CN114481606B - Nickel-containing carbon nano tube/copper composite fiber and preparation method thereof - Google Patents

Nickel-containing carbon nano tube/copper composite fiber and preparation method thereof Download PDF

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CN114481606B
CN114481606B CN202210197278.7A CN202210197278A CN114481606B CN 114481606 B CN114481606 B CN 114481606B CN 202210197278 A CN202210197278 A CN 202210197278A CN 114481606 B CN114481606 B CN 114481606B
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fiber
nano tube
carbon nano
nickel
carbon nanotube
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CN114481606A (en
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李会芳
金赫华
郭蕾
勇振中
刘丹丹
李清文
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/265—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur containing halogen atoms
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract

The invention discloses a nickel-containing carbon nano tube/copper composite fiber and a preparation method thereof. The preparation method comprises the following steps: densification treatment is carried out on the original carbon nano tube fiber, and a saw-tooth structure morphology is formed on the surface of the high-densification carbon nano tube fiber while the densified carbon nano tube fiber is obtained; depositing nickel nano particles on the surface of the densified carbon nano tube fiber with the sawtooth structure; and continuing 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 nickel-containing carbon nano tube/copper composite fiber is prepared by utilizing the synergistic effect of the densification process and the nickel nano particles, so that the comprehensive mechanical properties such as the elongation rate, the modulus and the tensile strength of the composite fiber can be improved, and the bonding strength of a composite interface can be improved; and no new substance is introduced, so that the purification of the carbon nano tube fiber is ensured, and the excellent performance of the carbon nano tube fiber is brought into play.

Description

Nickel-containing carbon nano tube/copper composite fiber and preparation method thereof
Technical Field
The invention relates to a nickel-containing carbon nano tube/copper composite fiber and a preparation method thereof, belonging to the technical field of carbon nano tube post-treatment.
Background
In the current society, electronic and electric devices are applied to various aspects of society, copper is used for its relatively low price and excellent conductive properties (5.8X105S cm -1 25 ℃ is an indispensable wire material in electronic equipment; copper also has good processability and corrosion resistance. However, copper wires have a low tensile strength, which is between 350 and 470MPa when copper is in a hard state, and a high copper density (8.9 g cm -3 ) This will cause the copper wire to deform continuously under the action of gravity during actual service, resulting in copperFailure of the wire breaks.
Carbon nanotube as one new kind of conducting material with density of 1g cm -3 About, the theoretical strength of the monomer can reach 50-200 GPa, and the mechanical property of the monomer is far higher than that of a copper wire. Meanwhile, the P orbit electron of the carbon atoms composing the carbon nano tube can form delocalized pi bond in a large range, the special conjugated effect of the electron structure endows the carbon nano tube with unique electrical property, and the unique length-diameter ratio of the carbon nano tube monomer ensures that the carbon nano tube has extremely large electron mean free path. Researches show that the average electron free path of the carbon nano tube can exceed 30 mu m (copper is 40 nm), and the extremely large 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 an order of magnitude higher than that of copper. Meanwhile, the carbon nano tube has the excellent characteristics of low density, good chemical stability, high thermal conductivity, high mechanical strength and the like, so the carbon nano tube is one of candidates of a new generation of high-strength high-conductivity materials.
However, the macroscopic bodies in various forms of the carbon nanotubes are difficult to overcome the influence of a series of factors such as structural defects (such as more gaps exist in the macroscopic body, less contact areas among the carbon nanotubes and poorer orientation of the carbon nanotubes) and the like in the preparation process, so that the actual electrical performance of the macroscopic body of the carbon nanotubes is far less than the theoretical performance; meanwhile, the grown carbon nano tube fiber tends to have loose microstructure and low mechanical property. The conductivity of the carbon nano tube fiber prepared by the current floating catalysis method is generally lower than that of copper by two orders of magnitude, and the conductivity level is lower; the mechanical property of the material is often about 1GPa, and the material has a larger gap relative to a theoretical value. In order to solve the problem of low conductivity of the carbon nanotube fiber, the carbon nanotube and copper are often compounded, and the composite fiber with high strength and high conductivity is obtained through the exertion of the respective advantages of the carbon nanotube and the copper. However, due to the atomic structural characteristics of the copper atoms and the carbon nanotubes, the combination of the copper atoms and the carbon nanotubes is at the level of Van der Waals force, so that the interface bonding strength of copper/carbon is low, and the final mechanical properties of the composite fiber are seriously affected.
