CN114016150A - High-conductivity nano carbon/metal composite fiber and preparation method thereof - Google Patents
High-conductivity nano carbon/metal composite fiber and preparation method thereof Download PDFInfo
- Publication number
- CN114016150A CN114016150A CN202111504916.7A CN202111504916A CN114016150A CN 114016150 A CN114016150 A CN 114016150A CN 202111504916 A CN202111504916 A CN 202111504916A CN 114016150 A CN114016150 A CN 114016150A
- Authority
- CN
- China
- Prior art keywords
- solution
- fiber
- metal composite
- conductivity
- nano carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
- D06M2101/08—Esters or ethers of cellulose
Abstract
The invention discloses a high-conductivity nano carbon/metal composite fiber and a preparation method thereof. The preparation method comprises the following steps: dispersing the nano-carbon material, a macromolecular surfactant and a micromolecular surfactant in water together to obtain a spinning solution; injecting the spinning stock solution into a rotating coagulating bath for liquid phase spinning to obtain the nano carbon fiber containing the macromolecular surfactant; adding a metal source compound and a reducing agent into a coagulating bath for reaction, and depositing generated metal particles on the surface of the carbon nanofiber containing a macromolecular surfactant to obtain a metal composite carbon nanofiber; and carrying out hot-pressing treatment to obtain the high-conductivity nano carbon/metal composite fiber. According to the preparation method, the two surfactants are mixed to disperse the nano carbon material together, so that the dispersion effect can be realized, the metal particle growth sites with proper content are introduced, the conductivity of the nano carbon fiber is greatly improved, and the nano carbon fiber has excellent stability of conductivity.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a high-conductivity nano carbon/metal composite fiber and a preparation method thereof.
Background
The nano carbon fiber generally comprises carbon nanotube fiber, graphene fiber and composite fiber thereof, and has the characteristics of high specific strength, high specific conductance, easy heat conduction, corrosion resistance, oxidation resistance and the like, so that the nano carbon fiber is expected to be used as a basic component of a transmission line and plays an important role in the aspects of aerospace, rail transit, biomedical treatment and the like. However, the existing carbon nanofibers cannot well meet the requirements of practical application, and mainly the carbon nanotubes or graphene are difficult to form a good electron transmission channel in one step in the assembly process, so that the overall electrical conductivity of the assembled fibers is often greatly lower than that of metal fibers. As a fiber material assembled from carbon nanotubes or graphene, the electrical conductivity of carbon nanofibers mainly depends on the internal network structure. Therefore, for expanding the application range of the carbon nanofiber in a large scale, an urgent task is to improve the conductive network of the carbon nanofiber by a relatively effective means, so that the conductive performance of the carbon nanofiber is further improved.
At present, the preparation methods of carbon nanotube fibers are mainly divided into three types: float spinning techniques (reference 1: Cheng H M, Li F, Sun X, Brown S D M, Pimenta M A, Marucci A, Dresselhaus G, Dresselhaus M S.chemical Physics Letters,1998,289(5-6): 602-), array spinning techniques (reference 2: Jiang K, Li Q, Fan S.Nature. 2002,419(6909),801) and solution spinning techniques (reference 3: Vigolo B, Penicaud A, Coulon C, Sauder C, Pailler R, Jour C, Bernier P, Poulin P science,2000,290(5495): 1331.). In the floating spinning, substances such as a carbon source, a catalyst, an accelerant and the like are injected into a high-temperature reaction cavity to generate the sock-shaped carbon nanotube aerogel, and then the sock-shaped carbon nanotube aerogel is blown out of a reaction area by carrier gas and is subjected to densification treatment to obtain fibers. The array spinning technology is very similar to the traditional silk weaving technology, and the core technology is that a carbon nanotube film is extracted from a carbon tube array and then is twisted to be converted into compact fibers. And in the solution spinning process, the carbon nano tube powder only needs to be uniformly dispersed in a solvent, then is continuously injected into a coagulating bath solution at a constant speed, and is subjected to gel curing and drying to obtain the fiber. Compared with the floating spinning technology and the array spinning technology, the solution spinning technology can purify the carbon nanotubes in a targeted manner, and meanwhile, the carbon nanotubes do not need to be arranged in an array on a substrate, so that the method is more suitable for producing the carbon nanotube fibers with stable performance in a large batch. The preparation method of the graphene fiber mainly adopts a solution spinning technology, generally, graphene is oxidized into graphene oxide, then graphene oxide dispersion liquid is extruded into a coagulating bath to obtain the graphene oxide fiber, and then the graphene oxide fiber can be obtained through post-treatment modes such as high temperature and reducing agent.
