CN109576822A - A method of preparing single-walled carbon nanotube fiber and its composite fibre - Google Patents
A method of preparing single-walled carbon nanotube fiber and its composite fibre Download PDFInfo
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- CN109576822A CN109576822A CN201811445746.8A CN201811445746A CN109576822A CN 109576822 A CN109576822 A CN 109576822A CN 201811445746 A CN201811445746 A CN 201811445746A CN 109576822 A CN109576822 A CN 109576822A
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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Abstract
The present invention relates to carbon nano-tube fibre and its composite fibre preparation field, specially a kind of method for preparing single-walled carbon nanotube fiber and its composite fibre.Using the single-walled carbon nanotube of floating catalytic agent chemical vapour deposition technique preparation as basis material, disperse single-walled carbon nanotube with amphiphilic surfactant, squeeze into and form fiber in coagulating bath, realizes the continuous preparation of high-intensitive, high conductivity fiber.The good material of property compatible is added in fiber stoste, composite fibre is prepared, and it is more functional to assign fiber.This method avoids the use in existing wet spinning technology to strong acid, reduces the security risk and environmental problem of production process；The use of insulating polymers adhesive is avoided simultaneously, improve the electric conductivity that wet spinning prepares fiber, overcome the problems, such as that functional material is unevenly distributed in the fibre in existing carbon nano tube composite fibre technology of preparing and loading is difficult to improve, realizes that high carrying capacity functional material is uniformly distributed fiber base is intracorporal.
Description
Technical field
It is specially a kind of to prepare single-walled carbon nanotube the present invention relates to carbon nano-tube fibre and its composite fibre preparation field
The method of fiber and its composite fibre.
Background technique
Single-walled carbon nanotube has excellent mechanics, electrology characteristic, high thermal conductivity, good thermal stability and chemistry
The characteristics such as stability, high-specific surface area and low-density.For example, the Young's modulus of single-walled carbon nanotube is up to 1TPa, tensile strength
More than 100GPa, elongation at break reaches 15%~30%；The resistance of single-walled carbon nanotube is lower (4.2k Ω/μm), and electronics exists
Wherein there is very long mean free path；It also has high thermal conductivity (3500Wm-1·K-1), high current-carrying capability (>
109A·cm-2).However, to realize the practical application of single-walled carbon nanotube, macrostructure need to be usually assembled them into, such as: fine
Dimension, film etc..Wherein, carbon nano-tube fibre is expected to be used as high-performance composite materials reinforcement, mechanics and biosensor, electric power
Transmission line, aerospace, bulletproof equipment, microelectrode etc..
Currently, the method for obtaining carbon nano-tube fibre mainly has array carbon nanotube to reel off raw silk from cocoons method, floating catalytic agent chemical vapor deposition
Product (CVD) direct spinning and solution spinning.Wherein, the array carbon nanotube method of reeling off raw silk from cocoons needs to prepare the carbon nanotube that can be reeled off raw silk from cocoons first
Array, equipment and cost needs are high, and prepared carbon nanotube is multi-walled pipes (Zhang X, Li Q, TuY, et
al.Strong carbon-nanotube fibers spun from long carbon-nanotube arrays[J]
.Small,2007,3(2):244-248.).Floating catalytic agent CVD direct spinning is the carbon nanotube gas that will be generated in CVD furnace
Colloidal sol is used directly to spinning, but its process high temperature, is unfavorable for introducing functional material preparation in situ in fiber assembling process again
Condensating fiber.Solution spinning is a kind of low temperature preparation method, and simple process can be with large scale preparation carbon nano-tube fibre (WANG
J N,LUO X G,WU T,et al.High-strength carbon nanotube fibre-like ribbon with
high ductility and high electrical conductivity.[J].Nature Communications,
2014,5:3848.)。
Wet spinning generallys use two kinds of techniques and obtains carbon nano-tube fibre.One is prepare single-walled carbon nanotube point first
Dispersion liquid, then by polyvinyl alcohol (PVA) solution of dispersion liquid injection flowing, carbon nano-tube solution solidifies to obtain fiber.It is this
The shortcomings that method, is, due to using PVA solution in preparation process, it is very high inevitably to introduce quality accounting in the fibre
Polymer, drop low-fiber overall conductivity (Dalton A B, Collins S,E,et al.Super-tough
carbon-nanotube fibres[J].Nature,2003,423(6941):703.).Another kind is existed using carbon nanotube
