CN107988645A - The preparation method of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor - Google Patents
The preparation method of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor Download PDFInfo
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
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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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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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- 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 present invention relates to the preparation method of a kind of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor, the High-elasticity conductive fiber is after being mixed using block copolymer solution with conductive filler dispersion liquid, the internal High-elasticity conductive fiber with conductive path is prepared by wet spinning, then by further lifting the electric conductivity of composite fibre on surface and internal deposited metal nano-particle, then using colloidal electrolyte prepare it is all solid state can drawing-off flexible fiber shape ultracapacitor, the preparation method process is simple, prepared fibrous elasticity is good, elongation is high, electrical conductivity is high, be particularly suited for it is flexible can drawn fiber shape ultracapacitor electrode material.
Description
Technical field
The present invention relates to a kind of preparation method of super-elasticity conductive fiber, the invention further relates to the superlastic obtained by this method
Property conductive fiber prepare flexibility can drawn fiber shape ultracapacitor.
Background technology
Can drawing-off electronic component since it is in wearable the field such as storage of Flexible Displays, flexible energy and intelligent skin
Etc. potential application and receive much concern, therefore it is flexible can drawing-off conductor material prepare it is most important.Though metallic fiber
Its right electrical conductivity is high, but be difficult to meet the characteristics of its rigidity it is flexible can drawing-off requirement, and high polymer fibre due to it is flexible,
Easily modified, the characteristics of can weaving, prospect can be widely applied on drawing-off electronic device by having shown, yet with most
Number high polymer fibre is except the electrical insulating property of conducting polymer, it is necessary to it is modified, prepares conductive fiber, realizes electronics
Element is elastomeric while keeps high conductivity to would is that the key for preparing fexible conductor.Mainly by leading in existing research
Electric macromolecule such as polyaniline（PANI）, polypyrrole（PPY）With poly- 3,4- ethene dioxythiophenes（PEDOT）Wet spinning prepares conductive
Fiber either prepares elastic conductive fiber or with metal alloy, silver and carbon nanotubes in the method for IR fiber face coat
Modified block copolymer, as publication number for CN101487148, CN105603603A, CN103390467A,
Elastic conductive fiber disclosed in CN104499272A is in elastic matrix fiber surface coated conductive particle, but prepared by these fibers
Method is difficult to meet the requirement that high conductivity is kept in the state of height drawing-off, and fibrous ultracapacitor will certainly be caused to exist
The increase of equivalent series resistance in drawing process, deteriorates the performance of ultracapacitor.For it is flexible can drawing-off it is fibrous super
It is few to use due to difficulty of the super-elasticity conductive fiber in preparation in the research of capacitor, mainly by fiber
The structure design of shape ultracapacitor realize can drawing-off purpose, fiber electrode coating colloid electrolyte such as is wrapped over one afterwards
It is fixed with the spandex yarn of strain, after being removed due to prestrain the contraction of fiber realize can drawing-off purpose, or to spandex
Yam surface looping carbon nano-tube film, reach can drawing-off requirement.But these can all make use of in drawing-off capacitor and not lead
The flexible base material of electricity, will certainly increase the weight of ultracapacitor, limit it in wearable electronic devices field
Using.
Block copolymer has the elongation and elasticity of superelevation, is super-elasticity due to its unique molecular chain structure
The ideal material of fiber.Nano-particle, nano wire and graphene by adding conduction in spinning solution etc., in polymer fiber
Conductive network is established in inside, so as to improve the electrical conductivity of composite fibre, while assigns the preferable elasticity of fiber and electric conductivity.Only need
Conductive filler ratio is set on conductive threshold values, while the net structure feature using nano wire in conductive filler, ensure
Conductive network is not destroyed still while stretching, keeps preferable elasticity and electric conductivity.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of super-elasticity conductive fiber and super-elasticity threadiness are super
The preparation method of capacitor, the preparation method process is simple, and prepared fibrous elasticity is good, and elongation is high, and electrical conductivity is high, more suitable
Share in it is flexible can drawn fiber shape ultracapacitor electrode material.