Solution spinning techniques for carbon nanotubes are mainly classified into two types according to the difference of dispersion media: the first type uses a dispersant to modify the carbon nanotubes non-covalently (document 3: Vigolo B, Penicaud A, Coulon C, Sauder C, Pailler R, Jourenet C, Bernier P, Poulin P. science,2000,290(5495):1331-1334.) to improve their dispersion in a solvent; the second category uses superacids for protonation of carbon nanotubes (document 4: Ericson L M, Fan H, Peng H Q, Davis VA, Zhou W, Sulpizio J, Wang Y H, Booker R, Vavoro J, Guthy C, Parra-Vasquez A N G, Kim M J, Ramesh S, Saini R K, Kittrell C, Lavin G, Schmidt H, Adams W W, Billups W E, Pasliqua M, Hwang W F, Hauge R H, Fischer J E, Smalley R E. science,2004, R5689), 1447-. Under the influence of a dispersion medium, the conductivity of the carbon nanotube fiber prepared by the first type is weaker than that of the second type, but the latter also puts higher requirements on experimental equipment and environment.
At present, the conductivity of the fiber prepared by using the dispersing agent or the super strong acid is far lower than that of the metal fiber. In consideration of the characteristics of solution spinning, the existing improvement schemes mainly have three types: densification (document 5: Mukai K, Asaka K, Wu XL, Morimoto T, Okazaki T. applied Physics Express,2016,9,055101.), doping (document 6: Behabtu N, Young C, Tsateralovich D E, Kleinerman O, Pasquali M.Sci, 2013,339(6116), 182-), and carbon nanotube/nanometal particle hybrid spinning (document 7: Han J T, Choi S, Jang J I, Seol S K, Woo J S, Jeong H J, Jeong S Y, Baeg K J, Lee G W.scientific Reports,2015,5, 9300.). The densification process increases the contact area between carbon nanotubes or graphene tubes primarily by applying mechanical force to reduce the resistance to electronic transitions. The doping treatment mainly changes the electronic structure of the carbon nanotubes or graphene by using conductive substances such as halogen and the like, thereby increasing the carrier concentration of the carbon nanotubes in the fiber. The carbon nano tube or graphene/nano silver particle mixed spinning is mainly characterized in that substances such as silver nanowires and the like are introduced into a dispersion system, so that an electron transmission passage in the formed fiber is increased.
For carbon nano tube or graphene/nano metal particle mixed spinning, the nano metal particles have high conductivity, and after being mixed with the carbon nano tube or graphene dispersion liquid, the transmission path of electrons in the formed fiber can be increased, so that the composite fiber with good conductivity can be obtained. However, the internal network structure of the fiber is also very vulnerable to the influence of the metal particles, so that the introduced metal nanoparticles must have proper size, size and content. The divergence of the sizes and the sizes of the nano metal particles prepared by various synthesis methods is large at present, and the product can be used after being separated and purified for many times. Therefore, the cost of carbon nanotube or graphene/nano-metal particle hybrid spinning is high, and the method is not suitable for mass production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-conductivity nano carbon/metal composite fiber and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides a method for preparing a highly conductive nanocarbon/metal composite fiber, comprising:
providing a nanocarbon material comprising carbon nanotubes and/or graphene;
dispersing the nano carbon material, a macromolecular surfactant and a micromolecular surfactant in water together to obtain a spinning solution;
injecting the spinning stock solution into a rotating coagulating bath for liquid phase spinning to obtain the nano carbon fiber containing the macromolecular surfactant;
adding a metal source compound and a reducing agent into the coagulating bath for reduction reaction, so that metal elements in the coagulating bath are reduced by the reducing agent, and the generated metal particles are deposited on the surface of the nano carbon fiber containing the macromolecular surfactant to obtain a metal composite nano carbon fiber;
and carrying out hot-pressing treatment on the metal composite nano carbon fiber to obtain the high-conductivity nano carbon/metal composite fiber.
In a second aspect, the present invention also provides a highly conductive carbon nanotube/metal composite fiber prepared by the above method, wherein the highly conductive carbon nanotube/metal composite fiber comprises carbon nanofibers and metal particles composited with the carbon nanofibers.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the high-conductivity carbon nanotube/metal composite fiber, provided by the invention, the macromolecular surfactant is added into the spinning solution, so that the dispersibility of the carbon nanotube in the spinning solution is improved, simultaneously, the sites for metal ion growth and deposition are provided, and then the metal ion is reduced by combining a reducing agent in a coagulating bath to react, so that a large amount of metal particles are deposited on the carbon nanotube fiber, the steps of separating and purifying the metal particles for multiple times during the mixed spinning of the carbon nanotube/metal particles are reduced, the preparation cost of the high-conductivity carbon nanotube/metal composite fiber is reduced, and the large-scale production of the high-conductivity carbon nanotube/metal composite fiber is facilitated.
