CN115450044A - Composite carbon fiber with high electromagnetic wave absorption performance and preparation method thereof - Google Patents
Composite carbon fiber with high electromagnetic wave absorption performance and preparation method thereof Download PDFInfo
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- 229910002651 NO3 Inorganic materials 0.000 claims description 2
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- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
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- 229910052799 carbon Inorganic materials 0.000 claims 2
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- Chemical Kinetics & Catalysis (AREA)
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- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Fibers (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention relates to the field of carbon fiber with integrated structure and function, and particularly discloses composite carbon fiber with high electromagnetic wave absorption performance and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, carbon fiber activation treatment; step 2, mixing a solution containing cobalt metal salt and zinc metal salt with a ligand solution, immersing the activated carbon fiber into the mixed solution, and washing and drying the fiber to obtain the carbon fiber coated by the bimetallic organic frame; and 3, carbonizing and annealing the carbon fiber coated by the bimetal organic frame to obtain the composite carbon fiber. The composite carbon fiber prepared by the method has excellent reflection loss performance, and has high bandwidth and high absorption characteristics. The method has the advantages of simple process, strong controllability, low cost and better universality.
Description
Technical Field
The invention relates to the field of carbon fiber with integrated structure and function, in particular to composite carbon fiber with high electromagnetic wave absorption performance and a preparation method thereof.
Background
In recent years, electromagnetic interference and electromagnetic pollution are increasingly serious, which not only affects normal use of functional devices, but also has adverse effects on human health and surrounding environment to a certain extent. The electromagnetic wave absorbing material is widely concerned because of little or no reflected electromagnetic wave and no secondary electromagnetic pollution and interference phenomenon, and especially in the field of military and national defense, the electromagnetic wave absorbing material can be used as a surface coating material of invisible fighters. Carbon fiber has a series of excellent characteristics of light weight, high strength, good heat conductivity, adjustable resistance and the like, so that the carbon fiber is widely used as a wave-absorbing and electronic shielding material. However, under the conditions of small thickness and low density, the development of a carbon fiber microwave absorbing material with high bandwidth and high absorption characteristics and an excellent structure is still very challenging.
CN112724686A discloses a carbon fiber wave-absorbing material and a preparation method thereof, wherein carbon fibers are added into aqua regia for pretreatment, and then magnetic particles are deposited on the surface. The ferrite is deposited on the surface of the carbon fiber by a chemical coprecipitation method during deposition, and the ferrite is easy to oxidize, so that the deposition effect is influenced, and further the coating uniformity is influenced, and the improvement of the wave-absorbing performance of the prepared carbon fiber wave-absorbing material is very limited. In addition, the use of aqua regia as a treatment agent is highly dangerous.
CN114517406A discloses a preparation method of a wave-absorbing material of carbon fiber, which comprises placing a carbon fiber body in a coating furnace of a vacuum coating machine, and performing particle bombardment on a coating target by adjusting the coating vacuum degree, temperature and working gas to sputter carbon fiber. The magnetron sputtering coating method adopted in the invention has relatively complex process, difficult operation, large control difficulty and higher cost; in addition, the physical coating method only can cause that the uniformity of the carbon fiber surface coating is not easy to control.
Disclosure of Invention
Aiming at the problems of complicated preparation method, large control difficulty, high cost, high danger and the like of the carbon fiber wave-absorbing material in the prior art, the invention provides a simple and quick hydrothermal synthesis method, a three-dimensional structure bimetal organic frame can be effectively constructed on the surface of carbon fiber by reaction below 100 ℃, and the carbon fiber wave-absorbing material with integrated structure and function is obtained by high-temperature heat setting.
In order to realize the purpose, the invention adopts the technical scheme that:
a preparation method of composite carbon fiber with high electromagnetic wave absorption performance comprises the following steps:
and 3, placing the carbon fiber coated by the bimetallic organic frame in a quartz boat, and carrying out carbonization annealing treatment in an inert atmosphere to obtain the composite carbon fiber with high electromagnetic wave absorption performance.
