CN104451961A - Method for preparing superconducting micron fiber - Google Patents
Method for preparing superconducting micron fiber Download PDFInfo
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- CN104451961A CN104451961A CN201410548429.4A CN201410548429A CN104451961A CN 104451961 A CN104451961 A CN 104451961A CN 201410548429 A CN201410548429 A CN 201410548429A CN 104451961 A CN104451961 A CN 104451961A
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Abstract
The invention discloses a method for preparing superconducting micron fiber. The method comprises the following steps: (1) enabling TEMPO oxidized cellulose to pass through a microfluidizer at a time to prepare NFC; (2) oxidizing graphite by a Hummer's method to obtain GO; (3) preparing high-strength micron fiber, namely, extruding a spinning solution into alcohol coagulation bath by a needle tube, and separating out to obtain gel fiber; then, pulling the gel fiber out from the coagulation bath, and drying in air, and in the drying process, applying certain acting force to the two ends of the micron fiber so as to improve the degree of orientation of the micron fiber; after the micron fiber is dried, putting the micron fiber into a 10wt% of CaCl2 water solution, dipping for 1 hour, and then drying again; (4) carrying out carbonization on the high-strength micron fiber to obtain the conductive micron fiber containing GO and NFC. The micron fiber c (GO+NFC) has the average conductivity of 649+/-60S/cm which is maximum in the reported conductivity nowadays, and the conductivity of the micron fiber is higher than the conductivities of carbonized NFC micron fiber and carbonized GO micron fiber. Furthermore, the NFC and the GO which have the low densities are used by the preparation, so that the raw material source is wide.
Description
Technical field
The present invention relates to superpower micrometer fibers technical field, particularly one prepares superconduct micrometer fibers (c(GO+NFC)) method.
Background technology
Nano-cellulose has excellent performance, has now been used to prepare superpower material, conductive material etc. for fields such as electronic equipment, biological medicine, food, packagings.Fiber is the material with extensive use, and its Application Areas relates to weaving, builds in the preparation of even aircraft, automobile etc.The preparation of current high-performance and low-cost micrometer fibers causes the extensive concern of people.The function micrometer fibers prepared by nano-cellulose becomes popular gradually.
The synthetic fiber (as carbon fiber) of excellent in mechanical performance play the part of important role in the turbo blade preparation of aircraft, wind-power electricity generation.But these synthetic fiber are expensive, limited capacity.Thus now focus is become to the fiber preparation research of low-cost and high-performance.Nano-cellulose has the features such as excellent in mechanical performance, wide material sources, green, has been used to the reinforcing agent preparing high-strength material or material.Two-dimensional nano graphene oxide (GO) is also have very good mechanical properties, high-specific surface area, can be used for the construction unit material preparing superpower material.There are great amount of hydroxy group, carboxyl and the epoxy radicals introduced because of chemical reaction in the surface of GO sheet and edge, and these groups make GO can stable dispersion in water, form strong active force in the material.For by the two-dimentional GO of low cost for the preparation of one-dimensional micron fiber, become study hotspot now.In order to improve the intensity of GO micrometer fibers, conventional method has chemical crosslinking, polymer wrapped coating, ionic bond combine and improve the quality etc. of GO monolithic.The GO micrometer fibers that the mechanical strength of current report is best, tensile strength can reach 442MPa, and elastic modelling quantity has 47GPa.But want to replace carbon fiber in actual applications, the intensity of GO fiber also needs further raising.
