CN114672994A - Graphene-reinforced carbon nanotube composite fiber, and preparation method and device thereof - Google Patents
Graphene-reinforced carbon nanotube composite fiber, and preparation method and device thereof Download PDFInfo
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Abstract
The invention discloses a graphene-reinforced carbon nanotube composite fiber, and a preparation method and a device thereof. The preparation method comprises the following steps: uniformly mixing expanded graphite and super acid serving as a dispersion solvent to form a graphene/super acid solution, wherein the super acid is chlorosulfonic acid; soaking carbon nanotube fibers in a graphene/super strong acid solution, and expanding the carbon nanotube fibers under the protonation action of a chlorosulfonic acid solvent to enable the graphene/super strong acid solution to enter the carbon nanotube fibers to form a uniform composite structure; and then soaking the fiber in a coagulating bath, dissolving the super acid to realize the precipitation of the graphene and the contraction of the carbon nanotube fiber, and obtaining the defect-free graphene reinforced carbon nanotube composite fiber. The method realizes the introduction of the defect-free graphene in the gaps of the carbon nanotube fibers in the preparation process, can effectively reduce the interfacial resistance between the tubes, simultaneously improves the load transfer efficiency between the tubes, and realizes the continuous enhancement of the mechanical and electrical properties of the carbon nanotube fibers.
Description
Technical Field
The invention relates to a graphene-reinforced carbon nanotube composite fiber, a preparation method thereof and a corresponding preparation device, and belongs to the technical field of high-performance fibers and composite materials.
Background
The carbon nanotube fiber is a continuous yarn assembled by carbon nanotubes and tube bundles, has the characteristics of high strength, high toughness, high conductivity and the like, and has wide prospect in the application field of composite material reinforced and multifunctional fibers. In the carbon nano tube fiber prepared by the chemical vapor deposition method, more inter-tube pores exist, which are very unfavorable for load transfer and electron transport between carbon nano tube interfaces, and the mechanical and electrical properties of the carbon nano tube fiber are obviously reduced. Therefore, introducing other reinforcing phases into the fiber gaps through a composite process is an effective means for improving the mechanical and electrical properties of the carbon nanotube fibers.
The existing preparation method of the carbon nanotube/graphene composite fiber comprises spray compounding of a graphene oxide aqueous solution, or compounding by dipping the carbon nanotube fiber in the graphene oxide aqueous solution, such as in the journal of Foroughi et al, adv.funct.mater, 2014, 24, 5859; sun et al, adv.mater, 2014, 26, 2868, patents CN103306132A, CN107324313A, CN107043962A, and the like.
As described above, the existing method for preparing the carbon nanotube/graphene composite fiber mainly comprises the steps of immersing or spraying the carbon nanotube fiber in a graphene oxide aqueous solution to obtain the carbon nanotube/graphene oxide composite fiber, and then reducing the carbon nanotube/graphene oxide composite fiber to prepare the carbon nanotube/graphene composite fiber. In the carbon nanotube fiber, a large number of small-sized gaps/holes from nanometer to micron are formed among the carbon nanotubes or among the tube bundles, and the carbon nanotubes have poor wettability to conventional solvents such as water, so that the graphene oxide sheets are difficult to enter the gaps. Secondly, the graphene oxide can be decomposed to generate gas in the reduction process, and the gas generated in the composite fiber can cause the phenomena of bubbles, bulges and the like in the fiber, destroy the structure of the composite fiber and reduce the performance of the composite fiber. Finally, the preparation mechanism of the reduced graphene oxide determines that the finally obtained graphene sheet has more sp3 carbon defects, so that the strength and the conductivity of the finally obtained graphene sheet are lower than those of a defect-free graphene sheet.
Disclosure of Invention
The invention mainly aims to provide a graphene-reinforced carbon nanotube composite fiber and a preparation method thereof, so as to overcome the defects in the prior art.
Another object of the present invention is to provide a device for preparing graphene-reinforced carbon nanotube composite fibers.
