CN116623422A - High-performance graphene/carbon nano tube composite fiber and preparation method thereof - Google Patents
High-performance graphene/carbon nano tube composite fiber and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 262
- 239000000835 fiber Substances 0.000 title claims abstract description 190
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 135
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 126
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 126
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 11
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000001112 coagulating effect Effects 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 4
- 230000005588 protonation Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000004050 hot filament vapor deposition Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- -1 oleum Chemical compound 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—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 carbon or compounds thereof
- D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses a graphene/carbon nano tube composite fiber with high tensile strength and conductivity, which mainly comprises a graphene material and carbon nano tube fibers, wherein the graphene material is filled in the carbon nano tube fibers under the action of strong acid; the graphene material comprises one or more of graphene and reduced graphene oxide, preferably graphene. Also discloses a specific preparation method of the composite fiber. The graphene/carbon nanotube composite fiber provided by the invention has excellent mechanical and electrical properties, and compared with pure carbon nanotube fibers, the composite fiber has a more compact structure and higher orientation degree. Meanwhile, the graphene/carbon nano tube composite fiber can be continuously prepared, has low equipment requirements, and has the advantages of simplicity in operation and easiness in batch preparation.
Description
Technical Field
The invention belongs to the field of new material preparation, and particularly relates to a high-performance graphene/carbon nano tube composite fiber and a preparation method thereof.
Background
The carbon nano tube has excellent mechanical and electrical properties, the tensile breaking strength and the tensile modulus are respectively up to 100GPa and 1TPa, and the conductivity of the metal type carbon nano tube is up to 10 8 S/m. The carbon nanotube fiber is a one-dimensional macroscopic assembly of the carbon nanotubes, is hopeful to inherit the excellent performance of the carbon nanotubes on a microscopic scale, and endows the carbon nanotubes with excellent mechanical, electrical and other characteristics. However, the mechanical and electrical properties of the carbon nanotube fiber are far from the intrinsic properties, which is mainly the problem that the fiber has multiple gaps, low orientation, weak acting force among tubes and the like.
The introduction of other components into the fiber or solution densification of the fiber is considered an effective method of improving the properties of the carbon nanotube fiber. Literature (adv. Mater.2015,27,3259) reports a method for obtaining dense fibers by treating carbon nanotube/Polydopamine (PDA) composite fibers at high temperature, which enhances the mechanical and electrical properties of the fibers, but the enhancement effect on the fiber properties of amorphous carbon obtained by pyrolyzing PDA is still to be further improved. Literature (Compos. Sci. Technology.2012, 72,1402) reports two enhancement methods of densification of carbon nanotube fibers with different solvent solutions and the introduction of bismaleimide polymers to produce carbon nanotube fibers with enhanced mechanical properties. However, the mechanical properties of the fibers are limited by the two treatment modes, and the electrical properties of the fibers are greatly influenced by the presence of the polymer. The patent CN107473203B prepares the carbon nanotube aggregate by a floating catalytic chemical vapor deposition method, continuously sprays graphene oxide dispersion liquid to the carbon nanotube aggregate, and then obtains the carbon nanotube/graphene composite fiber by a liquid seal tank filled with water. But the graphene/carbon nano tube composite fiber finally obtained by the method has lower mechanical property. The current method for improving the performance of the carbon nano tube fiber is single, and the structure and the performance of the carbon nano tube fiber still have room for further improvement.
Disclosure of Invention
In order to overcome the defects, the invention provides a graphene/carbon nano tube composite fiber with high tensile strength and conductivity and a preparation method thereof.
The invention provides a graphene/carbon nano tube composite fiber with high tensile strength and conductivity, which mainly comprises a graphene material and carbon nano tube fibers, wherein the graphene material is filled in the carbon nano tube fibers; the size of the graphene material is 50 nm-1 mu m, preferably 50 nm-500 nm; the fiber diameter of the carbon nanotube fiber is 10-100 mu m.
According to an embodiment of the present invention, the number of the sheets of the graphene-based material is 3 to 10, preferably 3 to 5.