2. The preparation method of the high-conductivity carbon nanotube/metal composite fiber provided by the invention carries out hot pressing treatment on the carbon nanotube fiber deposited with the metal particles, realizes the sintering of the metal particles, greatly improves the conductivity and phase of the carbon nanotube fiberCompared with the original nano carbon fiber which is not prepared by the preparation method, the promotion amplitude reaches 2500 percent, and the conductivity reaches 10 percent8S/m。
3. The high-conductivity carbon nanotube/metal composite fiber prepared by the method is not easy to interact with air and water in the environment, has excellent stability in conductivity, and is beneficial to expanding the application range of the carbon nanotube fiber.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical solutions of the present invention and to implement them according to the content of the description, the following description is made with reference to the preferred embodiments of the present invention and the detailed drawings.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a highly conductive carbon nanotube/metal composite fiber according to an embodiment of the present invention;
FIG. 2 is a transmission electron microscope image of the spinning solution provided in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of the dope of comparative example 1 of the present invention;
fig. 4 is a scanning electron microscope picture of the carbon nanotube/silver composite fiber provided in example 1 of the present invention;
FIG. 5 is a scanning electron microscope photograph of a carbon nanotube/silver composite fiber provided in comparative example 1 of the present invention;
FIG. 6 is a scanning electron microscope photograph of a highly conductive carbon nanotube/metal composite fiber provided in example 1 of the present invention;
FIG. 7 is a scanning electron microscope photograph of a highly conductive carbon nanotube/metal composite fiber according to comparative example 1 of the present invention;
fig. 8 is a graph showing a variation in conductivity of the highly conductive carbon nanotube/metal composite fiber provided in example 1 of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and thus the scope of the present invention is not limited by the specific embodiments disclosed below.
Moreover, relational terms such as "first" and "second," and the like, may be used solely to distinguish one element or method step from another element or method step having the same name, without necessarily requiring or implying any actual such relationship or order between such elements or method steps.
The embodiment of the invention provides a preparation method of a high-conductivity carbon nanotube/metal composite fiber, which comprises the following steps:
providing a nanocarbon material comprising carbon nanotubes and/or graphene;
dispersing the nano carbon material, a macromolecular surfactant and a micromolecular surfactant in water together to obtain a spinning solution;
the macromolecule surfactant and the micromolecule surfactant have a synergistic effect, so that sufficient dispersity is provided, the phenomenon that the conducting performance of the carbon nanofiber is affected by the macromolecule surfactant with high concentration when the carbon nanofiber is wrapped by the macromolecule surfactant with high concentration is avoided, the two surfactants are mixed to jointly disperse the carbon nanotube, a metal particle growth site with proper content is introduced while the dispersing effect can be achieved, and the improvement of the conductivity of the fiber is facilitated.
Injecting the spinning stock solution into a rotating coagulating bath for liquid phase spinning to obtain the nano carbon fiber containing the macromolecular surfactant;
adding a metal source compound and a reducing agent into the coagulating bath for reduction reaction, so that metal elements in the coagulating bath are reduced by the reducing agent, and the generated metal particles are deposited on the surface of the nano carbon fiber containing the macromolecular surfactant to obtain a metal composite nano carbon fiber;
and carrying out hot-pressing treatment on the metal composite nano carbon fiber to obtain the high-conductivity nano carbon/metal composite fiber.
In some embodiments, the carbon nanotubes include any one or a combination of two or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, and functionalized carbon nanotubes, and the graphene includes any one or a combination of two of graphene oxide and graphene.
In some embodiments, the macromolecular surfactant comprises any one or a combination of two or more of sodium carboxymethylcellulose, sodium alginate, chitosan, and polyvinylpyrrolidone; the micromolecular surfactant comprises one or the combination of more than two of sodium cholate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate. .
In some embodiments, the formulation of the dope specifically comprises:
dissolving the macromolecular surfactant in water to form a macromolecular surfactant solution with the concentration of 2-4 mg/mL; then adding the small molecular surfactant to obtain a mixed solution;
adding the nano carbon material into the mixed solution, stirring for 12h, and homogenizing under the pressure of 30-50MPa for 20-30min to obtain the spinning solution.
In some embodiments, the small molecule surfactant is present in the mixed solution at a concentration of 20-50 mg/mL.
In some embodiments, the mass ratio of the nanocarbon material to the small molecule surfactant is 1: 5.
In some embodiments, the coagulation bath includes an organic solvent, an aqueous salt ion solution, or an organic-inorganic mixed solution.
In some embodiments, the organic solvent comprises any one or a combination of two or more of isopropanol, acetone, butanol, and ethanol.
In some embodiments, the aqueous salt ion solution includes any one or a combination of two or more of an aqueous NaCl solution, an aqueous KCl solution, and an aqueous CuSO4 solution.
In some embodiments, the organic-inorganic mixture comprises an aqueous isopropanol solution or an aqueous acetone solution.
In some embodiments, the spinning dope is injected into the coagulation bath rotating at an injection speed of 10-15mL/h, wherein the diameter of an injection needle is 400 μm, and the rotation speed of the coagulation bath is 10-20 r/min.
In some embodiments, the reduction and deposition of the metallic element specifically comprises:
adding the solution of the metal source compound into the coagulating bath, sealing and standing for 1-3h to ensure that the concentration of the metal source compound in the coagulating bath is 0.05-0.2 mol/L;
and adding the solution containing the reducing agent into the coagulating bath for reduction reaction for 0.5-2h, wherein the molar ratio of the metal source compound to the reducing agent in the coagulating bath is 5:1-1: 5.
In some embodiments, the metal source compound comprises any one of or a combination of two or more of a silver salt, a gold salt, and a copper salt.
In some embodiments, the silver salt comprises silver nitrate, the gold salt comprises chloroauric acid, and the copper salt comprises copper nitrate.