The electrostatic repulsion dispersing Nano carbon tubes for being protonated and generating in super acids, to form the steady of high concentration (2~8wt%)
Determine solution, be then expressed into it in coagulating bath by capillary, finally collects and obtain fiber.But the use band of super acids
Carry out environmental and safety problems, is unfavorable for large scale preparation (Behabtu N, Young C C, Tsentalovich D E, et
al.Strong,light,multifunctional fibers of carbon nanotubes with ultrahigh
conductivity.[J].Science,2013,339(6116):182-6.)。
The composite modified of carbon nano-tube fibre can further expand its application field.In general, functional guest materials with
There are two types of combinations for carbon nano-tube fibre: one is coat active material on existing carbon nano-tube fibre surface；It is another
It is that guest materials is uniformly distributed in carbon nano-tube fibre matrix.In first way, functional guest materials such as MnO2, nitridation
Vanadium (VN), Ni (OH)2, conducting polymer PPy etc. can be by the methods of electrochemical deposition, chemical deposition, hydro-thermal in carbon nanometer
It is deposited on pipe fiber, guest materials hardly enters inside fiber skeleton, to form the structure of similar nucleocapsid.Fibre as core
Dimension only undertakes skeleton sum aggregate fluid matasomatism, and shell active material contributes energy storage capacity, and this mode can be very good that carbon is kept to receive
The electric conductivity of mitron fiber core, but because active material is in conjunction with outer surface, this method limits to active material loading
It improves, the building of active material and the contact and conductive path that support matrix.In the second way, usually first in carbon nanotube
It is wound into fiber again after coating guest materials on film, several functions guest materials can be loaded into fiber, such as: MnO2、
PEDOT、RGO、TiO2、LiFePO4、SiO2Deng to assign composite fibre different functions.The shortcoming of this method exists
In, the complicated preparation process vertical carbon nanotube array of membrane (need to prepare first can), low efficiency, thus limitation is actually answered
With.In addition, being simply to be physically contacted between guest materials and fibrous matrix, lack synergistic effect.Therefore, how high-efficient simple
Active material/the carbon nano tube composite fibre for preparing high loadings is still a huge challenge, this also becomes carbon nanotube base
A limiting factor (MENG F, LI Q, the ZHENG L.Flexible that fiber capacitor energy-storage property further increases
fiber-shaped supercapacitors:Design,fabrication,and multi-functionalities[J]
.Energy Storage Materials,2017,8:85-109.)。
Solution spinning is a kind of low temperature preparation method, and simple process is expected to a step and realizes connecting on a large scale for composite fibre
Continuous preparation.And current wet spinning technology is due to the system of the use limitation composite fibre of polymer and super acids in preparation process
Standby and performance.Therefore, current main problem is: how to prepare single wall carbon using simple, easy scale wet spinning technology and receives
Mitron fiber and its composite fibre.
Summary of the invention
The purpose of the present invention is to provide a kind of method for preparing single-walled carbon nanotube fiber and its composite fibre, use is wet
Method spining technology is simple, continuously prepares single-walled carbon nanotube fiber and its composite fibre.
The technical scheme is that
A method of preparing single-walled carbon nanotube fiber and its composite fibre, the specific steps are as follows:
(1) quality of single-walled carbon nanotube raw material influences the quality and performance of final fiber, is continuous producing carbon nano-tube
Composite fibre, the single-walled carbon nanotube prepared using floating catalytic agent chemical vapour deposition technique, it is micro- that length of carbon nanotube is greater than 50
Rice, Raman spectrum G/D ratio are greater than 100, purity and are higher than 90wt%；
(2) single-walled carbon nanotube of step (1) preparation is added water-soluble containing amphipathic cholic acid type surfactant
In liquid, ultrasonic disperse obtains dispersion liquid；
(3) dispersion liquid that step (2) obtains is expressed into the coagulating bath solution of rotation and carries out spinning, it is fine to form gel
Dimension, be drawn off and solvent volatilization after, obtain single-walled carbon nanotube fiber, remove remaining table by further impregnating in water
Face activating agent；
(4) in the dispersion liquid that step (2) obtains, easily dispersible functional material in aqueous solution is added, using
The spinning process of step (3) obtains single-walled carbon nanotube composite functional fiber.