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 graphene-reinforced carbon nanotube composite fiber, which comprises the following steps:
uniformly mixing expanded graphite and super acid serving as a dispersion solvent to form a graphene/super acid solution, wherein the super acid is chlorosulfonic acid;
soaking carbon nanotube fibers in a graphene/super strong acid solution, and expanding the carbon nanotube fibers under the protonation action of a chlorosulfonic acid solvent to enable the graphene/super strong acid solution to enter the carbon nanotube fibers to form a uniform composite structure;
and soaking the composite structure in a coagulating bath, dissolving the super acid to realize the precipitation of the graphene and the contraction of the carbon nanotube fiber, and finally obtaining the uniformly-compounded defect-free graphene-reinforced carbon nanotube composite fiber.
In some embodiments, the method of making comprises: the method comprises the steps of carrying out high-speed shearing dispersion on expanded graphite by using super acid as a dispersion solvent to form a defect-free graphene/super acid solution, and then filtering the graphene/super acid solution.
In some embodiments, the method of making comprises: the method comprises the steps of adopting a fiber unwinding device to enable carbon nanotube fibers to be continuously soaked in graphene/super strong acid solution for 1-3 min under the action of a lead shaft, enabling the carbon nanotube fibers to expand to 10-30 times in diameter under the protonation action of chlorosulfonic acid solvent, and enabling the graphene/super strong acid solution to enter the carbon nanotube fibers to form a uniform composite structure.
The embodiment of the invention also provides the graphene-reinforced carbon nanotube composite fiber prepared by the method, which comprises the carbon nanotube fiber and graphene uniformly distributed on the surface and/or inside the carbon nanotube fiber, wherein the content of the graphene in the graphene-reinforced carbon nanotube composite fiber is 2 wt% -10 wt%.
The embodiment of the invention also provides a preparation device of the graphene-reinforced carbon nanotube composite fiber, which is applied to the preparation method, and the preparation device comprises:
a high-speed shearing stirring mixing device at least used for uniformly mixing the expanded graphite and the super acid;
the carbon nanotube fiber unwinding device is at least used for soaking the carbon nanotube fibers in the graphene/super strong acid solution;
and the coagulating bath is at least used for dissolving the superacid to realize the precipitation of the graphene and the contraction of the carbon nano tube fiber.
Compared with the prior art, the invention has the advantages that:
according to the invention, the carbon nanotube spacing in the original carbon nanotube fiber is increased through the protonation expansion effect of the super acid solvent in the graphene/super acid solution on the carbon nanotube fiber, and simultaneously the graphene/super acid solution permeates into the pores formed by the expansion of the carbon nanotube fiber, and then the graphene precipitation and the carbon nanotube fiber shrinkage are realized under the action of the coagulating bath, so that the uniformly-compounded carbon nanotube/defect-free graphene composite fiber is finally formed, and the introduction of defect-free graphene in the carbon nanotube fiber gaps can effectively reduce the interface resistance between tubes, and simultaneously the load transfer efficiency between tubes is improved, so that the continuous enhancement of the mechanical and electrical properties of the carbon nanotube fiber is 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.
FIGS. 1a to 1c are structural diagrams of an apparatus for continuously preparing graphene-reinforced carbon nanotube composite fibers according to an exemplary embodiment of the present invention;
fig. 2a is a surface SEM image of graphene-reinforced carbon nanotube composite fiber in example 1 of the present invention;
fig. 2b is an internal SEM image of the graphene-reinforced carbon nanotube composite fiber in example 1 of the present invention;
fig. 3a is a graph comparing the tensile mechanical properties of the graphene reinforced carbon nanotube composite fiber and the carbon nanotube original fiber in example 1 of the present invention;
fig. 3b is a comparison graph of conductivity of the graphene-reinforced carbon nanotube composite fiber and the carbon nanotube original fiber in example 1 of the present invention.
