CN116575243A - Preparation method and application of hierarchical pore titanium carbide/carbon nanotube composite fiber - Google Patents
Preparation method and application of hierarchical pore titanium carbide/carbon nanotube composite fiber Download PDFInfo
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- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
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- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 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 4
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- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 4
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- 238000004108 freeze drying Methods 0.000 claims description 4
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a preparation method of a hierarchical porous titanium carbide/carbon nano tube composite fiber, which comprises the following steps: s1, preparing porous titanium carbide powder; s2, preparing PMMA microspheres. The porous titanium carbide sheet material is added into the carbon nanotube fiber, and the porous composite fiber with the micropore-mesopore-macropore structure is prepared by a PMMA (polymethyl methacrylate) nanometer microsphere hard template method, so that the problem of excessive stacking inside the carbon nanotube fiber is solved, and the energy density of the fiber electrode material is improved.
Description
Technical Field
The invention belongs to the technical development and application field of functional fiber materials, and relates to a preparation method and application of a hierarchical porous titanium carbide/carbon nano tube composite fiber, in particular to the preparation of a porous Ti3C2Tx sheet material, a wet spinning technology and a hard template method are utilized to continuously prepare a hierarchical porous conductive fiber, and a method for growing low-dimensional polyaniline in pores by in-situ polymerization is utilized on the basis, so that the prepared composite fiber can be applied to the field of flexible electrode materials.
Background
In recent years, with the continuous emergence of intelligent wearable electronic devices, a flexible energy storage technology is gradually becoming a hotspot in the current intelligent wearable field as a key support technology. The intelligent wearable electronic equipment needs the flexible energy storage device to be capable of being bent, and also has the characteristics of light weight, high strength, good packaging performance and the like. At present, the electrode of the flexible supercapacitor is mainly realized in the forms of flexible substrate electrode smear, film materials and the like, and along with the continuous progress of the technology, the structural design of the materials is greatly optimized and improved to the energy storage performance. However, these materials have poor integration in wearable devices, and durability and mechanical properties after packaging still need to be improved. In recent years, with the rapid development of material science and fiber forming technology, the eyesight of the flexible fiber electrode material is turned to have high performance and good integration at home and abroad.
The fiber electrode material based on the carbon nano tube has the characteristics of light weight, high strength, higher conductivity, better multiplying power performance, better cycling stability and the like compared with a pseudo-capacitance material. However, the electrode material based on carbon nanotube fibers has a low active material utilization rate due to a large packing density inside the fibers, and the overall energy density after integration is still relatively low, which limits practical applications. At present, three-dimensional carbon-based fiber materials are mainly constructed by introducing carbon materials with other dimensions into one-dimensional carbon nanotubes, so that the accumulation of the carbon nanotubes in the fibers can be effectively prevented, and the high specific surface area and high conductivity of the carbon nanotubes are maintained; on the other hand, the nanometer pseudo-capacitance component is introduced, the load rate of electrochemical active substances is increased in the fiber, and the carbon nanotube network provides electron and electrolyte ion transfer channels for pseudo-capacitance reaction, so that the electrochemical stability in the repeated charge and discharge process is improved.
In recent years, a conductive material having a two-dimensional lamellar morphology similar to graphene has been attracting attention, and a transition metal carbide or nitride having such a structure is called an MXene material, and MXene is widely used in the energy storage field due to its excellent conductivity, an ultra-high volume capacitance, and a simple preparation method, but a pure MXene material is mainly compounded with other materials or spun by a specific processing method due to its characteristics of small lamellar, easy oxidation and agglomeration.
