CN102995162B - Novel skin/core-layer composite fiber as well as preparation method and application thereof - Google Patents
Novel skin/core-layer composite fiber as well as preparation method and application thereof Download PDFInfo
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- CN102995162B CN102995162B CN201210388319.7A CN201210388319A CN102995162B CN 102995162 B CN102995162 B CN 102995162B CN 201210388319 A CN201210388319 A CN 201210388319A CN 102995162 B CN102995162 B CN 102995162B
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Abstract
The invention discloses a novel skin/core-layer composite fiber as well as a preparation method and application thereof. The novel skin/core-layer composite fiber comprises a carbon nanotube fiber and an electroconductive polymer coated on the carbon nanotube fiber. The preparation method comprises the following steps: firstly, preparing the carbon nanotube fiber by using an array spinning method, a floating catalytic spinning method, a solvent spinning method or the like, then acidizing the carbon nanotube fiber, and depositing the electroconductive polymer on the surface of the acidized carbon nanotube fiber to obtain the bicompoent composite fiber with electroconductive polymer as a skin layer and carbon nanotube fiber as a core layer. The composite fiber has the characteristics of good linear capacitance characteristic, light weight, high strength and the like, is simple, convenient and rapid in preparation method, and is formed through two steps, and the whole preparation process is performed at normal temperature and normal pressure and is low in energy consumption, high in efficiency and convenient to operate.
Description
Technical field
The present invention relates to a kind of novel core-skin layer composite fibre and preparation method thereof, particularly relate to a kind of take carbon nano-tube fibre as core, the conducting polymer novel core-skin layer composite fibre that be cortex and preparation method thereof, belong to the micro-field of compound material of nanometer.
Background technology
Capacitor has higher energy density, power density and long circulation life etc., clean as one, efficient novel energy-storing device, receive the concern of more and more researcher, in fields such as electric automobile, mobile communication, science and techniques of defence, there is wide application and development prospect.Wherein electrode material is the bottleneck of restriction capacitor, is also the key factor affecting ultracapacitor development.At present the research of electrode material is mainly concentrated on to the compound of exploitation hybrid capacitors, fake capacitance material transition metal oxide and conducting polymer and high-specific surface area material with carbon element, the high active material of height ratio capacity, high-energy-density, high power density, low equivalent resistance and cost performance can be prepared to reach.In order to reach these objects, electrode of super capacitor commercially available mostly at present is planar structure, to realize its energy storage to greatest extent and to transform object.But the electrode material of this two-dimensional structure just can not use in the occasion of some particular/special requirements, especially military affairs, Aero-Space etc. require very strict to equipment occupation space, and now the electrode material of one-dimensional linear structure just seems very important.Also have on a small quantity about the report of line style electrode for capacitors at present, but be mostly to do electrode with wire or non-conductive yarn, these materials are difficult to take into account in electric conductivity, specific area and flexibility etc., therefore the line style capacitor requirement of market to novel practical is very urgent.
Summary of the invention
An object of the present invention is to provide a kind of novel core-skin layer composite fibre, and it has the features such as lightweight, high-strength, flexible, electric property is good, can be used for preparing novel capacitor device, and overcomes deficiency of the prior art.
Another object of the present invention is to provide a kind of method preparing aforementioned novel core-skin layer composite fibre, it can effectively improve nanotube internal structure and surface topography, make it as having good mechanics, the electrode material of electric property applies in capacitor element, and the method is simple.
For achieving the above object, present invention employs following technical scheme:
A kind of novel core-skin layer composite fibre, comprising:
Carbon nano-tube fibre,
And, be wrapped in the conducting polymer on carbon nano-tube fibre.
One of preferably, described conducting polymer comprises polyaniline.
A preparation method for novel core-skin layer composite fibre, comprising:
The carbon nano-tube fibre of acidification of learning from else's experience is as working electrode, and using inert electrode as to electrode, and get described working electrode and insert in the electrolyte solution containing conducting polymer monomer to electrode and reference electrode, electrochemical reaction is carried out under setting reaction condition, obtain target product, described target product take carbon nano-tube fibre as core, and to be deposited on conducting polymer on carbon nano-tube fibre for cortex.
Further, described carbon nano-tube fibre comprises the carbon nano-tube fibre at least obtained by any one technique in array spinning technique, floating catalytic spinning technique and solution spinning processes.
As one of enforceable scheme, adopt carbon nano-tube fibre to be inserted the mode in acid solution and the acidification that realizes carbon nano-tube fibre in this preparation method, described acid solution be at least selected from nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid any one.
One of preferably, this preparation method also comprises:
Heat-treated by carbon nano-tube fibre after acidification again, then insert in the electrolyte solution containing conducting polymer monomer as working electrode, described heat treated temperature is at 50-80 DEG C, and the time is at more than 1h.