At present, the prior art can greatly reduce the elongation rate while improving the tensile strength of the composite fiber, and is not beneficial to the exertion of the comprehensive mechanical properties of the elongation rate, the rigidity and the tensile strength of the composite material.
In addition, in the prior art, a large amount of strong bonding intermediate phases are often added, and a strong bonding interface is constructed through a carbon nano tube-strong bonding phase-copper sandwich structure, so that the construction of the sandwich structure often prevents the transmission of electrons between a copper layer and carbon nano tube fibers, thereby being not beneficial to the exertion of the electrical properties of the composite fibers; in addition, after the carbon nano tube/copper composite material is prepared, heat treatment is often needed, 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 properties of the composite fiber is reduced, the alloying of a copper layer is caused, and finally, the electrical properties of the surface copper layer are reduced.
Disclosure of Invention
The invention mainly aims to provide a nickel-containing carbon nano tube/copper composite fiber and a preparation method thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of nickel-containing carbon nano tube/copper composite fiber, which comprises the following steps:
densification treatment is carried out on the original carbon nano tube fiber, and a saw-tooth structure morphology is formed on the surface of the high-densification carbon nano tube fiber while the densified carbon nano tube fiber is obtained;
depositing nickel nano particles on the surface of the densified carbon nano tube fiber with the sawtooth structure; the method comprises the steps of,
and continuing 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 includes:
(1) Fully soaking the original carbon nano tube fibers in chlorosulfonic acid, taking out, and standing in the air to enable chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid;
(2) Soaking the carbon nano tube fiber obtained in the step (1) in chlorosulfonic acid again at a first rate to enable the carbon nano tube fiber to rapidly expand, and continuing to stand in chlorosulfonic acid until the diameter and volume of the carbon nano tube fiber are reduced;
(3) Taking the carbon nano tube fiber obtained in the step (2) out of chlorosulfonic acid at a second rate, standing in air, and enabling chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid, wherein the first rate is greater than the second rate;
(4) And (3) carrying out high-temperature annealing treatment on the carbon nano tube fiber obtained in the step (3) under the vacuum condition, and volatilizing concentrated sulfuric acid to obtain the densified carbon nano tube fiber.
In some embodiments, the preparation method specifically includes:
immersing the densified carbon nanotube fiber with the sawtooth structure in nickel salt solution for more than 24 hours, placing the densified carbon nanotube fiber in an environment with the temperature of 0-20 ℃, taking out the densified carbon nanotube fiber, then performing pyrolysis at the temperature of 100-1000 ℃, immersing the carbon nanotube fiber in hydrochloric acid for 10-60 minutes, and then drying the carbon nanotube 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 nano tube/copper composite fiber prepared by the method.
