chemical property
Ultracapacitor, its direct wet spinning preparation method and system are tieed up, so that overcome the deficiencies in the prior art.
To reach above-mentioned purpose, the present invention uses following technical scheme：
An embodiment of the present invention provides a kind of core-sheath-type Flexible graphene fibre supercapacitors, it includes graphene fiber
Sandwich layer, around the polymer dielectric intermediate layer that the sandwich layer is set and the graphene fiber sheath set around the intermediate layer
Layer.
It is prepared by the direct wet spinning that the embodiment of the present invention additionally provides a kind of core-sheath-type Flexible graphene fibre supercapacitors
Method, it includes：By the first liquid stream formed by spinning solution, the second liquid stream formed by gel electrolyte aqueous solution, by spinning
The 3rd liquid stream that liquid is formed injects coagulating bath at the same time, and the first liquid stream is distributed around the second liquid stream, and the second liquid stream is around the 3rd
Liquid stream is distributed, so as to form core-sheath-type Flexible graphene fibre supercapacitors；Wherein, the spinning solution includes dispersed
Graphene oxide and reducing agent, the gel electrolyte aqueous solution include high molecular polymer.
The embodiment of the present invention additionally provides the core-sheath-type Flexible graphene fibre supercapacitors prepared by preceding method.
The embodiment of the present invention additionally provides the core-sheath-type Flexible graphene fiber applied to foregoing directly wet spinning preparation method
Ultracapacitor preparation system, it includes：
Spinning syringe needle, it include extruding respectively the first liquid stream, the second liquid stream, the 3rd liquid stream the first fluid course,
Second fluid course and the 3rd fluid course, first fluid course are distributed around the second fluid course, the second fluid course
It is distributed around the 3rd fluid course；
Coagulating bath, it receiving the first liquid stream, the second liquid stream and the 3rd liquid stream of spinning syringe needle extrusion at the same time.
Than the prior art, the present invention at least has the advantages that：
1st, the present invention can go out the graphene fiber super capacitor with core sheath structure with a step wet spinning, and technique is simply easy
OK, and core sheath fibers generation speed it is fast, it is efficient, can continuously generate.
2nd, core-sheath-type Flexible graphene fibre supercapacitors electrolyte intermediate layer of the invention is combined with core, sheaths electrode
Close and contact area is not big and thin, continuous, short-circuit, is conducive to electronics and ion quickly transmits so that capacitor has
High specific capacitance and energy density.
3rd, core-sheath-type Flexible graphene fibre supercapacitors pliability of the invention is good, can weave, be easy to amplificationization.
Brief description of the drawings
Fig. 1 is a kind of preparation stream of core-sheath-type Flexible graphene fibre supercapacitors in a typical embodiments of the invention
Journey schematic diagram.
Fig. 2 is a kind of optics picture of coaxial three layers of spinning syringe needle in an exemplary embodiments of the invention.
Fig. 3 is that a kind of structure of core-sheath-type Flexible graphene fibre supercapacitors is shown in a typical embodiments of the invention
It is intended to.
Fig. 4 is a kind of core-sheath-type Flexible graphene fibre supercapacitors cross section in an exemplary embodiments of the invention
SEM schemes.
Fig. 5 is the SEM that a kind of core-sheath-type Flexible graphene fibre supercapacitors knot in an exemplary embodiments of the invention
Figure.
Fig. 6 is a kind of light of core-sheath-type Flexible graphene fibre supercapacitors braid in an exemplary embodiments of the invention
Learn picture.
Fig. 7 is the core-sheath-type soft graphite prepared in the specific embodiment of the invention using various concentrations sodium carboxymethylcellulose
The cyclic voltammogram of alkene fibre supercapacitors.
Fig. 8 be in the specific embodiment of the invention core-sheath-type Flexible graphene fibre supercapacitors under different current densities
Constant current charge-discharge figure.
Fig. 9 is that core-sheath-type Flexible graphene fibre supercapacitors are surveyed in constant current charge-discharge in the specific embodiment of the invention
The cycle performance figure embodied in examination.
Figure 10 be in the specific embodiment of the invention core-sheath-type Flexible graphene fibre supercapacitors 100 times bending under
Capacity retention test chart.
