CN104451925B - A kind of water-soluble polymer/Graphene composite fibre and its preparation method and application - Google Patents
A kind of water-soluble polymer/Graphene composite fibre and its preparation method and application Download PDFInfo
- Publication number
- CN104451925B CN104451925B CN201410674600.6A CN201410674600A CN104451925B CN 104451925 B CN104451925 B CN 104451925B CN 201410674600 A CN201410674600 A CN 201410674600A CN 104451925 B CN104451925 B CN 104451925B
- Authority
- CN
- China
- Prior art keywords
- water
- soluble polymer
- composite fibre
- graphene
- graphene composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of water-soluble polymer/Graphene composite fibre and its preparation method and application, fibre section presents abnormity, and fiber surface has the fento shape structure of orientation；Fibre strength is more than 100MPa, and elongation at break is more than 2%, and electrical conductivity is more than 0.1S/cm.Preparation method includes preparing composite spinning liquid；Then it is expressed in coagulating bath solidification, after drawing-off, draws coagulating bath, be dried, wind acquisition water-soluble polymer/graphene oxide fiber；Chemically or physically method is finally used to reduce, it is thus achieved that water-soluble polymer/Graphene composite fibre.The composite fibre cross section that the present invention obtains is polymorphic structure, surface has abundant groove microstructure, its intensity and the purer graphene fiber of toughness are greatly improved, and still keep good electric conductivity, therefore have wide practical use in fields such as antistatic and conductive fabric, electro-magnetic wave absorption and loomage, energy storage device, sensor and water process.
Description
Technical field
The invention belongs to Graphene composite fibre field, particularly to a kind of water-soluble polymer/Graphene composite fibre and preparation thereof
Methods and applications.
Background technology
Graphene has very high-specific surface area and extremely excellent mechanics, calorifics, electrical and optical performance, has boundless
Application.The macroscopic material of Graphene includes the forms such as powder body, fiber, thin film, paper, aeroge, foam, wherein at present
Graphene fiber has extraordinary flexibility and textile processibility, and the performance such as its intensity, electric conductivity, heat conductivity is the most excellent,
Therefore there is broader practice prospect
But pure graphene fiber is piled up by graphene nanometer sheet and formed, intensity is relatively low, fragility is very big, and interlayer is tightly packed, makes
Its application is limited by bigger.Generally use the method adding other polymer that graphene fiber is changed for this research worker
Property.Such as, in patent CN102181961B, Graphene and sodium alginate are blended preparation spinning liquid, then carry out wet method
Spinning, it is thus achieved that there is the composite fibre of very high intensity；But wherein Graphene addition the lowest (less than 15%), leading of composite fibre
The lowest, and the high cost of sodium alginate can limit the extensive application of this composite fibre.And for example in patent CN103541043A,
In graphene oxide spinning, add dissaving polymer or polyvinyl alcohol, then obtained by rotary spinning and there is high intensity and break
Split the composite fibre of percentage elongation；But dissaving polymer has the problem that cost is high equally, and with polyvinyl alcohol compound tense, oxidation
Graphene is in liquid crystal state, and sheet interlayer has the strongest hydrogen bond action, and therefore the dispersion effect of PVA is poor, incorporation time is long, it is difficult to
Improving concentration of dope, production efficiency is low.
Summary of the invention
The technical problem to be solved be to provide a kind of water-soluble polymer/Graphene composite fibre and preparation method thereof and
Application, solves the defects such as pure graphene fiber fragility is big, intensity is low, and existing water-soluble polymer/Graphene composite fibre
Preparation process mixes the problem such as difficulties in dispersion, cost of material height.
A kind of water-soluble polymer/Graphene the composite fibre of the present invention, described fibre section presents abnormity, and fiber surface has and takes
To fento shape structure；Fibre strength is more than 100MPa, and elongation at break is more than 2%, and electrical conductivity is more than 0.1S/cm.
Described water-soluble polymer is polyvinyl alcohol, Polyethylene Glycol, polyvinylpyrrolidone, water soluble starch and they spread out
One or more in biology, preferably polyethylene alcohol.
A kind of preparation method of the water-soluble polymer/Graphene composite fibre of the present invention, including:
(1) graphene oxide (being called for short GO, it is also possible to for graphite oxide) is added in alkali liquor, obtain by peeling off dispersion process
0.2wt%～20wt%GO dispersion liquid (low viscosity, non-liquid crystal)；Then it is the water-soluble of 0.2wt%～20wt% with mass fraction
Property polymer (be called for short WSP) aqueous solution, dispersion processes, and finally adds alkali liquor regulation pH value, obtains WSP/GO multiple
Close spinning liquid；
Or graphene oxide adds pH to > 7, in the water-soluble polymer WSP aqueous solution of 0.1wt%-10wt%, by peeling off
Dispersion processes, and obtains finely dispersed composite solution, finally adds alkali liquor regulation pH value, obtains WSP/GO composite spinning liquid；
Wherein, described water-soluble polymer is 1:99～80:20, preferably 5:95～50:50 with the mass ratio of graphene oxide；
(2) above-mentioned spinning liquid is expressed in coagulating bath solidification, through drawing-off, be dried and winding obtain water-soluble polymer/graphite oxide
Alkene composite fibre；
(3) above-mentioned composite fibre is carried out in liquid environment or gaseous environment chemically or physically reduction treatment, obtain water-soluble polymer
/ Graphene composite fibre.