Compared with the prior art, the invention has the advantages that:
1) The nickel-containing carbon nano tube/copper composite fiber is prepared by utilizing the synergistic effect of the chlorosulfonic acid densification process and the nickel nano particles, so that the comprehensive mechanical properties such as the elongation rate, the modulus and the tensile strength of the composite fiber can be improved, and the bonding strength of a composite interface can be improved; in addition, no new substance is introduced into the invention, thereby ensuring the purification of the carbon nano tube fiber and being beneficial to the exertion of the excellent performance of the carbon nano tube fiber;
2) The nickel element is added in the preparation process, 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, meanwhile, alloying of a copper layer in the heat treatment process can be effectively avoided, and the dual purposes of improving the mechanical property and the electrical property at the same time are realized.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a process for densifying carbon nanotube fibers in an exemplary embodiment of the present invention;
FIG. 2a is a surface topography of the pristine carbon nanotube fibers prior to densification in accordance with example 1 of the present invention;
FIG. 2b is a cross-sectional morphology of the pristine carbon nanotube fibers prior to densification in accordance with example 1 of the present invention;
FIG. 2c is a surface topography of the densified carbon nanotube fiber after densification in accordance with example 1 of the present invention;
FIG. 2d is a cross-sectional morphology of the densified carbon nanotube fiber after densification in accordance with example 1 of the present invention;
FIG. 3 is a graph showing the results of densification treatment in example 1 of the present invention to enhance the mechanical properties of carbon nanotube fibers;
FIG. 4a is a morphology diagram of the composite interface structure of the original carbon nanotube fiber copper plated in example 1 of the present invention;
FIG. 4b is a morphology diagram of the composite interface structure of the carbon nanotube fiber with saw tooth structure formed after densification treatment in example 1 of the present invention after copper plating;
FIG. 4c is a graph showing the effect of copper plating of the pristine carbon nanotube fibers on the bonding force of the composite interface in example 1 of the present invention;
FIG. 4d is a graph showing the effect of copper plating on the composite interfacial bonding force of the carbon nanotube fiber with a sawtooth structure formed after densification treatment in example 1 of the present invention;
FIG. 5a is a morphology diagram of an interface structure of a deposited copper layer on the surface of a carbon nanotube fiber without nickel nanoparticles according to example 1 of the present invention;
FIG. 5b is a morphology diagram of an interfacial structure of a deposited copper layer on the surface of a carbon nanotube fiber containing nickel nanoparticles according to example 1 of the present invention;
FIG. 6a is a diagram showing the promotion of tensile mechanical properties of a carbon nanotube/Cu composite fiber by densification and nickel nanoparticle synergy in example 1 of the present invention;
FIG. 6b is a diagram showing the structure of the interfacial mechanical properties of the carbon nanotube/Cu composite fiber promoted by the synergistic effect of densification and nickel nanoparticles in example 1 of the present invention;
FIGS. 7a and 7b are graphs showing fracture morphology of the composite fiber after copper plating of the pristine carbon nanotube fiber in example 1 of the present invention;
FIGS. 7c and 7d are graphs showing the fracture morphology of the composite fiber after copper plating of the carbon nanotube fiber with saw tooth structure formed after densification treatment in example 1 of the present invention;
fig. 7e and 7f are fracture morphology diagrams of the carbon nanotube/Cu composite fiber subjected to densification treatment and nickel nanoparticle synergy in example 1 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor can put forward the technical scheme of the invention through long-term research and a large number of practices, mainly from strengthening the mechanical properties of the carbon nanotube fiber body material, and by utilizing the synergistic effect of the densification process and the nickel nano particles, the improvement of the mechanical properties of the carbon nanotube fibril is realized; meanwhile, the design and preparation of the sawtooth structure morphology are realized on the surface of the densified carbon nano tube fiber, and a foundation is laid for improving the bonding strength of a carbon nano tube/copper composite interface. The technical scheme, the implementation process, the principle and the like are further explained as follows.
One aspect of the embodiment of the invention provides a preparation method of 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"), which comprises the following steps:
densification treatment is carried out on the original carbon nano tube fiber, and a saw-tooth structure morphology is formed on the surface of the high-densification carbon nano tube fiber while the densified carbon nano tube fiber is obtained;
depositing nickel nano particles on the surface of the densified carbon nano tube fiber with the sawtooth structure; the method comprises the steps of,
and continuing 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 invention starts from strengthening the mechanical property of the carbon nano tube fiber body material, and greatly improves the mechanical property of the carbon nano tube fiber by utilizing the densification process of the carbon nano tube fiber; meanwhile, the design and preparation of the sawtooth structure morphology are realized on the surface of the densified carbon nano tube fiber, and a foundation is laid for improving the bonding strength of a carbon nano tube/copper composite interface. Secondly: the preparation of nickel nano particles below 5nm is carried out on the surface of the carbon nano tube fiber with the sawtooth structure, so that the quantity and 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 nano tube fiber with the sawtooth structure can be realized; on the nano-scale, under the action of the nickel nano-particles, 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 size, some are even in atomic level, and the bonding strength of Ni-C 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, alloying of a copper layer is avoided, and the maximum protection of the electrical property of the copper layer is finally realized.
