CN114554822B - Composite wave-absorbing film material and preparation method thereof - Google Patents

Composite wave-absorbing film material and preparation method thereof Download PDF

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CN114554822B
CN114554822B CN202210442128.8A CN202210442128A CN114554822B CN 114554822 B CN114554822 B CN 114554822B CN 202210442128 A CN202210442128 A CN 202210442128A CN 114554822 B CN114554822 B CN 114554822B
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absorbing film
graphene oxide
solution
film material
composite
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CN114554822A (en
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张步升
权斌
王宇
陈雨
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Nanjing University of Information Science and Technology
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Nanjing University of Information Science and Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
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  • Nanotechnology (AREA)
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Abstract

The invention discloses a composite wave-absorbing film material and a preparation method thereof, wherein the method comprises the following steps: respectively adding copper nitrate trihydrate and trimesic acid into deionized water and ethanol with equal volumes, respectively stirring and dissolving, and then mixing to obtain solution A; adding the graphite oxide hydrosol into ethanol and performing ultrasonic dispersion to obtain a graphene oxide solution; then adding the mixture into the solution A and stirring the mixture to obtain solution B; and (3) filtering the solution B, drying, naturally dropping attachments on the filter membrane to obtain the HKUST-1/graphene oxide composite film, and finally performing high-temperature treatment at 300-900 ℃ for 2-4 h in a nitrogen atmosphere. The method can simply prepare the light flexible HKUST-1/graphene oxide composite film in the air without heating and external electric fields, is more energy-saving and efficient, and is beneficial to industrial mass production. The composite wave-absorbing film derived from the composite film after high-temperature treatment has good comprehensive wave-absorbing performance, and the maximum electromagnetic wave absorption rate can reach 94.4%.