Cellulose is the large biological molecule polymer that occurring in nature reserves are maximum.It is the important source material for the preparation of material with carbon element.The material with carbon element prepared by cellulose has played important function in fields such as stored energy, carbon fiber preparation, water treatment, catalysis.The important means being prepared material with carbon element by cellulose carbonizes cellulose, is mainly included in heating charing and hydro-thermal under particular atmosphere and carbonizes two kinds.In carbonization process, there is glycosidic bond fracture, the degraded of fiber, the air release containing oxygen and hydrogen, finally form material with carbon element in cellulose.But the cellulose material with carbon element electric conductivity usually obtained is lower.Electric conductivity as carbon fiber is about 30S/cm when carbonization temperature is 1000 DEG C.For obtaining the material with carbon element of high conductivity, usually carbonization temperature will be improved.Because improve carbonization temperature can improve the inner degree of graphitization of material with carbon element, and then improve electric conductivity.When carbonization temperature being brought up to 2000 DEG C, the electric conductivity of carbon fiber can bring up to 100S/cm.But the requirement of high-temperature process to equipment is high, conductive fiber preparation cost is increased.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of the present invention is to provide a kind of method preparing superconduct micrometer fibers, GO is combined with nano-cellulose (NFC) and prepares high strength micrometer fibers, improve the intensity of blended fiber, and then charing process, obtain superconduct micrometer fibers.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is as follows:
Prepare a method for superconduct micrometer fibers, comprise the following steps:
1) TEMPO oxycellulose is once by preparing NFC after microfluidizer;
2) Hummer ' s method is adopted to be oxidized graphite and to obtain GO;
3) preparation of high strength micrometer fibers: spinning solution is expressed in alcohol coagulating bath by needle tubing and separates out, form gelatinous fibre, then gelatinous fibre is pulled out coagulating bath dry in atmosphere; In dry run, apply the active force of 0.5N at micrometer fibers two ends, to improve the degree of orientation of micrometer fibers; After drying, micrometer fibers is placed in 10wt% CaCl
2the aqueous solution in dipping again dry after 1 hour;
4) charing is carried out to high strength micrometer fibers and obtain conduction GO+NFC micrometer fibers.
In step 1): the over dry softwood pulp that 5g is not dried and 78mg TEMPO, 514mg NaBr fully mix; Reaction adds initiation by 30mL 12%NaClO, and reacts under stirring at room temperature; The pH value of system controls to be stabilized in 10.5 by NaOH; The end until system interior residue NaClO reacts completely; Reacted slurry is clean by filtration washing, to pH in neutral; The concentration fiber obtained being made into 1% is processed under 5 ~ 25KPa pressure by microfluidizer; Obtain transparent nanofiber element dispersion liquid; Dispersion liquid storage and 4 DEG C of refrigerators.
Step 2) in: by 3.0g graphite flakes, 1.5g NaNO
3mix at 0 DEG C; Then 69mL 98%H
2sO
4add mixing and stirring, finally slowly add 9.0g KMnO
4; Add KMnO
4time solution temperature control, lower than 20 DEG C, to add KMnO
4after temperature of reaction system is elevated to 35 DEG C and stirs 30min; Then 138mL deionized water is slowly dripped and enter reaction system, and control reaction temperature at 98 DEG C of maintenance 15min; And then reaction system is cooled to room temperature, add the H of 420mL deionized water and 3mL 30%C simultaneously in addition
2o
2; Deng reactant mixture cool to room temperature time, material is spent in Buchner funnel deionized water to neutral; The GO ultrasonic disperse obtained is stand-by in water.
In step 3), described spinning solution is the concentration that GO and NFC mass ratio 1:1 prepares is the liquid crystal solution of 1.1wt%.
In step 4), the charing of high strength micrometer fibers is carried out in 95% argon gas and 5% hydrogen mixed gas atmosphere; Heating schedule is as follows: be first raised to 400 DEG C from room temperature to the heating rate of 30 DEG C/h, be raised to 1000 DEG C afterwards, finally at 1000 DEG C, be incubated 2h with the heating rate of 200 DEG C/h.
The superconduct micrometer fibers that the described method preparing superconduct micrometer fibers obtains.
Described superconduct micrometer fibers is as the application of conductive material.
Beneficial effect: compared with prior art, tool of the present invention has the following advantages and high-lighting effect: the c(GO+NFC obtained) average conductivity of micrometer fibers is 649 ± 60 S/cm, the most conductance of the conductive fiber prepared by graphite, GO and GO compound reported now, higher than charing NFC micrometer fibers (average conductivity is 33S/cm) with carbonize GO micrometer fibers conductance (average conductivity is 137S/cm).Meanwhile, preparation uses low-density NFC and GO, and raw material sources are extensive, and fiber producing processes simply has the potential value of large-scale production.
