CN114574982B - Zirconium oxide/cobalt/carbon nano tube composite hollow fiber and preparation and application thereof - Google Patents
Zirconium oxide/cobalt/carbon nano tube composite hollow fiber and preparation and application thereof Download PDFInfo
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- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
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Abstract
The invention relates to a zirconia/cobalt/carbon nano tube composite hollow fiber and a preparation method and application thereof. According to the invention, zirconia, simple substance cobalt and carbon nano tubes are selected as components of the wave absorbing agent, and a wider effective absorption bandwidth and stronger loss of electromagnetic waves are realized by utilizing a synergistic effect. Performing electrostatic spinning by using cobalt salt, zirconium salt and a surfactant, pre-oxidizing to obtain a zirconium-cobalt-carbon fiber, calcining by using a muffle furnace to obtain a hollow fiber compounded by cobaltosic oxide and zirconium oxide, mixing with pyrrole, and reacting at high temperature to obtain the zirconium oxide, cobalt and carbon nano tube composite hollow fiber material. The method has simple process, and the hollow fiber wave absorbing agent compounded by three components of oxide compounds, simple substances and carbon nano tubes can be prepared only by one-step electrostatic spinning, muffle furnace calcination and high-temperature carbon coating.
Description
Technical Field
The invention belongs to the technical field of electromagnetic wave absorption materials, and particularly relates to a zirconia/cobalt/carbon nanotube composite hollow fiber and preparation and application thereof.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In recent decades, mobile electronic devices such as mobile phones and notebook computers have been developed rapidly, and meanwhile, people have come to pay attention to problems such as electromagnetic interference and electromagnetic radiation among the devices due to the fact that the upgrading of communication technologies such as 5G and wireless local area networks is on the rise, so people pay more attention to the protection against electromagnetic pollution. Among them, the electromagnetic wave absorbing material has become an important means for realizing electromagnetic protection because of its wide application range. Although the traditional magnetic metal powder wave-absorbing material has higher saturation magnetization and magnetic conductivity and stronger magnetic loss capacity, the material is easy to oxidize and has high density, the wave-absorbing performance of the material is obviously reduced, and the portability of equipment is not facilitated.
Disclosure of Invention
In order to solve the technical problems, the invention provides a zirconia/cobalt/carbon nanotube composite hollow fiber and preparation and application thereof. The zirconium oxide/cobalt/carbon nano tube composite hollow fiber has stronger loss capacity and wider effective absorption bandwidth, is applied to electromagnetic wave absorption, has wider effective absorption bandwidth and stronger loss capacity, and has stronger wave-absorbing performance under the condition of thin thickness.
In order to achieve the above object, the present invention provides the following technical solutions.
A preparation method of zirconia/cobalt/carbon nano tube composite hollow fiber comprises the following steps: dispersing zirconium salt, cobalt salt and a surfactant in a solution, performing electrostatic spinning, and performing pre-oxidation and heating calcination in a muffle furnace to obtain a cobaltosic oxide/zirconia hollow fiber; and finally, placing the cobaltosic oxide/zirconia hollow fiber and pyrrole in a cast iron reaction kettle together, and carrying out high-temperature reaction to obtain the cobaltosic oxide/zirconia hollow fiber.
Further, the solution is N, N-dimethylformamide;
further, the zirconium salt is zirconium n-butyl alcohol or zirconium acetylacetonate;
further, the cobalt salt is cobalt acetylacetonate or cobalt acetate tetrahydrate;
further, the surfactant is polyvinylpyrrolidone.
Further, the addition ratio of the cobalt salt, the zirconium salt, the surfactant and the solution is as follows: (0.4-1) g, (0.4-1.6) g, (0.8-1.5) g, (5-15) mL; preferably: (0.5-0.8) g, (0.8-0.9) g, (0.9-1.2) g, (9-12) mL.