Description of the drawings: 1-high-speed shearing, stirring and mixing device, 2-graphene/chlorosulfonic acid solution, 3-filtering device, 4-air extractor, 5-filtered graphene/chlorosulfonic acid solution, 6-carbon nanotube fiber unreeling device, 7-carbon nanotube fiber, 8-wire shaft, 9-solidification-cleaning bath, 10-drying device, 11-graphene-reinforced carbon nanotube composite fiber and 12-rolling device.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has made a long-term study and a great deal of practice to provide a technical scheme of the present invention, which mainly utilizes the protonation expansion effect of the super acid (chlorosulfonic acid) on the carbon nanotube fibers to significantly increase the gaps between the carbon nanotubes and the tube bundles, thereby facilitating the penetration of the composite substance (graphene) into the carbon nanotube fibers during the impregnation process, and finally realizing the uniform compounding of the graphene in the carbon nanotube fibers, and aiming at realizing the continuous preparation of the high-uniformity, high-strength and high-conductivity graphene-reinforced carbon nanotube composite fibers. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a method for preparing a graphene-reinforced carbon nanotube composite fiber, including:
uniformly mixing expanded graphite and super acid serving as a dispersion solvent to form a graphene/super acid solution, wherein the super acid is chlorosulfonic acid;
soaking carbon nanotube fibers in a graphene/super strong acid solution, and expanding the carbon nanotube fibers under the protonation action of a chlorosulfonic acid solvent to enable the graphene/super strong acid solution to enter the carbon nanotube fibers to form a uniform composite structure;
and soaking the composite structure in a coagulating bath, dissolving the super acid, and realizing the precipitation of the graphene and the contraction of the carbon nanotube fiber to obtain the uniformly-compounded defect-free graphene-reinforced carbon nanotube composite fiber.
In some embodiments, the concentration of graphene in the graphene/super acidic solution is 5-20 mg/mL.
In the invention, the protonation expansion effect of the super acid (chlorosulfonic acid) on the carbon nanotube fiber is utilized to obviously increase the gaps between the carbon nanotubes and the tube bundles, thereby being beneficial to the penetration of a composite substance (graphene) into the carbon nanotube fiber in the impregnation process and finally realizing the uniform compounding of the graphene in the carbon nanotube fiber.
In the invention, the expanded graphite is adopted as the graphene raw material and directly dissolved in the super acid (chlorosulfonic acid) to form the graphene solution, the graphene crystal structure is not damaged in the dispersing, compounding and solidification precipitation processes, and finally the defect-free graphene-reinforced carbon nanotube composite fiber is obtained, and compared with graphene oxide compounding, the defect-free graphene-reinforced carbon nanotube composite fiber has a simpler process and better mechanical and electrical property enhancing effects.
In the invention, the adopted carbon nanotube fiber is prepared by a floating catalytic chemical vapor deposition method, and the length of the carbon nanotube can reach more than 100 microns. The carbon nanotube fiber is formed by assembling numerous carbon nanotubes along the fiber direction, and the longer the carbon nanotube length is, the higher the mechanical and electrical properties of the prepared carbon nanotube fiber are.
In some embodiments, the method of making comprises: the method comprises the steps of carrying out high-speed shearing dispersion on expanded graphite by using super acid as a dispersion solvent to form a defect-free graphene/super acid solution, and then filtering the graphene/super acid solution.
Further, the preparation method further comprises the following steps: and performing air extraction treatment on the suction filtration system while performing filtration treatment.
In some embodiments, the method of making comprises: the method comprises the steps of adopting a fiber unwinding device to enable carbon nanotube fibers to be continuously soaked in graphene/super strong acid solution for 1-3 min under the action of a lead shaft, enabling the carbon nanotube fibers to expand to 10-30 times in diameter under the protonation action of chlorosulfonic acid solvent, and enabling the graphene/super strong acid solution to enter the carbon nanotube fibers to form a uniform composite structure.
Further, the speed of releasing the carbon nano tube fiber by the fiber unreeling device is 0.1-0.3 m/min.
In some embodiments, the method of making comprises: under the action of a lead shaft, the composite structure of the carbon nanotube fibers and the graphene/superstrong acid solution is soaked in a solidification-cleaning bath for 3-5 min, the superstrong acid in the carbon nanotube fibers is dissolved by a solvent in the solidification-cleaning bath, the graphene is separated out, meanwhile, the protonation of the superstrong acid on the carbon nanotube fibers is reduced, the carbon nanotube fibers are contracted, then drying treatment is carried out, the residual solvent is removed, and finally the uniformly-compounded defect-free graphene-reinforced carbon nanotube composite fibers are obtained and collected.