The mechanism of forming the sawtooth structure is as follows: after chlorosulfonic acid molecules act on the carbon nanotubes, the redistribution of the surface charges of the carbon nanotubes can be caused, so that a strong electrostatic attraction effect is generated between the carbon nanotubes, the diameter of the carbon nanotube fibers can be obviously reduced under the electrostatic attraction effect, and when the diameter of the fibers is reduced, the shrinkage degree of the fibers is different due to different densities of the fibers in each radial direction, and then saw teeth can be generated in adjacent areas with different shrinkage degrees.
In some embodiments, the preparation method specifically includes:
(1) Fully soaking the original carbon nano tube fibers in chlorosulfonic acid, taking out, and standing in the air to enable chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid;
(2) Soaking the carbon nano tube fiber obtained in the step (1) in chlorosulfonic acid again at a first rate to enable the carbon nano tube fiber to rapidly expand, and continuing to stand in chlorosulfonic acid until the diameter and volume of the carbon nano tube fiber are reduced;
(3) Taking the carbon nano tube fiber obtained in the step (2) out of chlorosulfonic acid at a second rate, standing in air, and enabling chlorosulfonic acid to fully react with moisture in the air to generate concentrated sulfuric acid, wherein the first rate is greater than the second rate;
(4) And (3) carrying out high-temperature annealing treatment on the carbon nano tube fiber obtained in the step (3) under the vacuum condition, and volatilizing concentrated sulfuric acid to obtain the densified carbon nano tube fiber.
In some embodiments, the pristine carbon nanotube fibers include carbon nanotube narrow bands, carbon nanotube fibers, and the like.
In some embodiments, step (1) comprises: fully soaking the original carbon nano tube fibers in chlorosulfonic acid for 1-2 h, taking out, and standing in the air for 30-60 min to fully react the chlorosulfonic acid with water in the air to generate concentrated sulfuric acid. The step of the invention skillfully uses the inherent characteristics of chlorosulfonic acid: chlorosulfonic acid is easy to infiltrate the carbon nanotube fibers, but electrostatic repulsive force caused by chlorosulfonic acid molecules is insufficient to cause the fibers to severely expand; when the fiber is taken out from 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 the fiber is absorbed with a large amount of moisture, when the fiber with a large amount of moisture is put into the chlorosulfonic acid again, the moisture in the fiber can react with chlorosulfonic acid molecules to form hydrogen chloride gas, strong air pressure causes the fiber to expand instantly, and the carbon nanotube fiber after expansion slowly contracts under the action of electrostatic repulsion of the chlorosulfonic acid molecules, so that the purpose of plastic rounding is achieved, but the contraction amount is smaller, and further densification also needs vacuum annealing treatment.
In some embodiments, step (2) comprises: and (3) soaking the carbon nano tube 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 nano tube fiber rapidly expands to 10-30 times within 1 second, and the appearance of the carbon nano tube fiber is in a cylindrical shape. Densification of the carbon nanotube fiber is based on electrostatic interaction between carbon nanotube monomers, and the cylindrical shape of the fiber can promote mutual attraction of more carbon nanotube monomers or more carbon nanotube bundles in a three-dimensional space, so that tight connection between the carbon nanotubes is realized, and finally densification of the carbon nanotube fiber is realized through electrostatic acting force. The rapid rate is adopted before the step, so that the violent reaction of water molecules and chlorosulfonic acid needs to be utilized, if the placing speed is low, the hydrogen chloride pressure generated by the reaction of the water molecules and the chlorosulfonic acid is insufficient to cause the fiber to be violently expanded, and the purpose of fiber expansion is not achieved, so that the placing speed is required to be high enough.
In some embodiments, step (2) comprises: and standing the expanded carbon nanotube fiber in chlorosulfonic acid for 3-6 hours until the diameter and volume of the carbon nanotube fiber are reduced to 20% -30% of the expansion volume, wherein the volume reduction is derived from inherent Van der Waals force of the carbon nanotube, and macromolecules tend to attract each other.