In some embodiments, the method of the activation treatment in step 1 includes any one of a gas phase oxidation method, a plasma oxidation method, a liquid phase oxidation method, an electrochemical deposition oxidation method, an anodic oxidation method; after surface treatment, the surface of the carbon fiber can be activated, and meanwhile, the surface roughness is increased, so that the subsequent grafting of the bimetallic organic framework compound is facilitated.
The treatment temperature of the activation treatment is 10-60 ℃, and the treatment time is 0.5-24 h.
Preferably, the activation treatment adopts a liquid phase oxidation method, the activation temperature is 15-40 ℃, and the activation time is 6-15h. Such as liquid phase oxidation activation treatment using a nitric acid solution.
In some embodiments, the carbon fibers comprise any one of polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, viscose-based fibers; the cobalt metal salt and the zinc metal salt comprise any one of nitrate, sulfate and phosphate;
in some embodiments, the ligand comprises any one of an imidazole, thiourea, quinoline, terephthalic acid, or like metal ion-localizing ligand.
In some embodiments, the molar ratio of cobalt metal to zinc metal in step 2 is 1 to 4;
preferably, the molar ratio of cobalt metal to zinc metal in step 2 is 2-3;
if the two metal salts are not mixed and stirred according to a certain molar ratio, the two metal salts are respectively complexed with the ligand due to different metal coordination abilities, the morphology of the formed ZIF is greatly different, and the uniformity and the integrity are also different.
The molar ratio of the ligand to the sum of the cobalt metal salt and the zinc metal salt is 6-12.
Preferably, the molar ratio of the ligand to the sum of the cobalt metal salt and the zinc metal salt is 6 to 8.
In the step 2, the solutions containing cobalt metal salt and zinc metal salt are aqueous solutions, the concentrations of the two solutions are 0.04-0.2M respectively, if the solute concentration of the prepared ZIF precursor aqueous solution is too high, particles of the ZIF precursor solution may form and precipitate before the carbon fibers are immersed into the solution, and the particles cannot be attached to the surfaces of the carbon fibers; the ligand solution is an aqueous solution with the ligand concentration of 0.2-0.8M, and the ligand solution and the aqueous solution are mixed and stirred for 5-20 min at the stirring speed of 300-700 rpm to obtain a mixed solution.
In some embodiments, the reaction temperature in step 2 is 20-80 ℃ and the reaction time is 2-12h.
Preferably, the reaction temperature in the step 2 is 60-75 ℃, and the reaction time is 6-12h. If the treatment temperature is too high, the surface grafting layer is too thick, and the optimal morphology is not easy to obtain; if the treatment temperature is too low, the ZIF morphology cannot grow on the surface of the carbon fiber. If the treatment time is too short, the growth amount of the ZIF is too small, and the carbon fiber cannot be uniformly coated, so that the surface is not uniform; if the treatment time is too long, the shapes are different, the accumulation and agglomeration of surface grafting layers are easily caused, and good wave-absorbing performance cannot be obtained.
Further preferably, the reaction temperature in step 2 is 65 ℃ and the reaction time is 6h.
And (2) drying to remove water at the temperature of 100-150 ℃ for 1-24 h.
Preferably, the step 2 carbon fibers and the mixed solution are placed in a relatively closed environment for reaction, so as to avoid solvent volatilization.
In some embodiments, the annealing treatment in step 3 is performed by gradient heating, wherein the temperature is increased from room temperature to above 300 ℃ at a rate of 3-15 ℃/min, then is increased to above 700 ℃ at a rate of 3-10 ℃/min, and is kept for 0.5-2 h after the temperature reaches a set value. If the temperature does not reach 700 ℃, ZIFs are not completely carbonized into a framework; if the temperature is too high, the cost is increased.
In some embodiments, the inert atmosphere is nitrogen or argon.