The technical solution adopted by the present invention to solve the technical problems is：A kind of super-elasticity conductive fiber and super-elasticity fiber
The preparation method of shape ultracapacitor, the High-elasticity conductive fiber are to be disperseed using block copolymer solution with conductive filler
After liquid mixing, the internal High-elasticity conductive fiber with conductive path is prepared by wet spinning, then by surface and interior
Portion's deposited metal nano-particle further lifts the electric conductivity of composite fibre, then prepares all solid state lead using colloidal electrolyte
Stretch flexible fiber shape ultracapacitor.
Further, the preparation method of elastic conductive fiber and super-elasticity the threadiness ultracapacitor includes following step
Suddenly：
It is prepared by step 1, spinning solution：First conductive filler is dispersed in polar solvent, is then added to conductive filler dispersion liquid
The mass fraction of block copolymer solution, wherein conductive filler is 0.1 ~ 60%, and the concentration of block copolymer is 5 ~ 30wt%, then
Be stirred at room temperature 1 ~ 24 it is small when, form uniform spinning solution.
Step 2, wet spinning：Spinneret orifice by the spinning solution prepared in step 1 by a diameter of 0.06 ~ 2mm, enters
Into coagulating bath, the block copolymer composite fibre that winding conductive filler is modified is collected.
Step 3, metal nanoparticle are modified：Composite fibre in step 2 is immersed into the gold that mass fraction is 0.1 ~ 50%
Belong in nanoparticle precursor solution, when 25 ~ 80 degree of drying 1 are small after washing, be then immersed in the reducing agent that concentration is 0.1 ~ 50%
In solution, when 25 ~ 80 degree of drying 1 are small after washing, repeat the above process 1 ~ 20 time.
Step 4, can the preparation of drawn fiber shape ultracapacitor：The composite fibre impregnated polymer that will be prepared in step 3
Colloidal electrolyte, after 20 ~ 80 degree of drying, impregnated polymer colloidal electrolyte again after twisting, is made fibrous ultracapacitor.
As a modification of the present invention, conductive filler is zero dimension metal nanoparticle in the step 1,1-dimention nano
Line, and two-dimensional graphene, molybdenum disulfide one or more therein；In the step 1 block copolymer for polystyrene-
Butadiene-styrene（SBS）, hydrogenated polystyrene-butadiene-styrene（SEBS）, polyurethane（PU）, it is polyisoprene, poly-
Isoprene-isobutene one or more therein；Conductive filler and the solvent used in block copolymer are in the step 1
N-N dimethylformamides（DMF）, N-N dimethylacetylamides（DMAC）, dimethyl sulfoxide (DMSO)（DMSO）, tetrahydrofuran, isopropanol,
Chloroform, ethanol, methanol, acetone and water one or more therein.
It is 5 ~ 50wt% to solidify bath concentration as a modification of the present invention, in the step 2, and coagulating bath is polyethylene
Alcohol, calcium chloride, potassium chloride, sodium chloride, magnesium chloride, zinc chloride, ammonium chloride, iron chloride, potassium sulfate, sodium sulphate, magnesium sulfate, sulfuric acid
One or more aqueous solutions in zinc, sodium carbonate, potassium carbonate, or be N-N dimethylformamides（DMF）, N-N dimethyl second
Acid amides（DMAC）, dimethyl sulfoxide (DMSO)（DMSO）, tetrahydrofuran, isopropanol, chloroform, ethanol, methanol, acetone and water one kind therein
It is or a variety of.
As a modification of the present invention, nanoparticle precursor solution is palladium bichloride, trifluoroacetic acid in the step 3
One or more in silver, gold chloride, copper chloride, iron chloride, aluminium chloride, nickel nitrate, cobalt chloride；Reducing agent for ascorbic acid,
One or more in hydrazine hydrate, sodium borohydride, potassium borohydride, hydroxylamine hydrochloride, sodium citrate.
As a modification of the present invention, polymeric colloid electrolyte is potassium hydroxide, sodium chloride, chlorine in the step 4
Change in potassium, ammonium chloride, ammonium sulfate, sodium sulphate, potassium sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, sulfuric acid, phosphoric acid, hydrochloric acid, lithium chlorate
One or more compositions polyvinyl alcohol（PVA）Aqueous solution.
