CN114411132A - Preparation method of cobalt-nickel alloy particle hydrophilic carbon cloth composite material with corn cob-like heterostructure - Google Patents
Preparation method of cobalt-nickel alloy particle hydrophilic carbon cloth composite material with corn cob-like heterostructure Download PDFInfo
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- CN114411132A CN114411132A CN202210089197.5A CN202210089197A CN114411132A CN 114411132 A CN114411132 A CN 114411132A CN 202210089197 A CN202210089197 A CN 202210089197A CN 114411132 A CN114411132 A CN 114411132A
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- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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Abstract
The invention discloses a preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob heterostructure, wherein nickel chloride (nickel nitrate and nickel sulfate) and cobalt chloride (cobalt nitrate and cobalt sulfate) are used as metal salts, hydrazine hydrate is used as a reducing agent, sodium hydroxide, deionized water and absolute ethyl alcohol are used as mixed solvents, and the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material is prepared by an in-situ hydrothermal method; the preparation method is green and environment-friendly, produces no toxic and harmful byproducts, and is simple; easy operation, and the flexible composite material has high electromagnetic wave absorption performance.
Description
Technical Field
The invention belongs to the technical field of electromagnetic wave absorption composite materials, and particularly relates to a preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure.
Background
With the rapid development of the electronic industry and information communication, electromagnetic radiation has become a serious environmental pollution problem. In order to solve the problem of electromagnetic wave pollution, electromagnetic wave absorbing materials capable of converting electromagnetic wave energy into heat energy and other forms of energy have been widely studied. Therefore, in recent years, scientists have been engaged in searching for highly efficient electromagnetic wave absorbing materials having strong absorption, wide absorption bandwidth and low thickness.
Nickel-cobalt alloys have been widely used in the field of electromagnetic absorbing materials due to their low manufacturing cost and excellent magnetic loss properties. However, nickel-cobalt alloy as an electromagnetic wave absorbing material has the following two disadvantages: firstly, the nickel-cobalt alloy has high density and cannot meet the requirement of light weight; secondly, the electromagnetic parameters of the nickel-cobalt alloy are often not matched, resulting in poor wave-absorbing performance. These disadvantages result in that it cannot meet the requirements of high-efficiency wave-absorbing materials. In order to improve the electromagnetic wave absorption performance of the nickel-cobalt alloy, researchers found that the electromagnetic wave absorption performance of the composite material can be effectively improved by compounding a dielectric material with a magnetic material to form a magnetic/dielectric composite material.
The carbon material is a typical representative of the dielectric material, and is the best choice for preparing the magnetic/dielectric composite material due to wide raw material sources, simple preparation process, high conductivity and low density. The carbon fiber is used as a common one-dimensional carbon material and has wide application in the field of electromagnetic wave absorption. In recent years, researchers find that through hydrophilic pretreatment of hydrophobic carbon fibers, active sites can be provided for magnetic alloy particles to be loaded on the surfaces of the carbon fibers, so that the alloy particles can be better compounded with the carbon fibers, and the electromagnetic wave absorption performance of the magnetic alloy particles can be improved. The hydrophilic carbon cloth contains rich oxygen-containing functional groups on the surface, so that the hydrophilic carbon cloth can be used as active sites for the combination of the nickel-cobalt alloy particles and the hydrophilic carbon cloth. In addition, the hydrophilic carbon cloth has a unique three-dimensional conductive network structure and good flexibility, so that the microwave absorption performance of the composite material can be improved, and the prepared composite material has good bending resistance. Therefore, the method has important application prospect in the field of electromagnetic wave absorption.
The invention adopts an in-situ hydrothermal method, and prepares the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material by modifying nickel-cobalt alloy particles on the surface of the hydrophilic carbon cloth. The composite material can realize the high-efficiency absorption of electromagnetic waves by simply changing the molar ratio of the nickel element to the cobalt element and the matching thickness.
Disclosure of Invention
The invention aims to provide a preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure, and the preparation method is used for solving the problems.