The coagulation-washing bath refers to the same solvent (which simultaneously plays roles of graphene coagulation and precipitation and super acid washing), has intersolubility with super acid, and is a poor solvent for graphene. The solidification-cleaning bath enters the interior of the expanded composite fiber and is mixed with the graphene/super acid solution, the protonation effect of the newly formed mixed solvent of the solidification-cleaning bath and the super acid is reduced, the protonation degree of the graphene is reduced, the solubility is reduced, and thus precipitation occurs, and the precipitation process occurs in the interior of the fiber (namely the graphene solidification process). The cleaning process refers to the cleaning of the super acid solvent in the composite fiber. When the graphene is solidified, due to the concentration difference between the inside and the outside of the composite fiber, the diffusion of the solidification-cleaning bath to the inside of the fiber and the diffusion of the super acid to the outside of the fiber occur simultaneously, and as the composite fiber is surrounded by a large number of solidification-cleaning baths, finally, most of the super acid will diffuse out of the fiber (i.e. the super acid cleaning process).
In some more specific embodiments, the preparation method and mechanism of the graphene-reinforced carbon nanotube composite fiber are as follows: the method is characterized in that super acid (chlorosulfonic acid) is used as a dispersing solvent to carry out high-speed shearing dispersion on graphite raw materials, a defect-free graphene/chlorosulfonic acid solution can be prepared, and the solution is used for carrying out continuous dipping composite treatment on carbon nano tube fibers. In the compounding process, the strong protonation of chlorosulfonic acid solvent can make the carbon nano-tubes positively charged, so that electrostatic repulsion is generated between the carbon nano-tubes to increase the distance between the carbon nano-tubes and tube bundles, and the carbon nano-tube fibers are expanded macroscopically, which is similar to the swelling phenomenon of polymer fibers in the solvent. The large-interval pores generated by the protonation expansion effect ensure that the graphene solution can easily enter the fiber, so that the uniform compounding of the graphene and the carbon nanotube fiber is realized. And (3) preparing the continuous graphene reinforced carbon nano tube composite fiber with uniform composition, high conductivity and high strength by subsequent coagulation bath precipitation/shrinkage treatment, cleaning, drying and winding.
In some embodiments, the preparation methods of the present invention comprise: the device comprises a uniform dispersion and filtration of defect-free graphene in chlorosulfonic acid and continuous compounding of carbon nanotube fibril and graphene, wherein the continuous compounding device comprises a fiber winding and unwinding system, a graphene chlorosulfonic acid dispersion liquid compounding tank, a coagulation bath and cleaning tank and a fiber drying device. According to the method, the distance between the carbon nanotubes in the original carbon nanotube fibers is increased through the protonation expansion effect of a chlorosulfonic acid solvent in the graphene chlorosulfonic acid dispersion liquid on the carbon nanotube fibers, meanwhile, the graphene chlorosulfonic acid dispersion liquid permeates into pores formed by fiber expansion, then, graphene precipitation and carbon nanotube fiber contraction are realized under the action of a coagulating bath, and finally, the uniformly-compounded graphene-reinforced carbon nanotube composite fibers are formed. Due to the introduction of the defect-free graphene in the carbon nanotube fiber gap, the interfacial resistance between tubes can be effectively reduced, the load transfer efficiency between tubes is improved, and the mechanical and electrical properties of the carbon nanotube fiber are continuously enhanced.
The mechanism and the beneficial effects of the introduction mode of the graphene in the carbon nanotube fiber are as follows: and adopting a chlorosulfonic acid solution of defect-free graphene as a composite medium. Chlorosulfonic acid contained in the solution has strong protonation ability and can make sp2Carbon atoms are protonated and positively charged to introduce electrostatic repulsion, so that expanded graphite which is extremely difficult to strip and dissolve in a conventional solvent is stripped and dissolved in chlorosulfonic acid to form a defect-free graphene solution, and simultaneously, the chlorosulfonic acid also enables carbon nanotubes in the carbon nanotube fibers to be protonated and positively charged, so that electrostatic repulsion is generated among the carbon nanotubes, the distance among the carbon nanotubes is increased, and the carbon nanotube fibers are expanded. After the carbon nano tube fiber enters the graphene/chlorosulfonic acid solution, the graphene/chlorosulfonic acid solution can easily enter the fiber through larger fiber inner pores generated by protonation expansion, and the graphene/chlorosulfonic acid solution and the carbon nano tube form a uniform composite structure, and then under the action of a solidification-cleaning bath, a solvent in the solidification-cleaning bath is mixed with chlorosulfonic acid in the fiber to reduce the protonation capacity of the chlorosulfonic acid, so that deprotonation is performed, the fiber is contracted, graphene is separated out, and finally the graphene-reinforced carbon nano tube composite fiber is obtained. Therefore, the composite fiber obtained by the invention has uniform graphene distribution inside, and graphene oxide sheets are prepared by the existing methods of graphene oxide aqueous solution soaking, spray deposition and the likeCan only enter a gap with larger size, and has poor distribution uniformity in the composite fiber. Finally, the uniformity of the graphene-reinforced carbon nanotube composite fiber prepared by the invention is superior to that of the composite fiber prepared by the prior art.