According to an embodiment of the present invention, the carbon nanotube fiber is prepared by one of a floating catalytic chemical vapor deposition method, an array spinning method, and a wet spinning method.
According to an embodiment of the present invention, the graphene material comprises one or more of graphene and reduced graphene oxide, preferably graphene.
The invention also provides a preparation method of the composite fiber, which specifically comprises the following steps:
s1, immersing the carbon nano tube fiber into the graphene material/strong acid dispersion liquid, and enabling the carbon nano tube fiber to undergo volume expansion so as to enable the graphene material to enter the carbon nano tube fiber;
s2, placing the carbon nanotube fiber in graphene/strong acid dispersion liquid for a period of time, and applying drafting with a certain drafting ratio;
s3, transferring the product obtained in the step S2 into a coagulating bath solution;
s4, transferring the product obtained in the step S3 into a cleaning bath solution for cleaning;
s5, drying to obtain the graphene/carbon nano tube composite fiber.
According to an embodiment of the present invention, the strong acid is one or more of sulfuric acid, oleum, nitric acid, chlorosulfonic acid, polyphosphoric acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid.
According to an embodiment of the present invention, in the step S1, the concentration of the graphene-based material in the dispersion is 0.001wt% to 1wt%, and preferably the concentration is 0.01wt% to 0.5wt%.
According to one embodiment of the invention, in said step S1, the strong acid in the dispersion has a pKa (acidity coefficient) value of-15 to 0.3.
According to an embodiment of the present invention, in the step S2, the treatment time of the carbon nanotube fiber in the graphene/strong acid dispersion is 0.5min to 60min, preferably 1min to 30min.
According to an embodiment of the invention, in said step S2, said draft ratio is between 5% and 30%, preferably between 15% and 30%.
According to an embodiment of the present invention, in the step S3, the component in the coagulation bath solution is one or more of acetone, diethyl ether, dichloromethane, ethyl acetate, and water.
According to an embodiment of the present invention, in the step S4, the component in the cleaning bath solution is one of water, ethanol, isopropanol, and acetone.
According to an embodiment of the present invention, in the step S5, the drying temperature is 20 ℃ to 1100 ℃.
The beneficial effects are that:
the graphene/carbon nanotube composite fiber provided by the invention has excellent mechanical and electrical properties, and compared with pure carbon nanotube fibers, the composite fiber is more compact and has higher orientation degree. At a draw ratio of 18%, the tensile strength of the graphene/carbon nanotube composite fiber is improved by 282% compared with that of the pure carbon nanotube fiber, and is improved by 23% compared with that of the carbon nanotube fiber treated by only strong acid; the conductivity of the graphene/carbon nanotube composite fiber is improved by 500% compared with that of the pure carbon nanotube fiber, and the conductivity of the carbon nanotube fiber treated by only strong acid is improved by 35%. Meanwhile, the graphene/carbon nano tube composite fiber can realize continuous preparation, has low equipment requirement, and has the advantages of simple operation and easy batch preparation.
Drawings
FIG. 1 is a flow chart of experiments for examples 1-10 and comparative examples 1-5.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the graphene/carbon nanotube composite fiber of examples 1, 2,7, 8, 9 and comparative example 1.
Fig. 3 is a graph showing tensile strength comparison of graphene/carbon nanotube composite fibers in examples 1 to 10 and comparative examples 1 to 5.
Fig. 4 is a graph showing comparison of electrical properties of graphene/carbon nanotube composite fibers in examples 1 to 10 and comparative examples 1 to 5.
Fig. 5 is a Raman characterization of untreated carbon nanotube fibers, chlorosulfonated carbon nanotube fibers, graphene/chlorosulfonic acid dispersion treated fibers.
Detailed Description
The draft ratio refers to the ratio of the increase in length of the fiber during drawing to the length of the original fiber.
The tensile strength is the breaking strength of the fiber and refers to the ratio of the tensile force of the fiber when breaking to the breaking cross-sectional area of the fiber.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are conventional methods unless otherwise specified. The following examples are illustrative of the invention and should not be construed as limiting the scope of the invention.