The technical scheme of the invention is as follows:
a preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure comprises the following steps:
(1) mixing deionized water and absolute ethyl alcohol to obtain a mixed solution;
(2) adding nickel salt and cobalt salt into the mixed solution, stirring, and obtaining a solution A after stirring;
(3) adding hydrophilic carbon cloth into the solution A for standing treatment to obtain a nickel-cobalt salt solution containing the hydrophilic carbon cloth;
(4) mixing a sodium hydroxide solution and a hydrazine hydrate solution to obtain a solution B;
(5) dropwise adding the solution B into the nickel-cobalt salt solution containing the hydrophilic carbon cloth while stirring the nickel-cobalt salt solution containing the hydrophilic carbon cloth to obtain a reaction solution containing the hydrophilic carbon cloth;
(6) transferring the reaction solution containing the hydrophilic carbon cloth into a hydrothermal reaction kettle for heat preservation treatment;
(7) and after the heat preservation is finished, taking out the reaction product from the hydrothermal reaction kettle, and repeatedly washing and drying the reaction product to obtain the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material.
Further, the nickel salt in the step (2) is one or more of nickel nitrate, nickel chloride and nickel sulfate.
Further, in the step (2), the cobalt salt is one or more of cobalt nitrate, cobalt chloride and cobalt sulfate.
Further, in the step (2), the molar ratio of the nickel salt to the cobalt salt is (5+ n): 5-n, and the value range of n is 0-2.
Further, the stirring treatment in the step (2) is magnetic stirring or mechanical stirring, and the stirring time is 30-120 min.
Further, the standing time of the hydrophilic carbon cloth in the solution in the step (3) is 6-24 h.
Further, the size of the hydrophilic carbon cloth in the step (3) is 1.0cm × 1.5 cm.
Further, the concentration of the sodium hydroxide solution in the step (4) is 1 mol/L-5 mol/L.
Further, the mass fraction of the hydrazine hydrate in the step (4) is 50 wt%.
Further, the stirring time for stirring and dissolving in the step (4) is 30-120 min, and the step
(5) The stirring time of the stirring treatment in (1) is 30-120 min.
Further, the temperature of the heat preservation treatment in the step (6) is 160-.
Further, the drying temperature of the drying treatment in the step (7) is 40-60 ℃, and the drying time is 12-24 h.
The invention provides a preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure, which has the following advantages:
firstly, the method comprises the following steps: the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption material with the corn-like heterostructure is prepared by an in-situ hydrothermal method, and is simple to operate, green, safe and free of toxic and harmful substances. Secondly, the method comprises the following steps: the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption material with the similar corn-shaped heterostructure is formed by coating spherical nickel-cobalt alloy on hydrophilic carbon cloth. The absorption capacity of the composite material to electromagnetic waves can be changed by changing the molar ratio of the nickel salt and the cobalt salt and the thickness of the composite material. Thirdly, the method comprises the following steps: the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material prepared by the invention has excellent electromagnetic wave absorption performance, and has the characteristics of low filling ratio, thin matching thickness, high absorption strength, wide absorption frequency band, easy regulation and control of wave absorption performance and the like.
Drawings
Fig. 1 is a synthetic process diagram of a nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material prepared in examples 1-3 in the preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure according to the present invention;
fig. 2 is an XRD spectrogram of a nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material prepared in examples 1-3 of the preparation method of a corncob-like heterostructure cobalt-nickel alloy particle hydrophilic carbon cloth composite material of the present invention;
FIG. 3 is a Raman spectrum of the flexible electromagnetic wave absorption composite material of the nickel-cobalt alloy @ hydrophilic carbon cloth prepared in examples 1-3 in the preparation method of the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure of the present invention;
FIG. 4 is an XPS survey spectrum of a flexible electromagnetic wave absorption composite of a cobalt-nickel alloy @ hydrophilic carbon cloth prepared in example 2 of a method for preparing a cobalt-nickel alloy particle hydrophilic carbon cloth composite of a corn cob-like heterostructure according to the present invention;
FIG. 5 is an SEM image of a flexible electromagnetic wave absorption composite of a cobalt-nickel alloy @ hydrophilic carbon cloth prepared in example 1 of a method for preparing a cobalt-nickel alloy particle hydrophilic carbon cloth composite of a corn cob-like heterostructure according to the present invention;
FIG. 6 is an SEM image of a flexible electromagnetic wave absorption composite of a cobalt-nickel alloy @ hydrophilic carbon cloth prepared in example 2 of a method for preparing a cobalt-nickel alloy particle hydrophilic carbon cloth composite of a corn cob-like heterostructure according to the present invention;
