CN109537263B - ZnO/carbon fiber flexible material and preparation method thereof - Google Patents
ZnO/carbon fiber flexible material and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 119
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 hydroxyl ions Chemical class 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000003980 solgel method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
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- 238000010923 batch production Methods 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
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- 238000000576 coating method Methods 0.000 abstract description 2
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- 150000003751 zinc Chemical class 0.000 description 11
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- 230000005684 electric field Effects 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
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- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention discloses a ZnO/carbon fiber flexible material and a preparation method thereof, and is characterized by comprising carbon fiber cloth and a ZnO nanowire composite material growing on the surface of the carbon fiber cloth, wherein the length of a ZnO nanowire is 5-10 mu m, and the diameter of the ZnO nanowire composite material is 30-50 nm. The sol-gel and hydrothermal preparation process adopted by the invention is simple, high in yield, low in cost and suitable for batch production; the ZnO nanowire material is directly grown on the carbon fiber, and the prepared nano composite material has the advantages of uniform shape, tight coating and the capability of bending the carbon fiber, and is an excellent field emission cathode material.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a ZnO/carbon fiber flexible material and a preparation method thereof.
Background
Field emission display devices are developing extremely rapidly as an emerging flat panel display. It combines many advantages of Cathode Ray Tube (CRT) and flat panel display, and has wide application prospect. As a wide bandgap oxide semiconductor material, the ZnO nano material has good field electron emission performance, has the characteristics of low opening electric field, high mechanical strength, oxidation resistance, high temperature resistance and the like, and has important application prospect in devices such as a field emission electron microscope, a miniature X-ray source, a cold cathode microwave amplifier, a flat panel display, a cathode fluorescent light source and the like. Therefore, ZnO nanomaterials are one of the most promising nanomaterials for practical field emission electron sources. ZnO is a wide band gap II-VI group oxide semiconductor material, and is suitable to be used as a field emission cathode material because of a plurality of excellent characteristics such as good chemical stability, small or even negative electron affinity, high thermal conductivity, good oxidation resistance and high temperature resistance, large breakdown field strength and high carrier mobility, large emission current and the like. Research shows that the carbon fiber has field emission performance, and the plane structure limits the electron emission capacity, so that the ZnO and the carbon fiber are compounded to form the ZnO/carbon fiber material, which has obviously improved field emission performance compared with ZnO material prepared on other substrates and can be bent to prepare curved-screen display devices. Therefore, the nano composite material with good quality and a specific hierarchical structure can be obtained by regulating the growth of the ZnO nano wire, and has important significance in the application.
At present, a great deal of researchers have engaged in the compounding of ZnO and carbon fiber and achieved certain results, and in 2010, a paper entitled "Flexible cooled cathode with ultra low threshold designed carbon fiber chemical route" published in the journal of Nanotechnology adopts a magnetron sputtering deposition method and a hydrothermal method to prepare a ZnO coated carbon fiber nanomaterial. In 2014, a paper entitled "contamination of High-Activity Hybrid Pt @ ZnO Catalyst on Carbon fiber by Atomic Layer Deposition for photo-assisted Electro-Oxidation of methane" published in The Journal of Physical Chemistry C adopted The Atomic Layer Deposition method and The hydrothermal method to prepare The nanomaterial of ZnO coated Carbon fiber. The two reports respectively adopt a measurement and control sputtering method and an atomic layer deposition method in the process of preparing the seed layer, although the seed layer prepared by the two methods has good uniformity and quality, the seed layer has high environmental requirements, the equipment is expensive, large-area deposition is not easy to realize, industrial production cannot be realized, and the process is easy to synthesize very dense ZnO nano-rods, the top ends of the ZnO nano-rods are in a plane hexagon shape instead of a pointed hexagonal cone shape, so that the field emission property and the application of the material are limited. In the hydrothermal preparation process, a large number of researchers all use hexamethylenetetramine as a hydroxide source, the growth speed is slow, the length of a grown ZnO nano material is insufficient, the required growth time is long, and the top ends of ZnO nanorods prepared by using hexamethylenetetramine as the hydroxide source are basically in a plane hexagon shape instead of a pointed hexagonal cone shape, so that how to obtain a ZnO/carbon fiber brush-shaped field emission cathode flexible material with a large length-diameter ratio is a research hotspot in the industry.