In some embodiments, step (3) comprises: slowly taking the carbon nano tube fiber obtained in the step (2) out of chlorosulfonic acid at a second rate (namely a slower rate), standing in the air for 30-60 min for a long time more than 15 min, and fully reacting the chlorosulfonic acid with water in the air to generate concentrated sulfuric acid. In this step, the carbon nanotube fiber is quite fluffy, the mechanical properties of the fluffy fiber are extremely reduced, and if the carbon nanotube fiber is taken out at an excessively high speed, the carbon nanotube fiber is broken.
In some embodiments, step (4) comprises: making the carbon nano tube fiber obtained in the step (3)Maintaining the tension 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 -4 Pa, and the time of the high-temperature annealing treatment is 15-25 h.
Specifically, the invention uses the slow volatilization process of chlorosulfonic acid and sulfuric acid under the vacuum condition, and the vacuum degree is 1-4 multiplied by 10 -4 Pa, and evaporating temperature between 150 ℃ and 350 ℃.
The densification treatment step starts from the action mechanism of chlorosulfonic acid on the carbon nano tube, and the carbon nano tube fiber is soaked, expanded and stood in the chlorosulfonic acid in sequence through the development of a new process, so that the change of the appearance and the appearance of the carbon nano tube fiber is finally realized, and the densification degree of the carbon nano tube fiber is greatly improved.
The invention is applied to long-time protonation and short-time expansion treatment of the carbon nano tube fiber in chlorosulfonic acid; the reaction of chlorosulfonic acid and carbon nano tube fiber, the reaction of chlorosulfonic acid and moisture in air and the slow shrinkage behavior of the carbon nano tube fiber in chlorosulfonic acid are synthesized, so that the appearance change and densification of the carbon nano tube fiber are realized.
In some embodiments, the preparation method specifically includes:
immersing the densified carbon nanotube fiber with the sawtooth structure in nickel salt solution for more than 24 hours, placing in an environment with the temperature of 0-20 ℃, taking out, then carrying out high-temperature decomposition at 100-1000 ℃ (after the high-temperature decomposition, nickel atoms can be decomposed by nickel salt, further realizing plating and attaching of the nickel atoms on the surface of the carbon nanotube, controlling the nickel salt decomposition temperature at 100-1000 ℃), then immersing the carbon nanotube fiber in hydrochloric acid for 10-60 minutes, and then drying, thereby depositing nickel nanoparticles on the surface of the densified carbon nanotube fiber with the sawtooth structure.
In the aspect of adding strong binding force metal, the addition amount of 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, meanwhile, alloying of a copper layer in the heat treatment process can be effectively avoided, and the dual purposes of improving the mechanical property and the electrical property at the same time are realized.
Further, the nickel nanoparticles have a particle size of 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 nickel acetate ethanol solution, but is not limited thereto.
In some embodiments, the preparation method specifically includes:
providing a copper protectant solution;
and electroplating the surface of the densified carbon nano tube fiber by adopting an electrochemical deposition technology to form a copper layer, taking out from the electroplating solution, and placing the copper layer in a copper protective agent solution for fully soaking for 5-30 seconds (ensuring complete soaking) to obtain the nickel-containing carbon nano tube/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 ℃.
Another aspect of an embodiment of the present invention also provides a nickel-containing carbon nanotube/copper composite fiber produced by the foregoing production method.
Further, the nickel element content in the nickel-containing carbon nanotube/copper composite fiber is below 0.01 wt%.
Further, the thickness of the copper layer on the surface of the nickel-containing carbon nano tube/copper composite fiber is 1-10 mu m.
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 stiffness of the nickel-containing carbon nanotube/copper composite fiber is about 600MPa to 1500 MPa.
Further, 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.
Further, the interface strength of the nickel-containing carbon nano tube/copper composite fiber is 15 MPa-25 MPa.