Embodiment
A kind of core-sheath-type Flexible graphene fibre supercapacitors that the one side of the embodiment of the present invention provides include stone
Black alkene core fiber layer, around the polymer dielectric intermediate layer that the sandwich layer is set and the graphene set around the intermediate layer
Fiber sheaths.
A kind of core-sheath-type Flexible graphene fibre supercapacitors that the other side of the embodiment of the present invention provides it is straight
Wet spinning preparation method is connect, including：By the first liquid stream formed by spinning solution, the second liquid formed by gel electrolyte aqueous solution
Stream, the 3rd liquid stream formed by spinning solution inject coagulating bath at the same time, and the first liquid stream is distributed around the second liquid stream, the second liquid stream
It is distributed around the 3rd liquid stream, so as to form core-sheath-type Flexible graphene fibre supercapacitors；Wherein, the spinning solution includes equal
Even scattered graphene oxide and reducing agent, the gel electrolyte aqueous solution include high molecular polymer.
Further, the preparation method may also include：By first liquid stream, the second liquid stream and the 3rd liquid stream at the same time
After injecting coagulating bath, more than 10min (such as 10~30min) is soaked, forms the super electricity of core-sheath-type Flexible graphene fiber
Container.
Preferably, the content of graphene oxide is 2~20mg/ml in the spinning solution, the concentration of reducing agent for 2~
200mg/ml。
Preferably, the reducing agent is including vitamin C etc..Certainly, in some cases, the reducing agent such as hydrazine hydrate
Apply to the present invention, but its effect be inferior to it is ascorbic.
Further, the high molecular polymer can be selected from known suitable polymer, such as polyvinyl alcohol, carboxymethyl
Sodium cellulosate, xanthans etc., and not limited to this, it is used to form ion transmission channel between sandwich layer and sheaths.
Preferably, the concentration of high molecular polymer is 2~20mg/ml in the gel electrolyte aqueous solution.
Further, the preparation method may also include：Respectively by the 3rd liquid stream, the second liquid stream, the first liquid stream with 0.2
~1ml/min, 0.5~5ml/min, the flow velocity of 5~25ml/min inject the coagulating bath.
In some preferred embodiments, the coagulating bath contains 1~8wt%CaCl2, solvent therein is ethanol/water
Solution, it is 1 that the ethanol/water solution, which includes volume ratio,:1~8:1 ethanol and the homogeneous mixture of water.
By the aforementioned preparation process of the present invention, it is possible to achieve a step of core-sheath-type Flexible graphene fibre supercapacitors
It is prepared by wet spinning.Further, the core-sheath-type Flexible graphene fibre supercapacitors prepared by foregoing any method include stone
Black alkene core fiber layer, around the polymer dielectric intermediate layer that the sandwich layer is set and the graphene set around the intermediate layer
Fiber sheaths.
Preferably, a diameter of 50~250 μm of aforementioned supercapacitors.
Preferably, the thickness in aforementioned polymer electrolyte intermediate layer is 1~20 μm.
Preferably, a diameter of 20~100 μm of foregoing graphites alkene core fiber layer.
Preferably, the thickness of foregoing graphites alkene fiber sheaths is 100~200 μm.
A kind of structure of core-sheath-type Flexible graphene fibre supercapacitors can join in an exemplary embodiments of the invention
Read shown in Fig. 3, wherein sheaths and sandwich layer can be that the graphene continuously extended by the length direction along the ultracapacitor is fine
Dimension aggregation is formed, and intermediate layer can be the pantostrat that polymer dielectric is formed.
Core-sheath-type Flexible graphene fibre that the other side of the embodiment of the present invention provides, applied to aforementioned preparation process
Dimension ultracapacitor preparation system includes：
Spinning syringe needle, it include extruding respectively the first liquid stream, the second liquid stream, the 3rd liquid stream the first fluid course,
Second fluid course and the 3rd fluid course, first fluid course are distributed around the second fluid course, the second fluid course
It is distributed around the 3rd fluid course；
Coagulating bath, it receiving the first liquid stream, the second liquid stream and the 3rd liquid stream of spinning syringe needle extrusion at the same time.
Further, in first fluid course, the second fluid course and the 3rd fluid course it is any between the two
It is separated.In some preferred embodiments, first fluid course, the second fluid course and the 3rd fluid course are coaxial
Set.