Description

Composite wave-absorbing film material and preparation method thereof
Technical Field
The invention belongs to the technical field of electromagnetic wave-absorbing materials, and particularly relates to a composite wave-absorbing film material and a preparation method thereof.
Background
In recent years, metal organic framework materials have important application in a plurality of fields such as gas adsorption, storage and separation, catalysis, sensing and the like, become a great hot door in the current research field, and as one member of metal organic framework composite materials, the application prospect of HKUST-1 materials is increasingly wide, and a great deal of research is carried out.
Chinese patent CN 113680320A discloses a carbonization method for HKUST-1 derived carbon material, which can be used for adsorbing organic dye, but the material is a powder material, so the application of the material is limited. The Chinese invention patent CN 108479434B discloses a preparation method and application of a Li-doped HKUST-1 membrane material, which can be used for gas separation, but has the disadvantages of complex preparation process, long time consumption and high energy consumption. The Chinese invention patent CN 113314356A discloses a preparation method of an electrode material of an HKUST-1-LDH super capacitor derived from electrodeposited MOF, which adopts an electrochemical deposition method to prepare the high-efficiency electrode material, but needs an external electric field and has higher energy consumption.
In addition, due to the characteristics of unique structure and the like, the derived metal/carbon material has great application in the field of electromagnetic wave absorption. The Chinese invention patent CN 111137874A discloses a method for preparing a composite wave-absorbing material by taking HKUST-1 as a template, the wave-absorbing material prepared by the method is of a powder structure, and a hydrogen fluoride solution with extremely high risk is required, so that the method is high in safety and cost and is not beneficial to large-area popularization.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical problems, the invention provides a composite wave-absorbing film material and a preparation method thereof, and the composite wave-absorbing film material has the characteristics of simple and efficient preparation and excellent wave-absorbing performance.
The technical scheme is as follows: a preparation method of a composite wave-absorbing film material comprises the following steps:
step 1, mixing the raw materials in a mass ratio of 1.1-1.5: 1, respectively adding copper nitrate trihydrate and trimesic acid into deionized water and ethanol with equal volumes, respectively stirring and dissolving, and then mixing to obtain solution A;
step 2, adding the graphite oxide hydrosol into ethanol and performing ultrasonic dispersion to obtain a graphene oxide solution with the concentration of 0.4-0.6 mg/mL;
step 3, adding the graphene oxide solution into the solution A with the same volume and stirring to obtain a solution B;
step 4, carrying out suction filtration on the solution B to obtain a suction filtration membrane attached with the HKUST-1/graphene oxide composite membrane;
step 5, drying the suction filtration membrane in the air, and naturally dropping attachments to obtain the HKUST-1/graphene oxide composite film;
and 6, treating the HKUST-1/graphene oxide composite film at the high temperature of 300-900 ℃ for 2-4 hours in a nitrogen atmosphere to obtain the HKUST-1/graphene oxide composite film.
Preferably, the high-temperature treatment temperature in the step 6 is 500 ℃, and the treatment time is 3 h.
Preferably, the time of ultrasonic dispersion in the step 2 is 20-40 min.
Preferably, the stirring time in the step 3 is 12-24 hours.
Preferably, the volume of the single suction filtration in the step 4 is 10-40 mL.
Preferably, the filtration in the step 4 is performed by using a polyvinylidene fluoride filter membrane or a polytetrafluoroethylene filter membrane with the aperture of 220-1000 nm.
Preferably, the suction filtration time in the step 4 is 5-20 min.
Preferably, the drying time in the step 5 is 5-20 min.
The composite wave-absorbing film material prepared by the method.
Has the advantages that: the normal-temperature suction filtration membrane preparation technology provided by the invention can be used for simply preparing the light flexible HKUST-1/graphene oxide composite membrane in the air without heating or external electric field, so that the energy consumption is saved, the membrane preparation time is greatly shortened, and the industrial mass production is facilitated. The copper/carbon/reduced graphene oxide film derived from the composite film after high-temperature treatment, namely the composite wave-absorbing film, has good comprehensive wave-absorbing performance, and the maximum electromagnetic wave absorption rate can reach 94.4%.
According to the preparation method, the HKUST-1/graphene oxide composite film is prepared by adopting the trimesic acid as the chelating agent, and can be prepared only by stirring at normal temperature, so that the defect that the conventional MOF ligand needs to be prepared by a hydrothermal method is overcome, the process time is greatly shortened, about 48 hours can be shortened only by carrying out suction filtration and drying operations for film formation, and great advantages are brought to industrial production. Meanwhile, the trimesic acid chelating agent is a key precursor for forming the HKUST-1 material, and is very important for the synthesis of the HKUST-1 and the mechanical property of the HKUST-1/graphene oxide composite film.
Drawings
FIG. 1 is a real object diagram of a HKUST-1/graphene oxide composite film;
FIG. 2 is a diagram of an HKUST-1/graphene oxide derived copper/carbon/reduced graphene oxide composite wave-absorbing film;
FIG. 3 is a physical diagram of the composite wave-absorbing film in a bending state;
FIG. 4 is a reflection loss diagram of the composite wave-absorbing film obtained by heat treatment at 400 ℃ in the range of 2-18 GHz;
FIG. 5 is a reflection loss diagram of the composite wave-absorbing film obtained by heat treatment at 500 ℃ in the range of 2-18 GHz;
FIG. 6 is a reflection loss graph of the composite wave-absorbing film obtained by heat treatment at 600 ℃ in the range of 2-18 GHz;
FIG. 7 is a reflection loss diagram of the composite wave-absorbing film obtained by heat treatment at 700 ℃ in the range of 2-18 GHz;
FIG. 8 is a reflection loss diagram of the composite wave-absorbing film obtained by heat treatment at 800 ℃ in the range of 2-18 GHz.
Detailed Description
The invention is further described below with reference to the accompanying drawings and specific embodiments.
Example 1
A preparation method of a composite wave-absorbing film material comprises the following steps:
step 1, respectively adding 1.9 g of copper nitrate trihydrate and 1.7 g of trimesic acid into 100 mL of deionized water and 100 mL of ethanol, stirring for 15 min until the copper nitrate trihydrate and the trimesic acid are dissolved, and mixing to obtain solution A;
step 2, adding 10 mL of graphite oxide hydrosol with the concentration of 10mg/mL into 200 mL of ethanol, and performing ultrasonic dispersion for 30 min to obtain a uniformly dispersed graphene oxide solution;
step 3, adding the graphene oxide solution obtained in the step 2 into the solution A obtained in the step 1, and stirring for 18 hours to obtain a solution B;
step 4, placing a polytetrafluoroethylene suction filtration membrane with the aperture of 450 nm on a sand core of a suction filtration bottle, building a suction filtration device, pouring 20 mL of liquid B into the suction filtration device, carrying out suction filtration for about 10 min, and taking down the suction filtration membrane attached with the HKUST-1/graphene oxide composite membrane;
and 5, drying the suction filtration membrane in the step 4 in the air for 10 min, and gradually and naturally falling off the HKUST-1/graphene oxide composite membrane from the edge when the edge of the suction filtration membrane is slightly bent to obtain the HKUST-1/graphene oxide composite membrane shown in the figure 1.
And 6, carrying out heat treatment on the HKUST-1/graphene oxide composite film dried in the step 5 at 400 ℃ for 3h in a nitrogen atmosphere.
The composite wave-absorbing film material prepared by the method is shown in figure 2.
Figure 3 shows the characteristics of flexibility, bending and the like of the wave-absorbing film after heat treatment. The reflection loss of the obtained wave-absorbing film in the range of 2-18 GHz is shown in figure 4.
Example 2
The preparation method of the composite wave-absorbing film material in the embodiment specifically comprises the following steps: the HKUST-1/graphene oxide composite film dried in the step 5 in the example 1 is subjected to heat treatment at 500 ℃ for 3 hours in a nitrogen atmosphere. The reflection loss of the obtained wave-absorbing film in the range of 2-18 GHz is shown in figure 5.
Example 3
The preparation method of the composite wave-absorbing film material in the embodiment specifically comprises the following steps: the HKUST-1/graphene oxide composite film dried in the step 5 in the example 1 is subjected to heat treatment at 600 ℃ for 3 hours in a nitrogen atmosphere. The reflection loss of the obtained wave-absorbing film in the range of 2-18 GHz is shown in figure 6.
Example 4
The preparation method of the composite wave-absorbing film material in the embodiment specifically comprises the following steps: the HKUST-1/graphene oxide composite film dried in the step 5 in the example 1 is subjected to heat treatment at 700 ℃ for 3 hours in a nitrogen atmosphere. The reflection loss of the obtained wave-absorbing film in the range of 2-18 GHz is shown in figure 7.
Example 5
The preparation method of the composite wave-absorbing film material in the embodiment specifically comprises the following steps: the HKUST-1/graphene oxide composite film dried in the step 5 in the example 1 is subjected to heat treatment at 800 ℃ for 3 hours in a nitrogen atmosphere. The reflection loss of the obtained wave-absorbing film in the range of 2-18 GHz is shown in figure 8.
Comparative example 1
The HKUST-1/graphene oxide composite film dried in the step 5 in the embodiment 1 is subjected to heat treatment at 1000 ℃ for 3 hours in a nitrogen atmosphere, the structure of the sample film is damaged, and the required composite wave-absorbing film material cannot be obtained.
Comparing the products of examples 1-5 with comparative example 1, it can be observed that the film structure is completely destroyed when the heat treatment temperature is too high and reaches 1000 ℃ or above.
The wave-absorbing film prepared in the embodiments 1 to 5 is subjected to an electromagnetic wave absorption performance test, when the reflection loss reaches-10%, 90% of electromagnetic waves are absorbed, as shown in fig. 4 to 8, the composite wave-absorbing film material obtained in the embodiment 2 by heat treatment at 500 ℃ for 3 hours has better comprehensive wave-absorbing capability than other embodiments, and can reach an electromagnetic wave absorption rate of 94.4% at a frequency of 10.5 GHz under the condition that the thickness is only 1.5 mm.