The invention also provides the composite carbon fiber with high electromagnetic wave absorption performance prepared by the preparation method.
The surface of the composite carbon fiber is coated with the bimetal ZIFs structure, the distribution is uniform, the thickness can be controlled to be 1-5 microns, the problems that the uniformity is poor in the preparation process of a traditional carbon fiber surface grafting layer and the like are solved, the reflection loss values are all below-10 dB and optimally reach-67 dB, the composite carbon fiber has excellent wave absorbing performance, and has high bandwidth and high absorption characteristics.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, through carbon fiber surface treatment, the carbon fibers are functionally modified by using a bimetal organic framework compound ZIFs, and the surface of the carbon fibers is carbonized, annealed and magnetized by combining a high-temperature furnace, so that a bimetal ZIFs grafting layer can be efficiently and quickly generated on the surface of the carbon fibers, and the problems of single wave absorption, complex preparation process, difficulty in process control and the like of the traditional carbon fibers are solved.
(2) According to the invention, through designing and optimizing parameters such as processing time, temperature and concentration in the grafting process, the thickness and the like of the surface of the bimetallic ZIFs coated carbon fiber can be controlled and adjusted, and can be uniformly distributed on the surface of the fiber, so that the problems of poor uniformity and the like in the traditional preparation process of a carbon fiber surface grafting layer are solved.
(3) The method has the advantages of simple process, strong controllability, low cost, good wave-absorbing performance of the carbon fiber, better universality and wide application, and solves the problems of high production cost and the like compared with other methods.
Drawings
Fig. 1 is a scanning electron microscope image of the surface-treated carbon fiber prepared in comparative example 1.
Fig. 2 is a graph showing reflection loss of the surface-treated carbon fiber prepared in comparative example 1.
FIG. 3 is a scanning electron microscope image of carbon fibers prepared in comparative example 2 without surface treatment and grafted with ZIF.
FIG. 4 is a scanning electron microscope image of the surface metal-modified carbon fiber prepared in example 1.
Fig. 5 is a scanning electron microscope image of the composite carbon fiber having high electromagnetic wave absorption property prepared in example 1.
Fig. 6 is a reflection loss of the composite carbon fiber having high electromagnetic wave absorption properties prepared in example 1.
Fig. 7 is a scanning electron microscope image of the surface metal-modified carbon fiber prepared in example 2.
Fig. 8 is a scanning electron microscope image of the composite carbon fiber having high electromagnetic wave absorption property prepared in example 2.
Fig. 9 shows the reflection loss of the composite carbon fiber having high electromagnetic wave absorption properties prepared in example 2.
Fig. 10 is a scanning electron microscope image of the surface metal-modified carbon fiber prepared in example 3.
Fig. 11 is a scanning electron microscope image of the composite carbon fiber with high electromagnetic wave absorption property prepared in example 3.
Fig. 12 shows reflection loss of the composite carbon fiber having high electromagnetic wave absorption property prepared in example 3.
Fig. 13 is a scanning electron microscope image of the surface metal-modified carbon fiber prepared in example 4.
Fig. 14 is a scanning electron microscope image of the surface-metal-modified carbon fiber prepared in example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and substitutions without departing from the spirit and scope of the present invention.
The carbon fibers used in the following embodiments are commercially available carbon fibers, and other reagent materials are also commercially available.
Comparative example 1
(1) Pretreatment of carbon fibers: selecting 6 k-specification polyacrylonitrile-based carbon fiber as Carbon Fiber (CF), and firstly adding unscreened CF in nitric acid (H) 2 O:HNO 3 And = 2) for 12h at room temperature. HNO 3 After treatment, washing the CF sample for 3 times by deionized water, and finally drying the CF sample in a 50 ℃ oven for 12 hours to completely remove residual HNO on the surface of the fiber 3 To obtain activated CF; the scanning electron microscope is shown in FIG. 1, and the surface of the film has etching traces.