In some specific embodiments, the spinning syringe needle includes the first syringe needle, the second syringe needle and the being coaxially disposed
Three syringe needles, the inner cavity of the 3rd syringe needle form the 3rd fluid course, and the first fluid course, the second fluid course form the first pin respectively
Between head and the second syringe needle, between the second syringe needle and the 3rd syringe needle.
Further, the spinning syringe needle can be made of the first syringe needle, the second syringe needle and the 3rd syringe needle coaxial three
Layer spinning syringe needle.More preferably, for separating the wall of the first fluid course and the second fluid course and for separating second
The thickness of the wall of fluid course and the 3rd fluid course is 0.05~0.5mm.
More preferably, first fluid course, the second fluid course, the diameter of the 3rd fluid course be respectively 1~
5mm, 0.5~2mm, 0.2~1mm.
For example, the internal diameter of foregoing first syringe needle, the second syringe needle and the 3rd syringe needle can be respectively 1~4mm, 0.5~
1.2mm, 0.2~0.8mm.
In some specific embodiments, the preparation system may also include：Driving device, it is at least used to drive spinning
Silk any one of syringe needle and coagulating bath are rotated relative to another one around an axis.Can so make injection coagulating bath by first
The composite fluid flow that liquid stream, the second liquid stream and the 3rd liquid stream are formed can be contacted more fully with coagulating bath, realize continuous production.
Please refer to Fig.1 a kind of super electricity of core-sheath-type Flexible graphene fiber shown in a typical embodiments of the invention
Container preparation system, it includes coaxial three layers of spinning syringe needle, coagulating bath etc., coagulating bath can be placed in one can rotation board
On.Wherein, spinning solution, gel electrolyte aqueous solution can be injected using the spinning syringe needle in coagulating bath at the same time, and even
During continuous injection spinning solution, gel electrolyte aqueous solution, by rotating coagulating bath, can also composite fluid flow be set to be more uniformly distributed
Ground is distributed in coagulating bath and is more fully contacted with coagulating bath.
For example, in the more specific case study on implementation of the present invention, the preparation method may comprise steps of：
(1) graphene oxide dispersion is mixed with out spinning solution with vitamin c solution, spare；
(2) high molecular polymer is configured to gel electrolyte aqueous solution, spare；
(3) spinning solution prepared by step (1) is injected separately into inner cavity and the exocoel of foregoing coaxial three layers of spinning syringe needle
In, electrolyte aqueous solution prepared by step (2) is injected into the intermediate channel of foregoing coaxial three layers of spinning syringe needle；
(4) extruded velocity of internal layer, intermediate layer and outer layer is controlled, spinning solution and electrolyte aqueous solution are injected at the same time
In coagulating bath；
(5) after soaking 10~30min, cleaning and dry 10h, obtain the super electricity of core-sheath-type Flexible graphene fiber
Container.By above-mentioned specific implementation case, high molecular polymer can be sodium carboxymethylcellulose.
By above-mentioned specific implementation case, the spinning solution described in step (1) can disperse for the graphene oxide of 18mg/ml
The mixed solution of the vitamin c solution of liquid and 150mg/ml, volume ratio 5:1.
By above-mentioned specific implementation case, the concentration of the polymer dielectric aqueous solution described in step (2) is 2~20mg/
ml。
By above-mentioned specific implementation case, the internal diameter of three needle tubings of coaxial three layers of spinning syringe needle described in step (3) can
To be respectively 0.4,0.8 and 1.6mm, wall thickness is 0.1mm.
By above-mentioned specific implementation case, the extruded velocity of internal layer, intermediate layer and outer layer described in step (4) can be distinguished
For 0.5,2 and 10ml/min.
By above-mentioned specific implementation case, the coagulating bath described in step (4) can be containing 5wt%CaCl2Ethanol/water
Solution, wherein ethanol/water solution can be by 5:Second alcohol and water is uniformly mixed to prepare by 1 volume ratio.
The ultracapacitor with core sheath structure fiber is prepared in a step wet spinning of the invention, and preparation method is simple and practicable, soft
Good toughness, can weave, and be easy to amplificationization, and made ultracapacitor specific capacitance is high, available for energy storage, flexible material
Deng field.The present invention is specifically described below by some embodiments, the present embodiment is served only for doing further the present invention
Explanation, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art's content according to the present invention is made
Some nonessential changes and adjustment, belong to protection scope of the present invention.