Besides selecting proper fiber electrode materials, the construction of a multi-stage pore structure in the fibers can lead the materials to have larger specific surface area and more electrochemical reaction active sites, and also provide an effective way for rapid diffusion of ions. The multi-stage pore structure is constructed, the synergistic advantage of macropores, mesopores and micropores is utilized to become one of the most important methods for breaking through the energy storage bottleneck of the supercapacitor, and the multi-stage pore structure is widely applied to the fields of films, aerogels, block materials and the like, but the technology for constructing the multi-stage pore structure in the fiber-based electrode material is still insufficient. In addition, under practical application conditions, the influence of collapse of the large-aperture structure on the fiber electrode material is not clear, and the stability of the fiber electrode material can be greatly improved by designing the support structure in the pores. The low-dimensional conductive polymer has good orientation and crystallinity, and the low-dimensional conductive polymer is directionally grown in the pores by an in-situ growth method, so that not only can the structural support of the pores be given, but also the electrochemical reaction sites in the pores can be increased to improve the overall energy density of the fiber. Therefore, there is a need to provide a method for preparing hierarchical porous titanium carbide/carbon nanotube composite fibers, while introducing a low-dimensional conductive polymer system to solve the above problems.
Disclosure of Invention
The invention aims to solve the defects of the existing continuous carbon nanotube fiber and provides a preparation method of a hierarchical porous titanium carbide/carbon nanotube composite fiber.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a hierarchical porous titanium carbide/carbon nano tube composite fiber comprises the following steps:
s1, preparing porous titanium carbide powder; s2, preparing PMMA microspheres; s3, preparing a fiber spinning solution by taking porous titanium carbide powder, carbon nanotubes and PMMA microspheres as raw materials, and cleaning and sintering the obtained fiber after wet spinning to obtain the multi-level porous titanium carbide/carbon nanotube composite fiber; s4, polyaniline in-situ polymerization of the composite fiber.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, S1 specifically comprises the following steps: adding lithium fluoride powder into hydrochloric acid, continuously stirring for full reaction, adding aluminum titanium carbide, stirring in an oil bath at 35-40 ℃ for reaction for 24 hours, centrifuging after the reaction is finished, washing reactants until the upper layer liquid of the solution is dark green and has pH value of 6-7 by using deionized water, carrying out ice bath ultrasonic treatment on the upper layer liquid, centrifuging to collect supernatant, carrying out centrifugal treatment on the supernatant continuously, adding an equal volume of copper sulfate solution into the obtained titanium carbide dispersion liquid, stirring for 30 minutes, repeatedly centrifuging and washing by using deionized water until the pH value of the solution is 6, adding hydrogen fluoride into the solution, etching for 10 minutes, carrying out ultrasonic dispersion, centrifuging and washing until the upper layer liquid is dark green, and taking the upper layer liquid for freeze drying to obtain the titanium carbide powder with holes.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the mass ratio of lithium fluoride to aluminum titanium carbide is 1.6:1.
as a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the concentration of hydrochloric acid is 9mol/L, and the use amount is 20ml.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the ice bath ultrasonic treatment time is 2 hours.
As a preferable scheme of the preparation method of the multistage pore titanium carbide/carbon nano tube composite fiber, the supernatant liquid is centrifuged for 5min, and the rotating speed is 7000rpm.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the concentration of the copper sulfate solution is 0.2mol/L.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the mass concentration of the hydrogen fluoride solution is 10%.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the etched titanium carbide powder is dispersed in deionized water, and the centrifugal speed is 3500-4000 rpm.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, S2 specifically comprises the following steps: and (3) dissolving azoisobutyronitrile and polyvinylpyrrolidone in methanol, purging the mixed solution with nitrogen, adding methyl methacrylate, stirring for reaction, centrifuging and washing to obtain a white product which is PMMA microspheres.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the mass concentration of azoisobutyronitrile in the mixed solution is 0.1 percent, and the mass concentration of polyvinylpyrrolidone is 4 percent.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the reaction temperature is 50-60 ℃.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the mass fraction of the added methyl methacrylate is 10-15%.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, S3 specifically comprises the following steps: weighing a certain mass of porous titanium carbide powder and PMMA microspheres, performing ultrasonic dispersion in 1ml of chlorosulfonic acid for 20min, adding single-wall carbon nanotube powder into the uniformly dispersed mixed solution, and stirring for 20min by using a rotation revolution deaeration stirrer. Filtering the mixed liquid crystal solution to remove undissolved impurities, and transferring the liquid crystal solution into a glass needle tube as spinning solution. The spinning solution was extruded into an acetone coagulation bath by a digitally controlled syringe pump. And (3) cleaning, drying, and sintering at high temperature to obtain the hierarchical porous titanium carbide/carbon nano tube composite fiber.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nanotube composite fiber, the mass ratio of the single-walled carbon nanotubes to the porous titanium carbide to the PMMA microspheres is 1:0.1-0.2:0.2-0.3, and the concentration of the single-walled carbon nanotubes is 35-40mg/ml.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, a rotation revolution deaeration stirrer is adopted, and the rotating speed is 1500-2000 r/min.