Another prioritization scheme, the metal particle deposition can be realized by the method for electrochemical deposition；Described
Fiber producing processes can be realized by the method for dry spinning；The mass fraction of the block copolymer of the spinning solution is 15
~ 20%, conductive filler mass fraction is 3 ~ 10%, and the concentration of coagulating bath is 8 ~ 15wt%, and orifice diameter is 500 microns.
Using above-mentioned technical proposal, the beneficial effects of the invention are as follows：
After being mixed using block copolymer solution with conductive filler dispersion liquid, preparing inside by wet spinning has conductive path
High-elasticity conductive fiber, then by further lifting the conduction of composite fibre on surface and internal deposited metal nano-particle
Property, fibrous elasticity is good, and elongation is high, and composite fibre still has preferable electric conductivity under super drawing, can further obtain
The fibrous ultracapacitor of excellent performance, the preparation method is quick and easy, easy to spread.
Embodiment
With reference to specific embodiment, the present invention is further explained：
Embodiment 1
A kind of super-elasticity conductive fiber and it is all solid state can drawn fiber shape ultracapacitor preparation method, comprise the following steps：
Step 1：Styrene-butadiene-styrene（SBS）It is dissolved in tetrahydrofuran（THF）In, wherein polystyrene-fourth two
Alkene-concentration of styrene is 20wt%, by finely dispersed copper nano-wire and graphene dispersing solution be added to styrene-butadiene-
In styrene solution, wherein the mass fraction of copper nano-wire and graphene is 5%, both mass ratioes are 1/1, after shearing homogeneous
Spinning solution is made.
Step 2：Styrene-butadiene-styrene/copper nano-wire/graphene spinning solution, passes through a diameter of 500 microns
Spinneret orifice, enter in 8wt% polyvinyl alcohol coagulating baths, winding collect after be made conducting particles be modified elastomer.
Step 3：By the fiber impregnation of above-mentioned preparation 30 minutes in the copper chloride solution of 0.5 mol/L, 60 degree of dryings
Afterwards after ten minutes with the sodium borohydride reduction of 0.5 mol/L, 60 degree of dryings 10 minutes, repeat above-mentioned mistake after deionization is washed
3 ~ 5 circulations of journey.
Step 4：By concentration of the super-elasticity conductive fiber of above-mentioned preparation through in-situ polymerization deposition polyaniline, wherein aniline
For 0.05 mol/L, the molar ratio of aniline and ammonium persulfate is 4/1, when ice bath reaction 24 is small.
Step 5：Composite fiber surface coating colloid electrolyte solution, after 20 ~ 80 degree of drying, impregnates glue again after twisting
Body electrolyte solution, prepared after drying it is all solid state can drawn fiber shape ultracapacitor.
Embodiment 2
The preparation method of a kind of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor, comprises the following steps：
Step 1：Polyurethane（PU）It is dissolved in N-N- dimethylformamides（DMF）, wherein polyurethane concentration is 15wt%, will be scattered
Uniform nano silver wire dispersion liquid is added in polyurethane solutions, and wherein nano silver wire is 1% to the mass fraction of polyurethane, is stirred
Obtained spinning solution after mixing uniformly.
Step 2：Polyurethane/nano silver wire spinning solution enters water and N-N- by a diameter of 500 microns of spinneret orifice
In dimethylformamide composition coagulating bath, wherein the concentration of N-N- dimethylformamides is 20wt%, and fiber is wound into after washing
Type.
Step 3：Polyurethane/nano silver wire composite fibre immerses Nano silver grain presoma（Silver trifluoroacetate）In solution,
Wherein the concentration of silver trifluoroacetate is 15wt%, and 60 degree of dryings are used the hydrazine hydrate reduction of 50wt%, repeated after washing and drying after five minutes
3 ~ 5 circulations of this process.