Disclosure of Invention
Aiming at the defects and the defects of the prior art, the invention provides a ZnO/carbon fiber flexible material and a preparation method thereof, which solve the problem that the material cannot simultaneously give consideration to bending and excellent field emission performance, and further obtain a ZnO/carbon fiber brush-shaped field emission cathode flexible material with a large length-diameter ratio.
In order to solve the problems, the invention adopts the technical scheme that:
the ZnO/carbon fiber flexible material comprises carbon fiber cloth and a ZnO nanowire composite material growing on the surface of the carbon fiber cloth, wherein the length of a ZnO nanowire is 5-10 mu m, and the diameter of the ZnO nanowire composite material is 30-50 nm.
Furthermore, the ZnO/carbon fiber flexible material is prepared by a sol-gel method and a hydrothermal method in sequence.
Specifically, the sol-gel method comprises the steps of dissolving zinc salt and a stabilizer in ethanol to obtain a mixed solution, then aging the mixed solution to form sol, and then dip-coating carbon fiber cloth in the sol to obtain a ZnO seed crystal layer wrapped carbon fiber structure;
the zinc salt comprises zinc acetate, the stabilizer comprises ethanolamine, and the molar ratio of the ethanolamine to the zinc acetate is 1: 1-2: 1.
Specifically, the hydrothermal method comprises the steps of adding a zinc salt solution into a strong base solution to serve as a precursor solution, and then adding the carbon fiber structure wrapped by the ZnO seed crystal layer into the precursor solution to carry out hydrothermal reaction;
the concentration of the zinc salt solution is 0.05-0.11 mol/L, the concentration of the strong base solution is 0.8-2.2 mol/L, and the concentration ratio of zinc ions to hydroxyl ions in the precursor solution is 1: 16-1: 20.
Furthermore, the temperature of the hydrothermal reaction is 70-100 ℃, and the time of the hydrothermal reaction is 3-4 h.
A preparation method of a ZnO/carbon fiber flexible material specifically comprises the following steps:
step (1): pretreating carbon fiber cloth;
step (2): sol-gel method for preparing ZnO crystal seed layer wrapped carbon fiber structure
Adding a stabilizer into a zinc salt solution, stirring to obtain a transparent solution, and then aging the transparent solution to form sol; then dip-coating the carbon fiber cloth in the sol, and carrying out heat treatment and annealing;
and (3): flexible material for preparing ZnO/carbon fiber by hydrothermal method
And (3) adding a zinc salt solution into a strong base solution to serve as a precursor solution, adding the ZnO seed crystal layer-wrapped carbon fiber structure obtained in the step (2) into the precursor solution to perform hydrothermal reaction, and then washing and drying to obtain the ZnO seed crystal carbon fiber.
Specifically, the zinc salt in the step (2) comprises zinc acetate, the stabilizer comprises ethanolamine, and the molar ratio of the ethanolamine to the zinc acetate is 1: 1-2: 1.
Further, in the step (2), the carbon fiber cloth is soaked in the sol for 10-15 s, the soaking time is 2-4 times, and the annealing temperature is 550-650 ℃.
Further, the concentration of the zinc salt solution in the step (3) is 0.05-0.11 mol/L, the concentration of the strong base solution is 0.8-2.2 mol/L, and the concentration ratio of zinc ions to hydroxyl ions in the precursor solution is 1: 16-1: 20.