In some embodiments, the reducing agent comprises any one or a combination of two or more of ascorbic acid, hydrazine hydrate, hydroiodic acid, and sodium borohydride.
In some embodiments, the temperature of the hot pressing treatment is 250-270 ℃ and the pressure is 1-50 MPa.
In some embodiments, the method of making further comprises:
cleaning and drying the nano carbon fiber or the highly conductive nano carbon/metal composite fiber containing the macromolecular surfactant;
in some embodiments, the rinsing and drying process comprises washing in deionized water and ethanol for 10min in sequence, and then drying at room temperature for 24 h.
In a typical embodiment, the preparation method of the high-conductivity nano carbon/metal composite fiber is mainly divided into four processes of preparation of spinning stock solution, spinning by a rotary coagulation bath method, silver particle deposition and hot pressing treatment.
1. Preparation of the spinning dope
Dissolving sodium carboxymethylcellulose in deionized water to obtain sodium carboxymethylcellulose solution with concentration of 2-4 mg/mL. Then, the sodium cholate is dissolved in the sodium carboxymethyl cellulose solution to obtain a mixed solution with the concentration of the sodium cholate of 20-50 mg/mL. And then adding the single-walled carbon nanotube into the mixed solution prepared previously and stirring the mixture for 12 hours by magnetic force, wherein the mass ratio of the carbon nanotube to the sodium cholate in the obtained solution is 1: 5. and finally, homogenizing the mixed solution containing the carbon nano tubes under the pressure of 30-50MPa for 20-30min to obtain the spinning solution.
In the preparation stage of the spinning solution, sodium cholate and sodium carboxymethyl cellulose are mixed to disperse the carbon nano tube. Sodium cholate is a small molecular surfactant, has a good dispersing effect on carbon nanotubes, but is very easy to diffuse into a coagulating bath in the fiber coagulating process. Sodium carboxymethyl cellulose is a macromolecular surfactant, is not easy to fall off after being wound on a carbon nano tube, can be used as a stable growth site of silver particles, and can generate adverse effect on the conductivity of the fiber when the content of the sodium carboxymethyl cellulose is too high. The carbon nano tube is dispersed by mixing two surfactants together, so that the dispersing effect is realized, and silver particle growth sites with proper content are introduced, thereby being beneficial to improving the conductivity of the fiber.
2. Spinning by rotary coagulation bath method
And injecting the spinning solution into a rotating isopropanol solution with the volume fraction of 80% through a needle at the speed of 10-15mL/h to obtain the carbon nano tube fiber containing the sodium carboxymethyl cellulose. The diameter of the injector needle in the spinning process is 400um, and the rotating speed of the rotating platform is 10-20 r/min.
3. Silver particle deposition
Adding silver nitrate water solution into the coagulating bath, sealing and standing for 1-3h to obtain silver nitrate water/isopropanol solution with the concentration of 0.05-0.2mol/L, wherein the volume content of the isopropanol is 40%. And adding the water/isopropanol solution of the ascorbic acid into a coagulating bath, and reacting for 0.5-2h to realize the deposition of the silver particles on the fibers. The volume content of isopropanol in the solvent of the ascorbic acid solution is also 40%, and the concentration ratio of silver nitrate to ascorbic acid in the coagulation bath is 2: 1. And taking the fiber obtained in the last step out of the coagulating bath, washing the fiber in deionized water and ethanol for 10min in sequence, and drying the fiber at room temperature for 24 h.
4. Hot pressing treatment
The dried carbon nano tube fiber is processed by hot pressing at the temperature of 250-270 ℃ and the pressure is 80-120N. Finally, washing the fibers subjected to the hot pressing treatment in deionized water and ethanol for 10min in sequence, and drying for 24h at room temperature.
And carrying out hot-pressing treatment on the fibers after the silver particles are deposited on the fibers. After silver nitrate is reduced in solidification, a large number of silver particles are deposited on the fibers, but the particles are not in close contact with each other, and the particles also have a certain supporting and expanding effect on a conductive network of the fibers, so that the effect of improving the conductive performance is limited. The hot pressing treatment can reduce the pores in the conductive network and can also sinter the nano silver particles, thereby greatly improving the effect of improving the conductivity of the fiber after the composite silver is compounded.
The embodiment of the invention also provides the high-conductivity nano carbon/metal composite fiber prepared by the method, and the high-conductivity nano carbon/metal composite fiber comprises nano carbon fibers and metal particles compounded with the nano carbon fibers.
In some embodiments, the metal particles have a particle size of 2 to 300 nm.
In some embodiments, 0.01 to 50 wt% of the metal particles in the highly conductive nanocarbon/metal composite fiber;
in some embodiments, the highly conductive nanocarbon/metal composite fibers have an electrical conductivity ranging from 0.05 to 1 × 108S/m。
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, however, the present application may be practiced otherwise than as specifically described herein and, therefore, the scope of the present application is not limited by the specific embodiments disclosed below.