(2) And (3) testing the wave absorbing performance: electromagnetic parameters were measured by a vector network analyzer (VNA, N5234A) using a coaxial method in the range of 2-18 GHz. Mixing 25wt% of carbon fiber composite wave-absorbing material with paraffin to form a coaxial ring (R =7.00mm, R =3.04mm, d = 2mm), preparing a test sample, and obtaining a minimum reflection loss RL value of-25.96 dB, an effective absorption bandwidth EAB of 0.94GHz and reflection loss shown in figure 2.
Comparative example 2
(1) Selection of carbon fiber: the CF sample is 6k polyacrylonitrile-based carbon fiber and is not etched by nitric acid.
(2) Hydrothermal synthesis of bimetallic ZIF coated untreated CF samples: mixing Co (NO) 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 Dissolving O (according to a molar ratio of Co to Zn of 2: 1) in 50mL of deionized water, and stirring at room temperature for 10min to obtain a solution A; dissolving 0.4M 2-methylimidazole (2-MIM) and a ligand and double metal salt in a ratio of 8 to 1 in 50mL of deionized water to obtain a ligand solution, and stirring at room temperature for 10min to obtain a solution B.
And (3) quickly adding the solution A into the solution B, magnetically stirring for 10min, placing the mixed solution and the CF sample into a closed container, and reacting for 6h in an oil bath at 65 ℃ to graft the ZIFs on the surface of the CF sample. And (3) after the reaction is finished, taking the CF sample out of the solution, repeatedly washing the CF sample with deionized water, drying the CF sample in a drying oven at 105 ℃ for 24 hours, and collecting the CF sample to obtain the sample, wherein a scanning electron microscope image of the CF sample is shown in figure 3, so that the ZIF grafting effect on the surface of the CF sample is poor, and only a small amount of load is sporadically carried.
The sample is subjected to wave absorption test, but the grafting effect is poor and good reflection loss cannot be obtained because the surface of the fiber is not subjected to activation treatment.
Example 1
(1) Pretreatment of carbon fibers: unsized CF is first washed in nitric acid (H) 2 O:HNO 3 Soaking in room temperature for 12h for etching in the temperature of = 2). HNO 3 After treatment, washing the CF sample for 3 times by deionized water, and finally drying the CF sample in a 50 ℃ oven for 12 hours to completely remove residual HNO on the surface of the fiber 3 。
(2) Hydrothermally synthesizing the bimetal ZIF coated carbon fiber: mixing Co (NO) 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 Dissolving O (according to a molar ratio of Co to Zn of 2: 1) in 50mL of deionized water, and stirring at room temperature for 10min to obtain a solution A; dissolving 0.4M 2-methylimidazole (2-MIM) in 50mL of deionized water to serve as a ligand solution, wherein the ratio of the ligand to the double metal salt is 8.
And (3) quickly adding the solution A into the solution B, magnetically stirring for 10min, placing the mixed solution and the pretreated carbon fiber into a closed container, and reacting for 6h in an oil bath at 65 ℃ to graft the ZIFs on the surface of the CF sample. And taking the CF sample out of the solution, repeatedly washing the CF sample with deionized water, drying the CF sample in a drying oven at 105 ℃ for 24 hours, and collecting the CF sample to obtain a sample, wherein a scanning electron microscope of the sample is a rod-shaped sample as shown in figure 4, and the metal is densely and uniformly grafted on the surface of the fiber.
(3) And (3) carbonizing the bimetal ZIF coated carbon fiber: placing the successfully grafted CF sample in a quartz boat, heating the sample to 300 ℃ from room temperature in a tube furnace under the protection of nitrogen, then heating the sample to 700 ℃ at the heating rate of 5 ℃/min, and carbonizing the sample for 2 hours to obtain the composite carbon fiber, wherein a scanning electron microscope is shown as figure 5.