Alkali liquor in described step (1) is hydroxide aqueous solution, water-soluble organic amine aqueous solution, carbonate aqueous solution, carbonic acid
One or more in hydrogen salt aqueous solution, aqueous phosphatic, pyridine solution, preferably sodium hydroxide, potassium hydroxide or ammonia.
The pH value of the spinning liquid in described step (1) is 4～13, preferably 7～11；Solid content (mass fraction shared by total solid)
For 0.2wt%～20wt%, preferably 2wt%～5wt%.
Coagulating bath in described step (2) is in the container of rotation or flows in the duct or be in coagulating basin holding and stands；
Coagulating bath is by one or more aqueous solutions formed in mineral acid and inorganic salt or by organic acid, alcohol, amine, ketone, acyl
The liquid of one or more compositions in amine, pyridine, pyrroles, water, preferably aqueous acetic acid.
The first is to use the coagulating bath stood, and controls jet stretch ratio by the i.e. winding speed of off speed of regulation hygrometric state fiber,
Setting time is controlled by length and the off speed of regulation solidification distance.
The second is to use the coagulating bath rotated, and is placed in by spinneret orifice from center of rotation a certain distance, and regulation coagulating bath rotates
Rotating speed i.e. regulates the linear velocity at spinneret orifice, thus controls jet stretch ratio, and setting time is by the length of regulation solidification distance
Degree and off speed control.
The third is the coagulating bath using flowing, and spinneret orifice is placed on the centrage of flowing coagulating bath, the mean flow of regulation coagulating bath
Speed i.e. controls the speed at spinneret orifice, thus controls jet stretch ratio, and setting time solidifies length and the solidification of distance by regulation
The flowing velocity of bath controls.
In drafting process in described step (2), jet stretch ratio is 0.2～5, preferably 0.5～2.
Being dried in described step (2) is dried for far infrared radiation, heat channel heating, Hot-blast Heating, microwave radiation add hankered
Planting or several, preferably far infrared radiation is dried.
Liquid environment in described step (3) be containing the aqueous solution of one or more in acid, alkali, salt or by organic acid,
The liquid of one or more compositions in alcohol, amine, ketone, amide, sulfone, pyridine, water；Gaseous environment is air, nitrogen, argon
One or more in gas, ammonia, hydrogen, ammonia, preferably nitrogen atmosphere.
Electronation in described step (3) is to carry out in the liquid environment containing reducing agent or gaseous environment, by oxidation also
Former reaction, removes most oxygen-containing functional group in GO.Wherein, described reducing agent is hydrogen halides, inorganic base, hydrazine chemical combination
Thing, phenolic compound, ammonia amine compounds, compound containing at a low price sulfur, containing the compound of phosphorus, vitamin C and salt thereof at a low price,
One or more in oxalic acid and salt, reducing sugar, active metal and organic complex thereof；The mass fraction of reducing agent be 1%～
80%；Reduction temperature is-50～300 DEG C；Recovery time is 5 seconds～24 hours.
Physics method of reducing in described step (3) is atmosphere heat treatment, solvent heat treatment, laser irradiation, ultraviolet irradiation, micro-
One or more in the irradiation of wave radiation, xenon lamp, remove major part oxygen-containing functional group in GO with physical method；Reduction temperature is
150～1500 DEG C；Recovery time is 5 seconds～24 hours.
The preparation method of the present invention illustrates: the preparation method of polyvinyl alcohol/Graphene composite fibre: consolidating of composite spinning liquid contains
Amount is 2%～5%, and polyvinyl alcohol/graphene oxide mass ratio is 5:95～50:50, and pH value is 7～11；Coagulating bath during spinning
For in the aqueous acetic acid of 50%-100%, it is in the middle of the container of rotation；During drawing-off, jet stretch ratio is 0.5～2；Reduction treatment
Method is to add thermal reduction 5 seconds-24 hours in the hydriodic acid aqueous solution of 5%-45% under 10～100 degree.
A kind of application of the water-soluble polymer/Graphene composite fibre of the present invention, including the following aspects:
(1) product processed for raw material with water-soluble polymer/Graphene composite fibre, at antistatic/conduction and electromagnetic wave
Application in absorption/shielding field.Mainly include following two application form:
One is that water-soluble polymer/Graphene composite fibre and other polymer fibers are carried out blending, adds according to composite fibre
Amount number, be processed into fabric application business wear and the industrial field with antistatic effect；And there is good conductive energy
The fabric of power, is applied to the fields such as conduction, electrical heating, electro-magnetic wave absorption and shielding.
Another kind is with this fiber as electroconductive stuffing, add to plastics are processed into have antistatic or conductive capability plastics,
Film article；Add in the middle of coating, after spraying, obtain antistatic or the coating of conductive capability.