Example 1
The embodiment of the invention provides a preparation method of a high-conductivity carbon nanotube/metal composite fiber, which comprises the following specific preparation processes:
1. preparing a spinning solution: sodium carboxymethylcellulose is dissolved in deionized water to obtain a sodium carboxymethylcellulose solution with the concentration of 2 mg/mL. Then, sodium cholate is dissolved in the sodium carboxymethyl cellulose solution to obtain a mixed solution with the concentration of the sodium cholate of 4 mg/mL. And then adding the single-walled carbon nanotube into the previously prepared mixed solution and magnetically stirring for 12 hours, wherein the mass ratio of the carbon nanotube to the sodium cholate in the obtained solution is 1: 5. And finally, homogenizing the mixed solution containing the carbon nano tubes for 30min under the pressure of 40MPa to obtain the spinning solution.
2. Spinning by a rotary coagulation bath method: and (3) injecting the spinning solution into a rotating 80% isopropanol aqueous solution at the speed of 10mL/h through a needle head to obtain the macromolecular composite carbon nanotube fiber containing sodium carboxymethylcellulose. The diameter of the injector needle in the spinning process is 400um, and the rotating speed of the rotating platform is 10 r/min.
3. Deposition of silver particles: adding silver nitrate water solution into a coagulating bath, sealing and standing for 1h to obtain 0.1mol/L silver nitrate water/isopropanol solution, wherein the volume content of isopropanol is reduced from 80% to 40%. And adding the water/isopropanol solution of the ascorbic acid into a coagulating bath, and reacting for 1h to realize the deposition of the silver particles on the fibers. The volume content of isopropanol in the solvent of the ascorbic acid solution was also 40%, so that the concentration of isopropanol in the coagulation bath did not change when the ascorbic acid solution was added, and the concentration ratio of silver nitrate to ascorbic acid in the coagulation bath was 2: 1. And taking out the metal composite carbon nanotube fiber obtained by the reaction from the coagulating bath, washing in deionized water and ethanol for 10min in sequence, and drying at room temperature for 24 h.
4. Hot pressing treatment: and (3) carrying out hot pressing treatment on the dried carbon nanotube fiber at the temperature of 250 ℃ under the pressure of 80N to obtain the high-conductivity carbon nanotube/metal composite fiber.
Example 2
Embodiment 2 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, which has the same process and parameters as those of embodiment 1, except that:
the concentration of the sodium carboxymethyl cellulose solution in the step 1 is 3mg/mL, and the concentration of the sodium cholate is 30 mg/mL; in the step 4, the hot pressing temperature is 260 ℃ and the pressure is 100N.
Example 3
Embodiment 3 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, which has the same process and parameters as those of embodiment 1, except that:
the concentration of the sodium carboxymethylcellulose solution in the step 1 is 4mg/mL, and the concentration of the sodium cholate is 40 mg/mL; in the step 4, the hot pressing temperature is 270 ℃, and the pressure is 120N.
Example 4
Embodiment 4 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, which has the same processes and parameters as those of embodiment 1, except that:
and (2) adding the single-walled carbon nanotube into the prepared mixed solution, and magnetically stirring for 2 hours, wherein the nano carbon material in the step (1) is a multi-walled carbon nanotube, and the mass ratio of the carbon nanotube to the sodium cholate in the obtained solution is 1: 1. And finally, homogenizing the mixed solution containing the carbon nano tubes for 30min under the pressure of 30MPa to obtain the spinning solution.
And 2, injecting the spinning solution into a rotary acetone coagulating bath at the speed of 15mL/h through a needle head to obtain the macromolecular composite carbon nanotube fiber containing sodium carboxymethyl cellulose. The diameter of the injector needle in the spinning process is 400um, and the rotating speed of the rotating platform is 20 r/min.
And 3, adding the copper nitrate aqueous solution into a coagulating bath, sealing and standing for 1h to obtain a copper nitrate acetone solution with the concentration of 0.05 mol/L. And then adding the acetone solution of hydroiodic acid into the coagulating bath, and reacting for 0.5h to realize the deposition of copper particles on the fibers. The concentration ratio of copper nitrate to ascorbic acid in the coagulation bath was 5: 1.
And 4, carrying out hot pressing treatment on the dried carbon nanotube fibers at 270 ℃ under the pressure of 50 MPa.
The highly conductive carbon nanotube/metal composite fiber having similar properties to the highly conductive carbon nanotube/metal composite fiber prepared in example 1 can be successfully prepared.
Example 5
Embodiment 5 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, which has the same process and parameters as those of embodiment 1, except that:
the nano-carbon material in the step 1 is graphene, the macromolecular surfactant is a combination of sodium alginate, chitosan and polyvinylpyrrolidone, and the micromolecular surfactant is sodium dodecyl benzene sulfonate.
The coagulating bath in step 2 is a 3 wt% KCl aqueous solution
And 3, sealing and standing for 3h by using a metal source compound of 2mol/L chloroauric acid and a reducing agent of a combination of hydrazine hydrate and hydroiodic acid, and carrying out a reduction reaction for 2h, wherein the molar ratio of the chloroauric acid to the hydrazine hydrate to the hydroiodic acid is 1: 5.