Further, the voltage of the electrostatic spinning is 10-15kV, and the distance between the needle head of the injector and the receiving plate is 15-30cm; preferably, the voltage is 11-13kV, and the distance between the needle of the syringe and the receiving plate is 22-26cm; more preferably: the voltage was 12kV and the distance of the syringe needle from the receiving plate was 25cm.
Further, the pre-oxidation temperature is 150-200 ℃, and the pre-oxidation time is 1-5h; preferably, the pre-oxidation temperature is 170-190 ℃, and the pre-oxidation time is 2-4h; more preferably: the pre-oxidation temperature is 180 ℃, and the pre-oxidation time is 3h.
Further, the calcining temperature of the muffle furnace is 400-700 ℃, the heating rate is 1-5 ℃/min, and the reaction time is 2-5h; preferably, the reaction temperature is 500-600 ℃, the heating rate is 1.5-2.5 ℃/min, and the reaction time is 2.5-3.5h; more preferably: the reaction temperature is 550 ℃, the heating rate is 2 ℃/min, and the reaction time is 3h.
Further, the adding proportion of cobaltosic oxide/zirconia hollow fiber and pyrrole is (50-200) mg (1-5) mL; preferably (80-150) mg (2-3) mL; further preferably 100mg.
A composite wave-absorbing material comprises the zirconia/cobalt/carbon nanotube composite hollow fiber and paraffin; further, the mass ratio of the zirconia/cobalt/carbon nanotube composite hollow fiber to the paraffin is 1:4.
further, the temperature for mixing the zirconium oxide/cobalt/carbon nano tube composite hollow fiber and the paraffin is 30-60 ℃.
The zirconia/cobalt/carbon nano tube composite hollow fiber or the composite wave-absorbing material is applied to the field of electromagnetic wave absorption.
The invention has the beneficial effects that:
(1) In the composite hollow fiber of the present invention, zrO 2 The material is a low-loss wave-transparent material, so that electromagnetic waves can smoothly enter the material without reflection; the metal cobalt has high saturation magnetization intensity and relatively good stability, improves the magnetism of the material and enhances the magnetic loss; the carbon nano tube has the advantages of large reserve, low density, strong chemical stability, strong corrosion resistance and the like, and can be used as a good coating material; and the existence of the hollow structure can enable electromagnetic waves to generate multiple scattering, and the loss of the material to the electromagnetic waves is enhanced. The composite hollow fiber has good wave absorbing effect, so thatIs expected to be widely applied to the preparation of electromagnetic wave absorption materials.
(2) The synthesis method is simple, the prepared zirconia/cobalt/carbon nano tube composite hollow fiber has uniform diameter and narrow diameter distribution, and no other by-products are generated in the heat treatment process.
(3) The composite wave-absorbing material disclosed by the invention has the advantages that the reflection loss of electromagnetic waves at a high frequency (17.92 GHz) reaches-12.46 dB, the matching thickness is only 1.34mm, and the effective absorption bandwidth at a 1.49mm position is 3.76GHz. The zirconium oxide, cobalt and carbon nano tube composite hollow fiber material has high wave-absorbing performance and wide application value.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is an XRD pattern of the zirconyl oxide/cobalt/carbon nanotube composite hollow fiber prepared in example 1.
In FIG. 2, a is a TEM image of a cobaltosic oxide/zirconia hollow fiber precursor of example 1, and b is an SEM image of a zirconia/cobalt/carbon nanotube composite hollow fiber of example 1.
In fig. 3, a is a TEM image of the zirconia/cobalt/carbon nanotube composite hollow fiber obtained in example 1, and b is an SEM image of the zirconia/cobalt/carbon nanotube composite hollow fiber containing individual coating unevenness.
In fig. 4, a is a real part of dielectric constant, b is an imaginary part of dielectric constant, and c is dielectric loss tangent of the zirconia/cobalt/carbon nanotube composite hollow fiber prepared in example 1.