Another aspect of the embodiments of the present invention also provides a graphene-reinforced carbon nanotube composite fiber prepared by the foregoing method, which includes a carbon nanotube fiber, and graphene uniformly distributed on the surface and/or inside of the carbon nanotube fiber.
Further, the content of graphene in the graphene-reinforced carbon nanotube composite fiber is 2 wt% to 10 wt%.
Further, the graphene-reinforced carbon nanotube composite fiber has a tensile strength of 4-6 GPa, a modulus of 150-200 GPa, and an electrical conductivity of 1-2 x 106S/m。
Furthermore, the graphene-reinforced carbon nanotube composite fiber prepared by the invention has a compact structure, the structural characteristics of the graphene-reinforced carbon nanotube composite fiber are beneficial to the mechanical and electrical properties of the fiber, and the graphene-reinforced carbon nanotube composite fiber can be applied to the fields of high-strength and high-conductivity high-performance fibers and the like through measurement.
Furthermore, the carbon nanotubes are used as a main material in the graphene-reinforced carbon nanotube composite fiber prepared by the invention, the graphene plays a role in connection and bridging among the carbon nanotubes, and the graphene has a small relative content and mainly plays a role in mechanical and electrical reinforcement.
Correspondingly, another aspect of the embodiments of the present invention further provides a preparation apparatus for graphene-reinforced carbon nanotube composite fibers, which is applied to the foregoing preparation method, and the preparation apparatus includes:
a high-speed shearing stirring mixing device at least used for uniformly mixing the expanded graphite and the super acid;
the carbon nanotube fiber unwinding device is at least used for soaking the carbon nanotube fibers in the graphene/super strong acid solution;
and the coagulating bath is at least used for dissolving the super acid to realize the precipitation of the graphene and the contraction of the carbon nano tube fiber.
Further, the preparation device further comprises: and the filtering device is at least used for filtering the graphene/super acidic solution.
Further, the preparation device also comprises an air exhaust device which is at least used for performing air exhaust treatment on the suction filtration system while performing filtration treatment.
Further, the preparation device further comprises: fiber drying device and coiling mechanism.
In summary, the beneficial effects of the invention are as follows:
(1) the graphene is distributed in the composite fiber more uniformly, and the mechanical and electrical properties of the graphene-reinforced carbon nanotube composite fiber are higher;
(2) the graphene has fewer defects, and is more beneficial to enhancing the performance of the fiber;
(3) the damage to the fiber structure possibly caused by the reduction process when the graphene oxide is used is avoided, and the process is simplified;
(4) the compounding process of the graphene and the carbon nano tube fiber can be continuously carried out, and the amplification is good.
In addition, chlorosulfonic acid is used as a solvent, expanded graphite is used as a graphene raw material, and the graphene/chlorosulfonic acid solution is prepared by high-speed shearing and stirring. In the dispersing process and the subsequent compounding, solidification and precipitation processes, the protonation and deprotonation effects can not act on sp of the graphene2And (3) the carbon junction structure is broken, and finally the graphene-reinforced carbon nanotube composite fiber is obtained. The graphene with complete structure and no defects has higher strength and electrical conductivity and better reinforcing effect on the composite fiber, and the graphene oxide adopted by the existing method still contains more sp after reduction3Carbon defects, and more gas can be generated in the reduction process, so that the composite fiber structure is damaged, and the reinforcing effect is poor. Finally, the mechanical and electrical properties of the graphene-reinforced carbon nanotube composite fiber prepared by the invention are superior to those of the composite fiber prepared by the prior art.