(2) product processed for raw material with water-soluble polymer/Graphene composite fibre, the application in energy field.Main
Including following three kinds of application forms:
The first is as the active electrode of ultracapacitor, coating polymerization using water-soluble polymer/Graphene composite fibre or yarn
Micro fibers type electricity ultracapacitor, the textile type capacitor of yarn type ultracapacitor or bigger it is assembled into, application after thing electrolyte
In fields such as microelectronic component, mobile electronic device and intelligent textiles
The second is as the electrode matrix of lithium battery, load lithium titanate etc. using water-soluble polymer/Graphene composite fibre or yarn
Negative material, as negative pole, is loaded with the anode material of lithium battery such as LiFePO4, LiMn2O4 and is electrolysed as positive pole, coated polymer
Be assembled into after matter micro fibers lithium battery, yarn type lithium battery or bigger textile type lithium battery applications in microelectronic component, movement
The field such as electronic equipment and intelligent textile.
The third be using water-soluble polymer/Graphene composite fibre as dye-sensitized cell to electrode, to load TiO2Lead
Electricity fiber, as photolytic activity electrode, is assembled into fibrous type solaode, resultant yarn line style solaode the most in parallel, finally
It is processed into textile type solaode, is applied to the fields such as microelectronic component, mobile electronic device and intelligent textile.
(3) product processed for raw material with water-soluble polymer/Graphene composite fibre, the application in sensor field.
It is used for detecting hydrogen peroxide, DOPA as the working electrode of sensor using water-soluble polymer/Graphene composite fibre or yarn
Chemical substance and the biomolecule such as amine, uric acid, vitamin C, enzyme.
Beneficial effect
(1) composite fibre of the present invention has higher intensity and good toughness, it is to avoid the fragility defect of pure graphene fiber, for
Follow-up textile process and actual application are provided convenience.
(2) in composite spinning liquid process for preparation, the graphene oxide solution viscosity of basification is low, mixes easily with water soluble polymer,
Uniform dispersion effect can be reached, be conducive to improving spinning liquid total concentration, it is achieved continuous print spinning smoothly；Preparation method can
Regulation fibre structure and performance, easy and simple to handle, efficiency is high, it is easy to scale continuously.
(3) the composite fibre cross section of the present invention is polymorphic structure, and surface has abundant groove microstructure, its intensity and the purer stone of toughness
Ink alkene fiber is greatly improved, and still keeps good electric conductivity, and the accumulation degree of Graphene is overcome, for sensor,
The electrochemical applications such as capacitor, battery is highly beneficial, therefore antistatic and conductive fabric, electro-magnetic wave absorption and loomage,
The fields such as energy storage device, sensor and water process have wide practical use.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope image under different amplification of the PVA/ Graphene composite fibre cross section prepared by embodiment 1, schemes a-c
In the every lattice of bottom-right scale be respectively 2 μm, 500nm and 100nm.
Fig. 2 is the scanning electron microscope image under different amplification of the PVA/ Graphene composite fibre cross section prepared by embodiment 2, schemes a-c
In the every lattice of bottom-right scale be respectively 2 μm, 500nm and 100nm.
Fig. 3 is PVA/ Graphene composite fibre cross section (a-c) prepared by embodiment 3 and surface (d-f) scanning under different amplification
Sem image, in figure a-c, the every lattice of bottom-right scale are respectively 2 μm, 500nm and 100nm, bottom-right mark in figure d-f
The every lattice of chi are respectively 2 μm, 500nm and 100nm.
Fig. 4 is the scanning electron microscope image under different amplification of the PVA/ Graphene composite fibre cross section prepared by embodiment 4, schemes a-c
In the every lattice of bottom-right scale be respectively 2 μm, 500nm and 100nm.
Fig. 5 is the scanning electron microscope image under different amplification of the PVA/ Graphene composite fibre cross section prepared by embodiment 5, schemes a-c
In the every lattice of bottom-right scale be respectively 2 μm, 500nm and 100nm.
Fig. 6 is the scanning electron microscope image under different amplification of the PVA/ Graphene composite fibre cross section prepared by embodiment 6, schemes a-c
In the every lattice of bottom-right scale be respectively 2 μm, 500nm and 100nm.
Fig. 7 is the stress-strain diagram of PVA/ Graphene composite fibre, and fibre spinning condition is: in solid contained by spinning liquid, PVA contains
Amount is respectively 0%, 5%, 10%, 20%, 30%, and jet stretch ratio R is 1.0.
Fig. 8 is the stress-strain diagram of PVA/ Graphene composite fibre, and fibre spinning condition is: in solid contained by spinning liquid, PVA contains
Amount is 20%, and jet stretch ratio R is respectively 1.0,1.5 and 2.0.
Fig. 9 is PVA/ Graphene composite fibre cross section (a-c) prepared by reference examples and surface (d-f) scanning electricity under different amplification
Mirror image, in figure a-c, the every lattice of bottom-right scale are respectively 3 μm, 500nm and 100nm；The every lattice of scale below figure d-f
It is respectively 5 μm, 2 μm and 500nm.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and not
For limiting the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art can
To make various changes or modifications the present invention, these equivalent form of values fall within the application appended claims limited range equally.
Raw material:
Graphene oxide is prepared according to Hummers oxidizing process, and the mean diameter of graphite used is 5 microns.Polyvinyl alcohol is
Model is 1799 (oil of SPCs).Remaining compound is purchased from traditional Chinese medicines group.