FIG. 7 is an SEM image of a flexible electromagnetic wave absorption composite of a cobalt-nickel alloy @ hydrophilic carbon cloth prepared in example 3 of a method for preparing a cobalt-nickel alloy particle hydrophilic carbon cloth composite of a corn cob-like heterostructure according to the present invention;
FIG. 8 is a graph showing the variation of reflection loss with frequency of a flexible electromagnetic wave absorption composite of a cobalt-nickel alloy @ hydrophilic carbon cloth made in example 1 of a method for making a cobalt-nickel alloy particle hydrophilic carbon cloth composite of a corn cob-like heterostructure according to the present invention;
FIG. 9 is a graph showing the variation of reflection loss with frequency of a flexible electromagnetic wave absorption composite material of a cobalt-nickel alloy @ hydrophilic carbon cloth made in example 2 of a method for making a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure according to the present invention;
FIG. 10 is a graph showing the variation of reflection loss with frequency of a flexible electromagnetic wave absorption composite of a cobalt-nickel alloy @ hydrophilic carbon cloth made in example 3 of a method for making a cobalt-nickel alloy particle hydrophilic carbon cloth composite of a corn cob-like heterostructure according to the present invention;
FIG. 11 is a graph showing the variation of the attenuation constant with frequency of the flexible electromagnetic wave absorption composite of the Ni-Co alloy @ hydrophilic carbon cloth prepared in examples 1-3 of the method for preparing a Co-Ni alloy particle hydrophilic carbon cloth composite of a corn cob-like heterostructure according to the present invention;
FIG. 12 is a curve showing the variation of impedance matching with frequency at a thickness of 3.5mm for a flexible electromagnetic wave absorption composite of Ni-Co alloy @ hydrophilic carbon cloth according to examples 1-3 of a method for preparing a Co-Ni alloy particle hydrophilic carbon cloth composite of a corn cob-like heterostructure of the present invention;
fig. 13 is a graph showing the bending resistance, the quality and the physical object of the flexible electromagnetic wave absorption composite material of the cobalt-nickel alloy @ hydrophilic carbon cloth prepared in example 2 of the preparation method of the cobalt-nickel alloy particle hydrophilic carbon cloth composite material of the corn cob-like heterostructure of the present invention.
Wherein, example 1 is a nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material prepared in example 1; example 2 is the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material prepared in example 2; example 3 is the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material prepared in example 3.
Detailed Description
A preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure comprises the following steps:
the method comprises the following steps: 7.5mL of deionized water and 7.5mL of absolute ethanol were mixed to obtain a mixed solution.
Step two: adding nickel salt (one or more of nickel nitrate, nickel chloride and nickel sulfate) and cobalt salt (one or more of cobalt nitrate, cobalt chloride and cobalt sulfate) into the mixed solution, and magnetically stirring for 30-90 min to obtain solution A.
Step three: adding hydrophilic carbon cloth into the solution A, and standing for 6-24 h to obtain a nickel-cobalt salt solution containing the hydrophilic carbon cloth;
step four: stirring 5mL of sodium hydroxide solution and 5mL of hydrazine hydrate for 30-120 min to obtain a solution B;
step five: dropwise adding the solution B into the nickel-cobalt salt solution containing the hydrophilic carbon cloth while stirring the nickel-cobalt salt solution containing the hydrophilic carbon cloth for 30-120 min to obtain a reaction solution containing the hydrophilic carbon cloth;
step six: transferring the reaction solution containing the hydrophilic carbon cloth into a hydrothermal reaction kettle, and carrying out heat preservation treatment at the temperature of 160-200 ℃ for 12-24 h;
step seven: and after the heat preservation is finished, taking out the reaction product from the hydrothermal reaction kettle, repeatedly washing the reaction product for three times, putting the reaction product into a vacuum drying oven for storage for 12 to 24 hours at the temperature of between 40 and 60 ℃, and taking out the reaction product to obtain the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material.
Wherein, the nickel salt in the second step is one or more of nickel nitrate, nickel chloride and nickel sulfate; the cobalt salt in the second step is one or more of cobalt nitrate, cobalt chloride and cobalt sulfate; in the second step, the total amount of the nickel salt and the cobalt salt is 3mmol, and the molar ratio of the nickel salt to the cobalt salt is (5+ n): (5-n), wherein the value range of n is an integer from 0 to 2; the stirring treatment in the step two is magnetic stirring or mechanical stirring, and the stirring time is 30-120 min; in the third step, the size of the hydrophilic carbon cloth is 1.0cm multiplied by 1.5 cm; in the fourth step, the concentration of the sodium hydroxide is 1-5 mol/L, the mass fraction of the hydrazine hydrate is 50 wt%, and the stirring time for stirring and dissolving is 30-120 min.