As a preferable scheme of the preparation method of the multistage pore titanium carbide/carbon nano tube composite fiber, the extrusion rate of the spinning solution is 10-30 ml/h, and the size of a spinning head is 18-25G.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the sintering temperature is 500-650 ℃.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, S4 specifically comprises the following steps: the hierarchical porous composite fiber was soaked in a mixed solution of aniline and hydrochloric acid and placed in an ultrasonic bath at 50 ℃ for 2 hours. Then, ammonium persulfate was added to the mixed solution in which the fibers were soaked, and left in an ultrasonic bath at 0 ℃ for 1 hour, and PANI in-situ polymerization was performed in the hierarchical pore fibers. The prepared composite fiber was washed with ethanol/water solution and dried at 50 ℃ for 4 hours.
As a preferable scheme of the preparation method of the hierarchical porous titanium carbide/carbon nano tube composite fiber, the concentration of aniline and hydrochloric acid is respectively 0.8-0.9M and 0.6-0.65M, and the concentration of ammonium persulfate is 0.8-0.9M.
It is another object of the present invention to provide the use of the hierarchical porous titanium carbide/carbon nanotube fibers obtained by the above preparation method, in particular as a flexible electrode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the porous titanium carbide sheet material is added into the carbon nanotube fiber, and the multi-level pore composite fiber with a micropore-mesopore-macropore structure is prepared by a PMMA (polymethyl methacrylate) nanometer microsphere hard template method, so that the problem of excessive stacking inside the carbon nanotube fiber is solved, and the energy density of the fiber electrode material is improved.
(2) The invention constructs the multi-stage pore structure of micropore, mesopore and macropore, greatly improves the specific surface area and the proportion of open structure of the material, provides a path for the inward diffusion of polymer monomer solution, and can directionally grow low-dimensional conductive polymer in the macropores by an in-situ growth method, thereby not only providing the structural support of the pore, but also increasing the electrochemical reaction sites in the pores and improving the energy density of the whole fiber.
Drawings
FIG. 1 is a schematic diagram of a preparation process and a structure of a hierarchical porous titanium carbide/carbon nanotube composite fiber provided by the invention;
FIG. 2 is a transmission 50nm electron microscope image of the prepared porous titanium carbide powder;
FIG. 3 is a transmission 5nm electron microscope image of the prepared porous titanium carbide powder;
FIG. 4 is a scanning electron microscope image of the PMMA microspheres prepared;
FIG. 5 is a drawing of a cross-section scanning electron microscope a of the grooved titanium carbide/carbon nanotube composite fiber prepared in comparative example 1;
FIG. 6 is a drawing of a scanning electron microscope b of a cross section of the grooved titanium carbide/carbon nanotube composite fiber prepared in comparative example 1;
FIG. 7 is a cross-sectional scanning electron microscope c diagram of the grooved titanium carbide/carbon nanotube composite fiber prepared in comparative example 1;
FIG. 8 is a graph of a scanning electron microscope d of a cross section of the grooved titanium carbide/carbon nanotube composite fiber prepared in comparative example 1;
FIG. 9 is a view of a 100 μm cross-section scanning electron microscope of an in situ grown PANI array;
fig. 10 is a view of a 10 μm cross-section scanning electron microscope of an in situ grown PANI array.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The raw materials used in the examples were commercially purchased unless otherwise specified.