(4) Testing the wave absorbing performance: electromagnetic parameters were measured by a vector network analyzer (VNA, N5234A) using a coaxial method in the range of 2-18 GHz. Mixing 25wt% of carbon fiber composite wave-absorbing material with paraffin to form a coaxial ring (R =7.00mm, R =3.04mm, d = 2mm), preparing a test sample, and obtaining a minimum reflection loss RL value of-67.67 dB and an effective absorption bandwidth EAB of 3.8GHz, wherein the reflection loss is shown in figure 6.
Example 2
Following the procedure of example 1, step (2) Co (NO) 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 And O is prepared according to the molar ratio of Co to Zn of 3. The microstructure of the fiber obtained after the reaction in the step (2) is shown in FIG. 7; the scanning electron microscope of the composite carbon fiber obtained after carbonization and annealing in the step (3) is shown in fig. 8.
The minimum reflection loss RL value obtained by the wave-absorbing test is-17.56 dB, the effective absorption bandwidth EAB is 1.28GHz, and the reflection loss is shown in figure 9.
Example 3
According to the process of example 1, the mass of the ligand in the step (2) is changed, the mass of 2-methylimidazole is increased by 1.5 times, the molar ratio of Co to Zn is 2; the scanning electron microscope of the composite carbon fiber obtained after carbonization and annealing in the step (3) is shown in fig. 11.
The minimum reflection loss RL value measured by wave absorption is-50.65 dB, the effective absorption bandwidth EAB is 4.28GHz, and the reflection loss is shown in figure 12.
To further explore the influence of the reaction conditions and the metal ratio relationship on the product, the following examples were prepared:
example 4
According to the process of example 1, in step (2), the molar ratio of Co to Zn and the reaction conditions are, respectively, co: zn =1 for 6h at room temperature, co: zn =2 for 6h at room temperature, co: zn =4 for 6h at room temperature, co: zn =1 for 12h at room temperature, co: zn =2 for 12h at room temperature, and Co: zn =4 for 12h at room temperature.
Example 5
According to the procedure of example 1, the reaction temperature of step (2) was changed to 60 deg.C oil bath, 75 deg.C oil bath, 60 deg.C oil bath and 75 deg.C oil bath, respectively, and other conditions and processes were not changed, and the microscopic morphology after the metal coating with the fiber was observed, and the result is shown in FIG. 14.
In comparative example 1, after the CF sample is subjected to liquid-phase oxidation etching by nitric acid, the fiber surface has a relatively obvious axial groove structure (fig. 1), but the fiber surface is not modified by metal, so that the wave-absorbing performance of the fiber is not substantially influenced. In comparative example 2, since the CF sample was not surface-treated with nitric acid, the fiber surface was not activated and thus was highly inert, and a uniform metal-modified structure could not be formed on the fiber surface after functional modification (fig. 3).
In example 1, after the surface of a CF sample is subjected to liquid phase oxidation etching treatment, a rod-like bimetallic organic framework compound is formed on the surface of the fiber through a hydrothermal synthesis method (fig. 4) and is uniformly distributed, and after the surface of the fiber is further carbonized, the metal framework on the surface of the fiber is fixed and molded (fig. 5), so that the composite carbon fiber with high wave absorption performance is obtained (fig. 6).
In example 2, by changing the molar ratio of metal ion salts, a uniformly distributed filamentous bimetallic organic framework compound is formed on the surface of the fiber (fig. 7), and after further carbonization, the metal framework on the surface of the fiber is fixed and molded (fig. 8), so that the composite carbon fiber with poor wave absorbing performance is obtained (fig. 9), but the effective absorption bandwidth is better than that of comparative example 1 (fig. 2).
In example 3, by changing the amount of the ligand solution, flower-shaped bimetallic organic framework compounds are uniformly distributed on the fiber surface (figure 10), and after further carbonization, the metal framework is fixed on the fiber surface, and the flower-shaped structure is basically remained (figure 11), so that the composite carbon fiber with wider effective absorption bandwidth is obtained (figure 12).