In summary, the invention utilizes the synergistic effect of chlorosulfonic acid densification process and nickel nano particles to realize the improvement of the mechanical property of carbon nano tube fibrils, and simultaneously realizes the construction of a sawtooth structure on the surface of carbon nano tube fibers through the densification process, and realizes the uniform and continuous coverage of copper layers on the surface of the carbon nano tube fibers by virtue of the promotion effect of the nickel nano particles on copper deposition; and 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 solution of the present invention will be described in further detail below with reference to a number of preferred embodiments and accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
Example 1
Referring to fig. 1, the specific technical steps of the preparation method of the nickel-containing carbon nanotube/copper composite fiber in this embodiment are as follows:
(1) Densification treatment of carbon nanotube fibers and preparation of saw tooth surface morphology
Slowly placing carbon nano tube fibers with the length of 35-45 cm into a measuring cylinder filled with chlorosulfonic acid, and placing for about 1-2 hours to enable the chlorosulfonic acid to fully infiltrate the carbon nano tube fibers; then taking out the carbon nano tube fiber from chlorosulfonic acid, and standing in the air for about 30-60 min to enable the chlorosulfonic acid in the carbon nano tube fiber to fully react with the moisture in the air to generate concentrated sulfuric acid; then, the carbon nano tube fiber is put into chlorosulfonic acid again at a faster speed (the fiber is completely put into chlorosulfonic acid solution within 3 to 5 seconds as much as possible to ensure that enough hydrogen chloride pressure is generated by the reaction), so that the fiber is obviously expanded in a short time (the volume expansion is 10 to 30 times of the original volume expansion), and the appearance of the fiber becomes obvious cylindrical shape; maintaining carbon nano-meterThe tube fiber is kept stand in chlorosulfonic acid for about 3 to 6 hours until the volume of the fiber is obviously reduced, as shown in figure 1; and then slowly taking out the carbon nano tube fiber from chlorosulfonic acid, keeping the duration of the whole taking-out process at least 15 minutes, and standing in the air for 30-60 minutes until the reaction of the carbon nano tube fiber and the moisture in the air is finished. Fixing the treated carbon nanotube fiber on a quartz frame, keeping the carbon nanotube fiber in a tensed 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 deg.c and the vacuum degree is 1-4 x 10 -4 Pa, the treatment time is about 15 to 25 hours. Finally, densification of the carbon nanotube fiber is realized, and a sawtooth interface of the carbon nanotube fiber is prepared.
(2) Preparation of nickel nano particles on surface of carbon nano tube fiber
Preparing nickel acetate ethanol solution with the concentration of 0.05 mol/L-saturated nickel acetate ethanol solution, magnetically stirring for about 4 hours, then placing the densified carbon nano tube fibers in the nickel acetate ethanol solution for soaking, placing the densified carbon nano tube fibers in a refrigerating chamber of a refrigerator, controlling the soaking time to be more than 24 hours, taking out the carbon nano tube fibers, performing pyrolysis at 100-1000 ℃, placing the carbon nano tube fibers in hydrochloric acid for soaking for 10-60 minutes after the pyrolysis, and drying. Finally, the preparation of nickel nano particles with the particle size below 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 fiber prepared in the step (2) on a copper bracket, and sealing the bracket carrying the carbon nanotube fiber by using a resin glue gun to ensure the insulativity of the bracket part. The output current of the electrochemical workstation is regulated to be 0.001A-0.01A, the electroplating time is controlled to be 10 s-100 s, copper protective agent solution with the concentration of 15 ml/L-25 ml/L is prepared, and the indoor temperature is regulated to be 5-35 ℃. And then electroplating the carbon nano tube fiber, rapidly taking out the fiber from the copper solution after electroplating, placing the fiber in a protective agent for full infiltration, and taking out and storing the fiber.
The inventor carries out microstructure characterization and performance test on the finally obtained nickel-containing carbon nano tube/copper composite fiber, and the microstructure characterization and performance test are as follows:
(1) Promotion of mechanical properties of carbon nanotube fiber bodies by densification processes
As shown in fig. 2a and 2b, the surface of the raw carbon nanotube fiber is relatively smooth, and has a large size, and takes on a narrow band shape. After densification treatment, the size of the carbon nanotube fiber is obviously reduced, and more folds are formed on the surface of the carbon nanotube, as shown in fig. 2 c; in its cross-sectional view, the folds in the surface of the carbon nanotube fiber can be observed to exhibit a saw tooth morphology, as shown in FIG. 2 d. Therefore, the cross-sectional area of the carbon nano tube fiber is obviously reduced after densification treatment, and the fluffy air hole structure in the carbon nano tube fiber is well eliminated.
