CN111944267B - Preparation method of boron-doped graphene composite material and application of boron-doped graphene composite material as negative dielectric material - Google Patents
Preparation method of boron-doped graphene composite material and application of boron-doped graphene composite material as negative dielectric material Download PDFInfo
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Abstract
The invention particularly relates to a preparation method of a boron-doped graphene composite material and application of the boron-doped graphene composite material as a negative dielectric material. At present, the composite material taking the carbon material as the conductive functional phase has less related researches on the regulation and control of the negative dielectric constant of the composite material in the atomic scale. The invention provides a boron-doped graphene material composite material, which is prepared by the following steps: the preparation method comprises the steps of carrying out hydrothermal reaction on dispersion liquid of boric acid and graphene oxide to obtain boron-doped graphene powder, mixing the boron-doped graphene powder with phenolic resin powder, grinding the mixture, and mechanically pressing the mixture to obtain the boron-doped graphene material. The uniformly distributed boron-doped graphene conductive network is constructed in the phenolic resin, and the negative dielectric property can be regulated and controlled by regulating and controlling the boron doping amount. The composite material has simple preparation method, economic and easily obtained raw materials and good industrial production significance.
Description
Technical Field
The invention belongs to the technical field of negative dielectric composite materials, and particularly relates to a preparation method of a boron-doped graphene negative dielectric composite material, a negative dielectric composite material obtained by the preparation method and application of the negative dielectric composite material.
Background
The information 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.
Generally, a metal material and a carbon material can be used as a conductive functional phase to prepare a negative dielectric composite material, and the conductive functional phase tends to form a three-dimensional conductive network which is mutually communicated in a system along with the change of conditions such as the increase of the content of the conductive functional phase, the change of morphology, the improvement of the dispersion degree of the conductive functional phase in an insulating matrix and the like, so that dielectric resonance of plasma oscillation or polarization is generated, and the composite material obtains negative dielectric properties. The negative dielectric composite material has a special negative dielectric constant, so that the negative dielectric composite material has wide research attention in the fields of optics, electrics, magnetics, acoustics, thermology, mechanics and the like, and has an important application prospect in the fields of aerospace, military, medical treatment, communication and the like.
The composite material taking metal as a conductive functional phase can obtain negative dielectric performance, but the negative value of the dielectric constant of the metal is large, so that impedance matching is not facilitated, and the application of the metal negative dielectric composite material is limited in a certain sense. The composite material using the carbon material as the conductive functional phase mainly studies the influence of the content of the conductive phase on the dielectric constant, and obtains the negative dielectric at a higher content of the conductive phase, and the negative dielectric constant of the composite material regulated and controlled at an atomic scale is rarely reported. Therefore, under the condition of keeping relatively high conductive phase content, the electronic structure of the carbon material is changed by doping to prepare the negative dielectric composite material, and the negative dielectric property of the negative dielectric composite material is effectively regulated and controlled, so that the negative dielectric composite material is an important problem which is urgently needed to be solved for developing the research of the negative dielectric composite material and realizing the potential application of the negative dielectric composite material.
Disclosure of Invention
Aiming at the defects of the prior art, the inventor provides a method for preparing a negative dielectric composite material by using boron-doped graphene and phenolic resin through long-term technical and practical exploration. The method is simple to operate and stable in process, and can enable the boron-doped graphene/phenolic resin composite material to obtain the negative dielectric constant and effectively regulate and control the negative dielectric constant.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, a preparation method of a boron-doped graphene composite material is provided, the preparation method comprising the following steps: adding boric acid into the graphene oxide dispersion liquid to obtain a uniform dispersion liquid, and carrying out hydrothermal reaction on the dispersion liquid to obtain boron-doped graphene powder; adding phenolic resin into the boron-doped graphene powder, and grinding to obtain composite powder; and mechanically pressing the composite powder to form the boron-doped graphene composite material.
In a second aspect of the present invention, there is provided a boron-doped graphene composite material prepared by the method for preparing a boron-doped graphene composite material according to the first aspect.