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying the present invention are further described below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The embodiment shows a preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure, which comprises the following steps:
the method comprises the following steps: 7.5mL of deionized water and 7.5mL of absolute ethanol were mixed to obtain a mixed solution.
Step two: 1.5mmol of nickel chloride and 1.5mmol of cobalt chloride are added to the mixed solution and mechanically stirred for 30min to obtain a solution A.
Step three: adding hydrophilic carbon cloth into the solution A, and standing for 6 hours to obtain a nickel-cobalt salt solution containing the hydrophilic carbon cloth;
step four: carrying out magnetic stirring on 5mL of 1mol/L sodium hydroxide solution and 5mL of 50 wt% hydrazine hydrate for 30min to obtain a solution B;
step five: dropwise adding the solution B into the nickel-cobalt salt solution containing the hydrophilic carbon cloth while stirring the nickel-cobalt salt solution containing the hydrophilic carbon cloth for 30min to obtain a reaction solution containing the hydrophilic carbon cloth;
step six: transferring the reaction solution containing the hydrophilic carbon cloth into a hydrothermal reaction kettle, and carrying out heat preservation treatment at 160 ℃ for 12 hours;
step seven: and after the heat preservation is finished, taking out the reaction product from the hydrothermal reaction kettle, repeatedly washing the reaction product for three times, putting the reaction product into a vacuum drying oven for storage at the temperature of 40 ℃ for 12 hours, and taking out the reaction product to obtain the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material. This is described as example 1.
Example 2
The embodiment shows a preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure, which comprises the following steps:
the method comprises the following steps: 7.5mL of deionized water and 7.5mL of absolute ethanol were mixed to obtain a mixed solution.
Step two: adding 1.8mmol of nickel nitrate and 1.2mmol of cobalt nitrate into the mixed solution, and magnetically stirring for 90min to obtain a solution A.
Step three: adding hydrophilic carbon cloth into the solution A, and standing for 18h to obtain a nickel-cobalt salt solution containing the hydrophilic carbon cloth;
step four: magnetically stirring 5mL of 3mol/L sodium hydroxide solution and 5mL of 50 wt% hydrazine hydrate for 90min to obtain a solution B;
step five: dropwise adding the solution B into the nickel-cobalt salt solution containing the hydrophilic carbon cloth while stirring the nickel-cobalt salt solution containing the hydrophilic carbon cloth for 90min to obtain a reaction solution containing the hydrophilic carbon cloth;
step six: transferring the reaction solution containing the hydrophilic carbon cloth into a hydrothermal reaction kettle, and carrying out heat preservation treatment at 180 ℃ for 18 h;
step seven: and after the heat preservation is finished, taking out the reaction product from the hydrothermal reaction kettle, repeatedly washing the reaction product for three times, putting the reaction product into a vacuum drying oven, preserving the reaction product for 18 hours at the temperature of 50 ℃, and taking out the reaction product to obtain the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material. This is described as example 2.
Example 3
The embodiment shows a preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure, which comprises the following steps:
the method comprises the following steps: 7.5mL of deionized water and 7.5mL of absolute ethanol were mixed to obtain a mixed solution.
Step two: adding 2.1mmol of nickel sulfate and 0.9mmol of cobalt sulfate into the mixed solution, and magnetically stirring for 120min to obtain a solution A.
Step three: adding hydrophilic carbon cloth into the solution A, and standing for 24 hours to obtain a nickel-cobalt salt solution containing the hydrophilic carbon cloth;
step four: stirring 5mL of 5mol/L sodium hydroxide solution and 5mL of 50 wt% hydrazine hydrate for 120min to obtain a solution B;
step five: dropwise adding the solution B into the nickel-cobalt salt solution containing the hydrophilic carbon cloth while stirring the nickel-cobalt salt solution containing the hydrophilic carbon cloth for 120min to obtain a reaction solution containing the hydrophilic carbon cloth;
step six: transferring the reaction solution containing the hydrophilic carbon cloth into a reaction kettle, and carrying out heat preservation treatment at 200 ℃ for 24 hours;
step seven: and after the heat preservation is finished, taking out the reaction product from the hydrothermal reaction kettle, repeatedly washing the reaction product for three times, putting the reaction product into a vacuum drying oven, preserving the reaction product for 24 hours at the temperature of 60 ℃, and taking out the reaction product to obtain the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material. This is described as example 3.
The nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material prepared in examples 1-3 was tested.