Further, the reaction temperature of the hydrothermal reaction in the step (3) is 70-100 ℃, and the reaction time of the hydrothermal reaction is 3-4 h.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) according to the ZnO/carbon fiber flexible material prepared by the invention, the length of the ZnO nanowire is 5-10 mu m, and the diameter is 30-50 nm; the microstructure can be observed that the ZnO/carbon fiber flexible material has a large specific surface area and a plurality of emission tips and is in a brush shape; the ZnO/carbon fiber flexible material has a large number of heterojunctions, so that the recombination of photon-generated carriers is reduced, and electron hole pairs are effectively separated, thereby prolonging the service life of the carriers and increasing the carrier concentration; from the physical property combination, the ZnO/carbon fiber flexible material has good emission capability of ZnO nano-wires to field emission electrons, also has the bendable capability of carbon fibers, and is an excellent field emission cathode material.
(2) According to the invention, when the ZnO/carbon fiber flexible material is prepared, the ZnO single crystal nanowire is grown on the side surface of the carbon fiber by adopting a sol-gel method and a hydrothermal method, no template or catalyst is needed in the preparation process, the process is simple, the yield is high, the cost is low, and the method is suitable for batch production;
(3) ZnO nanowires grow on the side surface of the carbon fiber, and the prepared nano composite material is uniform in shape and tight in coating.
Drawings
FIG. 1 is an XRD pattern of a flexible material of ZnO/carbon fiber of example 1 in the present invention;
FIG. 2 is an SEM photograph of a flexible ZnO/carbon fiber material of example 1 of the present invention;
FIG. 3 is a J-E diagram of the field emission of the ZnO/carbon fiber flexible material of example 1 in the invention;
FIG. 4 is a F-N diagram of the field emission of the ZnO/carbon fiber flexible material in the embodiment 1 of the invention;
FIG. 5 is SEM photograph of the ZnO/carbon fiber flexible material of example 2 in the invention;
FIG. 6 is SEM photograph of the ZnO/carbon fiber flexible material of example 2 in the invention;
FIG. 7 is an SEM photograph of a flexible material of ZnO/carbon fiber of example 3 in the present invention;
FIG. 8 is an SEM photograph of a flexible material of ZnO/carbon fiber of example 4 in the present invention;
FIG. 9 is an SEM photograph of a flexible material of ZnO/carbon fiber of comparative example 1 in the present invention;
the invention is described in detail below with reference to the drawings and the detailed description.
Detailed Description
The ZnO/carbon fiber flexible material prepared by the invention adopts a simple sol-gel method and a hydrothermal method to grow ZnO nanowires on the surface of carbon fibers, and carbon fibers are used as a primary structure, and the ZnO nanowires are used as a complex hierarchical structure material with a secondary structure.
Preparing a ZnO seed crystal layer on the side surface of the carbon fiber by mainly adopting a sol-gel method, and controlling reaction factors such as zinc salt concentration, the ratio of zinc salt to a stabilizer, dip-coating time, the number of dip-coating layers, annealing temperature, heat preservation time and the like; a hydrothermal method is adopted, the ZnO/carbon fiber flexible material is obtained by controlling the concentration of zinc salt in a reaction system, the alkali salt ratio, the reaction temperature, the reaction time and other factors, no template or catalyst is needed in the preparation process, the process is simple, the yield is high, the cost is low, and the method is suitable for batch production; the carbon fiber cloth is used as a main structure to directly grow ZnO nanowires, the prepared single crystal ZnO nanowires are uniform in shape and uniformly coated on the carbon fibers, and the carbon fiber cloth adopted by the invention is from Shanghai Shuo composite material science and technology company Limited (conductive flexible hydrophilic carbon fiber cloth).