The method for preparing single-walled carbon nanotube fiber and its composite fibre, in step (1), single-walled carbon nanotube heat
Resurvey examination catalyst residual quantity < 10wt.%.
The method for preparing single-walled carbon nanotube fiber and its composite fibre, in step (2), single-walled carbon nanotube exists
Adding proportion in aqueous solution is 0.2~1wt.%.
The method for preparing single-walled carbon nanotube fiber and its composite fibre, in step (2), amphipathic cholic acid salt
Surfactant is sodium taurocholate, NaTDC or sodium taurocholate, and concentration is 1.8~3wt.%.
The method for preparing single-walled carbon nanotube fiber and its composite fibre, in step (4), coagulating bath solution is second
Alcohol, propyl alcohol, isopropanol, methanol or acetone.
The method for preparing single-walled carbon nanotube fiber and its composite fibre, in step (4), functional material be
Well dispersed colloidal solution or suspension are formed in water, surface is negatively charged in water for material, and Zeta potential is negative value, function
It can concentration < 1wt.% of the property material in mixed liquor.
The method for preparing single-walled carbon nanotube fiber and its composite fibre, in step (4), functional material is counterfeit
Capacitance kind material: manganese dioxide, molybdenum disulfide, Mxene, hydrated ferric oxide FeOOH or polypyrrole.
The method for preparing single-walled carbon nanotube fiber and its composite fibre, single-walled carbon nanotube fiber and its compound
The technical indicator of fiber is as follows: conductivity > 2500Scm-1, tensile strength > 300MPa.
Design philosophy of the invention is:
Wet spinning technology prepares the key of single-walled carbon nanotube fiber and its composite fibre, is in single-walled carbon nanotube
Equalization point is found between solution dispersion and single-walled carbon nanotube cohesive force.That is, it is necessary first to obtain uniform, stable point
Scattered fiber stoste, then under certain treatment conditions, the cohesive force between single-walled carbon nanotube plays a role, and attracts each other
Form macroscopic fibres.Widely used long chain surface-active lauryl sodium sulfate, neopelex, it is intended to hang down
It is in line to be listed in carbon nano tube surface；And the cholic acid type surfactant with plane amphiphilic structure, then tend to be coated on
Carbon nano tube surface, thus cholic acid type surfactant has higher surface coverage, has preferably dispersion carbon nanometer
The ability of pipe.And by the way that fiber stoste to be injected into coagulating bath solution, the cholic acid type surfactant of small molecule also more holds
It is easily removed from carbon nano tube surface, carbon nanotube is promoted to attract each other to form fiber.And for single-walled carbon nanotube raw material,
The single-walled carbon nanotube of floating catalytic agent CVD method preparation has the characteristics that length is big, catalyst impurities are few, has between carbon nanotube
Have stronger interaction, be easier to combine form fiber.
In addition, there are two types of combinations for functional material and carbon nano-tube fibre: one is fine in existing carbon nanotube
Dimension table bread covers active material；Another kind is that active material is uniformly distributed in carbon nano-tube fibre matrix.In first way,
Functional material only in conjunction with outer surface, limits the raising of loading.In the second way, usually first in carbon nano-tube film
It is wound into fiber again after upper coating active material.This method is disadvantageous in that preparation process complexity (needs to prepare first
Can membrane vertical carbon nanotube array), low efficiency, and then limit its practical application.For this purpose, the present invention provides a kind of Wet-spinning
The method that silk prepares composite fibre, using can fine dispersion in water functional material, prepare composite fibre stoste first, so
Functional composite fiber is obtained by one step of spinning afterwards.