As one of enforceable scheme, described inert electrode comprises platinum electrode, carbon electrode, graphite electrode etc., and described reference electrode comprises SCE electrode, and described electrolyte solution is acidic electrolyte solution.
As one of enforceable scheme, described electrolyte solution is solvent with water, and comprises 0.01 ~ 10 mol/L aniline and 0.5-5 mol/L sulfuric acid.
One of preferably, in the method be adopt in constant-voltage method, constant flow method and cyclic voltammetry any one carry out electrochemical reaction, wherein,
In described constant-voltage method, voltage is 0.5-1V, and in described constant flow method, electric current is 0.01-10 A/cm
2, the condition of scanning of described cyclic voltammetry is: voltage range-0.2-0.8V, and sweep speed is 0.01-0.5 V/s.
Novel core-skin layer composite fibre described above and the novel core-skin layer composite fibre prepared according to the method described above are preparing the application in electronic device.
Compared with prior art, good effect of the present invention is embodied in:
(1) novel core-skin layer composite fibre of the present invention has superior mechanical property, intensity is higher, 1.7 GPa can be reached, toughness is better than carbon fiber, phosphorus content is still more than 99%, and the filamentary conductive after acidification is better than carbon nano-tube fibre before treatment, original three times can be brought up to, improve while obtaining mechanics and electric property;
(2) novel core-skin layer composite fibre performance of the present invention is better than common yarn, more than 80% of intensity can be maintained after knotting, possess the operability of common yarn, the preparation demand of various ways (as monofilament, multifilament, band, two-dimensional fabric etc.) electrode can be met;
(3) acid solution for carrying out acidification to carbon nano-tube fibre in preparation method of the present invention can reuse, and substantially nontoxic, environmental pollution is little;
(4) time in conducting polymers such as carbon nano-tube fibre surface deposition polyanilines in preparation method of the present invention is short, and efficiency is higher;
(5) preparation method of the present invention is simple and convenient, is spinning one-step method substantially, and post processing one-step method, is easy to accomplish scale production.
Accompanying drawing explanation
Fig. 1 is the SEM Electronic Speculum figure of the carbon nano-tube fibre in the embodiment of the present invention 1 after acidification;
Fig. 2 is the infrared spectrogram of the carbon nano-tube fibre in the embodiment of the present invention 1 after acidification;
Fig. 3 a-3c is mechanics (dotted line and solid line are respectively stress strain curve before and after treatment) and the electric property figure of two kinds of carbon nano-tube fibres in the embodiment of the present invention 1 after acidification respectively;
Fig. 4 is the deposition schematic diagram of electrochemical deposition polyaniline on carbon nano-tube fibre in the embodiment of the present invention 1;
Fig. 5 be with the embodiment of the present invention 1 obtain the line capacitance performance chart of electrode prepared by novel core-skin layer composite fibre.
Detailed description of the invention
As previously mentioned, because deficiency of the prior art, the present invention aims to provide and a kind ofly can be used for preparing the New-type composite fibre material of electrode with good mechanics, electric property, it has core-sheath composite structure, therefore can be described as novel core-skin layer composite fibre, it comprises carbon nano-tube fibre and is wrapped in the conducting polymer on carbon nano-tube fibre, wherein, described conducting polymer preferably can adopt polyaniline, but is not limited thereto.
As one of enforceable scheme, aforementioned novel core-skin layer composite fibre is prepared by following method, and it comprises:
A. from pulling out carbon nano-tube film spinning carbon nano pipe array, collection of carbon nano-tube film being twisted and reels thereafter, or the carbon nano-tube fibre of certain length is obtained by floating catalytic, solution spinning;
B. the fiber obtained in step a is put into chemical pretreatment solution to process;
C. carry out electrochemical deposition to through chemically treated carbon nano-tube fibre, obtain the novel core-skin layer composite fibre that surface has polyaniline or other conducting polymer;
D. the fiber obtained in step c is made into electrode, carries out performance test.
In the method, first carbon nano-tube fibre will be obtained.
Further, in the method, carbon nano-tube fibre has spiral angle, the length of setting, and diameter can regulate and control as required, such as, and spiral angle 15-20 degree, long 3 meters, diameter 10 microns.
In the method, in step a, chemical treatment object is that carbon nano-tube fibre carries out acidification, and carbon nano-tube fibre is subject to certain tension force effect in acidization, and carrying out chemically treated acid solution can be red fuming nitric acid (RFNA), but also can be hydrochloric acid, sulfuric acid etc.
Further, the time different acidification effect obtained of carbon nano-tube fibre being carried out to acidification is also different, and such as, if the processing time is 2 hours, then gained carbon nano-tube fibre just has good mechanics and electric property.