In order to make the objects and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
step (1): pretreatment of carbon fiber cloth
Will (1.5 x 1.5 cm)2) Soaking carbon fiber cloth in concentrated nitric acid at 100 deg.C for 1h, ultrasonically cleaning with deionized water, ethanol and deionized water for 3 times, each time for 30min, and drying for use;
step (2): sol-gel method for preparing ZnO crystal seed layer wrapped carbon fiber structure
2.2172g (0.20mol/L) of zinc acetate dihydrate is weighed and dissolved in 50mL of ethanol, stirred for 30min at room temperature, then 1.2mL of ethanolamine is slowly dropped into the solution, the molar ratio of the ethanolamine to the zinc acetate is 1:1, the stirring is continued for more than about 30min to obtain a uniform light transparent solution, and finally the obtained solution is put into an oven and aged for one day at 60 ℃ to obtain sol. And then dip-coating the carbon fiber cloth in the sol for 10s, taking out, putting the dip-coated carbon fiber cloth on a heating table at 90 ℃ for heat treatment for 10min, repeating the dip-coating heating process twice, putting the carbon fiber cloth in a muffle furnace for annealing after the dip-coating is finished, heating to 650 ℃ (the heating rate is 5 ℃/min), and preserving heat for 120min to prepare the ZnO seed crystal layer-coated carbon fiber structure.
And (3): flexible material for preparing ZnO/carbon fiber by hydrothermal method
0.08mol/L (1.240g) of Zn (CH)3COOH)2Adding the powder into 40ml of deionized water, and fully stirring to form Zn (CH)3COOH)2Solution, adding 1.6mol/L (4.6667g) NaOH powder into 30mL deionized water, fully stirring to form NaOH solution, and adding Zn (CH)3COOH)2The solution is slowly added into NaOH solution to form uniform precursor solution, and the concentration ratio of zinc ions to hydroxyl ions in the precursor solution is 1: 20.
Putting the carbon fiber structure wrapped by the ZnO seed crystal layer prepared in the step (2) into a reaction kettle (the volume of the lining is 50mL) filled with the precursor solution and provided with a polytetrafluoroethylene lining for hydrothermal reaction, sealing the reaction kettle and putting the reaction kettle in a drying oven at 100 ℃ for heat preservation for 4 hours, continuously cleaning the carbon fiber cloth after the reaction is finished, and washing the carbon fiber cloth with deionized water for multiple times until filtrate is obtainedAnd (3) drying the carbon fiber in an oven at 60 ℃ after the pH is 7 to obtain the ZnO/carbon fiber composite material, namely the ZnO/carbon fiber flexible material. Carrying out X-ray diffraction pattern analysis, scanning electron microscope analysis and field emission performance analysis on the obtained flexible material; the specific X-ray diffraction pattern is shown in figure 1, and XRD results show that: the product is a ZnO/carbon fiber composite material; the scanning electron microscope photograph is shown in FIG. 2; the ZnO/carbon fiber composite material is of a brush-shaped core-shell structure, the prepared single crystal ZnO nanowire is uniform in shape and uniformly coated on the carbon fiber, and the length of the obtained ZnO nanowire is 7-8 mu m and the diameter of the ZnO nanowire is 30-40 nm. FIGS. 3 and 4 illustrate that the turn-on electric fields of the flexible materials of carbon fiber cloth and "hairbrush" ZnO/carbon fiber are 1.109V/μm and 0.615V/μm, respectively (turn-on electric field: when the current density reaches 10 μ A/cm)2Electric field of time), the threshold electric field of the flexible material of ZnO/carbon fiber was 1.128V/μm (threshold electric field: when the current density reaches 1mA/cm2Electric field at the time) the field enhancement factors of the flexible materials of carbon cloth and "brush-like" ZnO/carbon fiber were 10635 and 23987, respectively. Compared with a ZnO nanowire array (the opening electric field: 3.16V/mum and the field enhancement factor: 2889) prepared on a Zn substrate, the opening electric field and the threshold electric field of the ZnO/carbon fiber flexible material are low, and the field enhancement factor is relatively high, so that the brush-shaped ZnO/carbon fiber flexible material has good field emission performance.