In fig. 5, a is a graph showing a real part of magnetic permeability, b is an imaginary part of magnetic permeability, and c is a magnetic loss tangent of the zirconia/cobalt/carbon nanotube composite hollow fiber prepared in example 1.
Fig. 6 is a reflection loss chart of the zirconia/cobalt/carbon nanotube composite hollow fiber absorber prepared in the experimental example.
Fig. 7 is a TEM image of the sample prepared in comparative example 1.
Fig. 8 is a graph of the reflection loss of the sample prepared in comparative example 1.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
At present, the wave-absorbing material with a single component has a single loss mechanism, and is difficult to realize strong loss and a wider effective absorption bandwidth at the same time, so that the components of the material are reasonably designed and combined to form a multi-component composite material, and the advantages of each component are exerted by utilizing a synergistic effect, therefore, the invention provides the zirconium oxide, cobalt and carbon nanotube composite hollow fiber, and the preparation method and the application thereof.
In one embodiment of the present invention, a method for preparing a zirconia/cobalt/carbon nanotube composite hollow fiber includes: dispersing zirconium salt, cobalt salt and a surfactant in a solution, performing electrostatic spinning, and performing pre-oxidation and heating calcination in a muffle furnace to obtain a hollow fiber compounded by cobaltosic oxide and zirconia; finally, the fiber and the pyrrole are placed in a cast iron reaction kettle together, and the zirconium oxide, cobalt and carbon nano tube composite hollow fiber material can be obtained after high-temperature reaction.
Compared with the prior art, the synthesis method is simple, the final product can be obtained only by one-time electrostatic spinning, one-time calcining and one-time high-temperature carbon coating, the prepared zirconium oxide, cobalt and carbon nano tube composite hollow fiber material has uniform diameter and narrow diameter distribution, and no other by-product is generated in the heat treatment process.
Further, the solution is N, N-dimethylformamide; adding cobalt salt, zirconium salt and polyvinylpyrrolidone into an N, N-dimethylformamide solution to form a uniform solution, carrying out electrostatic spinning and low-temperature preoxidation to obtain a zirconium-containing cobalt carbon fiber precursor, placing the zirconium-containing cobalt carbon fiber precursor in a muffle furnace, introducing protective gas, and calcining to obtain the cobaltosic oxide/zirconium oxide hollow fiber precursor.
Further, after uniformly mixing the cobaltosic oxide/zirconia hollow fiber and pyrrole, putting the mixture into a cast iron reaction kettle, and performing high-temperature treatment to obtain the zirconia/cobalt/carbon nano tube composite hollow fiber.
In some embodiments of the invention, the cobalt salt is cobalt acetylacetonate or cobalt acetate tetrahydrate.
In some embodiments of the invention, the zirconium salt is zirconium n-butoxide or zirconium acetylacetonate.
In some embodiments of the invention, the surfactant is polyvinylpyrrolidone.
In some embodiments of the invention, the carbon source is pyrrole or glucose.
In some embodiments of the invention, the cobalt salt, the zirconium salt, the polyvinylpyrrolidone and the N, N-dimethylformamide are added in the following proportions: (0.4-1) g, (0.4-1.6) g, (0.8-1.5) g, (5-15) mL; preferably: (0.5-0.8) g, (0.8-0.9) g, (0.9-1.2) g, (9-12) mL.
In some embodiments of the invention, the voltage of the electrospinning is 10-15kV, and the distance between the needle of the injector and the receiving plate is 15-30cm; preferably, the voltage is 11-13kV, and the distance between the needle of the syringe and the receiving plate is 22-26cm; more preferably: the voltage was 12kV and the distance of the syringe needle from the receiving plate was 25cm. In the process, a small amount of dimethylamine is decomposed from the N, N-dimethylformamide, so that the surfactant is easier to deprotonate, and is easy to combine with cobalt ions and zirconium ions to form a metal cluster; the polyvinylpyrrolidone can improve the viscosity of the solution, regulate and control the combination rate of metal clusters, ions and surfactants in the solution and contribute to the formation of a fiber structure. The formation of cobalt zirconium carbon fibers was facilitated within the range of the above addition ratio, voltage and distance of the syringe needle from the receiving plate.