The invention has the advantages and beneficial effects that:
1, the present invention is first using the single tube material of floating catalytic agent CVD method preparation high quality, high-purity, so
The single-walled carbon nanotube composite spinning stoste of stable dispersion is prepared afterwards, finally is prepared to have using wet spinning technology and well be led
The composite fibre of electrical property and functional characteristic.In particular, proposing living using small molecule, planar structure amphiphilic cholic acid salt surface
Property agent to the good dispersibility of single-walled carbon nanotube and readily removed feature, realize that wet spinning preparation is high-intensitive, height is led
Electrical single-walled carbon nanotube fiber.
2, single-walled carbon nanotube electrical conductivity of fibres > 2500Scm of the method for the present invention preparation-1, tensile strength > 300MPa.
3, the single-walled carbon nanotube fiber producing processes that the present invention is developed have simple, yield is big, is easy to scale etc.
Feature.
4, the method for the present invention provides a kind of method that wet spinning prepares composite fibre, using can fine dispersion in water
Functional material prepares composite fibre stoste, obtains composite fibre by one step of spinning.
In short, the single-walled carbon nanotube that the present invention is prepared using floating catalytic agent chemical vapour deposition technique as basis material, is used
Amphiphilic surfactant disperses single-walled carbon nanotube, squeezes into coagulating bath solution and forms fiber, realizes high-intensitive, high conductivity
The continuous preparation of fiber.By adding the good material of property compatible in fiber stoste, composite fibre is prepared, assigns
Fiber is more functional, expands its application.This method avoids the use in existing wet spinning technology to strong acid, reduces production
The security risk and environmental problem of process；The use of insulating polymers adhesive is avoided simultaneously, and it is fine to improve wet spinning preparation
The electric conductivity of dimension overcomes functional material in existing carbon nano tube composite fibre technology of preparing to be unevenly distributed and support in the fibre
Amount the problem of being difficult to improve, realizes that high carrying capacity functional material is uniformly distributed fiber base is intracorporal.
Detailed description of the invention
The optical photograph of fiber is formed in Fig. 1 spinning process in coagulating bath solution.
Stereoscan photograph (a), the transmission electron microscope photo for the single-walled carbon nanotube that Fig. 2 floating catalytic agent CVD method obtains
(b), laser Raman spectroscopy (c) and thermogravimetric curve (d).(c) in, abscissa Raman shift represents Raman shift (cm-1), it indulges
Coordinate Intensity represents relative intensity (a.u.)；(d) in, abscissa Tempertature represents temperature (DEG C), ordinate
Mass representation quality percentage (%).
The stereoscan photograph of Fig. 3 .1# fiber.
The stress-strain diagram of Fig. 4 .1#, 2# fiber.In figure, abscissa Strain represents strain (%), ordinate
Stress represents stress (MPa).
The i-v curve of two hold-carrying of Fig. 5 test 1# and 2# fabric resistor.
The 2# composite fibre photo that Fig. 6 is continuously prepared.
The stereoscan photograph of Fig. 7 .2# composite fibre.Wherein, (a) is scanning electron microscope (SEM) photograph under low power, (b) is to sweep under high power
Retouch electron microscope.
The cyclic voltammetric relation curve (a) of Fig. 8 (a)-Fig. 8 (c) .2# composite fibre, constant current charge-discharge relation curve (b) and
Volumetric capacitance and current density relation curve (c).In Fig. 8 (a), abscissa Potential (v vs SCE) represents current potential, indulges
Coordinate Current density represents current strength (A/cm2)；In Fig. 8 (b), abscissa Time represents time (s), ordinate
Potential (v vs SCE) represents current potential；In Fig. 8 (c), abscissa Current density represents current strength (A/
cm2), ordinate Capacitance represents volumetric capacitance (F/cm3)。
Fig. 9 injects the light in coagulating bath solution using lauryl sodium sulfate as spinning solution in surfactant, spinning process
Learn photo.