In a third aspect of the present invention, there is provided an application of the boron-doped graphene composite material of the second aspect in any one of the following fields:
(1) aerospace;
(2) the field of construction;
(3) the field of communications;
(4) field of optics
By adjusting the boron doping amount, the boron-doped graphene composite material realizes dielectric resonance when the external field frequency and the dipole frequency are close to each other, and shows that the real part of the dielectric constant is positive or negative in the test frequency range, and the energy loss corresponds to the maximum value at the moment, so that a theoretical basis is provided for the application of electromagnetic attenuation and wave absorption. In addition, the positive and negative phenomena of the dielectric real part of the boron-doped graphene composite material in the test range of the invention provide references for the preparation of the near-zero dielectric material and the regulation and application of the high-frequency dielectric material from positive to negative.
The beneficial effects of one or more technical schemes are as follows:
(1) according to the invention, the boron-doped graphene composite material with negative dielectric property is prepared by taking the boron-doped modified graphene as a conductive functional phase and compounding the boron-doped modified graphene with phenolic resin for the first time. The method is simple to operate and stable in process, a uniformly-distributed boron-doped graphene conductive network can be constructed in the phenolic resin, and the negative dielectric constant of the composite material can be effectively regulated and controlled by changing the boron doping amount;
(2) the raw materials are cheap and easy to obtain, the preparation method is simple, safe and pollution-free, meets the requirements of green chemical production, and has industrial production and potential application values.
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 shows dielectric properties of graphene composite materials with different boron doping amounts.
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.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, aiming at the research that a carbon material is a conductive functional phase composite material, the invention provides a composite material capable of regulating and controlling a negative dielectric constant at an atomic scale, and provides a preparation method of a boron-doped graphene composite material.
In a first aspect of the present invention, a preparation method of a boron-doped graphene composite material is provided, the preparation method comprising the following steps: adding boric acid into the graphene oxide dispersion liquid to obtain a uniform dispersion liquid, and carrying out hydrothermal reaction on the dispersion liquid to obtain boron-doped graphene powder; adding phenolic resin into the boron-doped graphene powder, and grinding to obtain composite powder; and mechanically pressing the composite powder to form the boron-doped graphene composite material.
Preferably, the concentration of the graphene oxide dispersion liquid is 4-6 mg/ml.
Preferably, the boric acid is added into the graphene oxide dispersion liquid and dissolved by ultrasonic, and the ultrasonic time is 4-6 h. Further preferably, the ultrasonic time is 5 h.
Preferably, the temperature of the hydrothermal reaction is 140-180 ℃, and the reaction time is 2-4 hours.
Preferably, the dispersion liquid is subjected to a hydrothermal reaction to obtain boron-doped graphene powder, and the specific preparation method is as follows: and carrying out centrifugal washing treatment on the boron-doped graphene hydrogel obtained by the hydrothermal reaction to obtain a boron-doped graphene suspension, and drying to obtain the boron-doped graphene powder.
Further preferably, the centrifugal rotating speed is 2000-4000 rpm, the centrifugal time is 2-5 min, and the centrifugal and washing cycle times are 4-6.
Further preferably, the drying is performed in a freeze drying mode, and the freeze drying time is 50-60 hours.
Preferably, the mass ratio of the boron-doped graphene powder to the phenolic resin is 1: 3.
Preferably, the mechanical pressing is carried out under the pressure of 15-25MPa and the dwell time of 1-3 min.
In some embodiments of the above preferred embodiments, the preparation method comprises the following steps:
s1, preparing a graphene oxide dispersion liquid: dispersing Graphene Oxide (GO) in a solvent to prepare a GO dispersion liquid with the concentration of 5 mg/ml;
s2, adding boric acid (H)3BO3): a certain mass of H3BO3Placing the GO in the GO dispersion liquid prepared in the step S1 for ultrasonic treatment and dissolution; the ultrasonic treatment time is 4-6 h, and the effect is most preferably 5 h;
s3, hydrothermal treatment: h prepared in step S23BO3Transferring the mixed solution with the GO dispersion liquid into the inner container of a reaction kettle, and carrying out hydrothermal treatment at 160 ℃ for 3 hours;
s4, centrifugal washing: carrying out centrifugal washing treatment on the boron-doped graphene hydrogel obtained in the step S3 through hydrothermal reaction to obtain a boron-doped graphene suspension; the centrifugal speed is 3000rpm, the centrifugal time is 3min, and the centrifugation and the washing are carried out for 5 times;
s5, freeze drying: and (5) carrying out freeze drying treatment on the boron-doped graphene suspension subjected to centrifugal washing in the step S4 to obtain boron-doped graphene powder, wherein the freeze drying time is 50-60 h.