In some embodiments of the invention, the pre-oxidation temperature is 150-200 ℃ and the pre-oxidation time is 1-5h; preferably, the pre-oxidation temperature is 170-190 ℃, and the pre-oxidation time is 2-4h; more preferably: the pre-oxidation temperature is 180 ℃, and the pre-oxidation time is 3h. In this process, a small amount of polyvinylpyrrolidone on the surface of the nanofiber is first decomposed, and at the same time, the cobalt salt becomes a metal oxide, and crystal growth starts to form a shell template, thereby effectively preventing collapse of the fiber during calcination.
In some embodiments of the invention, the muffle furnace has a calcination temperature of 400-700 ℃, a heating rate of 1-5 ℃/min, and a reaction time of 2-5h; preferably, the reaction temperature is 500-600 ℃, the heating rate is 1.5-2.5 ℃/min, and the reaction time is 2.5-3.5h; more preferably: the reaction temperature is 550 ℃, the heating rate is 2 ℃/min, and the reaction time is 3h. In the process, carbon is continuously heated and combined with oxygen in the air to form carbon dioxide, and zirconium and cobalt are oxidized and simultaneously diffuse outwards due to the Cokendall effect, so that the formation of the cobaltosic oxide and zirconia composite hollow fiber is facilitated.
In some embodiments of the invention, the proportion of cobaltosic oxide to zirconia composite hollow fibers added to the pyrrole is (50-200) mg (1-5) mL; preferably (80-150) mg (2-3) mL; further preferably 100 mg.
In an embodiment of the invention, the composite hollow fiber obtained by the preparation method of the zirconia, cobalt and carbon nanotube composite hollow fiber contains Co, zr, O, N and C elements, wherein Co exists in the form of a metal simple substance, and Zr and O elements are ZrO 2 The C element exists in the forms of amorphous carbon and graphitized carbon, the N is used as a doping element and exists in the amorphous carbon and the graphitized carbon, and the elements are uniformly mixed to finally form the zirconia/cobalt/carbon nanotube composite hollow fiber.
The structure of the fiber-containing precursor is that the cobalt ions and the zirconium ions are self-assembled with a surfactant through coordination bonds to form metal clusters, and then the metal clusters are mutually compounded to form the fiber-containing precursor. In the calcining condition of air in a muffle furnace, carbon combines with oxygen at high temperature to form carbon dioxide, and cobalt and zirconium are oxidized and simultaneously diffuse outwards due to the Cokendall effect to form the cobaltosic oxide and zirconium oxide composite hollow fiber. After being mixed with pyrrole, under the condition of high-temperature reaction, the pyrrole is firstly coated on the outer layer of the cobaltosic oxide and zirconia composite hollow fiber after being gasified, meanwhile, the cobaltosic oxide is reduced into a cobalt simple substance by carbon, and the carbon grows into a carbon nano tube under the catalysis of the cobalt, thereby finally forming the zirconia/cobalt/carbon nano tube composite hollow fiber.
In one embodiment of the invention, the composite wave-absorbing material comprises the zirconia/cobalt/carbon nano tube composite hollow fiber and paraffin; further, the mass ratio of the zirconia/cobalt/carbon nanotube composite hollow fiber to the paraffin is 1:4.
the paraffin is solid paraffin. The solid paraffin and the zirconia, the cobalt and the zirconia/cobalt/carbon nano tube composite hollow fiber are mixed by stirring or other methods, and the paraffin is not on the surface of the zirconia/cobalt/carbon nano tube composite hollow fiber.
In one embodiment of the invention, the preparation method of the composite wave-absorbing material is characterized in that the composite wave-absorbing material is prepared by mixing zirconia, cobalt and carbon nanotube composite hollow fibers and paraffin wax;
further, the mixing temperature of the zirconium oxide, the cobalt, the carbon nano tube composite hollow fiber and the paraffin is 30-60 ℃.