Specific embodiment
In the specific implementation process, the method that the present invention prepares single-walled carbon nanotube fiber and its composite fibre, be divided into
Lower step is poly-: (1) using the floating catalytic agent CVD method preparation single-walled carbon nanotube raw material that length is longer, impurity content is low, (2) match
The single-walled carbon nanotube and composite spinning stoste of stable dispersion processed, (3) are prepared using wet spinning technology with good conductive
The composite fibre of property and functional characteristic.Specific step is as follows:
1) chemical vapor deposition stove temperature first under protection of argon gas, is risen to 1100~1300 DEG C；Adjust argon flow to
Analog value, and it is passed through ethylene and hydrogen (ethene flow 10sccm, H2Flow 7000sccm)；By toluene, ferrocene, thiophene it is mixed
Close liquid be injected into reacting furnace (three's mass ratio be 100:6:1.5, injection speed 1.5mLh-1), carbon nanotube is being reacted
Furnace tail end filters online collection；
2) single-walled carbon nanotube, amphipathic cholic acid type surfactant are added in water, in ultrasonic cell disruptor
Middle ultrasonic disperse obtains spinning solution；Adding proportion is 0.2~1wt.% to single-walled carbon nanotube in aqueous solution；Amphipathic cholate
Class surfactant, such as: sodium taurocholate, NaTDC, sodium taurocholate, concentration are 1.8~3wt.%；Functional material is mixed
Close concentration < 1wt.% in liquid；
3) above-mentioned dispersion liquid is expressed into the coagulating bath solution of rotation by injection needle and carries out spinning, prepare single wall carbon
Nanotube fibers and its composite fibre, coagulating bath solution are ethyl alcohol, propyl alcohol, isopropanol, methanol, acetone and other organic solvent；
Using in product obtained by the method for the present invention, the characterization technique of single-walled carbon nanotube fiber quality is evaluated are as follows: scanning
Length, the fibre diameter of carbon nanotube are measured in Electronic Speculum, mechanical property measuring instrument tests fibre tensile strength, and the test of two hold-carryings is fine
Tie up resistance.
The present invention is described in further detail below by embodiment and attached drawing.
Embodiment 1.
In the present embodiment, the method for preparing single-walled carbon nanotube fiber is as follows:
The preparation of single-walled carbon nanotube: preparation temperature is 1200 DEG C, phase carbon source, catalyst precursor, growth promoter
Respectively toluene, ferrocene, thiophene, three's mass ratio are 100:6:1.5, injection speed 1.5mLh-1, carrier gas H2Flow velocity
For 7000sccm, gaseous carbon source C2H4Flow velocity be 10sccm.
Spinning solution preparation: single-walled carbon nanotube, hydration sodium taurocholate are added in water, surpasses in ultrasonic cell disruptor
Sound dispersion 30min (power 300W) obtains dispersion liquid, in which: the concentration of single-walled carbon nanotube is 0.2wt%, and hydration sodium taurocholate is dense
Degree is 2wt.%.
Fibre spinning process: fibre is formed as shown in Figure 1, dispersion liquid is injected into the coagulating bath solution of rotation by syringe
Gel is tieed up, coagulating bath solution is isopropanol, and coagulating bath solution revolving speed is 2.5rpm, syringe needle distance center 9cm, the solidification at syringe needle
Bath solution linear velocity is 2.4cm/s, syringe needle internal diameter 0.6mm, injection speed 5ml/min.Gelatinous fibre lifts from one end, isopropyl
Fiber can be formed after alcohol volatilization, then for 2h to remove remaining surfactant, last 60 DEG C dry in water by fiber impregnation
It is dry to obtain fiber.
It is scanned Electronic Speculum, transmission electron microscope, laser respectively to above-mentioned sample (being denoted as 1#) and to single-walled carbon nanotube raw material
Raman Characterization and mechanics, resistive performance test.Scanning electron microscope shows that single-walled carbon nanotube raw material is micro- by length > 50
Rice and pure carbon nano tube network composition (Fig. 2 a)；Transmission electron microscope shows clearly tube wall (Fig. 2 b)；Raman spectrum shows pole
High IG/IDIt is worth (120, Fig. 2 c), shows that the crystallinity of carbon nanotube is high；The residual of iron in sample is calculated by thermogravimetric curve
Amount only has 8.7wt% (Fig. 2 d).Fiber scanning electron microscope shows that fiber has the outer surface of fold, this is gelatinous fibre in isopropyl
It shrinks and is formed during alcohol volatile dry, fiber has more uniform diameter, is 21 μm (Fig. 3).By stress-strain diagram
In available fibre strength be 304MPa (Fig. 4).The resistance of fiber is measured by two hold-carryings, and conductivityσ (S/cm) is according to formula σ
=l/ (RS) is calculated, wherein l, and R, S are respectively length, resistance and the sectional area of fiber.Single-walled carbon nanotube fiber
Conductivity is up to 2500Scm-1(Fig. 5).