Method of testing:
In the examples below, surface and the cross-section morphology of fiber is seen by field emission scanning electron microscope (Hitach SU8010)
Examining, area of section is averaged after being added up by software measurement.Fibrous mechanical property passes through mono-fiber strong force instrument (XQ-1A, Shanghai
New fine instrument) test acquisition, clamping length is 10mm, and rate of extension is 2mm/min.Resistance uses two sonde methods to survey
Examination, electrical conductivity is calculated by formula.The chemical property of fiber tests acquisition in three-electrode system, to electrode is wherein
Platinum filament, working electrode is the fibre bundle (5-10 root) of 1cm, and electrolyte is 1M H2SO4, reference electrode is Hg/Hg2SO4。
Embodiment 1
Polyvinyl alcohol/Graphene composite fibre process is prepared as follows with the spinning liquid that PVA/GO mass ratio is 5/95:
(1) 1.9g graphene oxide is added in the NaOH aqueous solution that 96g pH value is 10, supersound process 30min,
Obtain graphene oxide solution.Then add the PVA aqueous solution of 2g 5wt% (mass fraction), and add 5M NaOH solution
Regulation pH value is 11, continues supersound process 30min, it is thus achieved that PVA/GO mass ratio is 5/95, pH value is 11, solid content
It is the composite spinning liquid of the composite spinning liquid of 2%.
(2) (1) gained composite spinning liquid is expressed in static methanol solidification by spinneret orifice with 1.5m/min speed, will
Coagulating bath drawn by hygrometric state fiber, is wound up on silk cylinder, it is thus achieved that PVA/GO composite fibre after hot-air dry；Wherein, silk cylinder
Convoluting speed be 1.5m/min, i.e. jet stretch ratio be 1.0 times.
(3) by (2) gained fiber impregnation to 20% ortho phosphorous acid sodium solution, at 90 DEG C, heating is reduced for 8 hours.So
Go the removal of impurity with water and ethanol alternately washing afterwards, after 100 DEG C are dried 3 hours, obtain polyvinyl alcohol/Graphene composite fibre.
The pattern of gained composite fibre as it is shown in figure 1, Typical tensile curve is as it is shown in fig. 7, elongation at break is 4.7%, intensity
For 141MPa；Electrical conductivity is 4.3Scm-1；At 1M H2SO4In ratio electric capacity be 36Fg-1(10mVs-1)。
Embodiment 2
Polyvinyl alcohol/Graphene composite fibre process is prepared as follows with the spinning liquid that PVA/GO mass ratio is 10/90:
(1) 1.8g graphene oxide, 4g 5wt%PVA aqueous solution are added in 94.2g water, use strong aqua ammonia regulation pH
Value is 9, then uses high-speed emulsifying machine to carry out dispersion mixing 1 hour, and finally continuing to add ammonia regulation pH is 11, it is thus achieved that
Composite spinning liquid.
(2) (1) gained composite spinning liquid is expressed into 1.5m/min speed by spinneret orifice 80% acetic acid water of PARALLEL FLOW
Solution is solidified into fiber.Wherein, the flowing velocity of acetic acid be 1.5m/min, i.e. jet stretch ratio be 1.0 times.Then by wet
Coagulating bath drawn by state fiber, is wound up into continuously on silk cylinder, it is thus achieved that PVA/GO composite fibre after hot-air dry.
(3) carry out adding thermal reduction in the nitrogen of 220 DEG C by (2) gained fiber.
The pattern of gained composite fibre as in figure 2 it is shown, Typical tensile curve is as it is shown in fig. 7, elongation at break is 7.6%, intensity
For 193MPa, electrical conductivity is 3.6Scm-1；At 1M H2SO4In ratio electric capacity be 65Fg-1(10mVs-1).
Embodiment 3
The compound fibre of polyvinyl alcohol/Graphene that jet stretch ratio is 1.0 times is prepared with the spinning liquid that PVA/GO mass ratio is 20/80
Dimension process is as follows:
(1) 1.6g graphene oxide, 8g 5wt%PVA aqueous solution are added in 90.4g water, use strong aqua ammonia regulation pH
Value is 9, then uses high-speed emulsifying machine to carry out dispersion mixing 1 hour, and finally continuing to add ammonia regulation pH is 10, it is thus achieved that
Composite spinning liquid.
(2) (1) gained composite spinning liquid is expressed in the acetic acid of rotation solidification fibroblast by spinneret orifice with 1.5m/min speed
Dimension, wherein spinning head distance center of rotation distance be 3cm, the speed of rotation be 8rpm, i.e. jet stretch ratio be 1.0 times.
Hygrometric state fiber is drawn coagulating bath, is wound up into the most continuously on silk cylinder through infrared lamp, it is thus achieved that PVA/GO composite fibre.
(3) by the hydriodic acid aqueous solution of (2) gained fiber impregnation 40%, at 95 DEG C, heating is reduced for 4 hours.Then
Go the removal of impurity with water and ethanol alternately washing, after 100 DEG C are dried 3 hours, obtain polyvinyl alcohol/Graphene composite fibre.