After the zirconium oxide, the cobalt and the carbon nano tube composite hollow fiber and the paraffin are uniformly mixed, the zirconium oxide, the cobalt and the carbon nano tube composite hollow fiber and the paraffin in the zirconium oxide, cobalt and carbon nano tube composite hollow fiber composite wave-absorbing material form a form of basically uniform distribution. The function of mixing at a certain high temperature is to enhance the fluidity of the paraffin and facilitate the uniform mixing of the paraffin and the zirconia, cobalt and carbon nanotube composite hollow fibers.
In an embodiment of the present invention, the preparation method of the zirconia/cobalt/carbon nanotube composite hollow fiber and/or the zirconia, cobalt and carbon nanotube composite hollow fiber composite wave-absorbing material and/or the preparation method of the composite wave-absorbing material are applied in the field of electromagnetic wave absorption.
The present invention is described in further detail below with reference to specific examples, which should be construed as illustrative rather than restrictive.
Example 1
(1) 1.4g of polyvinylpyrrolidone, 0.86g of cobalt acetylacetonate and 0.8g of zirconium n-butoxide are dissolved in 10mL of N, N-dimethylformamide, stirred for 120min, and then transferred into an injector for electrostatic spinning, wherein the voltage is 12kV, and the distance between a needle head and a receiving plate is 25cm. After spinning is finished, putting a sample into a 50 ℃ drying oven for drying for more than 6h, and then pre-oxidizing in a 180 ℃ drying oven for 3h; putting 0.2g of the obtained solid into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, calcining for 3 hours, and naturally cooling to room temperature;
(2) And (3) uniformly mixing 0.1g of the precursor obtained in the step (1) with 2.5mL of pyrrole, transferring the mixture into a cast iron reaction kettle, heating to 600 ℃ for 30min, preserving the heat for 5h, and naturally cooling to room temperature.
Fig. 1 is an XRD chart of the zirconia, cobalt and carbon nanotube composite hollow fiber prepared in example 1, and it was confirmed that zirconia, cobalt and carbon were prepared.
FIG. 2a is an SEM image of the solid obtained in example 1, and it can be seen that the carbon nanotubes are uniformly coated, and the length of the carbon nanotubes is about (100-150) 5m; in the b picture, the integral coating of the fiber is relatively uniform, and the core-shell structure is obvious.
FIG. 3, panel a, is a TEM image of the intermediate prepared in example 1, step (2), having a diameter of about 100 to 1505m and a uniform diameter distribution; the graph b is a TEM (transmission electron microscope) graph of the zirconium oxide, cobalt and carbon nanotube composite hollow fiber finally obtained in example 1, the cobalt particle size is about 30-405m, the fiber diameter is about 100-1505m, the length of the carbon nanotube is about 100-1505m, and the fiber shape is well maintained without breakage. As can be confirmed from fig. 3, the solid obtained in example 1 has a hollow structure.
Example 2
(1) 1.4g of polyvinylpyrrolidone, 0.86g of cobalt acetylacetonate and 0.8g of zirconium n-butyl alcohol were dissolved in 10mL of N, N-dimethylformamide, stirred for 120min, and then transferred to an injector for electrostatic spinning at a voltage of 14kV and a distance of a needle from a receiving plate of 25cm. After spinning is finished, putting the sample into a 50 ℃ oven for drying for more than 6h, and then pre-oxidizing in a 180 ℃ oven for 3h; putting 0.2g of sample into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/min, calcining for 3h, and naturally cooling to room temperature;
(2) And (3) uniformly mixing 0.1g of the solid obtained in the step (1) with 2.5mL of pyrrole, transferring the mixture into a cast iron reaction kettle, heating to 600 ℃ for 30min, preserving the heat for 5h, and naturally cooling to room temperature.