Example 1
As shown in fig. 1, the method for preparing the hierarchical porous titanium carbide/carbon nanotube composite fiber according to the embodiment comprises the following steps:
step one, preparing titanium carbide nano-sheets: adding 1.6g of lithium fluoride powder into 20ml of hydrochloric acid with the concentration of 9mol/L, continuously stirring for 5min to fully react, then adding 1g of aluminum titanium carbide, stirring for 24h in an oil bath with the low temperature of 35 ℃, centrifuging at 3500rpm, washing reactants with deionized water for multiple times until the upper layer liquid of the solution is dark green (the pH value is approximately equal to 7), and then carrying out ice bath super-cooling on the dispersion liquidSonicating for 2h at 3500rpm, centrifuging to collect supernatant, centrifuging the supernatant at 7000rpm for 5min to obtain large-sized Ti 3 C 2 T x Nanoplatelets (supernatant).
Step two, preparing a titanium carbide nanosheet with holes: taking 100mg of large-sheet Ti obtained in the step one 3 C 2 T x The nanoplatelets are dispersed in 100ml of deionized water and mixed with the same volume of 0.2mol/L copper sulfate solution, stirred for 30min by using a magnetic stirrer, and then repeatedly centrifugally washed by the deionized water until the pH value of the solution is 6.
Step three, preparing titanium carbide powder with holes: adding 20ml of 10% hydrogen fluoride solution into the solution obtained in the second step, maintaining the solution for etching for 10min, performing ultrasonic dispersion for 3min, performing centrifugal cleaning until the upper layer solution is dark green (pH value is 5-6), and freeze-drying the upper layer solution to obtain powder for later use, wherein the transmission electron microscope images of the obtained porous titanium carbide powder dispersion liquid are shown in fig. 2 and 3.
Step four, PMMA microsphere preparation: the radical initiator (azoisobutyronitrile) and polyvinylpyrrolidone as a stabilizer were dissolved in methanol at 0.1% and 4% by mass, respectively, at room temperature, the solution was purged with argon to remove oxygen in the mixed solution, and 10wt.% methyl Methacrylate Monomer (MMA) was added, then the reaction mixture was stirred at 50 ℃ for 24 hours, and after which white product was collected by centrifugation and washing with methanol, and a PMMA microsphere scanning electron microscopy image was obtained, as shown in fig. 4.
Fifthly, preparing hierarchical porous titanium carbide/carbon nanotube conductive fibers: 3.6mg of titanium carbide powder with holes and 7.2mg of PMMA nano-microspheres are dispersed in 1ml of chlorosulfonic acid, ultrasonic dispersion is carried out for 20min, 36mg of single-wall carbon nano-tube powder is added into a uniformly dispersed mixed solution, a rotation revolution deaeration stirrer is used for stirring for 20min at 1500rpm, undissolved impurities are removed by filtering the mixed liquid-state solution, the mixed liquid-state solution is transferred into a 5ml of glass needle tube as spinning solution, the spinning solution is injected into a spinning tank filled with acetone coagulation bath through a spinning head with the model of 22G at the spinning flow rate of 25ml/h by a numerical control injection pump, after cleaning and drying, vacuum sintering is carried out at 550 ℃ to obtain the multistage-hole titanium carbide/carbon nano-tube composite fiber, PMMA microspheres are decomposed in the sintering process, a regular spherical hole structure is left in the fiber, and the adjustment of the hole size can be realized by controlling preparation parameters.