The pattern of gained composite fibre is as it is shown on figure 3, Typical tensile curve is as it is shown in fig. 7, elongation at break is 11.4%, by force
Degree is 252MPa, and electrical conductivity is 3.3Scm-1；At 1M H2SO4In ratio electric capacity be 41Fg-1(10mVs-1)。
Embodiment 4
The compound fibre of polyvinyl alcohol/Graphene that jet stretch ratio is 1.5 times is prepared with the spinning liquid that PVA/GO mass ratio is 20/80
Dimension process is as follows:
(1) 1.6g graphene oxide, 8g 5wt%PVA aqueous solution are added in 90.4g water, use strong aqua ammonia regulation pH
Value is 9, then uses high-speed emulsifying machine to carry out dispersion mixing 1 hour, and finally continuing to add ammonia regulation pH is 10, it is thus achieved that
Composite spinning liquid.
(2) (1) gained composite spinning liquid is expressed in the acetic acid of rotation solidification fibroblast by spinneret orifice with 1.5m/min speed
Dimension, wherein spinning head distance center of rotation distance be 3cm, the speed of rotation be 12rpm, i.e. jet stretch ratio be 1.5 times.
Hygrometric state fiber is drawn coagulating bath, is wound up into the most continuously on silk cylinder through infrared lamp, it is thus achieved that PVA/GO composite fibre.
(3) by the hydriodic acid aqueous solution of (2) gained fiber impregnation 40%, at 95 DEG C, heating is reduced for 4 hours.Then
Go the removal of impurity with water and ethanol alternately washing, after 100 DEG C are dried 3 hours, obtain polyvinyl alcohol/Graphene composite fibre.
As shown in Figure 4, as shown in Figure 8, elongation at break is 6.1% to Typical tensile curve to the pattern of gained composite fibre, intensity
For 281MPa, electrical conductivity is 3.5Scm-1。
Embodiment 5
The compound fibre of polyvinyl alcohol/Graphene that jet stretch ratio is 2.0 times is prepared with the spinning liquid that PVA/GO mass ratio is 20/80
Dimension process is as follows:
(1) 1.6g graphene oxide, 8g 5wt%PVA aqueous solution are added in 90.4g water, use strong aqua ammonia regulation pH
Value is 9, then uses high-speed emulsifying machine to carry out dispersion mixing 1 hour, and finally continuing to add ammonia regulation pH is 10, it is thus achieved that
Composite spinning liquid.
(2) (1) gained composite spinning liquid is expressed in the acetic acid of rotation solidification fibroblast by spinneret orifice with 1.5m/min speed
Dimension, wherein spinning head distance center of rotation distance be 3cm, the speed of rotation be 16rpm, i.e. jet stretch ratio be 2.0 times.
Hygrometric state fiber is drawn coagulating bath, is wound up into the most continuously on silk cylinder through infrared lamp, it is thus achieved that PVA/GO composite fibre.
(3) by the hydriodic acid aqueous solution of (2) gained fiber impregnation 40%, at 95 DEG C, heating is reduced for 4 hours.Then
Go the removal of impurity with water and ethanol alternately washing, after 100 DEG C are dried 3 hours, obtain polyvinyl alcohol/Graphene composite fibre.
The pattern of gained composite fibre as it is shown in figure 5, Typical tensile curve as shown in Figure 8, elongation at break is 3.1%, intensity
For 285MPa, electrical conductivity is 5.4Scm-1。
Embodiment 6
Polyvinyl alcohol/Graphene composite fibre process is prepared as follows with the spinning liquid that PVA/GO mass ratio is 30/70:
(1) 1.4g graphene oxide, 12g 5wt%PVA aqueous solution are added in 86.6g water, use strong aqua ammonia regulation
PH value is 8, then uses high-speed emulsifying machine to carry out dispersion mixing 1 hour, and finally continuing to add ammonia regulation pH is 9, obtains
Obtain composite spinning liquid.
(2) (1) gained composite spinning liquid is expressed in the acetone of rotation solidification fibroblast by spinneret orifice with 1.5m/min speed
Dimension, wherein spinning head distance center of rotation distance be 3cm, the speed of rotation be 8rpm, i.e. jet stretch ratio be 1.0 times.
Hygrometric state fiber is drawn coagulating bath, is wound up into the most continuously on silk cylinder through infrared lamp, it is thus achieved that PVA/GO composite fibre.
(3) by the hydriodic acid aqueous solution of (2) gained fiber impregnation 40%, at 95 DEG C, heating is reduced for 4 hours.Then
Go the removal of impurity with water and ethanol alternately washing, after 100 DEG C are dried 3 hours, obtain polyvinyl alcohol/Graphene composite fibre.
As shown in Figure 6, as shown in Figure 8, elongation at break is 6.2% to Typical tensile curve to the pattern of gained composite fibre, intensity
For 244MPa, electrical conductivity is 1.9Scm-1；At 1M H2SO4In ratio electric capacity be 27Fg-1(10mVs-1)。
Reference examples
Graphene fiber preparation process without polymer is as follows:
(1) by 2g graphene oxide, 98g water, using strong aqua ammonia regulation pH value is 10, the most ultrasonic stripping 1 hour,
Finally continuing to add ammonia regulation pH is 11, it is thus achieved that spinning liquid.
(2) (1) gained spinning liquid is expressed in the acetic acid of rotation with 1.5m/min speed by spinneret orifice it is solidified into fiber,
Wherein spinning head distance center of rotation distance be 3cm, the speed of rotation be 8rpm, i.e. jet stretch ratio be 1.0 times.By wet
Coagulating bath drawn by state fiber, is wound up into the most continuously on silk cylinder through infrared lamp, it is thus achieved that graphene oxide fiber.