Embodiment 2:
In the present embodiment, by taking manganese dioxide as an example, shows preparation and its capacitive property of composite fibre, prepare single wall carbon and receive
The method of mitron composite fibre is as follows:
The preparation of single-walled carbon nanotube: preparation temperature is 1200 DEG C, phase carbon source, catalyst precursor, growth promoter
Respectively toluene, ferrocene, thiophene, three's mass ratio are 100:6:1.5, injection speed 1.5mLh-1, carrier gas H2Flow velocity
For 7000sccm, gaseous carbon source C2H4Flow velocity be 10sccm.
MnO2The preparation of colloidal sol: (1) lauryl sodium sulfate (200mg) and H in 500mL deionized water is added2SO4
(2mL, molar concentration 1M)；(2) above-mentioned solution is placed in 90 DEG C of water-baths and stirs 15min；(3) it is added in the above solution
KMnO4(200mg) continues to be stirred to react 1h, and solution gradually becomes grape wine red, light brown by aubergine, eventually becomes palm fibre
Brown simultaneously has flocculent deposit generation；(4) product finally is dispersed in water to be formed containing MnO through centrifuge washing2Colloidal suspensions it is standby
With.
Composite spinning stoste preparation: in the MnO of 12.5g2Colloidal suspensions (contain MnO2Single is added in 50mg)
Pipe 25mg is hydrated sodium taurocholate 250mg, and ultrasonic disperse 30min (power 300W), is dispersed in ultrasonic cell disruptor
Liquid.
Composite fiber spinning process: dispersion liquid is injected by syringe and forms fiber in the coagulating bath solution of rotation and coagulates
Glue, coagulating bath solution are ethyl alcohol, and coagulating bath solution revolving speed is 2.5rpm, syringe needle distance center 9cm, the coagulating bath solution at syringe needle
Linear velocity is 2.4cm/s, syringe needle internal diameter 0.6mm, injection speed 5ml/min.Gelatinous fibre lifts from one end, after ethyl alcohol volatilization
Fiber can be formed, then for 2h to remove remaining surfactant, last 60 DEG C are dried to obtain fibre in water by fiber impregnation
It ties up (Fig. 6).
2# sample is denoted as to above-mentioned sample, Electronic Speculum, Mechanics Performance Testing, resistance and electrochemical capacitor is scanned respectively and surveys
Examination.As shown in fig. 7, stereoscan photograph shows that composite fibre has the outer surface of fold, this is that gelatinous fibre volatilizees in ethyl alcohol
It shrinks and is formed in drying process, fibre diameter is 30 μm.It can be clearly seen that the MnO of laminated structure in high power scanning2, with
Carbon nanotube weave in is evenly distributed in fibrous matrix.By available compound fibre in stress-strain diagram (Fig. 4)
Dimension intensity is 65MPa.The conductivity that two hold-carryings measure composite fibre is 760Scm-1(Fig. 5).The carbon nanotube former material of high quality
Material is the reason of composite fibre keeps relatively high conductivity with nanometer sheet good combination.Composite fibre is carried on a shoulder pole with high active substance
Carrying capacity, high mechanical strength and high conductivity.Electro-chemical test uses three electrode test systems, and electrolyte is 1M LiCl solution, fine
Dimension is working electrode (length 2.5cm), and Pt piece is to electrode, saturated calomel electrode (Saturated Calomel
Electrode, SCE) it is reference electrode, potential region is 0~1V vs SCE.It is carried out on CHI 760D electrochemical workstation
Cyclic voltammetric, constant current charge-discharge test.Composite fibre is in 100mV s-Approximate square is presented in cyclic voltammetry curve under 1 scanning speed
The shape of shape, in 2Acm-2Constant current charge-discharge curve under current density is in the shape of near symmetrical, shows charge and discharge process
Invertibity.Increase with current density, composite fibre specific capacitance is from 428Fcm-3It is reduced to 323Fcm-3, capacity retention ratio
75%, show excellent high rate performance (Fig. 8).