According to the test results, the following conclusions are reached:
x-ray diffraction (XRD) of samples of the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material of examples 1-3 (substituted with examples 1-3 below) are shown in fig. 2-4. Fig. 2 shows that examples 1-3 exhibit three peaks at 44.5 °, 51.6 °, and 76.2 °. These diffraction peaks are located between the diffraction peaks of the (111), (200) and (220) crystal planes of the face centered cubic structures Co (JCPDS No.040805) and Ni (JCPDS No.15-0806), and in sample examples 1 and 3, the diffraction peaks of the (111) and (200) crystal planes gradually move toward Ni with increasing Ni content. These results show that nickel-cobalt alloys were synthesized in sample examples 1-3, rather than simple mixtures of metallic nickel and metallic cobalt. The raman spectra of sample examples 1 to 3 are shown in fig. 3. Raman spectroscopy is used to assess the degree of graphitization and defect properties of carbon-based materials. Examples 1 to 3 samples ID/IGThe ratios are 0.95, 0.96 and 0.98 respectively. The hydrophilic carbon cloth is shown to have good graphitization degree.
To further characterize the surface characteristics of sample example 2, X-ray photoelectron spectroscopy (XPS) measurements were performed. FIG. 4 is an XPS survey of example 2. We can see that example 2 contains mainly four elements including C, O, Co and Ni. The sample contained oxygen atoms, probably due to oxidation of part of the nickel-cobalt alloy particle surface during preparation. FIGS. 5 to 7 correspond to Scanning Electron Microscopes (SEM) of sample examples 1 to 3. We can clearly see that the nickel-cobalt alloy particles are uniformly loaded on the surface of the hydrophilic carbon cloth to form a unique corn-like rod-shaped heterostructure. The corn-like rod-shaped hydrophilic carbon cloth fibers are mutually interwoven to form a three-dimensional conductive network structure, and the special structure is favorable for improving the electromagnetic wave absorption performance of the composite material.
In order to evaluate the electromagnetic wave absorption performance of the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material, the reflection loss value of the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material can be calculated according to a transmission line theory. The reflection loss value of the sample was prepared in a ring shape (outer diameter 7.0mm, inner diameter 3.0mm, thickness 2.0mm) from 20 wt% of nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite and 80 wt% of paraffin wax, and measured by a vector network analyzer. The reflection loss vs. frequency plots for the samples are shown in fig. 8-10.
As can be seen from FIG. 8, when the matching thickness is 2.0mm, the best reflection loss is-21.3 dB at 9.6GHz in example 1, the reflection loss intensity is below-10 dB in the range of 8.7-11.2 GHz, and the effective absorption width is 2.5 GHz. As can be seen from FIG. 9, the optimum reflection loss was-42.6 dB at 5.3GHz in example 2 when the matching thickness was 3.5mm, and the reflection loss intensities were all below-10 dB in the range of 12.1-18.0 GHz when the matching thickness was 1.5mm, and the effective absorption bandwidth reached 5.9 GHz. As can be seen from FIG. 10, the optimum reflection loss was-25.4 dB at 14.4GHz in example 3 at a matching thickness of 5.0mm, and the reflection loss intensities were all below-10 dB at 5.0-7.0 GHz at a matching thickness of 4.0mm, with an effective absorption bandwidth of 2.0 GHz. As can be seen from the above experimental results, example 2 has excellent electromagnetic wave absorption performance, and at the same time, it can satisfy the requirements of high absorption strength, wide absorption bandwidth and low thickness of the high-performance electromagnetic wave absorption material.
According to the electromagnetic wave absorption theory, the electromagnetic wave absorption performance of the absorber is also related to the attenuation constant and the impedance matching. The attenuation constant influences the absorption efficiency of the composite material on incident electromagnetic waves, and the impedance matching characterizes the attenuation capacity of the composite material on the electromagnetic waves. The impedance matching value of an ideal electromagnetic wave absorbing material is 1. When the impedance matching value is in the range of 0.8 to 1.2, the resulting composite material can be considered to have good electromagnetic wave absorption performance in a practical application environment.
FIG. 11 is a graph showing the attenuation constants of sample examples 1 to 3. It can be seen that the attenuation constant value of example 2 is the largest, and the maximum value is 600, which indicates that example 2 has the strongest attenuation capability to the incident electromagnetic wave. FIG. 12 shows the impedance matching of examples 1-3 at a thickness of 3.5 mm. It can be seen that the peak of the impedance match of example 1 is below 0.8, indicating that it has a poor impedance match. The impedance matching of example 2 peaked at about 1, indicating that it had excellent impedance matching. The impedance matching peak of example 3 was greater than 1.2, indicating that it had a poor impedance match.