And 4, carrying out hot pressing treatment on the dried carbon nanotube fibers at 270 ℃, wherein the pressure is 1 MPa.
The highly conductive graphene/metal composite fiber with similar performance to the highly conductive carbon nanotube/metal composite fiber prepared in example 1 can be successfully prepared.
Example 6
Embodiment 6 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, which has the same process and parameters as those of embodiment 1, except that:
the nanocarbon material in the step 1 is graphene oxide, and the highly conductive graphene oxide/metal composite fiber with similar performance to the highly conductive carbon nanotube/metal composite fiber prepared in the example 1 can still be successfully prepared.
Example 7
Embodiment 7 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, which has the same process and parameters as those of embodiment 1, except that:
the nano carbon material in the step 1 is a mixture of graphene oxide and a single-walled carbon nanotube, and the mass ratio of the single-walled carbon nanotube to the graphene oxide is 3: 1, the high-conductivity carbon nano tube graphene oxide/metal composite fiber can still be successfully prepared, and the conductivity of the high-conductivity carbon nano tube graphene oxide/metal composite fiber can reach 1 multiplied by 108S/m。
Example 8
Embodiment 8 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, which has the same process and parameters as those of embodiment 1, except that:
the diameter of the injector needle in the spinning process in step 2 is 100um, and the highly conductive graphene oxide/metal composite fiber with similar performance to the highly conductive carbon nanotube/metal composite fiber prepared in example 1 can still be successfully prepared.
Comparative example 1
The comparative example 1 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, the process and parameters are substantially the same as those of the example 1, except that:
in step 1, sodium carboxymethylcellulose is not added.
Comparative example 2
The comparative example 2 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, the process and parameters are substantially the same as those of the example 1, except that:
after completion of step 3, the process of step 4 is not performed.
Comparative example 3
The comparative example 3 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, the process and parameters are substantially the same as those of the example 1, except that:
after completion of step 2, the processing of steps 3 and 4 is not performed.
Comparative example 4
The comparative example 4 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, the process and parameters are substantially the same as those of example 1, except that:
in step 1, no sodium carboxymethylcellulose was added, and after step 2 was completed, the treatments of steps 3 and 4 were not performed.
Comparative example 5
The comparative example 5 of the present invention provides a method for preparing a high-conductivity carbon nanotube/metal composite fiber, the process and parameters are substantially the same as those of example 1, except that:
in the step 1, sodium cholate is not added, and the sodium carboxymethyl cellulose is 20mg/mL, so as to ensure that the carbon nano tube is well dispersed.
Detection method and result analysis
1. TEM analysis of the spinning dope
The spinning dope obtained in step 1 in example 1 and comparative example 1 was observed by a transmission electron microscope to obtain a TEM image when the concentration of the sodium carboxymethylcellulose solution was 2mg/mL as shown in fig. 2 and a TEM image when the sodium carboxymethylcellulose solution was not added as shown in fig. 3.
As is clear from fig. 2 and 3, the carbon nanotubes in the spinning solution after the homogenization treatment are bundled in different sizes, and the addition of sodium carboxymethyl cellulose does not greatly affect the dispersion state of the carbon nanotubes.
2. SEM analysis of metal composite carbon nanotube fibers
Scanning electron microscope observation of the carbon nanotube/silver composite fiber obtained in step 3 of example 1 and comparative example 1 resulted in SEM pictures of the carbon nanotube/silver composite fiber containing sodium carboxymethylcellulose as shown in fig. 4 and the carbon nanotube/silver composite fiber without sodium carboxymethylcellulose as shown in fig. 5.
As is clear from fig. 4 and 5, the composite fiber containing sodium carboxymethylcellulose has a larger diameter, more silver particles deposited on the fiber, and a more uniform size. The introduction of sodium carboxymethylcellulose into the fiber can introduce silver particle growth sites, which is beneficial to the uniform deposition of silver particles.
3. SEM analysis of high-conductivity carbon nanotube/metal composite fiber
Scanning electron microscope observation of the carbon nanotube/silver composite fiber obtained in step 4 of example 1 and comparative example 1 resulted in SEM images after thermocompression treatment of the carbon nanotube/silver composite fiber containing sodium carboxymethyl cellulose as shown in fig. 6 and SEM images after thermocompression treatment of the carbon nanotube/silver composite fiber without sodium carboxymethyl cellulose as shown in fig. 7.
As is clear from fig. 6 and 7, the thermal pressing process changes the fiber cylinder structure into a narrow band structure, the pores in the conductive network are reduced, and the sintering phenomenon is generated between the silver nanoparticles.
4. Conductivity test of high conductivity carbon nanotube/metal composite fiber
The conductivity test of the carbon nanotube composite fibers obtained in the embodiments 1 to 3 and the comparative examples 1 to 5 was performed by a four-wire method, and the test results are shown in table 1:
TABLE 1 conductivity of carbon nanotube composite fiber obtained in each example and comparative example
As can be seen from table 1, the addition of a certain amount of sodium carboxymethylcellulose to the spinning dope does not change the conductivity of the fibril, but is beneficial to the deposition of silver particles; after the silver particles are deposited, the conductive network of the fiber is loose, and the conductive performance of the fiber can be greatly improved only by sintering the silver particles through hot-pressing treatment.