The invention aims to provide a high-performance graphene/carbon nano tube composite fiber and a preparation method thereof. In the composite fiber, graphene can enter the inside of the carbon nanotube fiber by virtue of the volume expansion phenomenon caused by the protonation of strong acid on the carbon nanotube fiber, so that fiber gaps are filled, carbon nanotube endpoints are connected, and the acting force between the tubes is enhanced. And further carrying out drafting treatment on the fiber in a certain proportion to finally obtain the graphene/carbon nano tube composite fiber with high density and high orientation degree, wherein the fiber shows excellent mechanical and electrical properties. The preparation method has the characteristics of low equipment requirement, simple operation and easy batch preparation, and can realize the continuous preparation of the graphene/carbon nano tube composite fiber.
The graphene/carbon nanotube composite fiber with high tensile strength and conductivity mainly comprises a graphene material and carbon nanotube fibers; the graphene material is filled in the carbon nanotube fiber; the size of the graphene material is 50 nm-1 mu m, preferably 50 nm-500 nm; the fiber diameter of the carbon nano tube fiber is 10-100 mu m; the number of the sheets of the graphene material is 3-10, preferably 3-5. The graphene with smaller size is selected because the gaps inside the fiber are hundred nanometers, and the graphene is easier to fill inside the carbon nanotube fiber; the graphene with larger size can not play a reinforcing effect in the fiber, mainly because the graphene sheet with larger size is easy to generate wrinkles, so that more gaps are formed in the fiber, and the performance of the fiber is reduced. The graphene with a small number of layers is selected, so that the fewer the number of layers of the graphene is, the more the intrinsic characteristics (such as conductivity) of the graphene can be reflected; meanwhile, the number of layers of graphene is increased, and gaps are also easily introduced into the fiber, so that stress concentration is caused, and the tensile strength of the fiber is reduced.
In an alternative embodiment, the graphene-based material comprises one or more of graphene, reduced graphene oxide, preferably graphene. Graphene and reduced graphene oxide are selected as reinforcing materials for reinforcing carbon nanotube fibers because: the graphene materials have a six-membered ring structure similar to that of carbon nanotubes, pi-pi interaction can be formed between the graphene materials and the carbon nanotubes, and meanwhile, the flaky graphene materials can play a role in lap joint between the carbon nanotubes and between carbon nanotube bundles, so that acting force in the fiber is further enhanced; the graphene can connect adjacent carbon nanotubes, so that more conductive paths are formed, and the conductivity of the fiber is improved. Graphene is preferred because: compared with the reduced graphene oxide, the graphene has a more complete structure, and has better mechanical and conductive properties; however, the reduced graphene oxide still contains oxygen-containing groups due to incomplete reduction process, and the oxygen-containing groups exist as defects to reduce the performance of the reduced graphene oxide. In summary, we prefer graphene as the more preferred reinforcing material.
The composite fiber can be prepared by the following method, S1, immersing the carbon nano tube fiber into the graphene material/strong acid dispersion liquid, and causing the volume expansion of the carbon nano tube fiber to promote the graphene material to enter the carbon nano tube fiber; s2, placing the carbon nanotube fiber in graphene/strong acid dispersion liquid for a period of time, and applying drafting with a certain drafting ratio; s3, transferring the product obtained in the step S2 into a coagulating bath solution; s4, transferring the product obtained in the step S3 into a cleaning bath solution for cleaning; s5, drying to obtain the graphene/carbon nano tube composite fiber. In the composite fiber, graphene can enter the inside of the carbon nanotube fiber by virtue of the volume expansion phenomenon caused by the protonation of strong acid on the carbon nanotube fiber, so that fiber gaps are filled, carbon nanotube endpoints are connected, and the acting force between the tubes is enhanced. The strong acid is chosen mainly because its protonation of graphene results in a uniform and stable dispersion. In addition, as the degree of protonation increases, the fibers may undergo a different degree of volume expansion, as can be observed by optical microscopy, in chlorosulfonic acid, the fibers may expand in volume to nearly 10 times themselves. And H is 2 O 2 The volume expansion effect of the solution on the fibers is not obvious.