Accompanying drawing explanation
Fig. 1 is the characterization result figure of TEMPO method oxycellulose;
Fig. 2 is TEMPO oxycellulose once just can obtain NFC later characterization result figure by microfluidizer;
Fig. 3 is the preparation flow figure of GO+NFC micrometer fibers;
Fig. 4 is the structural representation of high strength micrometer fibers;
Fig. 5 is the phenogram of raw materials and mixed liquor;
Fig. 6 is the phenogram of high strength micrometer fibers;
Fig. 7 is the phenogram of control sample;
Fig. 8 is the stress-strain curve diagram of GO micrometer fibers, NFC micrometer fibers and GO+NFC micrometer fibers;
Fig. 9 is the schematic diagram before and after fiber charing;
Figure 10 is the SEM figure after charing;
Figure 11 is c(GO+NFC) the I-V curve of fiber.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but the present invention is not limited by the following examples.
The main agents used in following examples and instrument as follows:
Bleaching needle-point leaf pulp plate is Brazilian snapper board, and it is 150mL that slurry first gets to Canadian freeness through a watt power beater.Ultraviolet spectrometer UV-Vis Spectrometer Lambda 35(PerkInElmer, USA); Transmission electron microscope (TEM, FEI QUANTA 200, the U.S.); Dynamic mechanical analyzer analyzes (DMA, Q800); Hitachi (HITACHI) S-510 ESEM; Ultrasound Instrument (FS 110D, Fisher Scientific).
Embodiment 1 NFC UV absorber
The over dry softwood pulp that 5g is not dried and 78mg TEMPO, 514mg NaBr fully mix.Reaction adds initiation by 30mL 12%NaClO, and reacts under stirring at room temperature.The pH value of system controls to be stabilized in 10.5 by NaOH.The end until system interior residue NaClO reacts completely.Reacted slurry is clean by filtration washing, to pH in neutral.The fiber obtained is made into the concentration of 1% by processing under microfluidizer 5 ~ 25KPa pressure.Obtain transparent nanofiber element (NFC) dispersion liquid.Dispersion liquid storage with 4 DEG C of refrigerators in stand-by.
ESEM (SEM) is observed: after testing sample is carried out vacuumize, and sticky platform, vacuum metal spraying, operating condition voltage is 20kV.
The length and width degree of nano-cellulose adopts transmission electron microscope and fiber morphology to be characterized by AFM (AFM).Drip 10 μ L nanofiber cellulose solutions during TEM sample preparation online at charcoal, unnecessary liquid filter paper siphons away, and operating voltage is 100kV.During AFM sample preparation, drip 10 μ L nanofiber cellulose solutions on the silicon chip of 1cm × 1cm, by spin coating instrument, nano-cellulose is smoothened on silicon chip.Under tapping-mode, carry out observation after drying characterize.
Solution Zeta potential is obtained by Zeta potential tester.During test, NFC liquid quality fraction is 0.7 mg/mL, pH is 7.8.
Characterization result as shown in Figure 1, wherein a-c is the SEM figure of TEMPO oxidized fibre, d is cellophane paper prepared by TEMPO oxidized fibre, conductive ink is write on paper prepared by TEMPO oxidized fibre by e, f is that ammeter test shows the conductor wire write and has good electric conductivity, and the paper prepared at TEMPO oxidized fibre obtains diode by ball stroke to g.After TEMPO oxidation processes fiber, fiber surface C 6 hydroxyls are oxidized to carboxyl, add the charged group content on fiber.Simultaneously due to oxidation reaction and the churned mechanically active force of fiber, interfibrous bond strength reduces, and longitudinal cracking (a-b in Fig. 1), even appears in the breakage of fiber surface generation cell membrane.Meanwhile, the length of fiber reduces, width reduces, and in solution, fines content increases.High power surface sweeping electricity Microscopic observation fiber surface (c in Fig. 1) is known, and surface containing a large amount of microfibres, and is meshy arrangement.This meets the structure of microfibre in timber primary wall.Although the fiber overwhelming majority after TEMPO oxidation is still micrometer fibers, solution has certain viscosity and transparency.Fiber after direct filtration TEMPO oxidation can obtain transparent and have the paper (d in Fig. 1) of certain mist degree.Paper maintains good writing quality, with surface flatness simultaneously.Surface flatness may mainly contain the nanofibres deposit produced in preparation process and cause at paper surface.E-g in Fig. 1, for write conductive material on paper, prepares the paper substrate electronic equipment that can write.