Step six, immersing the multi-level porous composite fiber in a mixed solution of 0.8M aniline and 0.6M hydrochloric acid, placing the mixed solution in an ultrasonic bath at 50 ℃ for 2 hours, then adding 0.8M ammonium persulfate into the mixed solution of the immersed fiber, placing the mixed solution in the ultrasonic bath at 0 ℃ for 1 hour, performing PANI in-situ polymerization in the multi-level porous fiber, flushing the prepared composite fiber with ethanol/water solution, and drying the composite fiber at 50 ℃ for 4 hours.
Comparative example 1:
the method for preparing the porous titanium carbide/carbon nano tube composite fiber in the comparative example comprises the following steps:
step one, preparing titanium carbide nano-sheets: adding 1.6g of lithium fluoride powder into 20ml of 9mol/L hydrochloric acid, continuously stirring for 5min to fully react, then adding 1g of aluminum titanium carbide, stirring in a low-temperature oil bath at 35 ℃ for 24h, centrifuging at 3500rpm, washing reactants with deionized water for multiple times until the upper layer liquid of the solution is dark green (pH value is approximately equal to 7), performing ice bath ultrasonic treatment on the dispersion liquid for 2h, centrifuging at 3500rpm to collect supernatant, centrifuging the obtained upper layer liquid at 7000rpm for 5min to obtain large-piece-layer Ti 3 C 2 T x Nanoplatelets (supernatant).
Step two, preparing a titanium carbide nanosheet with holes: taking 100mg of large-sheet Ti obtained in the step one 3 C 2 T x The nanoplatelets are dispersed in 100ml of deionized water and mixed with the same volume of 0.2mol/L copper sulfate solution, stirred for 30min by using a magnetic stirrer, and then repeatedly centrifugally washed by the deionized water until the pH value of the solution is 6.
Step three, preparing titanium carbide powder with holes: adding 20ml of 10% hydrogen fluoride solution into the solution obtained in the second step, maintaining etching for 10min, performing ultrasonic dispersion for 3min, performing centrifugal cleaning until the supernatant is dark green (pH value is 5-6), and freeze-drying the supernatant to obtain powder for later use.
Step four, preparing porous titanium carbide/carbon nano tube composite fibers: 3.6mg of porous titanium carbide powder and 7.2mg of PMMA nano-microspheres are dispersed in 1ml of chlorosulfonic acid, ultrasonic dispersion is carried out for 20min, 36mg of single-wall carbon nano-tube powder is added into a uniformly dispersed mixed solution, a rotation revolution deaeration stirrer is used for stirring for 20min at 1500rpm, the mixed liquid-state solution is filtered to remove undissolved impurities and then is transferred into a 5ml glass needle tube as spinning solution, the spinning solution passes through a spinning head with the model of 22G through a numerical control injection pump, the spinning solution is injected into a spinning tank filled with acetone coagulation bath at the spinning flow rate of 25ml/h, and the spinning solution is washed and dried to obtain the porous titanium carbide/carbon nano-tube composite fiber, as shown in fig. 5-8, the self-stacking problem of the carbon nano-tube is relieved by adding the porous titanium carbide sheet, the porous titanium carbide sheet layer is interweaved with the porous titanium carbide powder and the porous titanium carbide sheet, the porous titanium carbide sheet is formed into a cluster-like structure, the porous titanium carbide composite fiber is a variegated block structure on the surface of the fiber, and the unique structure is increased in pores in the fiber.
Step five, immersing the composite fiber in the step four in a mixed solution of 0.8M aniline and 0.6M hydrochloric acid, placing the composite fiber in an ultrasonic bath at 50 ℃ for 2 hours, then adding 0.8M ammonium persulfate into the mixed solution of the immersed fiber, placing the composite fiber in the ultrasonic bath at 0 ℃ for 1 hour, carrying out PANI in-situ polymerization in the multi-stage pore fiber, flushing the prepared composite fiber with an ethanol/water solution, and drying the composite fiber at 50 ℃ for 4 hours, wherein the composite fiber is a composite fiber surface scanning electron microscope image with a polyaniline directional growth structure as shown in fig. 9 and 10.