Fig. 3 shows the mechanical property change before and after densification of the carbon nanotube fiber, the lower line in fig. 3 shows the tensile property of the original carbon nanotube fiber, and the upper line shows the tensile property of the densified fiber. The tensile data show that after densification treatment, the tensile strength, the elongation and the rigidity of the carbon nano tube fiber are obviously improved, namely the densification treatment has an effect of promoting the mechanical property of the carbon nano tube fiber; wherein, the elongation is improved to 20% -50% of the original, the rigidity is improved to about 210% of the original, the tensile strength is improved to about 400% of the original, and the final value reaches about 4 GPa.
(2) Influence of carbon nanotube fiber saw tooth structure on carbon nanotube/copper composite interface
FIGS. 4 a-4 d show the characteristics of two composite interface structures of the original carbon nanotube fiber copper plating and the saw tooth interface carbon nanotube fiber copper plating, so as to demonstrate the effect of the saw tooth structure formed by densification on the bonding force of the composite interface. The results show that the bonding interface of 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, so that the bonding force of the composite interface is not improved; 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 the improvement of the composite strength of the composite interface.
(3) Influence of nanoparticles on deposition of copper layer on carbon nanotube fiber surface
FIGS. 5 a-5 b show the effect of nickel nanoparticles on the microstructure of the composite interface, and when no nickel nanoparticles are present on the surface of the carbon nanotube fiber, more voids exist at the junction between the copper layer and the surface of the carbon nanotube fiber, as shown in FIG. 5a, indicating that the bonding strength between the copper layer and the carbon nanotube is weaker; after the plating of the nickel nano particles on the surface of the carbon nano tube fiber, no void is observed at the joint of the copper carbon surface, as shown in fig. 5b, which shows that the bonding force between the copper layer and the surface of the carbon nano tube fiber is obviously improved under the action of the nickel nano particles.
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 carbon nanotube fiber copper plating, the tensile mechanical properties of the carbon nanotube fiber copper plating composite fiber of densified carbon nanotube fiber copper plating and the densified nickel nanoparticle copper plating composite fiber are obviously improved, and the fiber modulus, the elongation and the tensile strength of the latter two composite fibers are obviously superior to those of the fibril copper plating 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 pure densification of the carbon nano tube fiber does not promote the interface mechanics of the composite fiber, but the densified nickel nano particle-added carbon nano tube composite fiber has obvious positive effect on the strength improvement of a 'carbon nano tube/copper' composite interface, as shown in fig. 6 b. In conclusion, the research results show that under the synergistic effect of densification treatment and nickel nanoparticles, the mechanical properties of the composite fiber are promoted, and the tensile mechanical properties and interfacial mechanical properties of the composite fiber are obviously improved.
FIGS. 7 a-7 f are fracture morphology diagrams of three condition composite fibers, wherein the fracture microstructure of the original carbon nanotube fiber plated with copper is loose, more carbon nanotube filaments exist, the filaments show a certain rebound morphology, the number of carbon nanotube filaments pulled out is small, and the lengths of the carbon nanotube filaments are different, as shown in FIGS. 7a and 7 b; the number of carbon nanotube filaments at the fracture of the composite fiber plated with copper of the densified carbon nanotube fiber is obviously reduced, the rebound morphology of the filaments is obviously weakened, and the morphology feature of the integral fracture of the carbon nanotube fiber bundle can be observed at the fracture, as shown in fig. 7c and 7 d. The fracture of the copper plated composite fiber after densification of the nickel-loaded nanoparticles was flat and the presence of carbon nanotube filaments was hardly observed, as shown in fig. 7e and 7 f.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely 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 an illustrative embodiment, 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 the scope thereof. 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 (8)

1. The preparation method of the nickel-containing carbon nano tube/copper composite fiber is characterized by comprising the following steps:
densification treatment is carried out on the original carbon nano tube fiber, and a saw-tooth structure morphology is formed on the surface of the high-densification carbon nano tube fiber while the densified carbon nano tube fiber is obtained; the densification treatment specifically comprises:
(1) Fully soaking the original carbon nano tube fibers in chlorosulfonic acid for 1-2 hours, taking out, standing in the air for 30-60 minutes, fully reacting chlorosulfonic acid with moisture in the air to generate concentrated sulfuric acid, and fully entering water molecules into the carbon nano tube fibers by virtue of the water absorption of the concentrated sulfuric acid;
(2) Re-soaking the carbon nano tube fiber obtained in the step (1) in chlorosulfonic acid at a first speed within 3-5 seconds to enable moisture in the carbon nano tube fiber to react with chlorosulfonic acid molecules to generate hydrogen chloride gas, so that the volume of the carbon nano tube fiber is quickly expanded to 10-30 times within 1 second, and the appearance of the carbon nano tube fiber is in a cylindrical shape; and the expanded carbon nano tube fiber is kept stand in chlorosulfonic acid for 3 to 6 hours until the diameter and the volume of the carbon nano tube fiber are reduced to 20 to 30 percent of the expansion volume;
(3) Slowly taking out the carbon nano tube fiber obtained in the step (2) from chlorosulfonic acid at a second rate, standing in air for 30-60 min for a period of time longer than 15 min, and fully reacting the chlorosulfonic acid with water in the air to generate concentrated sulfuric acid, wherein the first rate is greater than the second rate;
(4) Under the vacuum condition, maintaining the carbon nano tube fiber obtained in the step (3) in a tightening state, and then carrying out high-temperature annealing treatment in a vacuum tube furnace to volatilize concentrated sulfuric acid to obtain densified carbon nano tube fiber; wherein the temperature of the high-temperature annealing treatment is 150-350 ℃ and the vacuum degree is 1-4 multiplied by 10 -4 Pa, and the time of high-temperature annealing treatment is 15-25 h;
immersing the densified carbon nanotube fiber with a sawtooth structure in a nickel salt solution for more than 24 hours, and placing at a temperature of 0 DEG C o C~20 o C, in the environment, taking out, then carrying out pyrolysis at 100-1000 ℃, then placing the carbon nano tube fiber in hydrochloric acid, immersing for 10-60 min, and then drying, so as to deposit nickel nano particles on the surface of the densified carbon nano tube fiber with a sawtooth structure; the method comprises the steps of,
providing a copper protectant solution;
electroplating the surface of the densified carbon nano tube fiber by adopting an electrochemical deposition technology to form a copper layer, taking out from the electroplating solution, and placing the copper layer in a copper protective agent solution for fully soaking for 5-30 seconds to obtain a nickel-containing carbon nano tube/copper composite fiber; 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 ℃;
the content of nickel element in the nickel-containing carbon nano tube/copper composite fiber is below 0.01 weight percent; compared with the original carbon nanotube fiber, the elongation of the nickel-containing carbon nanotube/copper composite fiber is improved by 20% -50%, the rigidity of the nickel-containing carbon nanotube/copper composite fiber is 600-1500 MPa, the tensile strength of the nickel-containing carbon nanotube/copper composite fiber is 1-4 GPa, and the interface strength of the nickel-containing carbon nanotube/copper composite fiber is 15-25 MPa.
2. The method of manufacturing according to claim 1, characterized in that: the original carbon nanotube fiber is a carbon nanotube narrowband or carbon nanotube fiber.
3. The method of manufacturing according to claim 1, characterized in that: the particle size of the nickel nano particles is below 5 nm.
4. The method of manufacturing according to claim 1, characterized in that: the concentration of the nickel salt solution is more than 0.05 mol/L.
5. The method of manufacturing according to claim 4, wherein: the concentration of the nickel salt solution is 0.05mol/L to saturated concentration.
6. The method of manufacturing according to claim 1, characterized in that: the nickel salt solution is nickel acetate ethanol solution.
7. Nickel-containing carbon nanotube/copper composite fiber produced by the production process according to any one of claims 1 to 6.
8. The nickel-containing carbon nanotube/copper composite fiber of claim 7, wherein: the thickness of the copper layer on the surface of the nickel-containing carbon nano tube/copper composite fiber is 1-10 mu m.
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