TEMPO oxycellulose once just can obtain NFC by microfluidizer later, result as shown in Figure 2, wherein, the TEM obtaining NFC under low power a and high power b schemes, c is the AFM figure of NFC, and d is NFC solution, and e is that green laser irradiates NFC solution, the petrographic microscope picture that f is NFC solution concentration when being 1%, g is NFC gel.Larger by the pressure of microfluidizer, the NFC size obtained is less.A in Fig. 2 is the NFC obtained by the microfluidizer process of 25KPa pressure.Its diameter is less than 10nm, and length is in hundreds of nanometer.High magnification TEM figure (b in Fig. 2) shows NFC and has beautiful crystalline texture.AFM is also used to characterize NFC pattern (c in Fig. 2), and the NFC diameter shown in AFM figure is slightly larger than TEM result, and this is relevant with characterization method.The feature of the aqueous solution of NFC is its optical transparence (d in Fig. 2), and the Tyndall phenomenon of nano-solution.Due to NFC show containing TEMPO oxidation introduce charged group, NFC can stable dispersion in water.Carry out Zeta potential test to NFC solution to know: the Zeta potential of solution is-64.9mV, confirms the good stability of solution.NFC has the characteristic of self assembly, and when NFC solution concentration is 1%, solution starts to embody liquid crystal form, as shown in the e in Fig. 2.The concentration of further raising NFC solution, the change of NFC gel can be formed, as the f in Fig. 2.The about 10nm of NFC diameter prepared, length, at 100-400nm scope (b in Fig. 5), starts to form liquid crystalline phase when NFC concentration is 1.0wt%.
The preparation of embodiment 2 graphene oxide (GO)
GO adopts Hummer ' s method be oxidized graphite and obtain.Concrete grammar is as follows: by graphite flakes (3.0g, 1wt. relative mass content), NaNO
3(1.5g, 0.5 wt. relative mass content) mixes at 0 DEG C.Then H
2sO
4(98%, 69mL) adds mixing and stirring, finally slowly adds KMnO
4(9.0g, 3wt. relative mass content).Add KMnO
4time solution temperature control, lower than 20 DEG C, to add KMnO
4after temperature of reaction system is elevated to 35 DEG C and stirs 30min.Then 138mL deionized water is slowly dripped and enter reaction system, and control reaction temperature at 98 DEG C of maintenance 15min.And then reaction system is cooled to room temperature, interpolation 420mL deionized water and 3mL concentration are the H of 30% in addition simultaneously
2o
2.Deng reactant mixture cool to room temperature time, material is spent in Buchner funnel deionized water to neutral.The GO ultrasonic disperse obtained is stand-by in water.The pattern of GO nano flake passes through atomic force microscope observation.About 1.5 μm of the lateral dimension (as shown in a in Fig. 5) of GO nano flake, its average transverse about 1.2
μm.The GO obtained is very well dispersed in water, forms liquid crystal form when concentration is 1.1wt%.
The UV absorber of embodiment 3 GO+NFC micrometer fibers
GO+NFC micrometer fibers adopts the method preparation of wet spinning, and flow chart as shown in Figure 3, to be namely expressed into spinning solution in alcohol coagulating bath by needle tubing and to separate out, form gelatinous fibre, then gelatinous fibre is pulled out coagulating bath dry in atmosphere.In dry run, apply the active force of 0.5N at micrometer fibers two ends, to improve the degree of orientation of micrometer fibers.After drying, micrometer fibers is placed in 10wt% CaCl
2the aqueous solution in dipping again dry after 1 hour.In the same way, preparation GO micrometer fibers and NFC micrometer fibers do performance test contrast.
The pattern ESEM (SEM) of micrometer fibers is observed: after testing sample is carried out vacuumize, sticky platform, vacuum metal spraying.
The tensile strength of micrometer fibers and elastic modelling quantity are measured on DMA-800 instrument.Test pattern is film/fiber bundle strength test pattern.