In alternative embodiments, the strong acid is one or more of sulfuric acid, oleum, nitric acid, chlorosulfonic acid, polyphosphoric acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid. The acid needs to be a stronger protic acid.
In an alternative embodiment, in step S1, the concentration of the graphene-based material in the dispersion is 0.001wt% to 1wt%, and preferably the concentration is 0.01wt% to 0.5wt%. When the concentration is higher, two main problems exist, namely, after the concentration of graphene is increased, the dispersion effect of the graphene is obviously reduced; secondly, under the same treatment time, the graphene entering the inside of the fiber is increased, obvious graphene aggregates can be seen, and the larger aggregates can cause more gaps in the fiber, so that the fiber performance is reduced.
In an alternative embodiment, in the step S2, the treatment time of the carbon nanotube fiber in the graphene/strong acid dispersion is 0.5min to 60min, preferably 1min to 30min. The processing time can have a significant impact on the properties of the fibers. When the treatment time of the fiber in the graphene dispersion liquid is less than 1min, the amount of graphene entering the inside of the fiber is small, and the performance of the fiber is not greatly improved. However, when the time is longer than 30 minutes, the amount of graphene filled into the fibers increases, and stacking of sheets and wrinkling between the graphene occur, resulting in a decrease in fiber performance.
In an alternative embodiment, in step S2, the draft ratio is 5% -30%, preferably 15% -30%. When the fibers are drawn in different proportions, the mechanical properties of the fibers are affected differently. When the drafting of the fiber is smaller, more carbon nanotube bundles are entangled in the fiber, the orientation degree of the fiber does not reach the optimal effect, and the improvement of the performance is not maximized; when the draft ratio of the fiber is more than 30%, slippage occurs between bundles in the fiber, and the decrease in contact area results in a decrease in the force acting between bundles, thereby resulting in a decrease in the performance of the fiber.
In an alternative embodiment, in the step S3, the coagulation bath component is one or more of acetone, diethyl ether, dichloromethane, ethyl acetate, and water. The coagulation bath has the functions of: when the fiber enters the coagulating bath from the graphene/strong acid dispersion liquid, double diffusion can occur between the dispersion liquid and the solution in the coagulating bath due to the differences of concentration difference, temperature difference and the like, and the fiber is changed from a volume expansion state to a compact state in the double diffusion process, so that the final shaping of the fiber is realized.
The inventive concept of the present invention is explained below by means of specific examples. The raw materials used in the examples were obtained from the publicly available commercial sources unless otherwise specified.
The tensile strength test method is as follows: the fiber is cut into small sections of about 3cm to test the tensile strength, the small sections of the fiber are fixed on a mechanical test paper, the fiber test distance is fixed to be 1cm, and the tensile speed is 1mm/min. At least 10 samples were tested for each set of fibers. The instruments used for the test are: an electronic universal testing machine; the model is as follows: shimadzu EZ-LX 5N.
The conductivity test method is as follows: and fixing two ends of a long section of fiber on the paperboard, clamping the test wire on the fiber, testing the resistance values of the fibers at different intervals by adjusting the distance between the two clamps, and calculating the conductivity of the fiber by a formula. The instruments used for the test are: a digital source table; model Keithley 2450.
Example 1
Immersing the carbon nano tube fiber in 0.05wt% of graphene/chlorosulfonic acid, wherein the size of the graphene is 200-400nm, the number of the sheets is 3-5, the treatment time is 1min, and the 18% draft ratio is applied;
transferring the drafted graphene/carbon nano tube composite fiber into a coagulating bath for 5min, and then transferring into a cleaning bath for 5min;
drying at 100deg.C, and rolling.