Example 2:
this embodiment differs from embodiment 1 in that: in the fourth step, the addition amount of the methyl methacrylate is 12wt percent, and the reaction temperature is 55 ℃; step five, the mass of titanium carbide with holes in the spinning solution is 4.3mg, the extrusion rate is 20ml/h, the spinning head size is 20G, and the sintering temperature is 600 ℃; the remaining operating steps and parameter settings are exactly the same as in example 1.
Example 3:
this embodiment differs from embodiment 1 in that: in the fourth step, the addition amount of the methyl methacrylate is 12wt percent, and the reaction temperature is 55 ℃; the mass of the single-walled carbon nanotube, the porous titanium carbide and the PMMA microsphere in the spinning solution is 38mg,4.5mg and 9mg respectively, the extrusion rate is 20ml/h, the spinning head size is 20G, and the sintering temperature is 600 ℃; in the sixth step, the concentrations of aniline and hydrochloric acid were 0.85M and 0.65M, respectively, the concentration of ammonium persulfate was 0.85M, and the other operation steps and parameter settings were exactly the same as those in example 1.
Example 4:
this embodiment differs from embodiment 1 in that: in the fourth step, the addition amount of methyl methacrylate is 15wt.%, and the reaction temperature is 60 ℃; the mass of the single-walled carbon nanotube, the porous titanium carbide and the PMMA microsphere in the spinning stock solution is 38mg,5.4mg and 9mg respectively, the extrusion rate is 30ml/h, the spinning head size is 18G, and the sintering temperature is 650 ℃; in the sixth step, the concentrations of aniline and hydrochloric acid were 0.85M and 0.65M, respectively, the concentration of ammonium persulfate was 0.85M, and the other operation steps and parameter settings were exactly the same as those in example 1.
Example 5:
this embodiment differs from embodiment 1 in that: in the fourth step, the addition amount of methyl methacrylate is 15wt.%, and the reaction temperature is 60 ℃; the mass of the single-walled carbon nanotube, the porous titanium carbide and the PMMA microsphere in the spinning solution is 40mg,7.2mg and 10.8 mg respectively, the extrusion rate is 30ml/h, the spinning head size is 18G, and the sintering temperature is 650 ℃; in the sixth step, the concentrations of aniline and hydrochloric acid were 0.9M and 0.65M, respectively, and the concentration of ammonium persulfate was 0.9M, and the other operation steps and parameter settings were exactly the same as those in example 1.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the hierarchical porous titanium carbide/carbon nanotube composite fiber is characterized by comprising the following steps of:
s1, preparing porous titanium carbide powder;
s2, preparing PMMA microspheres;
s3, preparing a fiber spinning solution by taking porous titanium carbide powder, carbon nanotubes and PMMA microspheres as raw materials, and cleaning and sintering the obtained fiber after wet spinning to obtain the multi-level porous titanium carbide/carbon nanotube composite fiber;
s4, polyaniline in-situ polymerization of the composite fiber.
2. The method for preparing the hierarchical porous titanium carbide/carbon nanotube composite fiber according to claim 1, wherein the step S1 is specifically as follows: adding lithium fluoride powder into hydrochloric acid, continuously stirring for full reaction, adding aluminum titanium carbide, stirring in an oil bath at 35-40 ℃ for reaction for 24 hours, centrifuging after the reaction is finished, washing reactants until the upper layer liquid of the solution is dark green and has pH of 6-7 by using deionized water, performing ice bath ultrasonic treatment on the upper layer liquid, centrifuging to collect supernatant, further performing centrifugal treatment on the supernatant, adding an equal volume of copper sulfate solution into the obtained titanium carbide dispersion, stirring for 25-35 min, repeatedly performing centrifugal washing by using deionized water until the pH value of the solution is 6-8, adding hydrogen fluoride into the solution, etching for 10-15 min, performing ultrasonic dispersion, centrifugally washing until the upper layer liquid is dark green, and taking the upper layer liquid for freeze drying to obtain the titanium carbide powder with holes.