The method combined by GO and NFC prepares high strength micrometer fibers, and as shown in Figure 4, wherein, a is the structural representation of the GO+NFC hybrid microscale fiber obtained to result, and in hybrid microscale fiber, GO and NFC has certain arrangement along the axis of fiber.Interfibrous adhesion is primarily of Hydrogenbond and Ca
2+introduce and the ionic bond of increase combines (b).The introducing of ionic bond further increases the intensity of blended fiber.
Spinning solution in the method is the liquid crystal solution (as shown in the c in Fig. 5) that GO and the NFC concentration that 1:1 prepares in mass ratio is 1.1wt%.Under same concentration, the GO+NFC spinning solution mixed, its liquid crystal texture structure is obviously different from independent GO liquid crystal texture structure.The liquid crystal texture gap of mixed liquor is significantly less than GO liquid crystal texture gap.By after mixed liquor air dry and the visible GO of polarized light microscopy Microscopic observation have and significantly align, this also demonstrates the liquid crystalline phase of mixed liquor, as the d in Fig. 5.In Fig. 5, a is the AFM figure of GO, and inserting figure is GO solution, and b is the AFM figure of NFC, and inserting figure is NFC solution, and c is the petrographic microscope figure of GO+NFC spinning solution, and inserting figure is GO+NFC spinning solution, and d is the dried petrographic microscope figure of GO+NFC spinning solution.
When wet spinning prepares high-strength GO+NFC micrometer fibers, first GO+NFC spinning solution is expressed into alcohol coagulating bath.When GO+NFC spinning solution alcohol exposure, one deck can be solidified in micrometer fibers surface first, and then slowly by solvent exchange, the water of fibrous inside is also out replaced, the gelatinous fibre that final formation is stable.After gelatinous fibre is pulled out coagulating bath, alcohol just can evaporate becomes dry micrometer fibers.Result as shown in Figure 6, wherein, a is that wet spinning spins 4 micrometer fibers simultaneously, b is that the Filament-wound Machine that prepared by 1mL spinning solution is on the steel column of diameter 1.5cm, c is the SEM figure of the rope that two fibers twist into, d is the gelatinous fibre just having clamp-oned coagulating bath, and e has been after the dry 10s of gelatinous fibre and f is dry fiber petrographic microscope figure.A in Fig. 6 illustrates and once can extrude four fibers, and every root fiber can have several meters long, and 1mL spinning solution can prepare tens meters of fibers within a few minutes, and b is that the micrometer fibers of 1mL spinning solution ejection is wrapped on steel column.Its diameter of micrometer fibers prepared by this method is controlled.By changing the size of needle diameter, just can obtain the micrometer fibers that diameter does not wait at 10-40 μm, the micrometer fibers that wet spinning obtains has good flexibility, and can tie a knot or twist is twisted into rope, as the c in Fig. 6; In order to mention fiber-wall-element model degree and intensity, fiber executes the active force of 0.5N in dry run at its two ends.The construction unit material forming fiber in dry run combines and becomes tight, and the diameter of fiber is reduced to 10 μm of final finished fiber from about 80 μm of gelatinous fibre.Petrographic microscope observes material whether to have the effective means of orientation, is the orientation characterizing fiber, fiber as polarized light microscopy Microscopic observation, when fiber orientation directions parallel with polarised light time, the background of black can only be seen.Rotating fibers, under polariscope, fiber starts to become bright, and when the direction of fiber and polarised light are 45 ° of angles, fiber reaches the brightest state, and the d-f fiber in Fig. 6 is more and more brighter, and texture is more and more clear, shows that the degree of orientation of fiber is more and more higher.