S6, mixing and grinding: and (4) putting 0.6g of the weighed boron-doped graphene powder and the weighed phenolic resin powder in the step (S2) into a mortar for mixing and grinding to obtain the boron-doped graphene/phenolic resin composite powder, wherein the content of the boron-doped graphene in the composite material is 25 wt%.
S7, tabletting: and (5) placing the composite powder mixed and ground in the step (S3) into a tabletting mold, pressurizing by a press machine for 15-25MPa, maintaining the pressure for 1-3min, and demolding to obtain the boron-doped graphene composite material.
In a second aspect of the present invention, there is provided a boron-doped graphene composite material prepared by the method for preparing a boron-doped graphene composite material according to the first aspect.
In a third aspect of the present invention, there is provided an application of the boron-doped graphene composite material of the second aspect in any one of the following fields:
(1) aerospace;
(2) the field of construction;
(3) the field of communications;
(4) the field of optics.
By adjusting the boron doping amount, the boron-doped graphene composite material realizes dielectric resonance when the external field frequency and the dipole frequency are close to each other, and shows that the real part of the dielectric constant is positive or negative in the test frequency range, and the energy loss corresponds to the maximum value at the moment, so that a theoretical basis is provided for the application of electromagnetic attenuation and wave absorption. In addition, the positive and negative phenomena of the dielectric real part of the boron-doped graphene composite material in the test range of the invention provide references for the preparation of the near-zero dielectric material and the regulation and application of the high-frequency dielectric material from positive to negative.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples, wherein the reagents described in the following examples are all commercially available products.
Example 1
In this embodiment, a preparation method of a boron-doped graphene composite material is provided, and the preparation method includes the following steps:
s1, preparing a graphene oxide dispersion liquid: dispersing Graphene Oxide (GO) in deionized water to prepare GO dispersion liquid with the solution concentration of 5 mg/ml;
s2, adding boric acid (H)3BO3): a certain mass of H3BO3Placing the GO in the GO dispersion liquid prepared in the step S1 for ultrasonic treatment and dissolution; the ultrasonic treatment time is 5 h;
s3, hydrothermal treatment: h prepared in step S23BO3Transferring the mixed solution with the GO dispersion liquid into the inner container of the reaction kettleHydrothermal for 3 hours at 160 ℃;
s4, centrifugal washing: carrying out centrifugal washing treatment on the boron-doped graphene hydrogel obtained in the step S3 through hydrothermal reaction to obtain a boron-doped graphene suspension; the centrifugal speed is 3000rpm, the centrifugal time is 3min, and the centrifugation and the washing are carried out for 5 times;
s5, freeze drying: carrying out freeze drying treatment on the boron-doped graphene suspension subjected to centrifugal washing in the step S4 to obtain boron-doped graphene powder, wherein the freeze drying time is 55 h;
s6, mixing and grinding: and (4) putting 0.6g of the weighed boron-doped graphene powder and the weighed phenolic resin powder in the step (S2) into a mortar for mixing and grinding to obtain the boron-doped graphene/phenolic resin composite powder, wherein the content of the boron-doped graphene in the composite material is 25 wt%.
S7, tabletting: and (5) placing the composite powder mixed and ground in the step (S3) into a tabletting mold, pressurizing by a press machine for 20MPa, maintaining the pressure for 2min, and demolding to obtain the boron-doped graphene composite material.