Examples of the experiments
The zirconium oxide, cobalt and carbon nanotube composite hollow fiber and paraffin wax of example 1 were mixed to obtain a zirconium oxide, cobalt and carbon nanotube composite hollow fiber composite wave-absorbing material, an Ag5le5t Tech 5es E8363A electromagnetic wave vector network analyzer was used to perform electromagnetic parameter testing, and the wave-absorbing properties of the material were calculated according to the electromagnetic parameters to obtain the results shown in fig. 4-6.
As can be seen from FIG. 4, the hollow fiber composite wave-absorbing material compounded by zirconia, cobalt and carbon nanotubes has strong dielectric loss.
As can be seen from FIG. 5, the hollow fiber composite wave-absorbing material compounded by zirconia, cobalt and carbon nanotubes has strong magnetic loss.
As can be seen from FIG. 6, the zirconium oxide, cobalt and carbon nanotube composite hollow fiber wave-absorbing material has excellent electromagnetic wave absorption performance. When the thickness is 1.34mm, the absorption effect on electromagnetic waves is best, and an effect of-12.46 dB is obtained; at 1.49mm, the effective absorption bandwidth is 3.76GHz.
Comparative example 1
The difference from example 1 is that in step (3), pyrrole was reduced to 0.125g, and the remainder was kept unchanged. An Ag5le5t Tech5 log5es E8363A electromagnetic wave vector network analyzer is used for carrying out electromagnetic parameter test, and the wave-absorbing performance of the material is calculated according to the electromagnetic parameters, so that the wave-absorbing effect is poor.
FIG. 7 is a TEM image of the material prepared in comparative example 1, and it can be seen that when the amount of carbon source is changed, the morphology of the product is a carbon nanotube-coated fiber structure, and the interior of the fiber is hollow, which indicates that reducing the amount of pyrrole added does not destroy the regular morphology of the product, and still allows the product to form a hollow fiber structure; FIG. 8 is a performance diagram of the sample prepared in comparative example 1, and it can be seen that the reflection loss is not as good as that of example 1 in the range of 2-18GHz, and the wave-absorbing performance is poor.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (20)
1. The preparation method of the zirconium oxide/cobalt/carbon nano tube composite hollow fiber is characterized by comprising the following steps of: dispersing zirconium salt, cobalt salt and a surfactant in a solution, performing electrostatic spinning, and performing pre-oxidation and heating calcination in a muffle furnace to obtain a cobaltosic oxide/zirconia hollow fiber; finally, placing the cobaltosic oxide/zirconia hollow fiber and pyrrole in a cast iron reaction kettle together, and carrying out high-temperature reaction to obtain the cobaltosic oxide/zirconia hollow fiber;
the surfactant is polyvinylpyrrolidone.
2. The method according to claim 1, wherein the solution is N, N-dimethylformamide; the zirconium salt is zirconium n-butyl alcohol or zirconium oxide acetylacetonate; the cobalt salt is cobalt acetylacetonate or cobalt acetate tetrahydrate.
3. The method according to claim 1, wherein the cobalt salt, the zirconium salt, the surfactant and the solution are added in the following proportions: (0.4-1) g, (0.4-1.6) g, (0.8-1.5) g, (5-15) mL.
4. The method according to claim 3, wherein the cobalt salt, the zirconium salt, the surfactant and the solution are added in the following proportions: (0.5-0.8) g, (0.8-0.9) g, (0.9-1.2) g, (9-12) mL.
5. The method of claim 1, wherein the electrospinning voltage is 10 to 15kV and the distance between the syringe needle and the receiving plate is 15 to 30cm.
6. The method according to claim 5, wherein the electrospinning voltage is 11 to 13kV, and the distance between the syringe needle and the receiving plate is 22 to 26cm.
7. The method of claim 6, wherein the electrospinning voltage is 12kV, and the distance between the syringe needle and the receiving plate is 25cm.
8. The method according to claim 1, wherein the pre-oxidation temperature is 150-200 ℃ and the pre-oxidation time is 1-5 hours.