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
The detailed structure of the apparatus for continuously preparing high-strength and high-conductivity graphene-reinforced carbon nanotube composite fiber according to this embodiment is shown in fig. 1a, 1b and 1 c. In the embodiment, the carbon nanotube fibers are subjected to composite treatment by adopting a chlorosulfonic acid solution of defect-free graphene, so that the graphene-reinforced carbon nanotube composite fibers with high composite uniformity are obtained, and the specific technical process and principle are as follows:
expanded graphite and chlorosulfonic acid are added in proportion to high-speed shearing stirring mixing arrangement 1, under the effect of high-speed shearing stirring, form graphite alkene/chlorosulfonic acid solution 2, wherein, the concentration of graphite alkene is 5 ~ 20mg/mL (preferably 5mg/mL), contain a certain amount of graphite particle that does not dissolve in graphite alkene/chlorosulfonic acid solution 2, adopt filter equipment 3 to filter graphite alkene/chlorosulfonic acid solution 2 in order to get rid of graphite particle that does not dissolve, utilize air exhaust device 4 to improve filtration efficiency in the filtering process, obtain even impurity-free graphite alkene/chlorosulfonic acid solution 5 after filtering. The carbon nanotube fiber unreeling device 6 releases carbon nanotube fibers 7 at a speed of 0.1m/min to 0.3m/min (preferably 0.1m/min), the carbon nanotube fibers 7 enter a groove filled with the filtered graphene/chlorosulfonic acid solution 5 under the action of a lead shaft 8 to perform composite infiltration for 1 min to 3min, and the carbon nanotube fibers 7 expand to a diameter of 10 times to 30 times under the protonation of a chlorosulfonic acid solvent, so that the filtered graphene/chlorosulfonic acid solution 5 can easily enter the carbon nanotube fibers to form a uniform composite structure. Under the action of the lead shaft 8, the carbon nanotube fiber 7 enters a tank provided with a solidification-cleaning bath 9 for 3-5 min, chlorosulfonic acid in the carbon nanotube fiber is dissolved by a solvent in the solidification-cleaning bath 9, graphene is precipitated, protonation on the carbon nanotube fiber 7 after the chlorosulfonic acid is dissolved is reduced, and the carbon nanotube fiber 7 is shrunk. And the fiber treated by the coagulation-cleaning bath 9 enters a drying device 10 to be dried to remove residual solvent, so that the defect-free graphene reinforced carbon nanotube composite fiber 11 is obtained, and finally the defect-free graphene reinforced carbon nanotube composite fiber is wound and collected by a winding device 12.
Fig. 2a is a surface SEM image of the graphene-reinforced carbon nanotube composite fiber obtained in this embodiment, and it can be seen that the composite fiber is composed of a large number of carbon nanotube bundles with diameters of several tens of nanometers, and the micrometer-sized graphene spans several tens to hundreds of carbon nanotube bundles, so that load transfer and electron transport between the bundles are improved, and mechanical and electrical properties of the composite fiber are improved; fig. 2b is an SEM image of the inside of the fiber after the graphene-reinforced carbon nanotube composite fiber is torn, and it can be seen that graphene sheet layers are also present inside the composite fiber, and the graphene sheet layers enter the inside of the fiber at the protonation expansion stage of the carbon nanotube fiber. The graphene sheet layers are uniformly compounded on the surface and the inside of the fiber, so that the mechanical and electrical properties of the composite fiber can be effectively improved, which is difficult to realize in the traditional graphene oxide aqueous solution soaking process.
Fig. 3a shows the tensile mechanical test result of the graphene-reinforced carbon nanotube composite fiber and the carbon nanotube original fiber obtained in this example, and it can be seen from fig. 3a that the tensile strength of the composite fiber reaches about 5GPa, the modulus reaches about 170GPa, and the strength (about 1.7GPa) and the modulus (about 70GPa) are respectively improved by about 2 times and about 1.4 times compared with the strength (about 1.7GPa) and the modulus (about 70GPa) of the carbon nanotube original fiber. And the strength of the graphene-reinforced carbon nanotube composite fiber exceeds that of T700 carbon fiber. Fig. 3b shows the conductive performance test result (I-V curve) of the graphene-reinforced carbon nanotube composite fiber and the carbon nanotube original fiber obtained in this embodiment, and as can be seen from fig. 3b, the graphene-reinforced carbon nanotube composite fiber has higher conductive performance, and the conductive performance of the composite fiber calculated by combining the fiber diameter data obtained by microscope measurement is about 1.1 × 106S/m, which is greater than the conductivity of the carbon nanotube primary fiber (about 2.75X 10)5S/m) increased by a factor of 3.