(3) carry out adding thermal reduction in the nitrogen of 220 DEG C by (2) gained fiber.
The pattern of gained composite fibre as it is shown in figure 9, Typical tensile curve is as it is shown in fig. 7, elongation at break is 5.2%, intensity
For 95MPa, electrical conductivity is 30.8Scm-1；At 1M H2SO4In ratio electric capacity be 31Fg-1(10mVs-1)。
Claims (12)
1. water-soluble polymer/Graphene composite fibre, it is characterised in that: described fibre section presents abnormity, including quadrangle, class " V " font, class " v " font, class " C " font and class " one " font；Fiber surface is more smooth at micro-meter scale, presents the nanoscale fold of orientation at nanoscale；Fibre strength is more than 100MPa, and elongation at break is more than 2%, and electrical conductivity is more than 0.1S/cm.
A kind of water-soluble polymer/Graphene composite fibre the most according to claim 1, it is characterised in that: described water-soluble polymer is one or more in polyvinyl alcohol, Polyethylene Glycol, polyvinylpyrrolidone, water soluble starch and their derivant.
3. a preparation method for water-soluble polymer as claimed in claim 1/Graphene composite fibre, including:
(1) graphene oxide GO is added in alkali liquor, obtain 0.2wt%～20wt%GO dispersion liquid by peeling off dispersion process；Then with the water-soluble polymer aqueous solution that mass fraction is 0.2wt%～20wt%, dispersion processes, and finally adds alkali liquor regulation pH value, obtains WSP/GO composite spinning liquid；
Or add graphene oxide GO to pH > 7, in the water-soluble polymer WSP aqueous solution of 0.1wt%-10wt%, process by peeling off dispersion, obtain finely dispersed composite solution, finally add alkali liquor regulation pH value, obtain WSP/GO composite spinning liquid；
Wherein, described water-soluble polymer is 1:99～80:20 with the mass ratio of graphene oxide；
(2) above-mentioned spinning liquid is expressed in coagulating bath solidification, through drawing-off, be dried and winding obtain water-soluble polymer/graphene oxide composite fibre；
(3) above-mentioned composite fibre is carried out in liquid environment or gaseous environment chemically or physically reduction treatment, obtain water-soluble polymer/Graphene composite fibre.
The preparation method of a kind of water-soluble polymer/Graphene composite fibre the most according to claim 3, it is characterised in that: the alkali liquor in described step (1) is one or more in hydroxide aqueous solution, water-soluble organic amine aqueous solution, carbonate aqueous solution, bicarbonate aqueous solution, aqueous phosphatic, pyridine solution.
The preparation method of a kind of water-soluble polymer/Graphene composite fibre the most according to claim 3, it is characterised in that: the pH value of the spinning liquid in described step (1) is 4～13, and solid content is 0.2wt%～20wt%.
The preparation method of a kind of water-soluble polymer/Graphene composite fibre the most according to claim 3, it is characterised in that: the coagulating bath in described step (2) is in the container of rotation or flows in the duct or be in coagulating basin holding and stands；Coagulating bath is by one or more aqueous solutions formed in mineral acid and inorganic salt or by one or more liquid formed in organic acid, alcohol, amine, ketone, amide, pyridine, pyrroles, water.
The preparation method of a kind of water-soluble polymer/Graphene composite fibre the most according to claim 3, it is characterised in that: in the drafting process in described step (2), jet stretch ratio is 0.2～5.
The preparation method of a kind of water-soluble polymer/Graphene composite fibre the most according to claim 3, it is characterised in that: being dried in described step (2) is dried for far infrared radiation, heat channel heating, Hot-blast Heating, microwave radiation add one or more hankered.
The preparation method of a kind of water-soluble polymer/Graphene composite fibre the most according to claim 3, it is characterised in that: the liquid environment in described step (3) is containing the aqueous solution of one or more in acid, alkali, salt or by one or more liquid formed in organic acid, alcohol, amine, ketone, amide, sulfone, pyridine, water；Gaseous environment is one or more in air, nitrogen, argon, ammonia, hydrogen.
The preparation method of a kind of water-soluble polymer/Graphene composite fibre the most according to claim 3, it is characterised in that: the electronation in described step (3) is to carry out in the liquid environment containing reducing agent or gaseous environment；Wherein, described reducing agent is hydrogen halides, inorganic base, hydrazine class compound, phenolic compound, ammonia amine compounds, contains the compound of sulfur at a low price, containing one or more in the compound of phosphorus, vitamin C and salt, oxalic acid and salt thereof, reducing sugar, active metal and organic complex thereof at a low price；The mass fraction of reducing agent is 1%～80%；Reduction temperature is-50～300 DEG C；Recovery time is 5 seconds～24 hours.
The preparation method of 11. a kind of water-soluble polymer/Graphene composite fibres according to claim 3, it is characterised in that: the physics in described step (3) is reduced to one or more in atmosphere thermal reduction, solvothermal, laser irradiation, ultraviolet irradiation, microwave radiation, xenon lamp irradiation；Reduction temperature is 150～1500 DEG C；Recovery time is 5 seconds～24 hours.