As reference sample, GO micrometer fibers and NFC micrometer fibers are prepared in the same way, as shown in Figure 7, wherein, a is the POM figure of GO spinning solution, b-d is for be expressed in ethanol by GO spinning solution, GO is diffused as GO band, and along with the increase of standing time, GO is dissolved in ethanol gradually, e for preparing GO micrometer fibers in the bath of 1%NaOH alcohol solidification, f is the POM figure of GO micrometer fibers, g is that the POM of NFC spinning solution schemes, and h for preparing NFC micrometer fibers in alcohol solidification bath, in figure, fiber uses blue dyes dyeing, and i is the POM figure of NFC micrometer fibers.A in Fig. 7 is GO spinning solution, presents obvious liquid crystal phase at polarisation Microscopic observation.Because GO is dissolved in ethanol, so fiber can not be formed when being directly expressed in ethanol by GO spinning solution, but occur that GO is with.GO band strength is poor, can not ensure that can completely is pulled out from ethanol; Along with the increase of standing time, GO band dissolves gradually, is finally dissolved in (b-d in Fig. 7) in ethanol.For preparation GO micrometer fibers, using 1%NaOH ethanolic solution as coagulating bath.E display in Fig. 7, can form GO micrometer fibers and can pull out in the bath of 1%NaOH alcohol solidification.The GO micrometer fibers obtained, at polarizing fiber Microscopic observation (f in Fig. 7), shows that fiber has the higher degree of orientation.NFC is insoluble to ethanol, is that coagulating bath can obtain NFC micrometer fibers easily with ethanol.G in Fig. 7 is the POM figure of the NFC spinning solution of concentration 1wt%, shows that NFC spinning solution is liquid crystalline phase.When NFC spinning solution is expressed into ethanol, NFC spinning solution forms gelatinous fibre immediately, as shown in the h in Fig. 7.In figure, NFC micrometer fibers dyes with blue dyes to demonstrate NFC micrometer fibers in ethanolic solution.NFC has self assembly performance, and in NFC micrometer fibers dry run, NFC arranges along machine direction.Polarized light microscope observing display is carried out to NFC micrometer fibers: NFC micrometer fibers has the good degree of orientation.
A-b in Fig. 8 is the stress-strain diagram of GO micrometer fibers, NFC micrometer fibers and GO+NFC micrometer fibers, and average elastic modulus and the mean tensile strength of the GO+NFC micrometer fibers obtained are respectively 20.6 ± 0.9GPa and 274.6 ± 22.4MPa.Higher than the intensity of pure NFC micrometer fibers (15.5 ± 4.5GPa, 139.1 ± 28.7MPa) and GO micrometer fibers (2.3 ± 2GPa, 84.0 ± 2.8MPa).
For improving the intensity of micrometer fibers further, Ca is carried out to micrometer fibers
2+dipping, introduces ionic bond in the fibre, improves interfibrous bond strength.In dipping process, can there is rewetting swollen in fiber, Ca
2+enter into fibrous inside, become again after drying and form ionic bond combination.B in Fig. 8 is GO micrometer fibers, NFC micrometer fibers and GO+NFC micrometer fibers flood later stress-strain diagram.After dipping, elastic modelling quantity and the tensile strength of GO micrometer fibers bring up to 9.7GPa and 96.3MPa respectively.Elastic modelling quantity and the tensile strength of NFC micrometer fibers bring up to 20.7GPa and 272MPa respectively.The elastic modelling quantity of GO+NFC micrometer fibers and tensile strength bring up to 31.6 ± 2.5GPa and 416.6 ± 25.8MPa respectively.Elastic modelling quantity and the tensile strength of GO+NFC micrometer fibers can reach 34.1GPa and 442.4MPa, and elongation at break is 2%.
The purposes of embodiment 4GO+NFC micrometer fibers
GO+NFC micrometer fibers has excellent mechanical performance, can be used for the preparation of superpower structural material, result as shown in Figure 9, a mentions with a GO+NFC micrometer fibers magnetic stirring bar that quality is 12.5g, b is the GO+NFC micrometer fibers be through on pin, and GO+NFC micrometer fibers is made different patterns by c-d on cloth, and e is for using the mesh grid of GO+NFC micrometer fibers, for the net of GO+NFC micrometer fibers braiding can bend arbitrarily, for GO+NFC micrometer fibers net supports magnetic stirring bar.The intensity illustrating GO+NFC micrometer fibers of image.For hitching with the GO+NFC micrometer fibers of about 80 μm an of diameter and mentioning the magnetic stirring bar that quality is 12.5g in figure.GO+NFC micrometer fibers not only has excellent mechanical performance, has good pliability simultaneously, can be sewn on clothing as line.Display GO+NFC micrometer fibers can be through on common pin, and clothing is made different patterns.Display GO+NFC micrometer fibers can be woven into the net with some strength.This net can be bent arbitrarily even folding, also can support 100 times to the weight of quality own.GO+NFC micrometer fibers density is low, and intensity is high, is the good selection preparing high-strength material.