Claims (9)

1. A preparation method of a composite wave-absorbing film material is characterized by comprising the following steps:
step 1, mixing the raw materials in a mass ratio of 1.1-1.5: 1, respectively adding copper nitrate trihydrate and trimesic acid into deionized water and ethanol with the same volume, respectively stirring and dissolving, and then mixing to obtain solution A;
step 2, adding the graphite oxide hydrosol into ethanol and performing ultrasonic dispersion to obtain a graphene oxide solution with the concentration of 0.4-0.6 mg/mL;
step 3, adding the graphene oxide solution into the solution A with the same volume and stirring to obtain a solution B;
step 4, carrying out suction filtration on the solution B to obtain a suction filtration membrane attached with the HKUST-1/graphene oxide composite membrane;
step 5, drying the suction filtration membrane in the air, and naturally dropping attachments to obtain the HKUST-1/graphene oxide composite membrane; and 6, treating the HKUST-1/graphene oxide composite film at the high temperature of 300-900 ℃ for 2-4 hours in a nitrogen atmosphere to obtain the HKUST-1/graphene oxide composite film.
2. The method for preparing the composite wave-absorbing film material according to claim 1, wherein the high temperature treatment temperature in the step 6 is 500 ℃ and the treatment time is 3 hours.
3. The preparation method of the composite wave-absorbing film material according to claim 1, wherein the time of ultrasonic dispersion in the step 2 is 20-40 min.
4. The preparation method of the composite wave-absorbing film material according to claim 1, wherein the stirring time in the step 3 is 12-24 hours.
5. The preparation method of the composite wave-absorbing film material according to claim 1, wherein the volume of the single suction filtration in the step 4 is 10-40 mL.
6. The method for preparing the composite wave-absorbing film material according to claim 1, wherein the filtration in the step 4 is performed by using a polyvinylidene fluoride filter membrane or a polytetrafluoroethylene filter membrane having a pore diameter of 220 to 1000 nm.
7. The preparation method of the composite wave-absorbing film material according to claim 1, wherein the suction filtration time in the step 4 is 5-20 min.
8. The method for preparing the composite wave-absorbing film material according to claim 1, wherein the drying time in the step 5 is 5-20 min.
9. The composite wave-absorbing film material prepared by the preparation method of any one of claims 1 to 8.
CN202210442128.8A 2022-04-26 2022-04-26 Composite wave-absorbing film material and preparation method thereof Active CN114554822B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107703195A (en) * 2017-08-16 2018-02-16 商丘师范学院 A kind of preparation method of graphene metal organic frame composite modified electrode
CN108807798A (en) * 2018-08-01 2018-11-13 南京大学 Composite battery separator film and its preparation method and application based on metal-organic framework materials
CN111659401A (en) * 2020-06-30 2020-09-15 齐鲁工业大学 Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180084351A (en) * 2017-01-17 2018-07-25 한국과학기술원 Wideband EMI shielding film based on a conducting polymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107703195A (en) * 2017-08-16 2018-02-16 商丘师范学院 A kind of preparation method of graphene metal organic frame composite modified electrode
CN108807798A (en) * 2018-08-01 2018-11-13 南京大学 Composite battery separator film and its preparation method and application based on metal-organic framework materials
CN111659401A (en) * 2020-06-30 2020-09-15 齐鲁工业大学 Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof

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