Example 2:
step (1) and step (2) are the same as in example 1;
step (3) hydrothermal method for preparing ZnO/carbon fiber flexible material
0.05mol/L of Zn (CH)3COOH)2The solution is dropwise added into 0.9mol/L NaOH solution, and after titration is finished, the solution is continuously stirred to obtain uniform precursor solution, so that the concentration ratio of zinc ions to hydroxyl ions in the precursor solution is 1: 16.
And (3) putting the carbon fiber structure wrapped by the ZnO seed crystal layer prepared in the step (2) into a reaction kettle (the volume of the lining is 50mL) filled with the precursor solution and lined with polytetrafluoroethylene for hydrothermal reaction, sealing the reaction kettle and putting the reaction kettle in a 70 ℃ oven for heat preservation for 4 hours, continuously cleaning the carbon fiber cloth after the reaction is finished, washing the carbon fiber cloth with deionized water for multiple times until the pH value of the filtrate is 7, and then putting the carbon fiber in the 60 ℃ oven for drying to obtain the ZnO/carbon fiber composite material, namely the ZnO/carbon fiber flexible material.
Scanning electron microscope analysis is carried out on the obtained flexible material, and photos under different magnification are shown in figures 5 and 6; fig. 5 and 6 illustrate that the ZnO/carbon fiber composite material prepared in the second embodiment has a brush-shaped core-shell structure on the surface, the prepared single crystal ZnO nanowires are uniform in shape and uniformly coated on the carbon fibers, the tops of the ZnO nanowires are hexagonal pyramid tips, and the obtained ZnO nanowires have a measured length of 5 to 6 μm and a diameter of 30 to 40 nm.
Example 3:
step (1) and step (2) are the same as in example 1;
step (3) hydrothermal method for preparing ZnO/carbon fiber flexible material
0.11mol/L of Zn (CH)3COOH)2The solution is dropwise added into 2.2mol/L NaOH solution, and after titration is finished, the solution is continuously stirred to obtain uniform precursor solution, so that the concentration ratio of zinc ions to hydroxyl ions in the precursor solution is 1: 20.
And (3) putting the carbon fiber structure wrapped by the ZnO seed crystal layer prepared in the step (2) into a reaction kettle (the volume of the lining is 50mL) filled with the precursor solution and lined with polytetrafluoroethylene for hydrothermal reaction, sealing the reaction kettle and putting the reaction kettle into a 100 ℃ oven for heat preservation for 3 hours, continuously cleaning the carbon fiber cloth after the reaction is finished, washing the carbon fiber cloth with deionized water for multiple times until the pH value of the filtrate is 7, and then putting the carbon fiber into the 60 ℃ oven for drying to obtain the ZnO/carbon fiber composite material, namely the ZnO/carbon fiber flexible material.
The scanning electron micrograph of this product is shown in FIG. 7; FIG. 7 shows that the product obtained in the third example is also a core-shell structure with a brush-like surface, and the obtained ZnO nanowire has a length of 6-8 μm and a diameter of 40-50 nm.
Example 4:
step (1) As in example 1
Step (2) preparing ZnO crystal seed layer wrapped carbon fiber structure by sol-gel method
3.8801g (0.35mol/L) of zinc acetate dihydrate is weighed and dissolved in 50mL of ethanol, stirred for 30min at room temperature, then 2.1mL of ethanolamine is slowly dropped, the molar ratio of the ethanolamine to the zinc acetate is 2:1, the stirring is continued for more than about 30min to obtain a uniform light transparent solution, and finally the obtained solution is put into an oven and aged for one day at 60 ℃ to obtain sol. And then, dip-coating the carbon fiber cloth in the sol for 15s, taking out, putting the dip-coated carbon fiber on a heating table at 90 ℃ for heat treatment for 10min, repeating the dip-coating heating process twice, putting the carbon fiber in a muffle furnace for annealing after the dip-coating is finished, then heating the muffle furnace to 550 ℃ (the heating rate is 5 ℃/min), and preserving heat for 120min to prepare the ZnO seed crystal layer-coated carbon fiber structure.