The basic morphology of the graphene/carbon nano tube composite fiber is shown in fig. 2, the tensile strength of the composite fiber is 4.3GPa, and the conductivity is 2.29MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Example 2
The specific process steps are basically the same as those of the embodiment 1 of the present invention, and the difference from the embodiment 1 is that the treatment time of the carbon nanotube fiber in the graphene/chlorosulfonic acid dispersion is 5min, so as to obtain the graphene/carbon nanotube composite fiber. The basic morphology of the graphene/carbon nano tube composite fiber is shown in fig. 2, the tensile strength of the composite fiber is 4.1GPa, and the conductivity is 2.55MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Example 3
The specific process steps are basically the same as those of the embodiment 1 of the present invention, and the difference from the embodiment 1 is that the treatment time of the carbon nanotube fiber in the graphene/chlorosulfonic acid dispersion liquid is 10min, so as to obtain the graphene/carbon nanotube composite fiber. The tensile strength of the carbon nano tube composite fiber is 4.0GPa, and the conductivity is 2.70MS/m.
The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Example 4
The specific process steps are basically the same as those of the embodiment 1 of the present invention, and the difference from the embodiment 1 is that the treatment time of the carbon nanotube fiber in the graphene/chlorosulfonic acid dispersion liquid is 15min, so as to obtain the graphene/carbon nanotube composite fiber. The tensile strength of the carbon nano tube composite fiber is 3.5GPa, and the conductivity is 2.64MS/m.
The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Example 5
The specific process steps are substantially the same as in example 1 of the present invention, except that the draft ratio of the graphene/carbon nanotube composite fiber is 10%. The tensile strength of the carbon nano tube composite fiber is 2.3GPa, and the conductivity is 1.65MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Example 6
The specific process steps are substantially the same as in example 1 of the present invention, except that the draft ratio of the graphene/carbon nanotube composite fiber is 12%. The tensile strength of the carbon nano tube composite fiber is 2.6GPa, and the conductivity is 1.71MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Example 7
The specific process steps are substantially the same as in example 1 of the present invention, except that the draft ratio of the graphene/carbon nanotube composite fiber is 14% as in example 1. The basic morphology of the graphene/carbon nano tube composite fiber is shown in figure 1, the tensile strength of the composite fiber is 2.8GPa, and the conductivity is 1.97MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Example 8
The specific process steps are basically the same as those of the embodiment 1 of the present invention, and the difference from the embodiment 1 is that the carbon nanotube fiber is in a graphene/concentrated sulfuric acid dispersion to obtain a graphene/carbon nanotube composite fiber. The basic morphology of the graphene/carbon nano tube composite fiber is shown in fig. 2, the tensile strength of the composite fiber is 3.5GPa, and the conductivity is 2.05MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Example 9
The specific process steps are basically the same as those of the embodiment 1 of the present invention, and the difference from the embodiment 1 is that the carbon nanotube fiber is in a graphene/nitric acid dispersion to obtain a graphene/carbon nanotube composite fiber. The basic morphology of the graphene/carbon nano tube composite fiber is shown in fig. 2, the tensile strength of the composite fiber is 3.4GPa, and the conductivity is 2.11MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Example 10
The specific process steps are basically the same as those of the embodiment 1 of the present invention, and the difference from the embodiment 1 is that the carbon nanotube fiber is in the reduced graphene oxide/chlorosulfonic acid dispersion to obtain the reduced graphene oxide/carbon nanotube composite fiber. The tensile strength of the carbon nano tube composite fiber is 3.7GPa, and the conductivity is 2.01MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Comparative example 1
The specific process steps are basically the same as those of the embodiment 1 of the invention, but graphene substances are not added, and the treated carbon nanotube fibers are obtained by only soaking the carbon nanotube fibers in chlorosulfonic acid. The basic morphology of the carbon nanotube fiber is shown in FIG. 2, the tensile strength of the fiber is 3.3GPa, and the electrical conductivity is 1.50MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Comparative example 2
The carbon nanotube fiber was not subjected to any treatment, and had a tensile strength of 1.1GPa and an electrical conductivity of 0.45MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Comparative example 3
Immersing the carbon nano tube fiber in 0.05wt% of graphene/H 2 O 2 Wherein the size of the graphene is 200-400nm, the number of the sheets is 3-5, the treatment time is 1min, and the 18% draft ratio is applied;
transferring the drafted graphene/carbon nano tube composite fiber into a coagulating bath for 5min, and then transferring into a cleaning bath for 5min;
drying at 100deg.C, and rolling.