9. The method according to claim 8, wherein the pre-oxidation temperature is 170-190 ℃ and the pre-oxidation time is 2-4h.
10. The method according to claim 9, wherein the pre-oxidation temperature is 180 ℃ and the pre-oxidation time is 3 hours.
11. The preparation method according to claim 1, wherein the muffle furnace has a calcination temperature of 400-700 ℃, a temperature rise rate of 1-5 ℃/min, and a reaction time of 2-5h.
12. The preparation method of claim 11, wherein the muffle furnace has a calcination temperature of 500-600 ℃, a temperature rise rate of 1.5-2.5 ℃/min, and a reaction time of 2.5-3.5h.
13. The method according to claim 12, wherein the muffle furnace has a calcination temperature of 550 ℃, a temperature rise rate of 2 ℃/min, and a reaction time of 3 hours.
14. The preparation method according to claim 1, wherein the proportion of the cobaltosic oxide/zirconia hollow fiber to the pyrrole is (50-200) mg (1-5) mL.
15. The preparation method of claim 14, wherein the proportion of the cobaltosic oxide/zirconia hollow fiber to the pyrrole is (80-150) mg (2-3) mL.
16. The preparation method according to claim 15, wherein the proportion of the cobaltosic oxide/zirconia hollow fiber to the pyrrole added is 100mg.
17. The zirconia/cobalt/carbon nanotube composite hollow fiber prepared by the preparation method according to any one of the preceding claims 1 to 16.
18. A composite wave-absorbing material, characterized in that the composite wave-absorbing material comprises the zirconia/cobalt/carbon nanotube composite hollow fiber of claim 17 and paraffin.
19. The composite wave-absorbing material of claim 18, wherein the mass ratio of the zirconia/cobalt/carbon nanotube composite hollow fiber to the paraffin is 1:4; the mixing temperature of the zirconium oxide/cobalt/carbon nano tube composite hollow fiber and paraffin is 30-60 ℃.
20. The zirconia/cobalt/carbon nanotube composite hollow fiber of claim 17 or the composite wave-absorbing material of claim 18 or 19, for use in the field of electromagnetic wave absorption.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105803580A (en) * | 2016-04-15 | 2016-07-27 | 东华大学 | Preparation method of cobalt phosphide hollow nano-fiber material |
| CN109295548A (en) * | 2018-09-13 | 2019-02-01 | 南京理工宇龙新材料科技股份有限公司 | A kind of zirconium oxide hollow fibre and preparation method thereof |
| CN109971420A (en) * | 2019-04-02 | 2019-07-05 | 安徽理工大学 | The preparation method and application of one-dimensional zirconium/carbon dioxide nano-tube nano composite material |
| CN110437800A (en) * | 2019-07-08 | 2019-11-12 | 山东大学 | ZrO derived from a kind of Co modified metal organic frame2/ C electromagnetic wave absorbent material and the preparation method and application thereof |
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| US20180001269A1 (en) * | 2016-06-30 | 2018-01-04 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Metallopolyimide precursor fibers for aging-resistant carbon molecular sieve hollow fiber membranes with enhanced selectivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803580A (en) * | 2016-04-15 | 2016-07-27 | 东华大学 | Preparation method of cobalt phosphide hollow nano-fiber material |
| CN109295548A (en) * | 2018-09-13 | 2019-02-01 | 南京理工宇龙新材料科技股份有限公司 | A kind of zirconium oxide hollow fibre and preparation method thereof |
| CN109971420A (en) * | 2019-04-02 | 2019-07-05 | 安徽理工大学 | The preparation method and application of one-dimensional zirconium/carbon dioxide nano-tube nano composite material |
| CN110437800A (en) * | 2019-07-08 | 2019-11-12 | 山东大学 | ZrO derived from a kind of Co modified metal organic frame2/ C electromagnetic wave absorbent material and the preparation method and application thereof |
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