Comparative example 1:
The preparation of single-walled carbon nanotube: preparation temperature is 1200 DEG C, phase carbon source, catalyst precursor, growth promoter
Respectively toluene, ferrocene, thiophene, three's mass ratio are 100:6:1.5, injection speed 1.5mLh-1, carrier gas H2Flow velocity
For 7000sccm, gaseous carbon source C2H4Flow velocity be 10sccm.
Prepared by spinning solution: addition single-walled carbon nanotube, lauryl sodium sulfate in water, in ultrasonic cell disruptor
Ultrasonic disperse 30min (power 300W) obtains dispersion liquid, and wherein single-walled carbon nanotube concentration is 0.2wt%, dodecyl sulphate
Na concn is 2wt.%.
Fibre spinning process: it as shown in figure 9, dispersion liquid is injected into the coagulating bath solution of rotation by syringe, solidifies
Bath solution is ethyl alcohol, and coagulating bath solution revolving speed is 2.5rpm, syringe needle distance center 9cm, the coagulating bath solution linear velocity at syringe needle
For 2.4cm/s, syringe needle internal diameter 0.6mm, injection speed 5ml/min.
Since surfactant is lauryl sodium sulfate, the dispersibility of single-walled carbon nanotube in the solution is poor, is dividing
During dispersion liquid injects ethyl alcohol by syringe, carbon nanotube drawout comes, and is formed by gel fiber in discontinuously separation shape
State cannot form the fiber that can lift.
Comparative example 2:
Single-walled carbon nanotube using HiPco single-walled carbon nanotube (Nanjing XFNANO Materials Tech Co.,
Ltd, China), length of carbon nanotube is 1~3 micron.
Spinning solution preparation: single-walled carbon nanotube, sodium taurocholate, ultrasonic disperse in ultrasonic cell disruptor are added in water
30min (power 300W) obtains dispersion liquid, and wherein single-walled carbon nanotube (SWCNT) concentration is 0.2wt%, lauryl sodium sulfate
Concentration is 2wt.%.
Fibre spinning process: dispersion liquid is injected into the coagulating bath solution of rotation by syringe, and coagulating bath solution is second
Alcohol, coagulating bath solution revolving speed are 2.5rpm, syringe needle distance center 9cm, and the coagulating bath solution linear velocity at syringe needle is 2.4cm/s,
Syringe needle internal diameter 0.6mm, injection speed 5ml/min.
Since the length of single-walled carbon nanotube used is shorter, continuous fiber cannot be formed.
Comparative example 3:
The preparation of single-walled carbon nanotube: preparation temperature is 1200 DEG C；Phase carbon source, catalyst precursor, growth promoter
Respectively toluene, ferrocene, thiophene, three's mass ratio are 100:6:1.5；Injection speed is 1.5mLh-1；Carrier gas H2Flow velocity
For 7000sccm, gaseous carbon source C2H4Flow velocity be 10sccm.
Spinning solution preparation: single-walled carbon nanotube, hydration sodium taurocholate, ultrasound in ultrasonic cell disruptor are added in water
Dispersion 30min (power 300W) obtains single-walled carbon nanotube dispersion liquid, and PVAC polyvinylalcohol (Sigma- is added in dispersion liquid
Aldrich, molecular weight: 146000~186000；99+%hydrolyze) particle is heated to 95 DEG C under ultrasound condition, keeps
30min, wherein single-walled carbon nanotube concentration is 0.2wt%, and lauryl sodium sulfate concentration is 2wt.%, and PVA concentration is
0.2wt%.
Fibre spinning process: dispersion liquid is injected into the coagulating bath solution of rotation by syringe, and coagulating bath solution is third
Ketone, coagulating bath solution revolving speed are 2.5rpm, syringe needle distance center 9cm, and the coagulating bath solution linear velocity at syringe needle is 2.4cm/s,
Syringe needle internal diameter 0.6mm, injection speed 5ml/min.Gelatinous fibre lifts from one end, can form fiber after acetone volatilization.