The UV absorber of embodiment 5 conductive micron fibers
Conduction GO+NFC micrometer fibers (c(GO+NFC)) preparation obtain by carrying out charing to GO+NFC precursor fibre.The charing of GO+NFC precursor fibre is carried out in 95% argon gas and 5% hydrogen mixed gas atmosphere.Heating schedule is as follows: be first raised to 400 DEG C from room temperature to the heating rate of 30 DEG C/h, be raised to 1000 DEG C afterwards, finally at 1000 DEG C, be incubated 2h with the heating rate of 200 DEG C/h.NFC and GO fiber with same program process, sample as a comparison.
The pattern of micrometer fibers characterizes with SEM, after testing sample is carried out vacuumize, and sticky platform, vacuum metal spraying.
The carbon structure of carbon fiber characterizes with TEM.During TEM sample preparation, first by carbon fiber ultrasonic disperse in aqueous, then drip 10 μ L solution at charcoal on the net, unnecessary liquid filter paper siphons away.
The conductance of micrometer fibers is obtained by the I-V curve testing micrometer fibers.With elargol, conductive micron fibers two ends are fixed, micrometer fibers length and average diameter are tested with light microscope.When calculating micrometer fibers electric conductivity, micrometer fibers is considered as the solid cylindrical of standard.
Use the method for charing to prepare the micrometer fibers of high conductivity, result as shown in Figure 9, wherein, for display carbonizes, rear NFC is become spherical a-b from threadiness, and c-d is after the NFC charing of display containing GO, only has flaky material, spheroidal material disappears, and e is the structural representation of GO+NFC fiber after charing.As shown in Figure 9, a-b is the pattern change before and after NFC charing, show fibrous NFC in figure and form Spherical Carbon particle in charing, c-d is schematic diagram before and after GO+NFC charing, spherical NFC carbonizing production is not had after showing charing, only there is the carbonized product of similar GO pattern, e illustrates c(GO+NFC after charing) pattern of micrometer fibers.Construction unit material is in the fibre along the axially-aligned of fiber, and micrometer fibers is inner owing to must to shrink in carbonization process and the rearrangement of construction unit material produces hollow structure.
As shown in Figure 10, wherein, a-b is that the SEM of the rear NFC fiber of charing schemes to SEM figure after carbonization, and c-d is the SEM figure of GO fiber after charing, e-f is the SEM figure carbonizing rear GO+NFC fiber.NFC micrometer fibers after charing, its pattern is as shown in the a-b of Figure 10, and the surface of fiber is made up of the carbon microspheres of about 1 μm of many diameters, and the average conductivity of NFC micrometer fibers is 33S/cm, similar to the conductance of carbon fiber.GO micrometer fibers after charing becomes rough porous, but GO still exists (c-d as Figure 10) with sheet form.The average conductivity of charing GO micrometer fibers is 137S/cm, higher than charing NFC micrometer fibers.The e-f of Figure 10 is GO+NFC micrometer fibers pattern after charing, structure is similar with carbonizing GO micrometer fibers: fiber is many hollow structures, does not carbonize NFC microballoon.Because GO is the model agent of NFC charing, NFC carbonated material is coated on charing GO sheet.The room that this carbon coating produces when can repair heat treatment GO and topological defect, thus improve electric conductivity.This carbon coating also plays the effect of carbon paste in addition, is coupled together by charing GO sheet, increases the contact in the middle of sheet and sheet, reduces electric transmission resistance, improves the electric conductivity of fiber further.
C(GO+NFC after charing) average conductivity of fiber is 649 ± 60 S/cm, is the most conductance of the conductive fiber prepared by graphite, GO and GO compound reported now.Figure 11 is c(GO+NFC) I-V curve under micrometer fibers room temperature, the long 35mm of test fiber, average fibre diameter is 18 μm.