Step 4：By above-mentioned 60 degree of gas-phase polymerization 1h of fiber, PEDOT is deposited in fiber surface
Step 5：Composite fiber surface coating 1M sulfuric acid/polyvinyl alcohol colloid electrolyte solution, after 60 degree of drying, after twisting again
It is secondary dipping colloidal electrolyte solution, prepared after drying it is all solid state can drawn fiber shape ultracapacitor.
Embodiment 3
The preparation method of a kind of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor, comprises the following steps：
Step 1：Styrene-butadiene-styrene（SBS）It is dissolved in tetrahydrofuran（THF）In, wherein polystyrene-fourth two
Alkene-concentration of styrene is 20wt%, and it is molten that finely dispersed carbon nano tube dispersion liquid is added to styrene-butadiene-styrene
In liquid, wherein the mass fraction of carbon nanotubes is 2%, and spinning solution is made after shearing homogeneous.
Step 2：Styrene-butadiene-styrene/carbon nanotubes spinning solution, passes through a diameter of 500 microns of spinneret
Hole, enters in 8wt% polyvinyl alcohol coagulating baths, and the elastomer that conducting particles is modified is made in winding after collecting.
Step 3：Styrene-butadiene-styrene/carbon nano tube composite fibre immerses the trifluoro second that concentration is 15wt%
In sour silver solution, the hydrazine hydrate reduction of 50wt% is used in 60 degree of dryings after five minutes, and 3 ~ 5 circulations of this process are repeated after washing and drying.
Step 4：By concentration of the super-elasticity conductive fiber of above-mentioned preparation through in-situ polymerization deposition polyaniline, wherein aniline
For 0.05 mol/L, the molar ratio of aniline and ammonium persulfate is 4/1, when ice bath reaction 24 is small.
Step 5：Composite fiber surface coating 1M phosphoric acid/polyvinyl alcohol colloid electrolyte solution, after 60 degree of drying, twisting
Afterwards again impregnate colloidal electrolyte solution, prepared after drying it is all solid state can drawn fiber shape ultracapacitor.
Embodiment 4
The preparation method of a kind of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor, comprises the following steps：
Step 1：Polyurethane（PU）It is dissolved in N-N- dimethylformamides（DMF）, wherein polyurethane concentration is 15wt%, will be scattered
Uniform nano silver wire and graphene DMF dispersion liquids are added in polyurethane solutions, wherein the quality of nano silver wire and graphene
Fraction is 5%, and the mass ratio of nano silver wire and graphene is 1/1, and spinning solution is made after stirring evenly.
Step 2：Polyurethane/nano silver wire/graphene spinning solution enters water and N- by 500 microns of spinneret orifice
In dinethylformamide composition coagulating bath, wherein the concentration of N-N- dimethylformamides is 20wt%, and fiber is wound after washing
Shaping.
Step 3：By the fiber impregnation of above-mentioned preparation 30 minutes in the copper chloride solution of 0.5 mol/L, 60 degree of dryings
Afterwards after ten minutes with the sodium borohydride reduction of 0.5 mol/L, 60 degree of dryings 10 minutes, repeat above-mentioned mistake after deionization is washed
3 ~ 5 circulations of journey.
Step 4：By above-mentioned 60 degree of gas-phase polymerization 1h of fiber, PEDOT is deposited in fiber surface
Step 5：Composite fiber surface coating 1M phosphoric acid/polyvinyl alcohol colloid electrolyte solution, after 60 degree of drying, after twisting again
It is secondary dipping colloidal electrolyte solution, prepared after drying it is all solid state can drawn fiber shape ultracapacitor.
It is to be understood that above example is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it should also be understood that,
After present disclosure has been read, those skilled in the art can make various modifications or changes to the present invention, these are of equal value
Form is also fallen within the scope of the appended claims of the present application.
Claims (9)
- A kind of 1. preparation method of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor, it is characterised in that：Described High-elasticity conductive fiber is after being mixed using block copolymer solution with conductive filler dispersion liquid, is prepared by wet spinning internal High-elasticity conductive fiber with conductive path, it is then multiple by further being lifted on surface and internal deposited metal nano-particle The electric conductivity of condensating fiber, using colloidal electrolyte prepare it is all solid state can drawing-off flexible fiber shape ultracapacitor.