Due to containing a large amount of PVA (with SWCNT mass ratio 1:1) in fiber, the conductivity of fiber is lower, only 30Scm-1, far below the fiber obtained without using PVA.
Embodiment and comparative example the result shows that, the method for the present invention preparation single-walled carbon nanotube fiber and its composite fibre,
With excellent mechanics, electric property, the intensity of single-walled carbon nanotube fiber is 304MPa, and conductivity is up to 2500Scm-1；
Compound with guest materials, it is more functional to assign fiber, such as: with MnO2The fiber specific capacitance of compound acquisition is up to
428F·cm-3, it is expected to be used as flexible capacitor part.The present invention realizes the continuous system of single-walled carbon nanotube fiber and its composite fibre
It is standby, it solves poor, the functional guest materials of the carbon nano-tube fibre conductivity that wet spinning technology obtains and is difficult to evenly dispersed etc. close
Key problem.
Claims (8)
1. a kind of method for preparing single-walled carbon nanotube fiber and its composite fibre, which is characterized in that specific step is as follows:
(1) quality of single-walled carbon nanotube raw material influences the quality and performance of final fiber, is that continuous producing carbon nano-tube is compound
Fiber, the single-walled carbon nanotube prepared using floating catalytic agent chemical vapour deposition technique, length of carbon nanotube are greater than 50 microns, drawn
Graceful spectrum G/D ratio is greater than 100, purity and is higher than 90wt%；
(2) single-walled carbon nanotube of step (1) preparation is added in the aqueous solution containing amphipathic cholic acid type surfactant,
Ultrasonic disperse obtains dispersion liquid；
(3) dispersion liquid that step (2) obtains is expressed into the coagulating bath solution of rotation and carries out spinning, form gel fiber,
Be drawn off and solvent volatilization after, obtain single-walled carbon nanotube fiber, remove remaining surface by further impregnating in water
Activating agent；
(4) in the dispersion liquid that step (2) obtains, easily dispersible functional material in aqueous solution is added, using step
(3) spinning process obtains single-walled carbon nanotube composite functional fiber.
2. the method described in accordance with the claim 1 for preparing single-walled carbon nanotube fiber and its composite fibre, which is characterized in that step
Suddenly in (1), single-walled carbon nanotube thermogravimetric tests catalyst residual quantity < 10wt.%.
3. the method described in accordance with the claim 1 for preparing single-walled carbon nanotube fiber and its composite fibre, which is characterized in that step
Suddenly in (2), the adding proportion of single-walled carbon nanotube in aqueous solution is 0.2~1wt.%.
4. the method described in accordance with the claim 1 for preparing single-walled carbon nanotube fiber and its composite fibre, which is characterized in that step
Suddenly in (2), amphipathic cholic acid type surfactant be sodium taurocholate, NaTDC or sodium taurocholate, concentration be 1.8~
3wt.%.
5. the method described in accordance with the claim 1 for preparing single-walled carbon nanotube fiber and its composite fibre, which is characterized in that step
Suddenly in (4), coagulating bath solution is ethyl alcohol, propyl alcohol, isopropanol, methanol or acetone.
6. the method described in accordance with the claim 1 for preparing single-walled carbon nanotube fiber and its composite fibre, which is characterized in that step
Suddenly in (4), functional material is to form well dispersed colloidal solution or suspension in water, and surface band is negative in water for material
Charge, Zeta potential are negative value, concentration < 1wt.% of the functional material in mixed liquor.
7. the method described in accordance with the claim 1 for preparing single-walled carbon nanotube fiber and its composite fibre, which is characterized in that step
Suddenly in (4), functional material is fake capacitance class material: manganese dioxide, molybdenum disulfide, Mxene, hydrated ferric oxide FeOOH or poly-
Pyrroles.
8. the method described in accordance with the claim 1 for preparing single-walled carbon nanotube fiber and its composite fibre, which is characterized in that single
The technical indicator of wall carbon nano tube fiber and its composite fibre is as follows: conductivity > 2500Scm-1, tensile strength > 300MPa.
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