The spinning syringe needle that following each embodiment uses is by the first syringe needle, the second syringe needle and the 3rd syringe needle group that are coaxially disposed
Into coaxial three layers of spinning syringe needle, the inner cavity of the 3rd syringe needle forms the 3rd fluid course (being referred to as inner cavity as follows), the first liquid stream
Passage (being referred to as exocoel as follows), the second fluid course (being referred to as intermediate channel as follows) form the first syringe needle and the second pin respectively
Between head, between the second syringe needle and the 3rd syringe needle.Wherein, the internal diameter of the first syringe needle, the second syringe needle and the 3rd syringe needle can be distinguished
For 1~4mm, 0.5~1.2mm, 0.2~0.8mm, for separate inner cavity, intermediate channel, exocoel the thickness of each wall can be equal
For 0.05~0.5mm.The physical form of three layers of spinning syringe needle of one of which typical coaxial is as shown in Figure 2.
The graphene oxide that following each embodiment uses can be purchased in market, or utilize the preparations such as hummers methods.
Embodiment 1
(1) by the graphene oxide dispersion that concentration is 18mg/ml and the vitamin c solution that concentration is 150mg/ml by body
Product ratio 5:1 is mixed with out spinning solution, spare；
(2) it is 2mg/ml, 3mg/ml, 4mg/ml, 5mg/ml, 5.5mg/ that sodium carboxymethylcellulose is configured to concentration respectively
The sodium carboxymethyl cellulose solution of ml, 6mg/ml, 7mg/ml, 10mg/ml, 15mg/ml, 20mg/ml, it is spare；
(3) spinning solution prepared by step (1) is injected separately into the inner cavity and exocoel of coaxial three layers of spinning syringe needle, will walked
Suddenly the sodium carboxymethyl cellulose solution that prepared by (2) is injected into the intermediate channel of the spinning syringe needle；
(4) to control internal layer, intermediate layer, the extruded velocity of outer layer be respectively 0.5,2,10ml/min, by spinning solution and electricity
Solution matter aqueous solution is injected into containing 5wt%CaCl at the same time2Ethanol/water (5:1v/v) in coagulating bath；
(5) after soaking 30min, clean and dry 10h obtains a series of core-sheath-type Flexible graphene fibre supercapacitors
Sample.A kind of pattern for typical core-sheath-type Flexible graphene fibre supercapacitors cross section that the present embodiment is obtained can refer to
Shown in Fig. 4, it can be rendered as continuous flexible wire or banding, and the pattern after knotting can be referred to shown in Fig. 5.Into one
Step, the pattern in kind for the braid being knitted to form using the core-sheath-type Flexible graphene fibre supercapacitors can refer to figure
Shown in 6.Other core-sheath-type Flexible graphene fibre supercapacitors samples that the present embodiment obtains also have approximate macroscopic view and
Microscopic appearance, wherein interbed are tightly combined with core, sheaths electrode and contact area is big, and thin, continuous, be conducive to electronics and
Ion quickly transmits, and pliability is good, can weave, be easy to amplificationization.
Fig. 7 shows each core-sheath-type Flexible graphene prepared in the present embodiment using various concentrations sodium carboxymethylcellulose
The cyclic voltammetry result of fibre supercapacitors.
Fig. 8 be in the present embodiment a series of core-sheath-type Flexible graphene fibre supercapacitors samples in different current densities
Under constant current charge-discharge test result, it is necessary to which explanation, the test data shown in this figure are aforesaid plurality of sample through more
The obtained average value of secondary test.
Fig. 9 be in the present embodiment a series of core-sheath-type Flexible graphene fibre supercapacitors samples in constant current charge-discharge
The cycle performance embodied in test, likewise, the test data shown in this figure is obtained by aforesaid plurality of sample through repeatedly test
Average value.
Figure 10 be in the present embodiment a series of core-sheath-type Flexible graphene fibre supercapacitors samples 100 times bending under
Capacity retention test result, the test data shown in this figure is also that aforesaid plurality of sample is averaged through what repeatedly test was obtained
Value.
Foregoing test result proves that the core-sheath-type Flexible graphene fibre supercapacitors electrolyte of the present embodiment has
It is resistant to bending, short circuit is not easy, there is high specific capacitance and energy density.