The application of 12. 1 kinds of water-soluble polymer as claimed in claim 1/Graphene composite fibres, it is characterized in that: weave or be processed into fabric with other fiber blends, fabric or composite fibre being directly used in and is processed into electrode and is assembled into ultracapacitor, metal ion battery, solaode or sensor；Or fabric is used for antistatic, conduction, electrical heating, electro-magnetic wave absorption and shielding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410674600.6A CN104451925B (en) | 2014-11-21 | 2014-11-21 | A kind of water-soluble polymer/Graphene composite fibre and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410674600.6A CN104451925B (en) | 2014-11-21 | 2014-11-21 | A kind of water-soluble polymer/Graphene composite fibre and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104451925A CN104451925A (en) | 2015-03-25 |
| CN104451925B true CN104451925B (en) | 2017-01-04 |
Family
ID=52898647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410674600.6A Active CN104451925B (en) | 2014-11-21 | 2014-11-21 | A kind of water-soluble polymer/Graphene composite fibre and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104451925B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107069033A (en) * | 2017-03-21 | 2017-08-18 | 中国科学院福建物质结构研究所 | A kind of battery electrode of graphene-containing fiber and its preparation method and application |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790067B (en) * | 2015-04-17 | 2017-10-03 | 东华大学 | Conductivity high molecule nanometer/graphene composite fibre and its preparation method and application |
| CN104947227B (en) * | 2015-07-13 | 2017-06-13 | 黑龙江大学 | Polyvinylpyrrolidone/Graphene composite nano-fiber material and preparation method thereof |
| CN104988592B (en) * | 2015-07-17 | 2017-05-17 | 黑龙江大学 | Polyvinyl alcohol/graphene composite nano fiber material and preparation method thereof |
| CN105088391B (en) * | 2015-07-17 | 2017-05-10 | 黑龙江大学 | Poly(p-phenylene vinylene)/graphene composite nanofiber material and preparation method thereof |
| CN105185600B (en) * | 2015-09-25 | 2018-05-15 | 东华大学 | A kind of method that electrophoresis prepares Graphene electrodes material |
| CN105442072A (en) * | 2015-12-31 | 2016-03-30 | 哈尔滨工业大学 | Method for preparing super tough fibers of shell-simulation structures and helical structures simultaneously in batches |
| CN107538951A (en) * | 2016-06-27 | 2018-01-05 | 林惠花 | A kind of graphene books |
| CN106192201B (en) * | 2016-07-18 | 2018-09-14 | 浙江大学 | A kind of graphene fiber non-woven fabrics and preparation method thereof |
| CN106370221B (en) * | 2016-08-23 | 2019-07-23 | 东华大学 | A kind of response PVDF/ graphene/elastic fabric compound sensor preparation method certainly |
| CN106245183B (en) * | 2016-09-21 | 2018-11-13 | 福建天守纺织新材料有限公司 | A kind of preparation method of the frivolous insulated bed fabric based on grapheme foam |
| CN106319710A (en) * | 2016-09-30 | 2017-01-11 | 无锡市长安曙光手套厂 | Composite textile material and preparation method |
| TWI790216B (en) * | 2016-12-09 | 2023-01-21 | 斯里蘭卡商約翰 基爾控股有限公司 | Electrospun collagen-graphene-polymer composite nanofibers for supercapacitors |
| US10626231B2 (en) | 2016-12-28 | 2020-04-21 | King Fahd University Of Petroleum And Minerals | Microwave irradiated poly(vinyl alcohol) and graphene nanocomposite |
| CN108511740A (en) * | 2017-03-13 | 2018-09-07 | 万向二三股份公司 | A kind of high-specific-capacity silicon carbon electrode coating preparation method |
| CN107215011A (en) * | 2017-05-08 | 2017-09-29 | 江苏联宏纺织有限公司 | A kind of compound fabric based on graphene composite fibre and preparation method thereof |
| CN107366181A (en) * | 2017-07-11 | 2017-11-21 | 滁州海川印刷包装有限公司 | A kind of preparation method for the antistatic corrugated paper for adding composite conducting fiber |
| CN107938009B (en) * | 2017-11-30 | 2020-06-05 | 山东省圣泉生物质石墨烯研究院 | Graphene oxide modified fiber and preparation method and application thereof |
| CN109161987A (en) * | 2018-08-09 | 2019-01-08 | 东华大学 | A kind of bionical wig fiber filament of sodium alginate/graphene and its preparation and application |
| CN109294131B (en) * | 2018-08-09 | 2021-03-19 | 东华大学 | Polyvinyl alcohol/graphene conductive nanocomposite and preparation and application thereof |
| CN110078951B (en) * | 2019-05-17 | 2022-05-31 | 湖北科技学院 | Radiation reduction and curing method of liquid polycarbosilane |
| CN112652741B (en) * | 2019-10-10 | 2022-09-06 | 中国科学技术大学 | Preparation method of graphene-based composite micron rod loaded with positive active material |
| CN110726754B (en) * | 2019-10-22 | 2021-11-02 | 南京信息工程大学 | Preparation method and gas-sensitive application of graphene aerogel assembled on surface of device in situ |
| CN110586640B (en) * | 2019-10-26 | 2022-07-12 | 重庆道润土壤修复有限责任公司 | Method for removing and recovering heavy metals in polluted soil |
| CN112376121B (en) * | 2020-10-27 | 2022-04-08 | 山东科技大学 | Preparation method and application of folded graphene fibers for improving shear orientation of graphene sheets |
| CN113782837A (en) * | 2021-08-03 | 2021-12-10 | 东风悦达起亚汽车有限公司 | Preparation method of high-quality graphene battery |