Example 2
In this embodiment, a preparation method of a boron-doped graphene composite material is provided, and the preparation method includes the following steps:
s1, preparing a graphene oxide dispersion liquid: dispersing Graphene Oxide (GO) in deionized water to prepare GO dispersion liquid with the solution concentration of 4 mg/ml;
s2, adding boric acid (H)3BO3): a certain mass of H3BO3Placing the GO in the GO dispersion liquid prepared in the step S1 for ultrasonic treatment and dissolution; the ultrasonic treatment time is 4 h;
s3, hydrothermal treatment: h prepared in step S23BO3Transferring the mixed solution with the GO dispersion liquid into a liner of a reaction kettle, and carrying out hydrothermal treatment at 140 ℃ for 4 hours;
s4, centrifugal washing: carrying out centrifugal washing treatment on the boron-doped graphene hydrogel obtained in the step S3 through hydrothermal reaction to obtain a boron-doped graphene suspension; the centrifugal speed is 2000rpm, the centrifugal time is 5min, and the centrifugation and the washing are carried out for 4 times;
s5, freeze drying: carrying out freeze drying treatment on the boron-doped graphene suspension subjected to centrifugal washing in the step S4 to obtain boron-doped graphene powder, wherein the freeze drying time is 60 hours;
s6, mixing and grinding: and (4) putting 0.6g of the weighed boron-doped graphene powder and the weighed phenolic resin powder in the step (S2) into a mortar for mixing and grinding to obtain the boron-doped graphene/phenolic resin composite powder, wherein the weight percentage of the boron-doped graphene in the composite material is 25%.
S7, tabletting: and (5) placing the composite powder mixed and ground in the step (S3) into a tabletting mold, pressurizing by a press machine for 15MPa, maintaining the pressure for 3min, and demolding to obtain the boron-doped graphene composite material.
Example 3
In this embodiment, a preparation method of a boron-doped graphene composite material is provided, and the preparation method includes the following steps:
s1, preparing a graphene oxide dispersion liquid: dispersing Graphene Oxide (GO) in deionized water to prepare GO dispersion liquid with the solution concentration of 6 mg/ml;
s2, adding boric acid (H)3BO3): a certain mass of H3BO3Placing the GO in the GO dispersion liquid prepared in the step S1 for ultrasonic treatment and dissolution; the ultrasonic treatment time is 6 h;
s3, hydrothermal treatment: h prepared in step S23BO3Transferring the mixed solution with the GO dispersion liquid into a liner of a reaction kettle, and carrying out hydrothermal treatment at 180 ℃ for 2 hours;
s4, centrifugal washing: carrying out centrifugal washing treatment on the boron-doped graphene hydrogel obtained in the step S3 through hydrothermal reaction to obtain a boron-doped graphene suspension; the centrifugal speed is 4000rpm, the centrifugal time is 2min, and the centrifugation and the washing are carried out for 6 times;
s5, freeze drying: carrying out freeze drying treatment on the boron-doped graphene suspension subjected to centrifugal washing in the step S4 to obtain boron-doped graphene powder, wherein the freeze drying time is 50 h;
s6, mixing and grinding: and (4) putting 0.6g of the weighed boron-doped graphene powder and the weighed phenolic resin powder in the step (S2) into a mortar for mixing and grinding to obtain the boron-doped graphene/phenolic resin composite powder, wherein the weight percentage of the boron-doped graphene in the composite material is 25%.
S7, tabletting: and (5) placing the composite powder mixed and ground in the step (S3) into a tabletting mold, pressurizing by using a press machine at 25MPa, maintaining the pressure for 1min, and demolding to obtain the boron-doped graphene composite material.
Referring to fig. 1, an impedance analyzer is used to analyze the dielectric properties of graphene composite materials with different boron doping amounts, curves a and b respectively correspond to dielectric spectra of doped graphene prepared with 5% and 10% of boric acid, and it can be found from the graph that when the boric acid dosage is 5%, a negative dielectric constant appears in a 810M-1GHz band, and when the boric acid dosage is increased to 10%, a negative dielectric constant appears in a 970M-1G band, so that the dosage of boric acid can effectively regulate and control the bandwidth of the negative dielectric.