Embodiment 2
(1) graphene oxide dispersion and vitamin c solution are mixed with out by different volumes ratio and include concentration point
Other 2,4,5,8,10,16, a series of spinning solutions of the graphene oxide of 20mg/ml, these spinning solutions are comprising 200mg/ml
Vitamin C, it is spare；
(2) polyvinyl alcohol is configured to the polyvinyl alcohol water solution that concentration is 10mg/ml, it is spare；
(3) some row spinning solutions prepared by step (1) are injected separately into inner cavity and the exocoel of coaxial three layers of spinning syringe needle
In, sodium carboxymethyl cellulose solution prepared by step (2) is injected into the intermediate channel of spinning syringe needle；
(4) control internal layer, the extruded velocity of intermediate layer and outer layer is respectively 0.2,0.8 and 5ml/min, by spinning solution and
Electrolyte aqueous solution is injected into containing 2wt%CaCl at the same time2Ethanol/water (1:1v/v) in coagulating bath；
(5) after soaking 10min, cleaning and dry 10h, obtain a series of core-sheath-type Flexible graphene fiber super capacitors
Device.
Embodiment 3
(1) graphene oxide dispersion and vitamin c solution are mixed with out by different volumes ratio and include concentration point
Other 2,4,5,8,10,16, a series of ascorbic spinning solutions of 200mg/ml, which includes the graphite oxide of 2mg/ml
Alkene, it is spare；
(2) xanthans is configured to the xanthan gum solution that concentration is 15mg/ml, it is spare；
(3) a series of spinning solutions prepared by step (1) are injected separately into inner cavity and the exocoel of coaxial three layers of spinning syringe needle
In, sodium carboxymethyl cellulose solution prepared by step (2) is injected into the intermediate channel of spinning syringe needle；
(4) control internal layer, the extruded velocity of intermediate layer and outer layer is respectively 0.8,4 and 20ml/min, by spinning solution and
Electrolyte aqueous solution is injected into containing 3wt%CaCl at the same time2Ethanol/water (4:1v/v) in coagulating bath；
(5) after soaking 25min, cleaning and dry 10h, obtain a series of core-sheath-type Flexible graphene fiber super capacitors
Device.
The diameter for the array of super capacitor that previous embodiment obtains can be controlled in about 80~120 μm, wherein polymerizeing
The thickness in thing electrolyte intermediate layer can be controlled in about 1~5 μm, and the diameter of graphene fiber sandwich layer can be controlled in about 20~80
μm, the thickness of graphene fiber sheaths can be controlled in about 100~200 μm.Through complete, braiding and a variety of electro-chemical test tables
Face, these core-sheath-type Flexible graphene fibre supercapacitors electrolyte are respectively provided with resistant to bending, are not easy short circuit, high specific capacitance and energy
The advantages that metric density.
It should be appreciated that although above the present invention is made with a general description of the specific embodiments to retouch in detail
State, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Scope.
Claims (15)
1. a kind of core-sheath-type Flexible graphene fibre supercapacitors, it is characterised in that including graphene fiber sandwich layer, around institute
The graphene fiber sheaths stated the polymer dielectric intermediate layer of sandwich layer setting and set around the intermediate layer.
2. core-sheath-type Flexible graphene fibre supercapacitors according to claim 1, it is characterised in that：The super electricity
A diameter of 80~120 μm of container；And/or the thickness in the polymer dielectric intermediate layer is 1~5 μm；And/or the stone
A diameter of 20~80 μm of black alkene core fiber layer；And/or the thickness of the graphene fiber sheaths is 100~200 μm.
A kind of 3. direct wet spinning preparation method of core-sheath-type Flexible graphene fibre supercapacitors, it is characterised in that including：Will
The first liquid stream for being formed by spinning solution, the second liquid stream formed by gel electrolyte aqueous solution, the 3rd liquid formed by spinning solution
Stream injects coagulating bath at the same time, and the first liquid stream is distributed around the second liquid stream, and the second liquid stream is distributed around the 3rd liquid stream, so that shape
Into core-sheath-type Flexible graphene fibre supercapacitors；Wherein, the spinning solution includes dispersed graphene oxide and goes back
Former agent, the gel electrolyte aqueous solution include high molecular polymer.