Further, aforementionedly carry out chemically treated acid solution and can reuse, substantially nontoxic, environmental pollution is little;
In the method, after acidification completes, the chemical deposition of conducting polymer is carried out in electrolytic solution, adopt method can be the method such as constant-voltage method, constant flow method, cyclic voltammetry.
Further, in chemical deposition process, constant-voltage method voltage range is 0.5-1V, and in constant flow method, electric current is 0.01-10 A/cm
2, the condition of scanning of cyclic voltammetry is: voltage range-0.2-0.8V, and sweep speed is 0.01-0.5 V/s.
Further, conducting polymer deposit thickness can control according to sedimentation time.
The method is simple and convenient, is spinning one-step method substantially, and post processing one-step method, is easy to accomplish scale production.
Obtain novel core-skin layer composite fibre by preceding method and can be used as application of electrode, ratio, can be fixed on slide by novel core-skin layer composite fibre with elargol, copper cash is electrically connected with novel core-skin layer composite fibre by elargol, extraction electrode, for performance test.
Novel core-skin layer composite fibre of the present invention has superior mechanical property, intensity is higher, 1.7 GPa can be reached, toughness is better than carbon fiber, phosphorus content is still more than 99%, and the filamentary conductive after acidification is better than carbon nano-tube fibre before treatment, original three times can be brought up to, improve while obtaining mechanics and electric property.And, novel core-skin layer composite fibre performance of the present invention is better than common yarn, more than 80% of intensity can be maintained after knotting, possess the operability of common yarn, the preparation of various ways (as monofilament, multifilament, band, two-dimensional fabric etc.) electrode can be met.
Below in conjunction with accompanying drawing and preferred embodiment, technical scheme of the present invention is further described.
embodiment 1the object of the present embodiment is to obtain lightweight, flexibility, high-strength line capacitance, basic fundamental thinking is carry out chemical treatment to the carbon nano-tube fibre of lightweight, to improve mechanics and the electric property of carbon nano-tube fibre, then deposit the polyaniline of one deck conduction at fiber surface by electrochemical method, obtain the bicomponent fibers (also can be described as novel core-skin layer composite fibre) with core-skin Rotating fields.
The method obtaining carbon nano-tube fibre in the present embodiment can for can spinning array spin processes, floating catalytic spin processes, solution spinning, and chemical reagent used is mainly (can directly buy) such as red fuming nitric acid (RFNA), aniline, the concentrated sulfuric acids.
The key step of the preparation technology of line capacitance is set forth as follows for the carbon nano-tube fibre prepared by array spin processes:
1, array spin processes is adopted to obtain carbon nano-tube fibre.First from array, carbon nano-tube film is pulled out, through twisting, reel by Filament-wound Machine on bobbin, the diameter of fiber can be controlled by adjustment thin-film width, the spiral angle of fiber can be controlled by adjustment twisting speed and draw speed, as: diameter 9 microns, spiral angle 20 degree, length 5 meters.
2, carbon nano-tube fibre acidification.The fiber obtained in step 1 is put into concentrated nitric acid solution (65%), the processing time can be determined as required, is treated to 2 hours in this example; Then the heat treatment of fiber processed is obtained the carbon nano-tube fibre of acidification, heat treatment temperature should not be too high, and heat treatment time is also unsuitable long, and in this example, heat treatment temperature is 80 DEG C, 1 hour time.After acidification, the mechanical strength of fiber improves 300-400MPa, and electrical conductivity brings up to original 2-3 doubly.
3, carbon nano tube surface polyaniline electrochemical deposition.Adopt method can for constant-voltage method, constant flow method, cyclic voltammetry, as shown in Figure 4, using the carbon nano-tube fibre obtained in step 2 as working electrode, platinum filament as being reference electrode to electrode, SCE, solution component is: aniline, the concentrated sulfuric acid, water.The voltage that in this example, constant-voltage method is selected is 0.75V, aniline 0.2 mol/L, the concentrated sulfuric acid 1 mol/L, and the chemical deposition time is 1 minute.Gained core-skin layer fiber surface is even, and diameter is greater than 10 microns, and mechanical property is greater than 1GPa.
4, the preparation of line capacitance and test.The novel core-skin layer composite fibre elargol with polyaniline cortex and carbon nano-tube fibre sandwich layer obtained in step 3 is fixed on slide, copper cash is connected with fiber by elargol, make electrode, and test the capacitive property of fiber, as shown in Figure 5, the ratio capacitance of this skin core fibers in different cycle-index situation is shown.