FIG. 13 is a graph showing the degree of bending resistance, quality and physical properties of sample example 2, and it can be seen that it has good flexibility and excellent bending resistance and is not damaged even when it is folded in half by 180 °. The density of sample example 2 was measured in accordance with GB/T1033.1-2008 and was calculated to be 0.56g/cm3Indicating that it has the characteristic of being lightweight.
According to the test results of the above embodiments, the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material with the corn-like heterostructure is prepared by an in-situ hydrothermal method, and the method is simple to operate, safe, green and free of toxic and harmful substances. The sample example 2 has comprehensive and optimal wave absorbing performance, when the thickness is 3.5mm, the maximum absorption strength can reach 42.6dB, when the thickness is 1.5mm, the effective absorption bandwidth can reach 5.9GHz, and meanwhile, the sample has strong flexibility and low density. Therefore, the prepared nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorbing material is an ideal light ultrathin wave absorbing material.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (11)
1. A preparation method of a cobalt-nickel alloy particle hydrophilic carbon cloth composite material with a corn cob-like heterostructure is characterized by comprising the following steps:
(1) mixing deionized water and absolute ethyl alcohol to obtain a mixed solution;
(2) adding nickel salt and cobalt salt into the mixed solution, stirring, and obtaining a solution A after stirring;
(3) adding hydrophilic carbon cloth into the solution A, and standing for a period of time to obtain a nickel-cobalt salt solution containing the hydrophilic carbon cloth;
(4) mixing a sodium hydroxide solution and a hydrazine hydrate solution to obtain a solution B;
(5) dropwise adding the solution B into the nickel-cobalt salt solution containing the hydrophilic carbon cloth while stirring the nickel-cobalt salt solution containing the hydrophilic carbon cloth to obtain a reaction solution containing the hydrophilic carbon cloth;
(6) transferring the reaction solution containing the hydrophilic carbon cloth into a hydrothermal reaction kettle for heat preservation treatment;
(7) and after the heat preservation is finished, taking out the reaction product from the hydrothermal reaction kettle, and repeatedly washing and drying the reaction product to obtain the nickel-cobalt alloy @ hydrophilic carbon cloth flexible electromagnetic wave absorption composite material.
2. The method for preparing the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with the corn cob-like heterostructure, which is characterized in that: the nickel salt in the step (2) is one or more of nickel nitrate, nickel chloride and nickel sulfate, and the cobalt salt in the step (2) is one or more of cobalt nitrate, cobalt chloride and cobalt sulfate.
3. The method for preparing the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with the corn cob-like heterostructure, which is characterized in that: in the step (2), the molar ratio of the nickel salt to the cobalt salt is (5+ n) to (5-n), and the value range of n is 0-2.
4. The method for preparing the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with the corn cob-like heterostructure, which is characterized in that: the stirring treatment in the step (2) is magnetic stirring or mechanical stirring, and the stirring time is 30-120 min.
5. The method for preparing the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with the corn cob-like heterostructure, which is characterized in that: and (4) standing for 6-24 h in the step (3).
6. The method for preparing the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with the corn cob-like heterostructure, which is characterized in that: the size of the hydrophilic carbon cloth in the step (3) is 1.0cm multiplied by 1.5 cm.
7. The method for preparing the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with the corn cob-like heterostructure, which is characterized in that: and (4) the concentration of the sodium hydroxide solution in the step (4) is 1-5 mol/L.
8. The method for preparing the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with the corn cob-like heterostructure, which is characterized in that: the mass fraction of the hydrazine hydrate solution in the step (4) is 50 wt%.
9. The method for preparing the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with the corn cob-like heterostructure, which is characterized in that: stirring time for stirring and dissolving in the step (4) is 30-120 min, and stirring time for stirring treatment in the step (5) is 30-120 min.
10. The method for preparing the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with the corn cob-like heterostructure, which is characterized in that: the temperature of the heat preservation treatment in the step (6) is 160-200 ℃, and the heat preservation time is 12-24 h.
11. The method for preparing the cobalt-nickel alloy particle hydrophilic carbon cloth composite material with the corn cob-like heterostructure, which is characterized in that: the drying temperature of the drying treatment in the step (7) is 40-60 ℃, and the drying time is 12-24 h.
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