3. The method for preparing the hierarchical porous titanium carbide/carbon nanotube composite fiber according to claim 2, wherein the mass ratio of the lithium fluoride to the aluminum titanium carbide is 1-1.6:1, the concentration of hydrochloric acid is 6-9 mol/L, the use amount is 10-20 ml, the mass concentration of the hydrogen fluoride solution is 10-15%, and the concentration of the copper sulfate solution is 0.2-0.4 mol/L.
4. The method for preparing the hierarchical porous titanium carbide/carbon nanotube composite fiber according to claim 2, wherein the supernatant is centrifuged for 5-10 min at 6000-7000 rpm, the ice bath is sonicated for 2-4 h, the etched titanium carbide powder is dispersed in deionized water, and the centrifugation speed is 3500-4000 rpm.
5. The method for preparing the hierarchical porous titanium carbide/carbon nanotube composite fiber according to claim 1, wherein the step S2 is specifically as follows: and (3) dissolving azoisobutyronitrile and polyvinylpyrrolidone in methanol, purging the mixed solution with nitrogen, adding methyl methacrylate, stirring for reaction, centrifuging and washing to obtain a white product which is PMMA microspheres.
6. The method for preparing the hierarchical porous titanium carbide/carbon nanotube composite fiber according to claim 5, wherein the S2 reaction temperature is 50-60 ℃, the mass concentration of azoisobutyronitrile in the mixed solution is 0.1-0.2%, the mass concentration of polyvinylpyrrolidone is 4%, and the mass fraction of the added methyl methacrylate is 10-15%.
7. The method for preparing the hierarchical porous titanium carbide/carbon nanotube composite fiber according to claim 1, wherein the step S3 is specifically as follows: weighing a certain mass of porous titanium carbide powder and PMMA microspheres, performing ultrasonic dispersion in 1-5-ml chlorosulfonic acid for 20-30 min, then adding single-wall carbon nanotube powder into the uniformly dispersed mixed solution, and stirring for 20-30 min by using a rotation revolution deaeration stirrer;
filtering the mixed liquid crystal solution to remove undissolved impurities, and transferring the liquid crystal solution into a glass needle tube as spinning solution;
extruding the spinning solution into an acetone coagulating bath through a numerical control injection pump;
and (3) cleaning, drying, and sintering at high temperature to obtain the hierarchical porous titanium carbide/carbon nano tube composite fiber.
8. The method for preparing the hierarchical porous titanium carbide/carbon nanotube composite fiber according to claim 7, wherein the mass ratio of the single-walled carbon nanotube to the porous titanium carbide to the PMMA microsphere is 1:0.1-0.2:0.2-0.3, the concentration of the single-walled carbon nanotube is 35-40mg/ml, the extrusion rate of the spinning solution is 10-30 ml/h, the size of a spinning head is 18-25G, the sintering temperature is 500-650 ℃, and the rotational revolution deaeration mixer is adopted, and the rotational speed is 1500-2000 r/min.
9. The method for preparing the hierarchical porous titanium carbide/carbon nanotube composite fiber according to claim 1, wherein the step S4 is specifically: immersing the hierarchical porous composite fiber in a mixed solution of aniline and hydrochloric acid, and placing in an ultrasonic bath at 40-60 ℃ for 2-3 hours;
then adding ammonium persulfate into the mixed solution for soaking the fibers, placing the mixed solution in an ultrasonic bath at the temperature of 0-4 ℃ for 0.5-1.5 hours, and carrying out PANI in-situ polymerization in the hierarchical pore fibers;
washing the prepared composite fiber with ethanol/water solution, and drying at 45-55deg.C for 3-5 hr.
10. The method for preparing a hierarchical porous titanium carbide/carbon nanotube composite fiber according to claim 9, wherein the concentration of aniline and hydrochloric acid is 0.8-0.9M and 0.6-0.65M, respectively, and the concentration of ammonium persulfate is 0.8-0.9M.
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