The tensile strength of the composite fiber was 2.8GPa, and the electrical conductivity was 0.73MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Comparative example 4
The specific process steps are basically the same as those of the embodiment 1 of the present invention, and the difference from the embodiment 1 is that the size of the selected graphene is 2-3 μm, so as to obtain the larger-size graphene/carbon nanotube composite fiber. The tensile strength of the carbon nano tube composite fiber is 3.4GPa, and the conductivity is 1.99MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Comparative example 5
The specific process steps are basically the same as those of the embodiment 1 of the invention, and the difference from the embodiment 1 is that the number of layers of the selected graphene is 10-15 layers, so as to obtain the graphene/carbon nano tube composite fiber. The tensile strength of the carbon nano tube composite fiber is 3.0GPa, and the conductivity is 1.87MS/m. The detailed mechanical property comparison is shown in fig. 3, and the electrical property comparison is shown in fig. 4.
Table 1 and FIG. 3, FIG. 4 show a comparison of the properties of the fibers of examples 1-10 and comparative examples 1-5.
TABLE 1 comparison of the Properties of graphene/carbon nanotube composite fibers
The foregoing is merely illustrative of some embodiments of the invention, and it will be apparent to those skilled in the art that other variations and modifications can be made without departing from the inventive concept of the present invention, which fall within the scope of the invention.
Claims (10)
1. The graphene/carbon nanotube composite fiber is characterized by mainly comprising a graphene material and carbon nanotube fibers, wherein the graphene material is filled in the carbon nanotube fibers; the size of the graphene material is 50 nm-1 mu m, preferably 50 nm-500 nm; the fiber diameter of the carbon nanotube fiber is 10-100 mu m.
2. The composite fiber according to claim 1, wherein the number of sheets of the graphene-based material is 3 to 10, preferably 3 to 5.
3. The composite fiber according to claim 1 or 2, wherein the graphene-based material comprises one or more of graphene, reduced graphene oxide, preferably graphene.
4. A method for preparing a composite fiber according to any one of claims 1 to 3, comprising the steps of:
s1, immersing the carbon nano tube fiber into the graphene material/strong acid dispersion liquid, and enabling the carbon nano tube fiber to undergo volume expansion so as to enable the graphene material to enter the carbon nano tube fiber;
s2, placing the carbon nanotube fiber in graphene material/strong acid dispersion liquid for a period of time, and applying drafting with a certain drafting ratio;
s3, transferring the product obtained in the step S2 into a coagulating bath solution;
s4, transferring the product obtained in the step S3 into a cleaning bath solution for cleaning;
s5, drying to obtain the graphene/carbon nano tube composite fiber.
5. The method according to claim 4, wherein the strong acid is one or more of sulfuric acid, fuming sulfuric acid, nitric acid, chlorosulfonic acid, polyphosphoric acid, methanesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid.
6. The method according to claim 4 or 5, wherein in step S1, the concentration of the graphene-like material in the dispersion is 0.001wt% to 1wt%, preferably 0.01wt% to 0.5wt%.
7. The method according to any one of claims 4 to 6, wherein in step S2, the carbon nanotube fiber is left in the graphene/strong acid dispersion for a time period of 0.5min to 60min, preferably 1min to 30min.
8. The process according to any one of claims 4 to 7, characterized in that in step S2 the draft ratio is between 5% and 30%, preferably between 15% and 30%.
9. The method according to any one of claims 4 to 8, wherein in step S3, the components in the coagulation bath solution are one or more of acetone, diethyl ether, methylene chloride, ethyl acetate, and water.
10. The method according to any one of claims 4 to 9, wherein in step S4, the component in the cleaning bath solution is one of water, ethanol, isopropanol, acetone.
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