In conclusion, the graphene solution compounding, solidification and precipitation, composite fiber cleaning and drying processes are effectively integrated, and efficient and continuous preparation of the graphene-reinforced carbon nanotube composite fiber is realized.
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 preparation method of graphene reinforced carbon nanotube composite fiber is characterized by comprising the following steps:
uniformly mixing expanded graphite and super acid serving as a dispersion solvent to form a graphene/super acid solution, wherein the super acid is chlorosulfonic acid;
soaking carbon nanotube fibers in a graphene/super strong acid solution, and expanding the carbon nanotube fibers under the protonation action of a chlorosulfonic acid solvent to enable the graphene/super strong acid solution to enter the carbon nanotube fibers to form a uniform composite structure;
and soaking the composite structure in a coagulating bath, dissolving the super acid, and realizing the precipitation of the graphene and the contraction of the carbon nanotube fiber to obtain the uniformly-compounded defect-free graphene-reinforced carbon nanotube composite fiber.
2. The method of claim 1, wherein: the concentration of the graphene in the graphene/superstrong acid solution is 5-20 mg/mL.
3. The method of claim 1, comprising: carrying out high-speed shearing dispersion on expanded graphite by adopting super acid as a dispersion solvent to form a defect-free graphene/super acid solution, and then filtering the graphene/super acid solution; preferably, the preparation method further comprises: and performing air extraction treatment on the suction filtration system while performing filtration treatment.
4. The method of claim 1, comprising: adopting a fiber unwinding device to enable carbon nanotube fibers to be continuously soaked in graphene/super strong acid solution for 1-3 min under the action of a lead shaft, and under the protonation action of chlorosulfonic acid solvent, enabling the carbon nanotube fibers to expand to 10-30 times in diameter, so that the graphene/super strong acid solution enters the carbon nanotube fibers to form a uniform composite structure; preferably, the speed of releasing the carbon nanotube fibers by the fiber unwinding device is 0.1-0.3 m/min.
5. The method of claim 1, comprising: under the action of a lead shaft, soaking a composite structure of carbon nanotube fibers and graphene/super strong acid solution in a solidification-cleaning bath for 3-5 min, dissolving super strong acid in the carbon nanotube fibers by a solvent in the solidification-cleaning bath, separating out graphene, simultaneously reducing protonation of the super strong acid on the carbon nanotube fibers, shrinking the carbon nanotube fibers, then drying, finally obtaining the uniformly-compounded defect-free graphene-reinforced carbon nanotube composite fibers, and collecting; the coagulation-cleaning bath and the super acid have intersolubility, and are poor solvents of graphene.
6. The graphene-reinforced carbon nanotube composite fiber prepared by the preparation method according to any one of claims 1 to 5, which comprises a carbon nanotube fiber and graphene uniformly distributed on the surface and/or inside of the carbon nanotube fiber, wherein the graphene content in the graphene-reinforced carbon nanotube composite fiber is 2 to 10 wt%.
7. The graphene-reinforced carbon nanotube composite fiber according to claim 6, wherein: the graphene-reinforced carbon nanotube composite fiber has the tensile strength of 4-6 GPa, the modulus of 150-200 GPa and the conductivity of 1-2 x 106S/m。
8. A production apparatus for graphene-reinforced carbon nanotube composite fibers, which is used in the production method according to any one of claims 1 to 5, and which comprises:
a high-speed shearing stirring mixing device at least used for uniformly mixing the expanded graphite and the super acid;
the carbon nanotube fiber unwinding device is at least used for soaking the carbon nanotube fibers in the graphene/super strong acid solution;
and the coagulating bath is at least used for dissolving the super acid to realize the precipitation of the graphene and the contraction of the carbon nano tube fiber.
9. The manufacturing apparatus according to claim 8, further comprising: the filtering device is at least used for filtering the graphene/super acidic solution; preferably, the preparation device further comprises an air extraction device, and the air extraction device is at least used for carrying out air extraction treatment on the suction filtration system while carrying out filtration treatment.
10. The manufacturing apparatus according to claim 8, further comprising: fiber drying device and coiling mechanism.
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