Step (3) same as example 2;
the scanning electron micrograph of this product is shown in FIG. 8; FIG. 8 illustrates the core-shell structure of the product obtained in the fourth example, wherein the surface of the product is in a brush shape, and the ZnO nanowire obtained by measurement has a length of 5-7 μm and a diameter of 30-40 nm.
Comparative example 1:
similar to example 1, but different from example 1, in step (3), 0.11mol/L of Zn (CH)3COOH)2The solution is dropwise added into 2.42mol/L NaOH solution, and after titration is finished, the solution is continuously stirred to obtain uniform precursor solution, so that the concentration ratio of zinc ions to hydroxyl ions in the precursor solution is 1: 22.
The scanning electron micrograph of this product is shown in FIG. 9; only a small amount of ZnO nanoparticles was observed to cover the carbon fibers. It is clear that in this case, the ZnO/carbon fiber structure cannot be formed at a ratio of the zinc ion and hydroxide ion concentrations in the precursor solution of 1/22.
In conclusion, the sol-gel method and the hydrothermal preparation process adopted by the invention have the advantages of simple process, strong controllability, high yield and low cost, and are suitable for batch production.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (2)
1. A preparation method of a ZnO/carbon fiber flexible material is characterized by specifically comprising the following steps:
step (1): pretreating carbon fiber cloth;
step (2): sol-gel method for preparing ZnO crystal seed layer wrapped carbon fiber structure
Weighing zinc acetate dihydrate, dissolving the zinc acetate dihydrate in ethanol, stirring at room temperature to obtain 0.2 mol/L ethanol solution of the zinc acetate dihydrate, slowly dripping ethanolamine with the molar ratio of the ethanolamine to the zinc acetate being 1:1, continuously stirring to obtain uniform light transparent solution, finally putting the obtained solution into a drying oven, and aging for one day at 60 ℃ to obtain sol; then dipping the carbon fiber cloth in the sol for 10s, taking out, putting the dipped carbon fiber cloth on a heating table at 90 ℃ for heat treatment for 10min, repeating the dipping and heating process twice, putting the carbon fiber cloth in a muffle furnace for annealing after the dipping, raising the temperature to 650 ℃ at the temperature rise speed of 5 ℃/min, and preserving the temperature for 120min to prepare a ZnO seed crystal layer-wrapped carbon fiber structure;
and (3): flexible material for preparing ZnO/carbon fiber by hydrothermal method
Adding Zn (CH)3COOH)2Adding the powder into deionized water, and fully stirring to form Zn (CH)3COOH)2Adding NaOH powder into deionized water, stirring to obtain NaOH solution, and adding Zn (CH)3COOH)2Adding the solution into NaOH solution to form uniform precursor solution, wherein Zn (CH)3COOH)2The concentration of the precursor is 0.08mol/L, and the concentration ratio of zinc ions to hydroxyl ions in the precursor solution is 1: 20;
and (3) putting the carbon fiber structure wrapped by the ZnO seed crystal layer prepared in the step (2) into a reaction kettle filled with a polytetrafluoroethylene lining and provided with the precursor solution for hydrothermal reaction, sealing the reaction kettle and putting the reaction kettle in a drying oven at 100 ℃ for heat preservation for 4 hours, continuously cleaning the carbon fiber cloth after the reaction is finished, washing the carbon fiber cloth for multiple times by using deionized water until the pH =7 of filtrate, and then arranging the carbon fiber in the drying oven at 60 ℃ for drying to obtain a ZnO/carbon fiber flexible material, wherein the ZnO/carbon fiber flexible material is of a core-shell structure with a brush-shaped surface, the prepared single crystal ZnO nanowire is uniform in shape, the carbon fiber is uniformly wrapped, and the obtained ZnO nanowire is 7-8 mu m in length and 30-40 nm in diameter.
2. A ZnO/carbon fiber flexible material, which is characterized by being prepared by the preparation method of the ZnO/carbon fiber flexible material according to claim 1.
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