- 2. the preparation method of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor according to claim 1, it is special Sign is that the preparation method comprises the following steps：It is prepared by step 1, spinning solution：First conductive filler is dispersed in polar solvent, is then added to conductive filler dispersion liquid The mass fraction of block copolymer solution, wherein conductive filler is 0.1 ~ 60%, and the concentration of block copolymer is 5 ~ 30wt%, then Be stirred at room temperature 1 ~ 24 it is small when, form uniform spinning solution；Step 2, wet spinning：Spinneret orifice by the spinning solution prepared in step 1 by a diameter of 0.06 ~ 2mm, enters solidifying Gu in bath, collect the block copolymer composite fibre that winding conductive filler is modified；Step 3, metal nanoparticle are modified：Composite fibre in step 2 is immersed the metal that mass fraction is 0.1 ~ 50% to receive In rice corpuscles precursor solution, when 25 ~ 80 degree of drying 1 are small after washing, the reducing agent solution that concentration is 0.1 ~ 50% is then immersed in In, when 25 ~ 80 degree of drying 1 are small after washing, repeat the above process 1 ~ 20 time；Step 4, can the preparation of drawn fiber shape ultracapacitor：The composite fibre impregnated polymer colloid that will be prepared in step 3 Electrolyte, after 20 ~ 80 degree of drying, impregnated polymer colloidal electrolyte again after twisting, is made fibrous ultracapacitor.
- 3. the preparation method of super-elasticity conductive fiber as claimed in claim 2 and super-elasticity threadiness ultracapacitor, its feature It is：Conductive filler is zero dimension metal nanoparticle, one-dimensional nano line, and two-dimensional graphene, curing in the step 1 Molybdenum it is therein more than one.
- 4. the preparation method of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor according to claim 2, it is special Sign is：Block copolymer is styrene-butadiene-styrene, hydrogenated polystyrene-butadiene-benzene in the step 1 Ethene, polyurethane, polyisoprene, polyisoprene-isobutene it is therein more than one.
- 5. the preparation method of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor according to claim 2, it is special Sign is：In the step 1 conductive filler and solvent used in block copolymer be N-N dimethylformamides, N-N dimethyl More than one aqueous solution of acetamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, isopropanol, chloroform, ethanol, methanol, acetone.
- 6. the preparation method of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor according to claim 2, it is special Sign is：It is 5 ~ 50wt% that bath concentration is solidified in the step 2, coagulating bath be polyvinyl alcohol, calcium chloride, potassium chloride, sodium chloride, One kind in magnesium chloride, zinc chloride, ammonium chloride, iron chloride, potassium sulfate, sodium sulphate, magnesium sulfate, zinc sulfate, sodium carbonate, potassium carbonate Aqueous solution above.
- 7. the preparation method of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor according to claim 2, it is special Sign is：It is 5 ~ 50wt% that bath concentration is solidified in the step 2, and coagulating bath is N-N dimethylformamides, N-N dimethylacetamides More than one aqueous solution of amine, dimethyl sulfoxide (DMSO), tetrahydrofuran, isopropanol, chloroform, ethanol, methanol, acetone.
- 8. the preparation method of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor according to claim 2, it is special Sign is：Nanoparticle precursor solution includes palladium bichloride, silver trifluoroacetate, gold chloride, copper chloride, chlorination in the step 3 One or more in iron, aluminium chloride, nickel nitrate, cobalt chloride；Reducing agent is ascorbic acid, hydrazine hydrate, sodium borohydride, hydroboration One or more of potassium, hydroxylamine hydrochloride, sodium citrate.
- 9. the preparation method of super-elasticity conductive fiber and super-elasticity threadiness ultracapacitor according to claim 2, it is special Sign is：Polymeric colloid electrolyte is potassium hydroxide, sodium chloride, potassium chloride, ammonium chloride, ammonium sulfate, sulphur in the step 4 One or both of sour sodium, potassium sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, sulfuric acid, phosphoric acid, hydrochloric acid, lithium chlorate composition described above Polyvinyl alcohol water solution.