Above-described embodiment is only and technical conceive of the present invention and feature is described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (5)
1. a novel core-skin layer composite fibre, is characterized in that, it comprises successively through acidification and heat treated carbon nano-tube fibre and the conducting polymer that is wrapped on described carbon nano-tube fibre, and described conducting polymer is polyaniline;
Wherein, the described mechanical strength through acidification and heat treated carbon nano-tube fibre improves 300-400MPa than the carbon nano-tube fibre before acidification and heat treatment, and electrical conductivity is 2-3 times of the carbon nano-tube fibre before acidification and heat treatment,
Described acidification by by carbon nano-tube fibre, the mode inserted in acid solution realizes, described acid solution be at least selected from nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid any one,
Described heat treated temperature is at 50-80 DEG C, and the time is at more than 1h;
Further, the intensity of described novel core-skin layer composite fibre is 1.7GPa to the maximum, and phosphorus content is more than 99%, and the intensity after knotting can maintain more than 80% of the front intensity of knotting.
2. a preparation method for novel core-skin layer composite fibre, it is characterized in that, it comprises:
Carbon nano-tube fibre is inserted the mode in acid solution and the acidification realized carbon nano-tube fibre, again the carbon nano-tube fibre after acidification is heat-treated, described acid solution be at least selected from nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid any one, described heat treated temperature is at 50-80 DEG C, and the time is at more than 1h;
Acidification of learning from else's experience and heat treated carbon nano-tube fibre are as working electrode, and using inert electrode as to electrode, and get described working electrode and electrode and reference electrode are inserted and be solvent with water and comprise in the electrolyte solution of 0.01 ~ 10mol/L aniline and 0.5-5mol/L sulfuric acid, any one adopting in constant-voltage method, constant flow method and cyclic voltammetry under setting reaction condition carries out electrochemical reaction, obtain target product
Described target product take carbon nano-tube fibre as core, and to be deposited on conducting polymer on carbon nano-tube fibre for cortex,
Wherein, in described constant-voltage method, voltage is 0.5-1V, and in described constant flow method, electric current is 0.01-10A/cm
2, the condition of scanning of described cyclic voltammetry is: voltage range-0.2-0.8V, and sweep speed is 0.01-0.5V/s.
3. the preparation method of novel core-skin layer composite fibre according to claim 2, it is characterized in that, described carbon nano-tube fibre comprises the carbon nano-tube fibre at least obtained by any one technique in array spinning technique, floating catalytic spinning technique and solution spinning processes.
4. the preparation method of novel core-skin layer composite fibre according to claim 2, it is characterized in that, described inert electrode comprise in platinum electrode, carbon electrode and graphite electrode any one, described reference electrode comprises SCE electrode, and described electrolyte solution is acidic electrolyte solution.
5. novel core-skin layer composite fibre and preparing the application in electronic device according to novel core-skin layer composite fibre prepared by method according to any one of claim 2-4 as claimed in claim 1.
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| CN103714972A (en) * | 2013-11-25 | 2014-04-09 | 浙江大学 | Linear secure high-energy-density supercapacitor and preparation method thereof |
| CN104592778B (en) * | 2015-02-11 | 2017-04-05 | 苏州捷迪纳米科技有限公司 | Carbon nano tube network/polymer composites and preparation method thereof |
| CN105244188A (en) * | 2015-10-22 | 2016-01-13 | 东莞市鸿愃实业有限公司 | Preparation method of carbon nano tube yarn flexible super capacitor composite electrode material |
| CN108103766B (en) * | 2017-12-29 | 2021-07-30 | 澄江市力点科技有限公司 | Molybdenum disulfide composite fiber photocatalyst for sewage treatment and preparation method thereof |
| CN110284213B (en) * | 2019-07-09 | 2020-07-14 | 西南交通大学 | Carbon nanotube fiber composite material, preparation method and application thereof |
| CN111705391B (en) * | 2020-06-08 | 2022-05-17 | 深圳烯湾科技有限公司 | Carbon nanotube fiber hybrid fabric, preparation method thereof and reinforced composite material |
| CN111763459A (en) * | 2020-06-23 | 2020-10-13 | 杭州立兴新材料科技有限公司 | Composite modified electromagnetic shielding water-based paint and preparation method thereof |
| CN112301462B (en) * | 2020-11-16 | 2022-11-11 | 江西省纳米技术研究院 | High-performance carbon nanotube composite fiber, and preparation method and system thereof |
| CN113737512B (en) * | 2021-09-15 | 2023-08-08 | 武汉纺织大学 | Method for preparing elastic conductive fiber by micro-fluid coating technology and elastic conductive fiber |
| CN113889348B (en) * | 2021-09-26 | 2023-01-17 | 常州大学 | Polyaniline/continuous enhanced carbon nanotube film-based flexible self-supporting electrode material and electrochemical controllable polymerization preparation method thereof |
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