Based on the conclusion, the boron-doped graphene composite material provided by the invention is substantially a composite material with both dielectric and negative dielectric properties, and the frequency band of the property transition can be adjusted by adjusting the boron doping amount. Based on the performances, the boron doping amount of the composite material can be adjusted according to the requirements of the use environment, so that the transition between the dielectric and negative dielectric stages is met, and the technical requirements can be met more flexibly.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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.
Claims (12)
1. A preparation method of a boron-doped graphene composite material for regulating and controlling a negative dielectric constant is characterized by comprising the following steps: adding boric acid into the graphene oxide dispersion liquid to dissolve so as to obtain dispersion liquid, and carrying out hydrothermal reaction on the dispersion liquid so as to obtain boron-doped graphene powder; adding phenolic resin into the boron-doped graphene powder, and grinding to obtain composite powder; and mechanically pressing the composite powder to form the boron-doped graphene composite material.
2. The method for preparing the boron-doped graphene composite material capable of regulating the negative dielectric constant of claim 1, wherein the concentration of the graphene oxide dispersion liquid is 4-6 mg/ml.
3. The preparation method of the boron-doped graphene composite material with the negative dielectric constant regulated and controlled according to claim 1, wherein the boric acid is added into the graphene oxide dispersion liquid and dissolved by ultrasonic, and the ultrasonic time is 4-6 h.
4. The preparation method of the boron-doped graphene composite material for regulating the negative dielectric constant of claim 3, wherein the ultrasonic time is 5 hours.
5. The method for preparing the boron-doped graphene composite material capable of regulating the negative dielectric constant according to claim 1, wherein the temperature of the hydrothermal reaction is 140-180 ℃ and the reaction time is 2-4 hours.
6. The preparation method of the boron-doped graphene composite material for regulating the negative dielectric constant as claimed in claim 1, wherein the dispersion liquid is subjected to a hydrothermal reaction to obtain boron-doped graphene powder, and the specific preparation method is as follows: and carrying out centrifugal washing treatment on the boron-doped graphene hydrogel obtained by the hydrothermal reaction to obtain a boron-doped graphene suspension, and drying to obtain the boron-doped graphene powder.
7. The preparation method of the boron-doped graphene composite material with the negative dielectric constant adjusted and controlled according to claim 6, wherein the centrifugal rotation speed is 2000-4000 rpm, the centrifugal time is 2-5 min, and the number of cycles of centrifugation and washing is 4-6.
8. The preparation method of the boron-doped graphene composite material with the negative dielectric constant adjusted and controlled according to claim 6, wherein the drying is performed in a freeze drying mode, and the freeze drying time is 50-60 hours.
9. The method for preparing the boron-doped graphene composite material for regulating the negative dielectric constant of claim 1, wherein the mass ratio of the boron-doped graphene powder to the phenolic resin is 1: 3.
10. The method for preparing the boron-doped graphene composite material capable of regulating the negative dielectric constant of claim 1, wherein the mechanical pressing is performed under the pressure of 15-25MPa for 1-3 min.
11. The boron-doped graphene composite material prepared by the preparation method of the boron-doped graphene composite material for regulating the negative dielectric constant of any one of claims 1 to 10.
12. The boron-doped graphene composite material of claim 11, wherein the boron-doped graphene composite material is applied to any one of the following fields:
(1) aerospace;
(2) the field of construction;
(3) the field of communications;
(4) the field of optics.
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| CN103896258A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method for boron-doped graphene |
| CN103949234A (en) * | 2014-04-23 | 2014-07-30 | 上海荣富新型材料有限公司 | Preparation method of boron-doped graphene/TiO2 nanorod photocatalytic material |
| CN105802123A (en) * | 2016-05-19 | 2016-07-27 | 山东大学 | Method for preparing negative permittivity material from graphene, carbon nanometer tubes and phenolic resin |
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| CN103896258A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method for boron-doped graphene |
| CN103949234A (en) * | 2014-04-23 | 2014-07-30 | 上海荣富新型材料有限公司 | Preparation method of boron-doped graphene/TiO2 nanorod photocatalytic material |
| CN105802123A (en) * | 2016-05-19 | 2016-07-27 | 山东大学 | Method for preparing negative permittivity material from graphene, carbon nanometer tubes and phenolic resin |
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