In example 4, the ratio of Co to Zn is found to be better under 2, such as the Co content is too high or too low, the obtained metal appearance is relatively irregular, such as further increasing or reducing Co, the obtained product has poor performance, even the reflection loss is not lower than-10 dB, and the product cannot be preferred, which is found by comparing different metal salt concentrations at room temperature.
In example 5, the reaction at 60 to 75 ℃ gave a fiber with good metal grafting and excellent results by changing the water bath or oil bath and adjusting the treatment temperature.
In conclusion, the embodiment shows that the method can effectively graft the metal organic framework ZIF on the surface of the carbon fiber, and greatly improve the wave-absorbing performance and the effective absorption bandwidth of the carbon fiber after further carbonization treatment.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (10)
1. A preparation method of composite carbon fiber with high electromagnetic wave absorption performance is characterized by comprising the following steps:
step 1, pretreatment of carbon fibers: carrying out activation treatment on the surface of carbon fiber which is not sized or desized;
step 2, mixing a solution containing cobalt metal salt and zinc metal salt with a ligand solution, immersing activated carbon fibers into the mixed solution, carrying out reaction to load a Co-Zn bimetal organic framework structure on the surfaces of the carbon fibers, and then washing and drying the carbon fibers to obtain the carbon fibers coated by the bimetal organic framework;
and 3, placing the carbon fiber coated by the bimetallic organic frame in a quartz boat, and carrying out carbonization annealing treatment in an inert atmosphere to obtain the composite carbon fiber with high electromagnetic wave absorption performance.
2. The method for preparing composite carbon fiber having high electromagnetic wave absorption properties as claimed in claim 1, wherein the activation treatment in step 1 comprises any one of a gas phase oxidation method, a plasma oxidation method, a liquid phase oxidation method, an electrochemical deposition oxidation method, and an anodic oxidation method;
the treatment temperature of the activation treatment is 10-60 ℃, and the treatment time is 0.5-24 h.
3. The method for preparing composite carbon fiber with high electromagnetic wave absorption property as claimed in claim 1, wherein the carbon fiber comprises any one of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, and viscose-based fiber.
4. The method for preparing composite carbon fiber having high electromagnetic wave absorption properties as claimed in claim 1, wherein the cobalt metal salt and the zinc metal salt include any one of nitrate, sulfate and phosphate thereof;
and/or the ligand comprises any one of imidazole, thiourea, quinoline and terephthalic acid.
5. The method for preparing composite carbon fiber with high electromagnetic wave absorption performance according to claim 1, wherein the molar ratio of cobalt metal to zinc metal in step 2 is 1-4;
the molar ratio of the ligand to the sum of the cobalt metal salt and the zinc metal salt is 6-12.
6. The method for preparing composite carbon fiber having high electromagnetic wave absorption properties as claimed in claim 1, wherein the reaction temperature in step 2 is 20-80 ℃ and the reaction time is 2-12 hours.
7. The method for preparing the composite carbon fiber with high electromagnetic wave absorption performance according to claim 1, wherein the annealing treatment in the step 3 adopts gradient temperature rise, the temperature is raised from room temperature to above 300 ℃ at a rate of 3-15 ℃/min, then is raised to above 700 ℃ at a rate of 3-10 ℃/min, and is kept for 0.5-2 h after the temperature reaches a set value.
8. The method for preparing composite carbon fiber having high electromagnetic wave absorption properties as claimed in claim 1, wherein the inert atmosphere is nitrogen or argon.
9. The composite carbon fiber having high electromagnetic wave absorption properties obtained by the production method according to any one of claims 1 to 8.
10. The carbon composite fiber with high electromagnetic wave absorption performance according to claim 9, wherein a three-dimensional bimetallic organic frame with a thickness of 1-5 μm is distributed on the surface of the carbon composite fiber, and the reflection loss value is below-10 dB.
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