| CN113862853B (en) * | 2021-10-27 | 2022-09-02 | 内蒙古爱立特纺织股份有限公司 | Cashmere graphene blended yarn capable of preventing static reactance pilling and preparation process thereof |
| CN115341307A (en) * | 2022-09-23 | 2022-11-15 | 内蒙古大学 | High-orientation-degree graphene oxide fiber and preparation method thereof |
| CN116876109B (en) * | 2023-08-21 | 2024-04-12 | 哈尔滨工业大学 | Graphene composite fiber and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103541043A (en) * | 2013-08-01 | 2014-01-29 | 华为技术有限公司 | Preparation method of electric graphene composite fiber |
| CN103726133A (en) * | 2014-01-02 | 2014-04-16 | 东华大学 | High-strength, compact and ordered porous graphene fiber and continuous preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5257813B2 (en) * | 2009-03-13 | 2013-08-07 | 国立大学法人信州大学 | Polyvinyl alcohol-based composite fiber and method for producing the same |
| KR101195490B1 (en) * | 2011-03-15 | 2012-10-29 | 한양대학교 산학협력단 | Graphene composite fiber and the method for preparing the fiber |
-
2014
- 2014-11-21 CN CN201410674600.6A patent/CN104451925B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103541043A (en) * | 2013-08-01 | 2014-01-29 | 华为技术有限公司 | Preparation method of electric graphene composite fiber |
| CN103726133A (en) * | 2014-01-02 | 2014-04-16 | 东华大学 | High-strength, compact and ordered porous graphene fiber and continuous preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107069033A (en) * | 2017-03-21 | 2017-08-18 | 中国科学院福建物质结构研究所 | A kind of battery electrode of graphene-containing fiber and its preparation method and application |
| CN107069033B (en) * | 2017-03-21 | 2020-02-21 | 中国科学院福建物质结构研究所 | Battery electrode containing graphene fibers and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104451925A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104451925B (en) | A kind of water-soluble polymer/Graphene composite fibre and its preparation method and application | |
| CN104790067B (en) | Conductivity high molecule nanometer/graphene composite fibre and its preparation method and application | |
| CN103726133B (en) | High strength, compact neat porous graphene fiber and continuous production method thereof | |
| CN104392845B (en) | A kind of stretchable linear supercapacitor and preparation method of lithium ion battery | |
| Chen et al. | Electrospinning of thermo-regulating ultrafine fibers based on polyethylene glycol/cellulose acetate composite | |
| Chronakis | Novel nanocomposites and nanoceramics based on polymer nanofibers using electrospinning process—A review | |
| CN105239184B (en) | A kind of bacteria cellulose/graphene/ferroso-ferric oxide composite membrane and preparation method thereof | |
| CN106848314A (en) | The method that lithium-sulfur cell prepares positive electrode with the preparation method of double-layer porous carbon nano-fiber and using it | |
| CN103011778A (en) | Porous alumina nano fiber and preparation method thereof | |
| Liang et al. | Continuous and integrated PEDOT@ Bacterial cellulose/CNT hybrid helical fiber with “reinforced cement-sand” structure for self-stretchable solid supercapacitor | |
| CN105958073B (en) | A kind of carbon nano-fiber film/compound membrane preparation method of cobalt acid lithium three-dimensional coaxial | |
| CN109763210A (en) | The method that ionic liquid prepares cellulose base carbon fiber or carbon film | |
| Raza et al. | Ultrathin honeycomb-like MnO2 on hollow carbon nanofiber networks as binder-free electrode for flexible symmetric all-solid-state supercapacitors | |
| Jiang et al. | Centrifugally-spun tin-containing carbon nanofibers as anode material for lithium-ion batteries | |
| CN108597901A (en) | A kind of method that the double spray of electrostatic spinning prepare cobalt acid nickel carbon fiber flexibility electrode material | |
| CN105671686A (en) | Preparation method of alginate-graphene-nano-cuprous oxide composite antibacterial fiber | |
| WO2017214741A1 (en) | Process for preparing chitosan/polyvinyl alcohol composite electrically-conductive nanofibre | |
| CN102586920A (en) | Preparation method of polyacrylonitrile nanometer fibers | |
| Shao et al. | MgO nanofibres via an electrospinning technique | |
| CN107164820A (en) | A kind of highly oriented composite conducting nanofiber | |
| Huang et al. | Electrospun nanofibers: from rational design, fabrication to electrochemical sensing applications | |
| Zhao et al. | Microstructure and electrochemical properties of polyacrylonitrile-based carbon micro-and nanofibers fabricated by centrifugal spinning | |
| CN108277556A (en) | A kind of superhigh-flexibility graphene fiber and preparation method thereof prepared by dry spinning | |
| Bai et al. | PVA/sodium alginate multi-network aerogel fibers, incorporated with PEG and ZnO, exhibit enhanced temperature regulation, antibacterial, thermal conductivity, and thermal stability | |
| Li et al. | Electrospun cerium nitrate/polymer composite fibres: synthesis, characterization and fibre-division model |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |