CN114481606A - Nickel-containing carbon nanotube/copper composite fiber and preparation method thereof - Google Patents
Nickel-containing carbon nanotube/copper composite fiber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nickel-containing carbon nanotube/copper composite fiber and a preparation method thereof. The preparation method comprises the following steps: carrying out densification treatment on the original carbon nanotube fiber to obtain a densified carbon nanotube fiber and simultaneously form a sawtooth structure shape on the surface of the highly densified carbon nanotube fiber; depositing nickel nanoparticles on the surface of the densified carbon nanotube fiber with the sawtooth structure; and continuously depositing a copper layer on the surface of the densified carbon nanotube fiber by adopting an electrochemical deposition technology to obtain the nickel-containing carbon nanotube/copper composite fiber. According to the invention, the nickel-containing carbon nanotube/copper composite fiber is prepared by utilizing the synergistic effect of the densification process and the nickel nanoparticles, the improvement of comprehensive mechanical properties such as elongation, modulus and tensile strength of the composite fiber can be realized, and the bonding strength of a composite interface can be improved; and no new substance is introduced, so that the purification of the carbon nanotube fiber is ensured, and the excellent performance of the carbon nanotube fiber is favorably exerted.
Description
Technical Field
The invention relates to a nickel-containing carbon nanotube/copper composite fiber and a preparation method thereof, belonging to the technical field of post-treatment of carbon nanotubes.
Background
In the modern society, electronic and electric appliances are used in various aspects of society, and copper is used at its relatively low price and excellent conductivity (5.8X 105S cm)-125 ℃ to become an indispensable wire material in electronic equipment; meanwhile, copper also has better processing performance and corrosion resistance. However, the tensile strength of the copper wire is low, when the copper is in a hard state, the tensile strength is 350-470 MPa, and the density of the copper is high (8.9g cm)-3) Therefore, the copper wire is continuously deformed under the action of self gravity in the actual service process, and finally the copper wire is failed and broken.
The carbon nano tube is used as a novel conductive material, and the density of the carbon nano tube is 1g cm-3About, the theoretical strength of the monomer can reach 50-200 GPa, and the mechanical property of the monomer far exceeds that of a copper wire. Meanwhile, the P orbital electrons of the carbon atoms forming the carbon nano tube can form delocalized pi bonds in a large range, the unique electrical property of the carbon nano tube is endowed by the special conjugation effect of the electronic structure, and the unique length-diameter ratio of the carbon nano tube monomer enables the carbon nano tube to have a great electron mean free path. Research shows that the average electron free path of the carbon nano tube can exceed 30 mu m (copper is 40nm), the maximum electron average free path has important significance for improving the conductivity of the carbon nano tube, and the theoretical conductivity of the carbon nano tube can be one order of magnitude higher than that of copper. Meanwhile, the carbon nanotube also has the excellent characteristics of low density, good chemical stability, high thermal conductivity, high mechanical strength and the like, so the carbon nanotube is one of candidates of a new generation of high-strength and high-conductivity materials.
However, the macroscopic bodies of carbon nanotubes in various forms are difficult to overcome the influence of a series of factors such as structural defects (such as more gaps existing inside the macroscopic bodies, less contact areas among the carbon nanotubes and poorer orientation of the carbon nanotubes) in the preparation process, and the like, so that the actual electrical property of the macroscopic body of the carbon nanotube is far from the theoretical property; meanwhile, the grown carbon nanotube fiber often has a loose microstructure and is often low in mechanical property. For example, the electrical conductivity of the carbon nanotube fiber prepared by the existing floating catalysis method is usually two orders of magnitude lower than that of copper, and the electrical conductivity level is lower; the mechanical property is often about 1GPa, and the difference is larger compared with the theoretical value. In order to solve the problem of low electrical conductivity of the carbon nanotube fiber, the carbon nanotube is often compounded with copper, and the high-strength and high-conductivity composite fiber is obtained by exerting the respective advantages and properties of the carbon nanotube and the copper. However, due to the respective atomic structural characteristics of the copper atom and the carbon nanotube, the bonding between the two is at the level of van der waals force, resulting in low interfacial bonding strength of "copper/carbon", which seriously affects the exertion of final mechanical properties of the composite fiber.
At present, the prior art can cause the elongation to be greatly reduced while improving the tensile strength of the composite fiber, and is not beneficial to the exertion of the comprehensive mechanical properties of the elongation, the rigidity and the tensile strength of the composite material.
Furthermore, in the prior art, a strong bonding interface is often constructed by adding a large amount of strong bonding intermediate phase and by using a carbon nanotube-strong bonding phase-copper sandwich structure, and the construction of the sandwich structure often hinders the transmission of electrons between a copper layer and carbon nanotube fibers, so that the electrical properties of the composite fibers are not favorably exerted; moreover, after the carbon nanotube/copper composite material is prepared, heat treatment is often required, the content of alloy elements in a strong bonding phase is high, and a large amount of alloy elements are inevitably diffused in the high-temperature heat treatment process, so that the promotion effect of the strong bonding phase on the mechanical property of the composite fiber is reduced, the alloying of a copper layer is caused, and the electrical property of the surface copper layer is finally reduced.
Disclosure of Invention
The invention mainly aims to provide a nickel-containing carbon nanotube/copper composite fiber and a preparation method thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a nickel-containing carbon nanotube/copper composite fiber, which comprises the following steps:
carrying out densification treatment on the original carbon nanotube fiber to obtain a densified carbon nanotube fiber and simultaneously form a sawtooth structure shape on the surface of the highly densified carbon nanotube fiber;
depositing nickel nanoparticles on the surface of the densified carbon nanotube fiber with the sawtooth structure; and the number of the first and second groups,
and continuously depositing a copper layer on the surface of the densified carbon nanotube fiber by adopting an electrochemical deposition technology to obtain the nickel-containing carbon nanotube/copper composite fiber.
In some embodiments, the preparation method specifically comprises:
(1) fully soaking original carbon nanotube fibers in chlorosulfonic acid, taking out the carbon nanotube fibers, and standing the carbon nanotube fibers in the air to enable chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid;
(2) soaking the carbon nanotube fiber obtained in the step (1) in chlorosulfonic acid again at a first speed to rapidly expand the carbon nanotube fiber, and continuously standing in the chlorosulfonic acid until the diameter and the volume of the carbon nanotube fiber are reduced;
(3) taking the carbon nano tube fiber obtained in the step (2) out of chlorosulfonic acid at a second speed, standing in air, and enabling the chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid, wherein the first speed is higher than the second speed;
(4) and (4) carrying out high-temperature annealing treatment on the carbon nanotube fiber obtained in the step (3) under a vacuum condition, and volatilizing and removing concentrated sulfuric acid to obtain the densified carbon nanotube fiber.
In some embodiments, the preparation method specifically comprises:
soaking the densified carbon nanotube fiber with the sawtooth structure in a nickel salt solution for more than 24 hours, placing the fiber in an environment with the temperature of 0-20 ℃, taking out the fiber, then performing pyrolysis at the temperature of 100-1000 ℃, then soaking the carbon nanotube fiber in hydrochloric acid for 10-60 min, and then drying the fiber, thereby depositing nickel nanoparticles on the surface of the densified carbon nanotube fiber with the sawtooth structure.
The embodiment of the invention also provides the nickel-containing carbon nanotube/copper composite fiber prepared by the method.
Compared with the prior art, the invention has the advantages that:
1) according to the invention, the nickel-containing carbon nanotube/copper composite fiber is prepared by utilizing the synergistic effect of the chlorosulfonic acid densification process and the nickel nanoparticles, the improvement of comprehensive mechanical properties such as elongation, modulus and tensile strength of the composite fiber can be realized, and the bonding strength of a composite interface can be improved; in addition, no new substance is introduced in the method, so that the purification of the carbon nanotube fiber is ensured, and the excellent performance of the carbon nanotube fiber is favorably exerted;
2) according to the invention, the nickel element is added in the preparation process, so that the good deposition of copper on the surface of the carbon nanotube fiber can be promoted, the bonding strength between C and Cu can be directly improved, the alloying of a copper layer in the heat treatment process can be effectively avoided, and the dual purposes of simultaneously improving the mechanical property and the electrical property are realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of a densification process for carbon nanotube fibers in accordance with an exemplary embodiment of the present invention;
FIG. 2a is a surface topography of a pristine carbon nanotube fiber prior to densification treatment in example 1 of the present invention;
FIG. 2b is a cross-sectional profile of the pristine carbon nanotube fibers prior to densification in example 1 of the present invention;
FIG. 2c is a graph of the surface topography of the densified carbon nanotube fiber after densification in example 1 of the present invention;
FIG. 2d is a cross-sectional profile of a densified carbon nanotube fiber after densification in example 1 of the present invention;
FIG. 3 is a graph showing the results of the densification treatment on the promotion of the mechanical properties of carbon nanotube fibers in example 1 of the present invention;
FIG. 4a is a structural morphology diagram of a composite interface of the original carbon nanotube fiber after copper plating in example 1 of the present invention;
FIG. 4b is a graph of the morphology of the copper-plated composite interface structure of the carbon nanotube fiber with a sawtooth structure formed after densification in example 1 of the present invention;
FIG. 4c is a graph showing the effect of copper plating on the bonding force of the composite interface of the original carbon nanotube fiber in example 1 of the present invention;
FIG. 4d is a graph showing the effect of copper plating on the bonding force of the composite interface of the carbon nanotube fibers with a sawtooth structure formed after densification in example 1 of the present invention;
FIG. 5a is a schematic diagram of the interface structure of the copper layer deposited on the surface of the carbon nanotube fiber without the nickel nanoparticles in example 1 of the present invention;
FIG. 5b is a schematic diagram of the interface structure of the copper layer deposited on the surface of the carbon nanotube fiber containing nickel nanoparticles in example 1;
FIG. 6a is a structural diagram of the synergistic effect of densification treatment and Ni nanoparticles on the tensile mechanical properties of carbon nanotube/Cu composite fiber in example 1 of the present invention;
FIG. 6b is a structural diagram illustrating the synergistic effect of densification treatment and Ni nanoparticles on the interfacial mechanical properties of the carbon nanotube/Cu composite fiber in example 1 of the present invention;
FIGS. 7a and 7b are fracture morphology graphs of the composite fiber after copper plating of the original carbon nanotube fiber in example 1 of the present invention;
FIGS. 7c and 7d are fracture morphology graphs of copper-plated composite fibers of sawtooth-structure carbon nanotube fibers formed after densification treatment in example 1 of the present invention;
FIGS. 7e and 7f are fracture morphology graphs of carbon nanotube/Cu composite fibers subjected to densification treatment and nickel nanoparticle synergistic effect in example 1 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, and mainly starts from enhancing the mechanical properties of the carbon nanotube fiber body material, and utilizes the synergistic effect of the densification process and the nickel nanoparticles to realize the improvement of the mechanical properties of carbon nanotube fibril; meanwhile, the design and preparation of the sawtooth structure appearance are realized on the surface of the densified carbon nanotube fiber, and a foundation is laid for improving the bonding strength of the carbon nanotube/copper composite interface. The technical solution, its implementation and principles, etc. will be further explained as follows.
An aspect of the embodiments of the present invention provides a method for preparing a nickel-containing carbon nanotube/copper composite fiber (also referred to as "a post-treatment method for improving mechanical properties of a carbon nanotube-copper composite fiber"), including:
carrying out densification treatment on the original carbon nanotube fiber to obtain a densified carbon nanotube fiber and simultaneously form a sawtooth structure shape on the surface of the highly densified carbon nanotube fiber;
depositing nickel nanoparticles on the surface of the densified carbon nanotube fiber with the sawtooth structure; and the number of the first and second groups,
and continuously depositing a copper layer on the surface of the densified carbon nanotube fiber by adopting an electrochemical deposition technology to obtain the nickel-containing carbon nanotube/copper composite fiber.
The reaction mechanism of the invention is as follows: the mechanical property of the carbon nanotube fiber is greatly improved by utilizing the densification process of the carbon nanotube fiber from the aspect of strengthening the mechanical property of the carbon nanotube fiber body material; meanwhile, the design and preparation of the sawtooth structure appearance are realized on the surface of the densified carbon nanotube fiber, and a foundation is laid for improving the bonding strength of the carbon nanotube/copper composite interface. Secondly, the method comprises the following steps: the preparation of nickel nano particles with the size of less than 5nm is carried out on the surface of the carbon nano tube fiber with the sawtooth structure, so that the quantity and the quality of copper nucleation in the electroplating process are improved. On the microscopic scale, the uniform and continuous deposition of copper on the surface of the carbon nanotube fiber with the sawtooth structure can be realized; on the nano scale, under the action of the nickel nanoparticles, the improvement of the bonding strength of C-Ni-Cu can be directly realized. The nickel nano particles on the surface of the carbon nano tube have smaller sizes, some nickel nano particles are even in an atomic order, and meanwhile, the Ni-C bonding strength is stronger than that of Ni-Cu, so that nickel atoms are mainly distributed on the surface of the carbon nano tube in the heat treatment process, the copper layer cannot be alloyed, and the maximum protection of the electrical property of the copper layer is finally realized.
Wherein, the mechanism of forming the sawtooth structure is as follows: after chlorosulfonic acid molecules act on the carbon nanotubes, the redistribution of charges on the surfaces of the carbon nanotubes can be caused, and then a strong electrostatic attraction effect is generated between the carbon nanotubes, under the electrostatic attraction effect, the diameter of carbon nanotube fibers can be obviously reduced, when the diameter of the fibers is reduced, the shrinkage degrees of the fibers are different due to different densities of the fibers in all radial directions, and then sawteeth can be generated in adjacent regions with different shrinkage degrees.
In some embodiments, the preparation method specifically comprises:
(1) fully soaking original carbon nanotube fibers in chlorosulfonic acid, taking out the carbon nanotube fibers, and standing the carbon nanotube fibers in the air to enable chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid;
(2) soaking the carbon nanotube fiber obtained in the step (1) in chlorosulfonic acid again at a first speed to rapidly expand the carbon nanotube fiber, and continuously standing in the chlorosulfonic acid until the diameter and the volume of the carbon nanotube fiber are reduced;
(3) taking the carbon nano tube fiber obtained in the step (2) out of chlorosulfonic acid at a second speed, standing in air, and enabling the chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid, wherein the first speed is higher than the second speed;
(4) and (4) carrying out high-temperature annealing treatment on the carbon nanotube fiber obtained in the step (3) under a vacuum condition, and volatilizing and removing concentrated sulfuric acid to obtain the densified carbon nanotube fiber.
In some embodiments, the pristine carbon nanotube fibers comprise carbon nanotube ribbons, carbon nanotube fibers, and the like.
In some embodiments, step (1) comprises: fully soaking the original carbon nanotube fibers in chlorosulfonic acid for 1-2 h, taking out the original carbon nanotube fibers, and standing the original carbon nanotube fibers in the air for 30-60 min to enable chlorosulfonic acid to fully react with water in the air to generate concentrated sulfuric acid. The method skillfully utilizes the inherent characteristics of chlorosulfonic acid: chlorosulfonic acid easily infiltrates the carbon nanotube fiber, but electrostatic repulsion force brought by chlorosulfonic acid molecules is not enough to cause the fiber to generate violent expansion; when the fiber is taken out of chlorosulfonic acid, chlorosulfonic acid reacts with moisture in the air to form concentrated sulfuric acid, the concentrated sulfuric acid has strong water absorption, so that a large amount of moisture is absorbed in the fiber, when the fiber with a large amount of moisture is placed in chlorosulfonic acid again, the moisture in the fiber can react with chlorosulfonic acid molecules violently to form hydrogen chloride gas, the strong air pressure causes the fiber to expand instantly, and the expanded carbon nanotube fiber can contract slowly under the electrostatic repulsion action of the chlorosulfonic acid molecules to achieve the purpose of plastic deformation and roundness, but the contraction amount is small, and further densification needs vacuum annealing treatment.
In some embodiments, step (2) comprises: and (2) soaking the carbon nanotube fiber obtained in the step (1) in chlorosulfonic acid again at a first speed within 3-5 seconds (namely, at a faster speed), so that the volume of the carbon nanotube fiber is rapidly expanded to 10-30 times within 1 second, and the carbon nanotube fiber is cylindrical in appearance. The densification of the carbon nanotube fiber is based on the electrostatic interaction between the carbon nanotube monomers, the cylindrical shape of the fiber can promote more carbon nanotube monomers or the mutual attraction of more carbon nanotube bundles in a three-dimensional space, so that the tight connection between the carbon nanotubes is realized, and finally the densification of the carbon nanotube fiber is realized through electrostatic acting force. The rapid speed is adopted in the step, so that the violent reaction of water molecules and chlorosulfonic acid is needed, and if the putting speed is slow, the pressure of hydrogen chloride generated by the reaction of the water molecules and the chlorosulfonic acid is not enough to cause the violent expansion of the fibers, so that the purpose of fiber expansion cannot be achieved, and the putting speed must be fast enough.
In some embodiments, step (2) comprises: and standing the expanded carbon nanotube fiber in chlorosulfonic acid for 3-6 h until the diameter and the volume of the carbon nanotube fiber are reduced to 20-30% of the expanded volume, wherein the volume reduction is derived from the inherent van der Waals force of the carbon nanotube, and macromolecules tend to attract each other.
In some embodiments, step (3) comprises: and (3) slowly taking out the carbon nano tube fiber obtained in the step (2) from chlorosulfonic acid at a second speed (namely a slower speed), keeping the taking-out process for more than 15 minutes, and standing in the air for 30-60 min to enable chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid. At this time, the carbon nanotube fibers are quite fluffy, the mechanical properties of the fluffy fibers are extremely reduced, and if the carbon nanotube fibers are taken out at an excessively high speed, the carbon nanotube fibers are broken.
In some embodiments, step (4) comprises: keeping the carbon nano tube fiber obtained in the step (3) in a tensioned state, and then carrying out high-temperature annealing treatment in a vacuum tube furnace, wherein the temperature of the high-temperature annealing treatment is 150-350 ℃, and the vacuum degree is 1-4 multiplied by 10-4Pa, and the time of high-temperature annealing treatment is 15-25 h.
Specifically, the invention applies the slow volatilization process of chlorosulfonic acid and sulfuric acid under the vacuum condition, and the vacuum degree is 1-4 multiplied by 10-4Pa, and the evaporation temperature is between 150 and 350 ℃.
The densification treatment step of the invention is based on the action mechanism of chlorosulfonic acid on the carbon nano tube, and through the development of a new process, the carbon nano tube fiber is sequentially soaked, expanded and stood in chlorosulfonic acid, thereby finally realizing the change of the appearance of the carbon nano tube fiber and greatly improving the densification degree of the carbon nano tube fiber.
The invention is applied to the long-time protonation and short-time expansion treatment of the carbon nano tube fiber in chlorosulfonic acid; the appearance change and densification of the carbon nano tube fiber are realized by integrating the reaction of chlorosulfonic acid and the carbon nano tube fiber, the reaction of chlorosulfonic acid and moisture in the air and the slow shrinkage behavior of the carbon nano tube fiber in chlorosulfonic acid.
In some embodiments, the preparation method specifically comprises:
the densified carbon nanotube fiber with the sawtooth structure is soaked in a nickel salt solution for more than 24 hours, is placed in an environment with the temperature of 0-20 ℃, is taken out and is then decomposed at the high temperature of 100-1000 ℃ (after the high temperature decomposition, nickel atoms can be decomposed by nickel salt, and then the plating of the nickel atoms on the surface of the carbon nanotube is realized; the decomposition temperature of the nickel salt is controlled at 100-1000 ℃), and then the carbon nanotube fiber is soaked in hydrochloric acid for 10-60 min and is dried, so that nickel nanoparticles are formed on the surface of the densified carbon nanotube fiber with the sawtooth structure by deposition.
In the aspect of adding the metal with strong binding force, the addition amount of the nickel element is small, so that the good deposition of copper on the surface of the carbon nano tube fiber can be promoted, the bonding strength between C and Cu can be directly improved, the alloying of a copper layer in the heat treatment process can be effectively avoided, and the double purposes of simultaneously improving the mechanical property and the electrical property are realized.
Further, the particle size of the nickel nanoparticles is 5nm or less.
Further, the concentration of the nickel salt solution is 0.05mol/L or more, preferably 0.05mol/L to a saturated concentration.
Further, the nickel salt solution may be a nickel acetate ethanol solution, but is not limited thereto.
In some embodiments, the preparation method specifically comprises:
providing a copper protectant solution;
and (3) electroplating the surface of the densified carbon nanotube fiber to form a copper layer by adopting an electrochemical deposition technology, taking out the copper layer from the electroplating solution, and putting the copper layer into a copper protective agent solution to fully soak for 5-30 seconds (ensuring complete soaking) to obtain the nickel-containing carbon nanotube/copper composite fiber.
Further, the process conditions of the electrochemical deposition technique include: the output current is 0.001A-0.01A, the electroplating time is 10 s-100 s, and the electroplating temperature is 5-35 ℃.
In another aspect of the embodiments of the present invention, there is also provided a nickel-containing carbon nanotube/copper composite fiber prepared by the foregoing preparation method.
Furthermore, the content of nickel element in the nickel-containing carbon nanotube/copper composite fiber is below 0.01 wt%.
Furthermore, the thickness of the copper layer on the surface of the nickel-containing carbon nanotube/copper composite fiber is 1-10 μm.
Furthermore, compared with the original carbon nanotube fiber, the elongation of the nickel-containing carbon nanotube/copper composite fiber is improved by 20-50%.
Further, the rigidity of the nickel-containing carbon nanotube/copper composite fiber is about 600MPa to 1500 MPa.
Furthermore, the tensile strength of the nickel-containing carbon nanotube/copper composite fiber is 1 GPa-4 GPa, and the final value reaches about 4 GPa.
Furthermore, the interface strength of the nickel-containing carbon nanotube/copper composite fiber is 15MPa to 25 MPa.
In conclusion, the invention utilizes the synergistic effect of the chlorosulfonic acid densification process and the nickel nanoparticles to realize the improvement of the original fiber mechanical property of the carbon nano tube, simultaneously realizes the construction of a sawtooth structure on the surface of the carbon nano tube fiber through the densification process, and realizes the uniform and continuous coverage of the copper layer on the surface of the carbon nano tube fiber by the aid of the promotion effect of the nickel nanoparticles on copper deposition; finally, based on the construction of the sawtooth composite interface structure, the tight occlusion of the metal copper layer and the carbon nano tube fiber is realized, and the bonding strength of the composite interface is further improved.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Example 1
Referring to fig. 1, the specific steps of the method for preparing a composite fiber containing nickel-carbon nanotubes/copper of this embodiment are as follows:
(1) densification treatment of carbon nano tube fiber and preparation of sawtooth surface morphology
Slowly putting carbon nanotube fibers with the length of 35-45 cm into a measuring cylinder filled with chlorosulfonic acid, and standing for about 1-2 hours to enable the chlorosulfonic acid to fully infiltrate the carbon nanotube fibers; then taking out the carbon nano tube fiber from chlorosulfonic acid, and standing in the air for about 30-60 min to ensure that chlorosulfonic acid in the carbon nano tube fiber and moisture in the air are subjected to full reaction to generate concentrated sulfuric acid; then, the carbon nano tube fiber is put into chlorosulfonic acid again at a fast speed (the fiber is completely put into chlorosulfonic acid solution in 3-5 seconds as much as possible to ensure that enough hydrogen chloride gas pressure is generated by reaction) within 3-5 seconds, so that the fiber is obviously expanded (the volume is expanded to 10-30 times of the original volume) in a short time, and the appearance of the fiber is changed into an obvious cylindrical shape; keeping the carbon nano tube fiber standing in chlorosulfonic acid for about 3-6 hours until the volume of the fiber is obviously reduced, as shown in figure 1; and slowly taking out the carbon nano tube fiber from chlorosulfonic acid, standing in the air for 30-60 min until the carbon nano tube fiber reacts with moisture in the air, wherein the duration of the whole taking-out process is not less than 15 minutes. Fixing the treated carbon nanotube fiber on a quartz frame, keeping the carbon nanotube fiber in a tightened state in the process, and then placing the quartz frame in a vacuum tube furnace for high-temperature vacuum treatment; the treatment temperature is 150-350 ℃, and the vacuum degree is 1-4 multiplied by 10-4Pa, and the treatment time is about 15-25 h. Finally realizing the densification of the carbon nano tube fiber and the preparation of the sawtooth interface of the carbon nano tube fiber.
(2) Preparation of nickel nanoparticles on surface of carbon nanotube fiber
Preparing 0.05 mol/L-saturated nickel acetate ethanol solution, magnetically stirring for about 4 hours, then placing the densified carbon nano tube fiber in the nickel acetate ethanol solution for soaking, placing the carbon nano tube fiber in a cold storage chamber of a refrigerator, controlling the soaking time to be more than 24 hours, then taking out the carbon nano tube fiber for pyrolysis at 100-1000 ℃, placing the carbon nano tube fiber in hydrochloric acid for soaking for 10-60 min after the pyrolysis, and then drying. Finally, the preparation of the nickel nano-particles with the particle size of less than 5nm is realized on the surface of the carbon nano-tube fiber with the sawtooth structure.
(3) Electroplating of carbon nanotube fibers
And (3) fixing the carbon nanotube fibers prepared in the step (2) on a copper bracket, and sealing the bracket loaded with the carbon nanotube fibers by using a resin glue gun to ensure the insulativity of the bracket part. Adjusting the output current of the electrochemical workstation to 0.001-0.01A, controlling the electroplating time to 10-100 s, preparing a copper protective agent solution with the concentration of 15-25 ml/L, and adjusting the indoor temperature to 5-35 ℃. And then electroplating the carbon nanotube fiber, quickly taking out the fiber from the copper solution after the electroplating is finished, putting the fiber in a protective agent for full soaking, and then taking out and storing the fiber.
The inventor of the present application performed structural characterization and performance tests on the finally obtained nickel-containing carbon nanotube/copper composite fiber in terms of microstructure, specifically as follows:
(1) promotion of mechanical property of carbon nanotube fiber body by densification process
As shown in fig. 2a and 2b, the surface of the raw carbon nanotube fiber is smooth, has a large size, and has a narrow band shape. After densification, the size of the carbon nanotube fiber is significantly reduced, and more wrinkles are formed on the surface of the carbon nanotube, as shown in fig. 2 c; in its cross-sectional view, the folds of the carbon nanotube fiber surface can be observed to exhibit a saw-tooth topography, as shown in fig. 2 d. Therefore, the cross-sectional area of the carbon nanotube fiber is obviously reduced after densification treatment, and the fluffy air hole structure in the carbon nanotube fiber is well eliminated.
Fig. 3 shows the change of mechanical properties of the carbon nanotube fiber before and after densification treatment, in fig. 3, the lower line shows the tensile properties of the raw carbon nanotube fiber, and the upper line shows the tensile properties of the densified fiber. Tensile data show that after densification treatment, the tensile strength, elongation and rigidity of the carbon nanotube fiber are obviously improved, namely the densification treatment has a promoting effect on the mechanical property of the carbon nanotube fiber; wherein, the elongation is improved to 20-50 percent of the original elongation, the rigidity is improved to about 210 percent of the original rigidity, the tensile strength is improved to about 400 percent of the original tensile strength, and the final value reaches about 4 GPa.
(2) Influence of sawtooth structure of carbon nanotube fiber on 'carbon nanotube/copper' composite interface
Fig. 4 a-4 d show two composite interface structure characteristics of the original carbon nanotube fiber after copper plating and the sawtooth interface carbon nanotube fiber after copper plating, so as to demonstrate the influence of the sawtooth structure formed by densification on the composite interface bonding force. The results show that the interface of the bonding interface between the original carbon nanotube fiber and the copper layer is relatively straight and the microstructure inside the fiber is fluffy, as shown in fig. 4a and 4c, which is not beneficial to improving the bonding force of the composite interface; and the composite interface formed by the sawtooth interface carbon nanotube fiber and the copper layer has obvious occlusion characteristics, as shown in fig. 4b and 4d, which is beneficial to improving the composite strength of the composite interface.
(3) Effect of nanoparticles on copper layer deposition on carbon nanotube fiber surface
5 a-5 b show the effect of nickel nanoparticles on the microstructure of the composite interface, when there are no nickel nanoparticles on the surface of the carbon nanotube fiber, there are more voids at the junction of the copper layer and the surface of the carbon nanotube fiber, as shown in FIG. 5a, indicating that the bonding strength of the copper layer and the carbon nanotube is weak; when the surface of the carbon nanotube fiber is plated with the nickel nanoparticles, no voids are observed at the junctions of the copper and carbon surfaces, as shown in fig. 5b, indicating that the bonding force between the copper layer and the surface of the carbon nanotube fiber is significantly improved by the nickel nanoparticles.
Fig. 6 a-6 b show the tensile mechanical and interfacial mechanical characteristics of the composite fiber under three conditions. The results show that, compared with the original copper plating of the carbon nanotube fiber, the tensile mechanical properties of the composite fiber of the copper plating of the densified carbon nanotube fiber and the copper plating of the densified nickel nanoparticle carbon nanotube fiber are both obviously improved, and the modulus, the elongation and the tensile strength of the latter two are obviously superior to those of the fibril copper-plated composite fiber, as shown in fig. 6 a. Meanwhile, the interface mechanics of the composite fiber is also tested and analyzed, and the result shows that the simple densification of the carbon nanotube fiber does not promote the interface mechanics of the composite fiber, but the densified nickel nanoparticle-doped carbon nanotube composite fiber has an obvious positive effect on the strength improvement of the carbon nanotube/copper composite interface, as shown in fig. 6 b. In conclusion, research results show that under the synergistic effect of densification treatment and nickel nanoparticles, the mechanical property of the composite fiber is promoted, and the tensile mechanical property and the interface mechanical property of the composite fiber are obviously improved.
7 a-7 f show fracture morphology diagrams of composite fibers under three conditions, wherein the copper-plated fracture microstructure of the original carbon nanotube fiber is loose, more carbon nanotube filaments exist, the filaments show a certain springback morphology, and the drawn carbon nanotube filaments are less in number and different in length, as shown in FIG. 7a and FIG. 7 b; the number of carbon nanotube filaments at the fracture of the copper-plated composite fiber of the densified carbon nanotube fiber is obviously reduced, the rebound morphology of the filaments is obviously weakened, and the morphology of the overall fracture of the carbon nanotube fiber bundle at the fracture can be observed, as shown in fig. 7c and 7 d. The copper plated composite fiber fracture was flat after densification of the nickel added nanoparticles and the presence of carbon nanotube filaments was hardly observed, as shown in fig. 7e and 7 f.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. A method for preparing nickel-containing carbon nanotube/copper composite fiber is characterized by comprising the following steps:
carrying out densification treatment on the original carbon nanotube fiber to obtain a densified carbon nanotube fiber and simultaneously form a sawtooth structure shape on the surface of the highly densified carbon nanotube fiber;
depositing nickel nanoparticles on the surface of the densified carbon nanotube fiber with the sawtooth structure; and the number of the first and second groups,
and continuously depositing a copper layer on the surface of the densified carbon nanotube fiber by adopting an electrochemical deposition technology to obtain the nickel-containing carbon nanotube/copper composite fiber.
2. The preparation method according to claim 1, which specifically comprises:
(1) fully soaking original carbon nanotube fibers in chlorosulfonic acid, taking out the carbon nanotube fibers, and standing the carbon nanotube fibers in the air to enable chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid;
(2) soaking the carbon nanotube fiber obtained in the step (1) in chlorosulfonic acid again at a first speed to rapidly expand the carbon nanotube fiber, and continuously standing in the chlorosulfonic acid until the diameter and the volume of the carbon nanotube fiber are reduced;
(3) taking the carbon nano tube fiber obtained in the step (2) out of chlorosulfonic acid at a second speed, standing in air, and enabling the chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid, wherein the first speed is higher than the second speed;
(4) and (4) carrying out high-temperature annealing treatment on the carbon nanotube fiber obtained in the step (3) under a vacuum condition, and volatilizing and removing concentrated sulfuric acid to obtain the densified carbon nanotube fiber.
3. The method of claim 2, wherein: the original carbon nanotube fiber comprises a carbon nanotube narrow band or a carbon nanotube fiber;
and/or, step (1) comprises: fully soaking the original carbon nanotube fibers in chlorosulfonic acid for 1-2 h, taking out the original carbon nanotube fibers, and standing the original carbon nanotube fibers in the air for 30-60 min to enable chlorosulfonic acid to fully react with water in the air to generate concentrated sulfuric acid.
4. The method according to claim 2, wherein the step (2) comprises: and (2) soaking the carbon nanotube fiber obtained in the step (1) in chlorosulfonic acid again within 3-5 seconds at a first speed, so that the volume of the carbon nanotube fiber is rapidly expanded to 10-30 times within 1 second, and the carbon nanotube fiber is cylindrical in appearance.
5. The method according to claim 2, wherein the step (2) comprises: and standing the expanded carbon nanotube fiber in chlorosulfonic acid for 3-6 h until the diameter and the volume of the carbon nanotube fiber are reduced.
6. The method according to claim 2, wherein the step (3) comprises: and (3) slowly taking the carbon nano tube fiber obtained in the step (2) out of chlorosulfonic acid at a second speed, keeping the taking-out process for more than 15 minutes, and standing in the air for 30-60 minutes to enable chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid.
7. The method according to claim 2, wherein the step (4) comprises: keeping the carbon nano tube fiber obtained in the step (3) in a tensioned state, and then carrying out high-temperature annealing treatment in a vacuum tube furnace, wherein the temperature of the high-temperature annealing treatment is 150-350 ℃, and the vacuum degree is 1-4 multiplied by 10-4Pa, and the time of high-temperature annealing treatment is 15-25 h.
8. The preparation method according to claim 1, which specifically comprises:
immersing the densified carbon nanotube fiber with the sawtooth structure in a nickel salt solution for more than 24 hours, placing the fiber in an environment with the temperature of 0-20 ℃, taking out the fiber, then performing pyrolysis at the temperature of 100-1000 ℃, immersing the carbon nanotube fiber in hydrochloric acid for 10-60 min, and then drying the carbon nanotube fiber, thereby depositing nickel nanoparticles on the surface of the densified carbon nanotube fiber with the sawtooth structure;
preferably, the particle size of the nickel nanoparticles is below 5 nm;
preferably, the concentration of the nickel salt solution is more than 0.05mol/L, and preferably 0.05mol/L to the saturated concentration;
preferably, the nickel salt solution comprises a nickel acetate ethanol solution.
9. The preparation method according to claim 1, which specifically comprises:
providing a copper protectant solution;
adopting an electrochemical deposition technology to electroplate the surface of the densified carbon nanotube fiber to form a copper layer, taking out the copper layer from the electroplating solution, and placing the copper layer in a copper protective agent solution to fully soak for 5-30 seconds to obtain the nickel-containing carbon nanotube/copper composite fiber;
preferably, the process conditions of the electrochemical deposition technique include: the output current is 0.001A-0.01A, the electroplating time is 10 s-100 s, and the electroplating temperature is 5-35 ℃.
10. The nickel-containing carbon nanotube/copper composite fiber prepared by the preparation method according to any one of claims 1 to 9, wherein the nickel content in the nickel-containing carbon nanotube/copper composite fiber is preferably less than 0.01 wt%, and the thickness of the copper layer on the surface of the nickel-containing carbon nanotube/copper composite fiber is preferably 1 μm to 10 μm;
preferably, compared with the original carbon nanotube fiber, the elongation of the nickel-containing carbon nanotube/copper composite fiber is improved by 20-50%;
preferably, the rigidity of the nickel-containing carbon nanotube/copper composite fiber is 600MPa to 1500 MPa;
preferably, the tensile strength of the nickel-containing carbon nanotube/copper composite fiber is 1 GPa-4 GPa;
preferably, the nickel-containing carbon nanotube/copper composite fiber has an interfacial strength of 15 to 25 MPa.
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