5. Test of conductivity stability of highly conductive carbon nanotube/metal composite fiber
The stability of the highly conductive carbon nanotube/metal composite fiber obtained in example 1 was tested, and the results of the change of the electrical conductivity with time after the composite fiber after the thermocompression treatment was placed in the air were recorded, thereby obtaining the electrical conductivity change curve shown in fig. 8.
As can be clearly seen from fig. 8, the conductivity of the carbon nanotube/silver fiber after the thermocompression treatment is stable, and the conductivity does not change greatly with the passage of time.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of high-conductivity nano carbon/metal composite fiber is characterized by comprising the following steps:
providing a nanocarbon material comprising carbon nanotubes and/or graphene;
dispersing the nano carbon material, a macromolecular surfactant and a micromolecular surfactant in water together to obtain a spinning solution;
injecting the spinning stock solution into a rotating coagulating bath for liquid phase spinning to obtain the nano carbon fiber containing the macromolecular surfactant;
adding a metal source compound and a reducing agent into the coagulating bath for reduction reaction, so that metal elements in the coagulating bath are reduced by the reducing agent, and the generated metal particles are deposited on the surface of the nano carbon fiber containing the macromolecular surfactant to obtain a metal composite nano carbon fiber;
and carrying out hot-pressing treatment on the metal composite nano carbon fiber to obtain the high-conductivity nano carbon/metal composite fiber.
2. The method according to claim 1, wherein the carbon nanotubes comprise any one or a combination of two or more of single-walled carbon nanotubes, multi-walled carbon nanotubes and functionalized carbon nanotubes, and the graphene comprises any one or a combination of two of graphene oxide and graphene.
Preferably, the macromolecular surfactant comprises any one or the combination of more than two of sodium carboxymethylcellulose, sodium alginate, chitosan and polyvinylpyrrolidone; the micromolecular surfactant comprises one or the combination of more than two of sodium cholate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
3. The method according to claim 2, wherein the preparation of the spinning dope specifically comprises:
dissolving the macromolecular surfactant in water to form a macromolecular surfactant solution with the concentration of 2-4 mg/mL; then adding the small molecular surfactant to obtain a mixed solution;
adding the nano carbon material into the mixed solution, stirring for 2-24h, and homogenizing under the pressure of 30-50MPa for 20-30min to obtain the spinning solution.
4. The preparation method according to claim 3, wherein the concentration of the small molecule surfactant in the mixed solution is 20-50 mg/mL;
and/or the mass ratio of the nano carbon material to the small molecular surfactant is 1:1-1: 5.
5. The method according to claim 1, wherein the coagulation bath includes an organic solvent, an aqueous salt ion solution, or an organic-inorganic mixed solution;
preferably, the organic solvent comprises any one or a combination of more than two of isopropanol, acetone, butanol and ethanol;
preferably, the salt ion aqueous solution includes an aqueous NaCl solution, an aqueous KCl solution, and CuSO4Any one or a combination of two or more of the aqueous solutions;
preferably, the organic-inorganic mixed solution comprises an isopropanol aqueous solution or an acetone aqueous solution.
And/or, the method comprises: and injecting the spinning solution into the rotating coagulating bath at an injection speed of 10-15mL/h, wherein the diameter of an injection needle is 100-400 mu m, and the rotating speed of the coagulating bath is 10-20 r/min.
6. The preparation method according to claim 5, which specifically comprises:
adding the solution of the metal source compound into the coagulating bath, sealing and standing for 1-3h to ensure that the concentration of the metal source compound in the coagulating bath is 0.05-0.2 mol/L;
and adding the solution containing the reducing agent into the coagulating bath for reduction reaction for 0.5-2h, wherein the molar ratio of the metal source compound to the reducing agent in the coagulating bath is 5:1-1: 5.
7. The method according to claim 1, wherein the metal source compound comprises any one or a combination of two or more of silver salt, gold salt and copper salt, preferably the silver salt comprises silver nitrate, preferably the gold salt comprises chloroauric acid, and preferably the copper salt comprises copper nitrate.
8. The method according to claim 1, wherein the reducing agent comprises any one or a combination of two or more of ascorbic acid, hydrazine hydrate, hydroiodic acid, and sodium borohydride.
9. The method as claimed in claim 1, wherein the hot pressing treatment is carried out at a temperature of 250 ℃ and a pressure of 1 to 50 MPa.