The application of embodiment 5 conductive micron fibers
Flexible electrical equipment and wearable electrical equipment because of its be easy to carry about with one, integration receives much concern well.As the main composition part of this class of electronic devices, the research of high conductivity fiber is got more and more, because it is easily knitted in textile product or is integrated in other mechanisms.Conductive fiber prepared by embodiment 4 at wearable nano generator, ultracapacitor, battery, actuator, and extensive use on flexible solar battery.Such as: using c(GO+NFC) micrometer fibers is used for the assembling of sodium-ion battery as electrode material, and result shows: the efficiency of first circulation is lower, and the discharge capacity of second, battery circulation is 317.3mAh/g, and efficiency is 62.2%.After 63 circulations, the discharge capacity of battery is that 312mAh/g is substantially identical with the discharge capacity that second circulates.This good electrochemical reaction mainly gives the credit to the high conductivity of fiber.Simultaneously c(GO+NFC) micrometer fibers shows certain pliability, and the preparation of flexible, wearable electronic has application potential.
Claims (7)
1. prepare a method for superconduct micrometer fibers, it is characterized in that, comprise the following steps:
1) TEMPO oxycellulose is once by preparing NFC after microfluidizer;
2) Hummer ' s method is adopted to be oxidized graphite and to obtain GO;
3) preparation of high strength micrometer fibers: spinning solution is expressed in alcohol coagulating bath by needle tubing and separates out, form gelatinous fibre, then gelatinous fibre is pulled out coagulating bath dry in atmosphere; In dry run, apply the active force of 0.5N at micrometer fibers two ends, to improve the degree of orientation of micrometer fibers; After drying, micrometer fibers is placed in 10wt% CaCl
2the aqueous solution in dipping again dry after 1 hour;
4) charing is carried out to high strength micrometer fibers and obtain conduction GO+NFC micrometer fibers.
2. the method preparing superconduct micrometer fibers according to claim 1, is characterized in that: in step 1): the over dry softwood pulp that 5g is not dried and 78mg TEMPO, 514mg NaBr fully mix; Reaction adds initiation by 30mL 12%NaClO, and reacts under stirring at room temperature; The pH value of system controls to be stabilized in 10.5 by NaOH; The end until system interior residue NaClO reacts completely; Reacted slurry is clean by filtration washing, to pH in neutral; The concentration fiber obtained being made into 1% is processed under 5 ~ 25KPa pressure by microfluidizer; Obtain transparent nanofiber element dispersion liquid; Dispersion liquid storage and 4 DEG C of refrigerators.
3. the method preparing superconduct micrometer fibers according to claim 1, is characterized in that: step 2) in: by 3.0g graphite flakes, 1.5g NaNO
3mix at 0 DEG C; Then 69mL 98%H
2sO
4add mixing and stirring, finally slowly add 9.0g KMnO
4; Add KMnO
4time solution temperature control, lower than 20 DEG C, to add KMnO
4after temperature of reaction system is elevated to 35 DEG C and stirs 30min; Then 138mL deionized water is slowly dripped and enter reaction system, and control reaction temperature at 98 DEG C of maintenance 15min; And then reaction system is cooled to room temperature, interpolation 420mL deionized water and 3mL concentration are the H of 30 % in addition simultaneously
2o
2; Deng reactant mixture cool to room temperature time, material is spent in Buchner funnel deionized water to neutral; The GO ultrasonic disperse obtained is stand-by in water.
4. the method preparing superconduct micrometer fibers according to claim 1, is characterized in that: in step 3), and described spinning solution is the concentration that GO and NFC mass ratio 1:1 prepares is the liquid crystal solution of 1.1wt%.
5. the method preparing superconduct micrometer fibers according to claim 1, is characterized in that: in step 4), and the charing of high strength micrometer fibers is carried out in 95% argon gas and 5% hydrogen mixed gas atmosphere; Heating schedule is as follows: be first raised to 400 DEG C from room temperature to the heating rate of 30 DEG C/h, be raised to 1000 DEG C afterwards, finally at 1000 DEG C, be incubated 2h with the heating rate of 200 DEG C/h.
6. the superconduct micrometer fibers that the method preparing superconduct micrometer fibers described in any one of claim 1-5 obtains.
7. superconduct micrometer fibers according to claim 6 is as the application of conductive material.
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