4. preparation method according to claim 3, it is characterised in that including：By first liquid stream, the second liquid stream and
After three liquid streams inject coagulating bath at the same time, more than 10min is soaked, forms the core-sheath-type Flexible graphene fibre supercapacitors.
5. preparation method according to claim 3, it is characterised in that：The content of graphene oxide is 2 in the spinning solution
~20mg/ml, the concentration of reducing agent is 2~200mg/ml.
6. the preparation method according to claim 3 or 5, it is characterised in that：The reducing agent includes vitamin C；And/or
The high molecular polymer includes polyvinyl alcohol, sodium carboxymethylcellulose or xanthans.
7. preparation method according to claim 3, it is characterised in that：High molecular polymerization in the gel electrolyte aqueous solution
The concentration of thing is 2~20mg/ml.
8. preparation method according to claim 3, it is characterised in that including：Respectively by the 3rd liquid stream, the second liquid stream, first
Liquid stream injects the coagulating bath with the flow velocity of 0.2~0.8ml/min, 0.8~4ml/min, 5~20ml/min.
9. the preparation method according to claim 3 or 6, it is characterised in that：The coagulating bath contains 2~5wt%CaCl2, its
In solvent be ethanol/water solution, it is 3 that the ethanol/water solution, which includes volume ratio,:1~5:1 ethanol is uniformly mixed with water
Thing.
10. core-sheath-type Flexible graphene fibre supercapacitors prepared by the method as any one of claim 3-9, it is special
Sign is to include graphene fiber sandwich layer, around the polymer dielectric intermediate layer that the sandwich layer is set and around the intermediate layer
The graphene fiber sheaths of setting.
11. core-sheath-type Flexible graphene fibre supercapacitors according to claim 10, it is characterised in that：It is described super
A diameter of 80~120 μm of capacitor；And/or the thickness in the polymer dielectric intermediate layer is 1~5 μm；It is and/or described
A diameter of 20~80 μm of graphene fiber sandwich layer；And/or the thickness of the graphene fiber sheaths is 100~200 μm.
12. prepared by the core-sheath-type Flexible graphene fibre supercapacitors applied to method any one of claim 3-9
System, it is characterised in that including：
Spinning syringe needle, it includes extruding the first liquid stream, the second liquid stream, the first fluid course of the 3rd liquid stream, second respectively
Fluid course and the 3rd fluid course, first fluid course are distributed around the second fluid course, and the second fluid course is surround
3rd fluid course is distributed；
Coagulating bath, it receiving the first liquid stream, the second liquid stream and the 3rd liquid stream of spinning syringe needle extrusion at the same time.
13. preparation system according to claim 12, it is characterised in that：First fluid course, the second fluid course
With being arbitrarily separated between the two in the 3rd fluid course；And/or first fluid course, the second fluid course and
3rd fluid course is coaxially disposed.
14. the preparation system according to claim 12 or 13, it is characterised in that：The spinning syringe needle includes what is be coaxially disposed
First syringe needle, the second syringe needle and the 3rd syringe needle, the inner cavity of the 3rd syringe needle form the 3rd fluid course, the first fluid course, second
Fluid course is formed between the first syringe needle and the second syringe needle respectively, between the second syringe needle and the 3rd syringe needle；And/or for separating
The thickness of the wall and the wall for separating the second fluid course and the 3rd fluid course of first fluid course and the second fluid course
Spend for 0.05~0.3mm；And/or first fluid course, the second fluid course, the diameter of the 3rd fluid course are respectively 1
~3mm, 0.6~1.2mm, 0.2~0.5mm.
15. preparation system according to claim 12, it is characterised in that further include：Driving device, it is at least used to drive
Any one of spinning syringe needle and coagulating bath are rotated relative to another one around an axis.
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| CN108962624A (en) * | 2018-07-27 | 2018-12-07 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Fibrous type parallel construction Flexible graphene fibre supercapacitors, preparation method and system |
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| CN110195271A (en) * | 2019-06-27 | 2019-09-03 | 中素新科技有限公司 | Graphene aerogel fiber and its preparation method and application |
| CN110195271B (en) * | 2019-06-27 | 2021-11-12 | 中素新科技有限公司 | Graphene aerogel fibers, and preparation method and application thereof |
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