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| CN109338717A (en) * | 2018-09-28 | 2019-02-15 | 西安理工大学 | Compliant conductive fiber based on silver nanowires and preparation method thereof |
| CN110230113A (en) * | 2019-06-14 | 2019-09-13 | 武汉纺织大学 | A kind of silver nanowires/fibroin albumen composite fibre and preparation method thereof |
| CN110725024A (en) * | 2019-10-24 | 2020-01-24 | 中山大学 | Preparation method of fibrous photothermal conversion material |
| WO2020062223A1 (en) * | 2018-09-30 | 2020-04-02 | 哈尔滨工业大学（深圳） | One-stop supercapacitor and preparation method therefor |
| CN113062116A (en) * | 2021-03-01 | 2021-07-02 | 东华大学 | Bionic structure strain insensitive conductive fiber and preparation method thereof |
| CN113265721A (en) * | 2021-04-19 | 2021-08-17 | 浙江大学 | Fibrous dielectric elastomer driver and preparation method thereof |
| CN113668088A (en) * | 2021-08-09 | 2021-11-19 | 江南大学 | SEBS/CNT/MXene composite conductive rubber fiber and preparation and application thereof |
| KR20220091005A (en) * | 2020-12-23 | 2022-06-30 | 재단법인대구경북과학기술원 | Method for manufacturing conductive fiber using ascorbic acid and o2 plasma treatment |
| CN114836845A (en) * | 2022-05-20 | 2022-08-02 | 武汉纺织大学 | Flexible conductive polyurethane fiber and preparation method thereof |
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| CN108962945A (en) * | 2018-06-22 | 2018-12-07 | 武汉华星光电半导体显示技术有限公司 | Display panel and electronic equipment |
| CN109338717A (en) * | 2018-09-28 | 2019-02-15 | 西安理工大学 | Compliant conductive fiber based on silver nanowires and preparation method thereof |
| CN109338717B (en) * | 2018-09-28 | 2021-04-06 | 西安理工大学 | Flexible conductive fiber based on silver nanowires and preparation method thereof |
| WO2020062223A1 (en) * | 2018-09-30 | 2020-04-02 | 哈尔滨工业大学（深圳） | One-stop supercapacitor and preparation method therefor |
| CN110230113B (en) * | 2019-06-14 | 2021-12-03 | 武汉纺织大学 | Silver nanowire/silk fibroin composite fiber and preparation method thereof |
| CN110230113A (en) * | 2019-06-14 | 2019-09-13 | 武汉纺织大学 | A kind of silver nanowires/fibroin albumen composite fibre and preparation method thereof |
| CN110725024A (en) * | 2019-10-24 | 2020-01-24 | 中山大学 | Preparation method of fibrous photothermal conversion material |
| KR20220091005A (en) * | 2020-12-23 | 2022-06-30 | 재단법인대구경북과학기술원 | Method for manufacturing conductive fiber using ascorbic acid and o2 plasma treatment |
| KR102474402B1 (en) * | 2020-12-23 | 2022-12-06 | 재단법인대구경북과학기술원 | Method for manufacturing conductive fiber using ascorbic acid and o2 plasma treatment |
| CN113062116A (en) * | 2021-03-01 | 2021-07-02 | 东华大学 | Bionic structure strain insensitive conductive fiber and preparation method thereof |
| CN113062116B (en) * | 2021-03-01 | 2021-12-21 | 东华大学 | Bionic structure strain insensitive conductive fiber and preparation method thereof |
| CN113265721A (en) * | 2021-04-19 | 2021-08-17 | 浙江大学 | Fibrous dielectric elastomer driver and preparation method thereof |
| CN113668088A (en) * | 2021-08-09 | 2021-11-19 | 江南大学 | SEBS/CNT/MXene composite conductive rubber fiber and preparation and application thereof |
| CN114836845A (en) * | 2022-05-20 | 2022-08-02 | 武汉纺织大学 | Flexible conductive polyurethane fiber and preparation method thereof |
| CN114836845B (en) * | 2022-05-20 | 2023-08-25 | 武汉纺织大学 | Flexible conductive polyurethane fiber and preparation method thereof |
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