10. A highly conductive nanocarbon/metal composite fiber produced by the method of any one of claims 1 to 9, comprising a nanocarbon fiber and metal particles composited with the nanocarbon fiber;
preferably, the particle size of the metal particles is 2-300 nm;
preferably, the content of the metal particles in the highly conductive nanocarbon/metal composite fiber is 0.01 to 50 wt%;
the range of the conductivity of the high-conductivity nano carbon/metal composite fiber is 0.05-1 multiplied by 108S/m。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111504916.7A CN114016150B (en) | 2021-12-10 | 2021-12-10 | High-conductivity nano carbon/metal composite fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111504916.7A CN114016150B (en) | 2021-12-10 | 2021-12-10 | High-conductivity nano carbon/metal composite fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114016150A true CN114016150A (en) | 2022-02-08 |
| CN114016150B CN114016150B (en) | 2023-10-10 |
Family
ID=80068623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111504916.7A Active CN114016150B (en) | 2021-12-10 | 2021-12-10 | High-conductivity nano carbon/metal composite fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114016150B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017191887A1 (en) * | 2016-05-04 | 2017-11-09 | 재단법인차세대융합기술연구원 | Method for producing graphene oxide/carbon nanotube composite fiber, graphene oxide/graphene composite fiber or graphene oxide/graphene/carbon nanotube composite fiber using wet spinning process |
| CN109576822A (en) * | 2018-11-29 | 2019-04-05 | 中国科学院金属研究所 | A method of preparing single-walled carbon nanotube fiber and its composite fibre |
| CN111334897A (en) * | 2020-03-30 | 2020-06-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nano-based fiber, and preparation method and application thereof |
| CN112538596A (en) * | 2020-05-08 | 2021-03-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nano tube-metal composite conductor and preparation method thereof |
| CN113122961A (en) * | 2021-05-26 | 2021-07-16 | 南通大学 | Preparation method of silver/graphene composite fiber |
-
2021
- 2021-12-10 CN CN202111504916.7A patent/CN114016150B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017191887A1 (en) * | 2016-05-04 | 2017-11-09 | 재단법인차세대융합기술연구원 | Method for producing graphene oxide/carbon nanotube composite fiber, graphene oxide/graphene composite fiber or graphene oxide/graphene/carbon nanotube composite fiber using wet spinning process |
| CN109576822A (en) * | 2018-11-29 | 2019-04-05 | 中国科学院金属研究所 | A method of preparing single-walled carbon nanotube fiber and its composite fibre |
| CN111334897A (en) * | 2020-03-30 | 2020-06-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nano-based fiber, and preparation method and application thereof |
| CN112538596A (en) * | 2020-05-08 | 2021-03-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nano tube-metal composite conductor and preparation method thereof |
| CN113122961A (en) * | 2021-05-26 | 2021-07-16 | 南通大学 | Preparation method of silver/graphene composite fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114016150B (en) | 2023-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102936357B (en) | Antistatic agent made from silver nanowire and functional carbon nano tube (CNT) and preparation method | |
| JP5135620B2 (en) | Cohesive spinning structure and electric wire | |
| WO2012070537A1 (en) | Coagulation spinning structure and production method therefor, and electric wire using same | |
| CN1194121C (en) | Super high molecular mass polythylene/carbon nano tube composite fiber used in jelly glue spinning and its preparation | |
| CN105133293B (en) | A kind of preparation method of conductive nano composite material | |
| Yao et al. | Graphene oxide-assisted preparation of poly (vinyl alcohol)/carbon nanotube/reduced graphene oxide nanofibers with high carbon content by electrospinning technology | |
| CN113913970A (en) | High-performance carbon nanofiber and continuous preparation method thereof | |
| KR100652065B1 (en) | A method for producing a conductive cellulose film and the same manufactured by the same | |
| CN112210849B (en) | Preparation method of single-walled carbon nanotube fiber with high conductivity | |
| Lay et al. | Combined effect of carbon nanotubes and polypyrrole on the electrical properties of cellulose-nanopaper | |
| Zhao et al. | Achieving a better mechanical enhancing effect of carbonized polymer dots than carbon nanotubes and graphene in copper matrix | |
| CN113832572B (en) | Wave-absorbing composite large fiber and preparation method and application thereof | |
| CN105040409A (en) | Preparation method for magnetic nanocomposite | |
| CN114212778A (en) | Preparation method of nitrogen-doped graphene film and nitrogen-doped graphene film | |
| CN114016150B (en) | High-conductivity nano carbon/metal composite fiber and preparation method thereof | |
| CN113136096A (en) | Preparation method of three-dimensional carbon nanotube/polylactic acid conductive composite material | |
| Zhang et al. | Uniform doping of onion-like carbon nanofillers in carbon nanofibers via functionalization and in-situ polymerization for improved fiber graphitic structure and mechanical properties | |
| CN108329651B (en) | Polyether ether ketone based electromagnetic shielding material based on modified multi-walled carbon nanotube and preparation method thereof | |
| Qiao et al. | Homogeneous and stable carbon nanotube dispersion assisted by cellulose in NaOH/thiourea aqueous solution | |
| KR20100134479A (en) | Cnt powder coated metal nano particles and manufacturing method of thereof | |
| CN114672994A (en) | Graphene-reinforced carbon nanotube composite fiber, and preparation method and device thereof | |
| CN113698639A (en) | Carbon nano tube composite material electromagnetic shielding film and preparation method thereof | |
| CN113122961A (en) | Preparation method of silver/graphene composite fiber | |
| CN113060723A (en) | Nano-silver amino modified reduced graphene oxide framework material and preparation method thereof | |
| Yu et al. | Conductive composites based on core–shell polyaniline nanoclay by latex blending |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |