CN114561805A - Flexible electromagnetic shielding material and preparation method thereof - Google Patents
Flexible electromagnetic shielding material and preparation method thereof Download PDFInfo
- Publication number
- CN114561805A CN114561805A CN202210084507.4A CN202210084507A CN114561805A CN 114561805 A CN114561805 A CN 114561805A CN 202210084507 A CN202210084507 A CN 202210084507A CN 114561805 A CN114561805 A CN 114561805A
- Authority
- CN
- China
- Prior art keywords
- flexible substrate
- coni
- mofs
- electromagnetic shielding
- flexible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
-
- 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
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
- D06M10/025—Corona discharge or low temperature plasma
-
- 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
-
- 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
- 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
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
Abstract
The invention discloses a preparation method of a flexible electromagnetic shielding material, which comprises the following steps: step 1, pretreating a flexible substrate; step 2, preparing CoNi MOFs on the surface of the treated flexible substrate; step 3, carrying out thermal shock treatment on the CoNi MOFs on the surface of the flexible substrate to obtain a CoNi/C flexible electromagnetic shielding material; the thermal shock treatment process is carried out according to the heating at 1100-1300 ℃ for 1s, standing at room temperature for 10s, heating at 1100-1300 ℃ for 1s and storing at room temperature. The flexible electromagnetic shielding material prepared by the method has the characteristics of light weight and good thermal stability, and has high-efficiency electromagnetic shielding efficiency in a 2-18GHz wave band.
Description
Technical Field
The invention belongs to the field of preparation of electromagnetic shielding materials, and particularly relates to a flexible electromagnetic shielding material and a preparation method thereof.
Background
With the development of modern radio technology and the popularization of electronic equipment, electromagnetic radiation is becoming more serious, and the health of human beings and the safety of military information are threatened all the time. Therefore, the development of safe, efficient and light electromagnetic shielding materials has important significance. The excellent electromagnetic shielding material not only needs to meet the characteristics of light weight, wide working frequency band and the like, but also needs to meet the requirements of practical application, such as preparation of wearable flexible electromagnetic shielding materials. The design and development of flexible electromagnetic shielding materials is particularly important.
Patent CN113386412A discloses a graphite alkene/carbon nanotube aerogel electromagnetic shield composite fabric, carries out reduction reaction after mixing graphite alkene oxide, oxidation carbon nanotube, dispersant and water, obtains RGO/CNTs dispersion, carries out drying after the cross-linking reaction, obtains RGO/CNTs aerogel, laminates it on the fabric, obtains graphite alkene/carbon nanotube aerogel electromagnetic shield composite fabric, and electromagnetic shield efficiency reaches 34.5 dB. Patent CN111364236A discloses a flexible electromagnetic shielding fabric and a preparation method thereof, wherein graphene oxide/Fe is self-assembled on the upper surface of a fabric layer3O4And mixing the nano particle layer to obtain the composite material with better electromagnetic shielding performance.
However, the traditional ferrite electromagnetic shielding material has high magnetic conductivity and low cost, but has high density and poor corrosion resistance; carbon materials are lightweight but nonmagnetic and thus have limited electromagnetic shielding properties. The emerging metal-organic framework material can combine magnetic metal and organic ligand, combines the advantages of carbon material and metal material, and becomes a star material in the field of electromagnetic shielding.
Based on the above discussion, the existing process for preparing the electromagnetic shielding material is usually complicated, and the heat resistance and corrosion resistance of the sample need to be improved, so that a universal method for rapidly preparing the flexible electromagnetic shielding material is urgently needed to obtain the high-efficiency electromagnetic shielding material with light weight, safety, wide absorption frequency band, corrosion resistance and high temperature resistance.
Disclosure of Invention
In order to solve the problems of complex preparation process, no high temperature resistance and the like of the conventional flexible electromagnetic shielding material, the invention aims to provide a preparation method of the flexible electromagnetic shielding material, which is used for quickly preparing the flexible electromagnetic shielding material by adopting a simple and easy thermal shock method and realizing the broadband absorption of a microwave band.
The invention also aims to provide a flexible electromagnetic shielding material.
In order to achieve one of the purposes, the invention adopts the following technical scheme:
a preparation method of a flexible electromagnetic shielding material is provided, wherein the electromagnetic shielding material has high-efficiency electromagnetic shielding effectiveness in a 2-18GHz wave band; the preparation method comprises the following steps:
step 1, pretreating a flexible substrate;
step 2, preparing CoNi MOFs on the surface of the treated flexible substrate;
step 3, carrying out thermal shock treatment on the CoNi MOFs on the surface of the flexible substrate to obtain a CoNi/C flexible electromagnetic shielding material;
wherein the process of the thermal shock treatment is carried out according to the following steps in sequence:
step 3.1, heating CoNi MOFs on the surface of the flexible substrate for 1s at 1100-1300 ℃;
step 3.2, standing the CoNi MOFs on the surface of the flexible substrate for 10s at room temperature;
3.3, heating the CoNi MOFs on the surface of the flexible substrate for 1s at 1100-1300 ℃;
and 3.4, storing the treated flexible substrate at room temperature.
Further, the pretreatment is to bombard the flexible substrate for 3-5 min in an argon plasma atmosphere.
Further, the step 2 comprises the following substeps:
step 2.1, preparing 20-30mL of methanol solution A containing cobalt salt and nickel salt, vertically immersing the pretreated flexible substrate into a container containing the solution A, and then carrying out ultrasonic treatment for 10-30 min.
The concentration of the cobalt salt is 2-10 g/L; the concentration of the nickel salt is 2-10 g/L.
Step 2.2, preparing a methanol solution B with the volume of 180-200mL and the organic ligand concentration of 20-100 g/L, then dripping the solution B into the solution A with the flexible substrate at the dripping speed of 10mL/s, stirring for 10-30 min, and aging for 24h to obtain the flexible substrate loaded with the CoNi MOFs;
and 2.3, after taking out the flexible substrate loaded with the CoNi MOFs, washing the flexible substrate loaded with the CoNi MOFs by using a methanol solvent, and then putting the flexible substrate into a vacuum drying oven for vacuum drying.
Further, the cobalt salt is cobalt nitrate hexahydrate; the nickel salt is nickel nitrate; the organic ligand is 2-methylimidazole.
Further, the temperature of the vacuum drying is 60-70 ℃, and the time is 20-28 h.
Further, during thermal shock treatment, a direct-current power supply is used as an energy supply power supply, two leads are led out from the positive electrode and the negative electrode of the energy supply power supply and are respectively connected to two ends of the flexible substrate loaded with the CoNi MOFs.
Further, the thermal shock treatment is performed under an Ar atmosphere.
Further, the flexible substrate is a carbon felt or a hydrophilic carbon cloth.
Further, the dimensions of the flexible substrate are cut to the respective sizes:
the size of the flexible substrate of 3.94-5.99 GHz is 47.549 multiplied by 22.149 multiplied by 1 mm;
the size of the flexible substrate of 5.38-8.17 GHz is 34.849 multiplied by 15.799 multiplied by 1 mm;
the size of the flexible substrate of 8.2-12.5 GHz is 22.86 multiplied by 10.16 multiplied by 1 mm;
the flexible substrate size of 11.9-18GHz is 15.799 × 7.899 × 1 mm.
In order to achieve the second purpose, the invention adopts the following technical scheme:
the flexible electromagnetic shielding material is prepared by the preparation method of the flexible electromagnetic shielding material.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
(1) the CoNi MOFs in the invention directly grows on the flexible substrate, the process is simple, and any precursor can also grow on the flexible substrate according to actual requirements.
(2) The flexible electromagnetic shielding material prepared by the method has the characteristics of light weight and good thermal stability, and has high-efficiency electromagnetic shielding efficiency in a 2-18GHz wave band.
(3) CoNi MOFs on the discontinuous thermal impact carbon felt completes the rapid preparation of the CoNi/C electromagnetic shielding material within seconds, has reliable repeatability and is suitable for industrial production.
Drawings
FIG. 1a is a scanning electron micrograph of CoNi MOFs on a carbon felt prepared in example 1 of the present invention;
FIG. 1b is a scanning electron micrograph of a CoNi/C electromagnetic shielding material on a carbon felt prepared according to example 1 of the present invention;
FIG. 2 is an X-ray photoelectron spectrum characterization of a CoNi/C electromagnetic shielding material on a carbon felt prepared in example 1 of the present invention;
FIG. 3 is a thermogravimetric plot of a CoNi/C electromagnetic shielding material on a carbon felt prepared in example 1 of the present invention;
FIG. 4 shows the results of testing electromagnetic shielding of CoNi/C electromagnetic shielding materials with different carbon felt sizes prepared in example 1 of the present invention at microwave frequency bands of 3.94-5.99 GHz, 5.38-8.17 GHz, 8.2-12.5 GHz, and 11.9-18GHz, respectively.
Detailed Description
The technical solution and the specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.
The embodiment provides a preparation method of a flexible electromagnetic shielding material, and the electromagnetic shielding material has high-efficiency electromagnetic shielding effectiveness in a 2-18GHz wave band. The preparation method comprises the following steps.
Step 1, preprocessing a flexible substrate. The pretreatment is to bombard the flexible substrate for 3-5 min in the argon plasma atmosphere to remove impurities on the surface of the flexible substrate.
Wherein, the flexible substrate is a carbon felt or a hydrophilic carbon cloth, and the carbon felt is preferred.
Cutting the dimensions of the flexible substrate to the respective sizes:
the size of the flexible substrate of 3.94-5.99 GHz is 47.549 multiplied by 22.149 multiplied by 1 mm;
the size of the flexible substrate of 5.38-8.17 GHz is 34.849 multiplied by 15.799 multiplied by 1 mm;
the size of the flexible substrate of 8.2-12.5 GHz is 22.86 multiplied by 10.16 multiplied by 1 mm;
the flexible substrate size of 11.9-18GHz is 15.799 × 7.899 × 1 mm.
And 2, preparing CoNi MOFs on the surface of the treated flexible substrate, wherein the method comprises the following steps.
Step 2.1, preparing a methanol solution A containing 2-10 g/L of cobalt nitrate hexahydrate and 2-10 g/L of nickel nitrate, vertically immersing the pretreated flexible substrate into a container containing the solution A, and then carrying out ultrasonic treatment for 10-30 min to ensure that cobalt and nickel metal ions are fully adsorbed on the flexible substrate.
And 2.2, preparing a methanol solution B of 20-100 g/L organic ligand, then dripping the solution B into the solution A with the flexible substrate at a dripping speed of 10mL/s, stirring for 10-30 min, and aging for 24h to obtain the flexible substrate loaded with the CoNi MOFs.
Wherein the volume of the solution A is 20-30mL, and the volume of the solution B is 180-200 mL.
And performing coordination reaction on metal ions adsorbed on the flexible substrate and an organic ligand, and growing CoNi MOFs on the surface of the substrate in situ, wherein the binding force between the CoNi MOFs and the substrate can be improved by an in situ growth method.
And 2.3, after taking out the flexible substrate loaded with the CoNi MOFs, washing the flexible substrate loaded with the CoNi MOFs by using a methanol solvent, and then putting the substrate into a vacuum drying box at the temperature of 60-70 ℃ for vacuum drying for 20-28 h.
And 3, using a direct current power supply as an energy supply power supply, leading out two leads from the anode and the cathode of the energy supply power supply, and respectively connecting the two ends of the flexible substrate loaded on the CoNi MOFs. And carrying out thermal shock treatment on the CoNi MOFs on the surface of the flexible substrate in an Ar atmosphere to obtain the CoNi/C flexible electromagnetic shielding material.
Wherein the process of the thermal shock treatment is carried out according to the following steps in sequence:
step 3.1, heating CoNi MOFs on the surface of the flexible substrate for 1s at 1100-1300 ℃;
step 3.2, standing the CoNi MOFs on the surface of the flexible substrate for 10s at room temperature;
3.3, heating the CoNi MOFs on the surface of the flexible substrate for 1s at the temperature of 1100-1300 ℃;
and 3.4, storing the treated flexible substrate at room temperature.
When the CoNi MOFs are subjected to high-temperature thermal shock treatment at 1100-1300 ℃, metal ions in the CoNi MOFs are reduced into Co and Ni nanocrystals with high crystallinity, and the size of nanocrystal particles is 20-50 nm; at the same time, the carbon skeleton loses the corresponding connecting particles, and amorphous C is formed. Compared with the metal ions without obvious effect on the electromagnetic wave reflection, the metal nano-crystal has obviously enhanced electromagnetic wave reflection, and the skin effect can inhibit the electromagnetic wave from entering to reflect the electromagnetic wave, thereby realizing the shielding of the electromagnetic wave.
The invention can rapidly prepare the CoNi MOFs into the CoNi/C composite material by adopting a discontinuous thermal impact method. Compared with the continuous thermal impact method, the discontinuous thermal impact method has the advantages that: firstly, the problem that the flexibility of the flexible substrate is lost due to embrittlement at high temperature is avoided; and secondly, if the continuous high-temperature thermal shock causes the C to be completely oxidized and the metal nanocrystalline to be completely gasified, the C-modified CoNi composite material cannot be obtained.
Another embodiment of the present invention provides a flexible electromagnetic shielding material.
All reagents used in the following examples are commercially available.
Firstly, cutting the carbon felt, wherein the cut carbon felt has the following dimensions:
the size of the carbon felt of 3.94-5.99 GHz is 47.549 multiplied by 22.149 multiplied by 1 mm;
the size of the carbon felt of 5.38-8.17 GHz is 34.849 multiplied by 15.799 multiplied by 1 mm;
the size of the carbon felt of 8.2-12.5 GHz is 22.86 multiplied by 10.16 multiplied by 1 mm;
the size of the carbon felt of 11.9-18GHz is 15.799 multiplied by 7.899 multiplied by 1 mm.
Example 1
Step 1, bombarding carbon felts with different sizes for 4min in an argon plasma atmosphere.
Step 2.1, preparing a methanol solution A of 5g/L cobalt nitrate hexahydrate and 5g/L nickel nitrate, putting a carbon felt into the solution A, and then carrying out ultrasonic treatment for 20 min.
And 2.2, preparing a methanol solution B of 50 g/L2-methylimidazole, dripping the solution B into the solution A with the carbon felt at the dripping speed of 10mL/s, stirring for 20min, and aging for 24h to obtain the carbon felt loaded with the CoNi MOFs.
Wherein the volume of the solution A is 20-30mL, and the volume of the solution B is 180-200 mL.
And 2.3, after taking out the carbon felt loaded with the CoNi MOFs, washing the carbon felt loaded with the CoNi MOFs by using a methanol solvent, and then putting the carbon felt loaded with the CoNi MOFs into a vacuum drying box at 60 ℃ for vacuum drying for 24 hours.
And 3, taking the stabilized voltage power supply as an energy supply, leading out two leads from the anode and the cathode of the direct current power supply, and respectively connecting the two ends of the flexible substrate loaded on the CoNi MOFs. And carrying out thermal shock treatment on the CoNi MOFs on the surface of the flexible substrate in an Ar atmosphere to obtain the CoNi/C flexible electromagnetic shielding material.
Wherein the process of the thermal shock treatment is carried out according to the following steps in sequence:
step 3.1, heating CoNi MOFs on the surface of the flexible substrate for 1s at 1200 ℃;
step 3.2, standing the CoNi MOFs on the surface of the flexible substrate for 10s at room temperature;
3.3, heating the CoNi MOFs on the surface of the flexible substrate at 1200 ℃ for 1s again;
and 3.4, storing the treated flexible substrate at room temperature.
FIG. 1a is a scanning electron micrograph of CoNi MOFs prepared on a carbon felt with a size of 47.549X 22.149X 1mm by the preparation method in example 1 of the present invention; FIG. 1b is a scanning electron microscope photograph of the CoNi/C electromagnetic shielding material obtained by hot stamping the carbon felt loaded with CoNi MOFs. As can be seen, the CoNi MOFs has a micron-scale three-dimensional structure, and after thermal shock treatment, the original skeleton structure is destroyed, the particle structure is in an amorphous state, and the nanometer-scale CoNi/C particles are formed. FIG. 2 is an X-ray photoelectron spectrum representation of the CoNi/C electromagnetic shielding material on the carbon felt prepared in example 1 of the present invention, further confirming the existence of Co, Ni and C.
FIG. 3 is a thermogravimetric plot of the CoNi/C electromagnetic shielding material on the carbon felt prepared in example 1 of the present invention. The CoNi/C electromagnetic shielding material prepared by the method has excellent heat resistance, and the loss of the material quality does not exceed 30% under the condition of the temperature of 1000 ℃.
FIG. 4 shows the results of testing electromagnetic shielding of CoNi/C electromagnetic shielding materials with different carbon felt sizes prepared in example 1 of the present invention at microwave frequency bands of 3.94-5.99 GH, 5.38-8.17 GHz, 8.2-12.5 GHz, and 11.9-18GHz, respectively. 20dB is generally used as the application standard of commercial electromagnetic shielding materials, and the shielding performance of the electromagnetic shielding material prepared by the method is far superior to the current commercial standard.
Example 2
Step 1, bombarding carbon felts with different sizes for 5min in an argon plasma atmosphere.
Step 2.1, preparing a methanol solution A of 2g/L cobalt nitrate hexahydrate and 2g/L nickel nitrate, putting a carbon felt into the solution A, and then carrying out ultrasonic treatment for 30 min.
And 2.2, preparing a methanol solution B of 20 g/L2-methylimidazole, then dripping the solution B into the solution A with the carbon felt at the dripping speed of 10mL/s, stirring for 30min, and aging for 24h to obtain the carbon felt loaded with the CoNi MOFs.
Wherein the volume of the solution A is 20-30mL, and the volume of the solution B is 180-200 mL.
And 2.3, taking out the carbon felt loaded with the CoNi MOFs, washing the carbon felt loaded with the CoNi MOFs by using a methanol solvent, and then putting the carbon felt into a vacuum drying oven at 70 ℃ for vacuum drying for 20 hours.
And 3, taking the stabilized voltage power supply as an energy supply, leading out two leads from the anode and the cathode of the direct current power supply, and respectively connecting the two ends of the flexible substrate loaded on the CoNi MOFs. And carrying out thermal shock treatment on the CoNi MOFs on the surface of the flexible substrate in an Ar atmosphere to obtain the CoNi/C flexible electromagnetic shielding material.
Wherein the process of the thermal shock treatment is carried out according to the following steps in sequence:
step 3.1, heating CoNi MOFs on the surface of the flexible substrate for 1s at 1100 ℃;
step 3.2, standing the CoNi MOFs on the surface of the flexible substrate for 10s at room temperature;
step 3.3, heating the CoNi MOFs on the surface of the flexible substrate for 1s at 1100 ℃;
and 3.4, storing the treated flexible substrate at room temperature.
Example 3
Step 1, bombarding carbon felts with different sizes for 3min in an argon plasma atmosphere.
Step 2.1, preparing a methanol solution A of 10g/L cobalt nitrate hexahydrate and 10g/L nickel nitrate, putting a carbon felt into the solution A, and then carrying out ultrasonic treatment for 30 min.
And 2.2, preparing a methanol solution B of 100 g/L2-methylimidazole, dripping the solution B into the solution A with the carbon felt at the dripping speed of 10mL/s, stirring for 10min, and aging for 24h to obtain the carbon felt loaded with the CoNi MOFs.
Wherein the volume of the solution A is 20-30mL, and the volume of the solution B is 180-200 mL.
And 2.3, taking out the carbon felt loaded with the CoNi MOFs, washing the carbon felt loaded with the CoNi MOFs by using a methanol solvent, and then putting the carbon felt into a 65-DEG C vacuum drying oven for vacuum drying for 28 hours.
And 3, taking the stabilized voltage power supply as an energy supply, leading out two leads from the anode and the cathode of the direct current power supply, and respectively connecting the two ends of the flexible substrate loaded on the CoNi MOFs. And carrying out thermal shock treatment on the CoNi MOFs on the surface of the flexible substrate in an Ar atmosphere to obtain the CoNi/C flexible electromagnetic shielding material.
Wherein the process of the thermal shock treatment is carried out according to the following steps in sequence:
step 3.1, heating CoNi MOFs on the surface of the flexible substrate at 1300 ℃ for 1 s;
step 3.2, standing the CoNi MOFs on the surface of the flexible substrate for 10s at room temperature;
3.3, heating the CoNi MOFs on the surface of the flexible substrate at 1300 ℃ for 1s again;
and 3.4, storing the treated flexible substrate at room temperature.
It will be evident to those skilled in the art that the embodiments of the present invention are not limited to the details of the foregoing illustrative embodiments, and that the embodiments of the present invention are capable of being 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 embodiments 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.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the embodiments of the present invention and not for limiting, and although the embodiments of the present invention are described in detail with reference to the above preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the embodiments of the present invention without departing from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the flexible electromagnetic shielding material is characterized in that the electromagnetic shielding material has high-efficiency electromagnetic shielding effectiveness in a 2-18GHz wave band; the preparation method comprises the following steps:
step 1, pretreating a flexible substrate;
step 2, preparing CoNi MOFs on the surface of the treated flexible substrate;
step 3, carrying out thermal shock treatment on the CoNi MOFs on the surface of the flexible substrate to obtain a CoNi/C flexible electromagnetic shielding material;
wherein the process of the thermal shock treatment is carried out according to the following steps in sequence:
step 3.1, heating CoNi MOFs on the surface of the flexible substrate for 1s at 1100-1300 ℃;
step 3.2, allowing the CoNi MOFs on the surface of the flexible substrate to stand for 10s at room temperature;
3.3, heating the CoNi MOFs on the surface of the flexible substrate for 1s at 1100-1300 ℃;
and 3.4, storing the treated flexible substrate at room temperature.
2. The method according to claim 1, wherein the pretreatment is performed by bombarding the flexible substrate in argon plasma atmosphere for 3-5 min.
3. The method of claim 1, wherein the step 2 comprises the substeps of:
step 2.1, preparing a methanol solution A containing cobalt salt and nickel salt with the volume of 20-30mL, vertically immersing the pretreated flexible substrate into a container containing the solution A, and then carrying out ultrasonic treatment for 10-30 min;
the concentration of the cobalt salt is 2-10 g/L; the concentration of the nickel salt is 2-10 g/L;
step 2.2, preparing a methanol solution B with the volume of 180-200mL and the organic ligand concentration of 20-100 g/L, then dripping the solution B into the solution A with the flexible substrate at the dripping speed of 10mL/s, stirring for 10-30 min, and aging for 24h to obtain the flexible substrate loaded with the CoNi MOFs;
and 2.3, after taking out the flexible substrate loaded with the CoNi MOFs, washing the flexible substrate loaded with the CoNi MOFs by using a methanol solvent, and then putting the flexible substrate into a vacuum drying oven for vacuum drying.
4. The method of claim 3, wherein the cobalt salt is cobalt nitrate hexahydrate; the nickel salt is nickel nitrate; the organic ligand is 2-methylimidazole.
5. The preparation method according to claim 3, wherein the temperature of the vacuum drying is 60 to 70 ℃ and the time is 20 to 28 hours.
6. The preparation method of claim 1, wherein during the thermal shock treatment, a direct current power supply is used as an energy supply, and two leads are led out from the positive electrode and the negative electrode of the energy supply and are respectively connected to two ends of the flexible substrate loaded with the CoNi MOFs.
7. The production method according to claim 1, wherein the thermal shock treatment is performed under an Ar atmosphere.
8. The method of claim 1, wherein the flexible substrate is a carbon felt or a hydrophilic carbon cloth.
9. The method of manufacturing of claim 8, wherein the dimensions of the flexible substrate are cut to respective sizes:
the size of the flexible substrate of 3.94-5.99 GHz is 47.549 multiplied by 22.149 multiplied by 1 mm;
the size of the flexible substrate of 5.38-8.17 GHz is 34.849 multiplied by 15.799 multiplied by 1 mm;
the size of the flexible substrate of 8.2-12.5 GHz is 22.86 multiplied by 10.16 multiplied by 1 mm;
the flexible substrate size of 11.9-18GHz is 15.799X 7.899X 1 mm.
10. A flexible electromagnetic shielding material prepared by the preparation method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210084507.4A CN114561805B (en) | 2022-01-25 | 2022-01-25 | Flexible electromagnetic shielding material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210084507.4A CN114561805B (en) | 2022-01-25 | 2022-01-25 | Flexible electromagnetic shielding material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114561805A true CN114561805A (en) | 2022-05-31 |
| CN114561805B CN114561805B (en) | 2023-04-18 |
Family
ID=81713068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210084507.4A Active CN114561805B (en) | 2022-01-25 | 2022-01-25 | Flexible electromagnetic shielding material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114561805B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115450044A (en) * | 2022-08-11 | 2022-12-09 | 中国科学院宁波材料技术与工程研究所 | Composite carbon fiber with high electromagnetic wave absorption performance and preparation method thereof |
| CN115942728A (en) * | 2022-11-15 | 2023-04-07 | 中国人民解放军国防科技大学 | Fusiform Co @ C-Mxene electromagnetic shielding material and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110295498A (en) * | 2019-04-15 | 2019-10-01 | 武汉理工大学 | The thin polymer film and its preparation method and application of metal organic frame modification |
| CN110938407A (en) * | 2019-12-21 | 2020-03-31 | 哈尔滨工业大学 | Hierarchical-structure hollow CNTs/Co/C fiber wave-absorbing material and preparation method thereof |
| CN111001821A (en) * | 2019-12-21 | 2020-04-14 | 哈尔滨工业大学 | Metal organic framework derived Co/C nanoparticle coated carbonized cotton fiber wave-absorbing material and preparation method thereof |
| CN112175390A (en) * | 2020-10-16 | 2021-01-05 | 西安工程大学 | Flexible carbon fiber composite electromagnetic shielding film and preparation method thereof |
| CN112981960A (en) * | 2021-02-24 | 2021-06-18 | 北京科技大学 | Preparation method of metal organic framework/nano fiber with beaded structure |
| CN113444357A (en) * | 2021-07-27 | 2021-09-28 | 上海交通大学 | Preparation method of flexible regenerated carbon fiber electromagnetic shielding composite material |
| CN113511640A (en) * | 2021-05-26 | 2021-10-19 | 中国人民解放军国防科技大学 | Metal nanocrystalline-amorphous carbon composite wave-absorbing particle and preparation method thereof |
| CN113912038A (en) * | 2021-09-01 | 2022-01-11 | 浙江工业大学 | Wave-absorbing material from NiCo-MOF/biomass cotton and preparation method thereof |
-
2022
- 2022-01-25 CN CN202210084507.4A patent/CN114561805B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110295498A (en) * | 2019-04-15 | 2019-10-01 | 武汉理工大学 | The thin polymer film and its preparation method and application of metal organic frame modification |
| CN110938407A (en) * | 2019-12-21 | 2020-03-31 | 哈尔滨工业大学 | Hierarchical-structure hollow CNTs/Co/C fiber wave-absorbing material and preparation method thereof |
| CN111001821A (en) * | 2019-12-21 | 2020-04-14 | 哈尔滨工业大学 | Metal organic framework derived Co/C nanoparticle coated carbonized cotton fiber wave-absorbing material and preparation method thereof |
| CN112175390A (en) * | 2020-10-16 | 2021-01-05 | 西安工程大学 | Flexible carbon fiber composite electromagnetic shielding film and preparation method thereof |
| CN112981960A (en) * | 2021-02-24 | 2021-06-18 | 北京科技大学 | Preparation method of metal organic framework/nano fiber with beaded structure |
| CN113511640A (en) * | 2021-05-26 | 2021-10-19 | 中国人民解放军国防科技大学 | Metal nanocrystalline-amorphous carbon composite wave-absorbing particle and preparation method thereof |
| CN113444357A (en) * | 2021-07-27 | 2021-09-28 | 上海交通大学 | Preparation method of flexible regenerated carbon fiber electromagnetic shielding composite material |
| CN113912038A (en) * | 2021-09-01 | 2022-01-11 | 浙江工业大学 | Wave-absorbing material from NiCo-MOF/biomass cotton and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| ARIEF INJAMAMUL等: ""Tunable CoNi microstructures in flexible multilayered polymer films can shield electromagnetic radiation"", 《COMPOSITES PART B》 * |
| LIU GUANG等: ""High-Yield Two-Dimensional Metal−Organic Framework Derivatives for Wideband Electromagnetic Wave Absorption"", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| MA MINGLIANG等: ""Magnetic CoNi alloy particles embedded N-doped carbon fibers with polypyrrole for excellent electromagnetic wave absorption"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| ZHAO XIAOXIAO等: ""Magnetic porous CoNi@C derived from bamboo fiber combined with metal-organic-framework for enhanced electromagnetic wave absorption"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115450044A (en) * | 2022-08-11 | 2022-12-09 | 中国科学院宁波材料技术与工程研究所 | Composite carbon fiber with high electromagnetic wave absorption performance and preparation method thereof |
| CN115450044B (en) * | 2022-08-11 | 2024-04-05 | 中国科学院宁波材料技术与工程研究所 | Composite carbon fiber with high electromagnetic wave absorption performance and preparation method thereof |
| CN115942728A (en) * | 2022-11-15 | 2023-04-07 | 中国人民解放军国防科技大学 | Fusiform Co @ C-Mxene electromagnetic shielding material and preparation method thereof |
| CN115942728B (en) * | 2022-11-15 | 2023-08-29 | 中国人民解放军国防科技大学 | Spindle-shaped Co@C-Mxene electromagnetic shielding material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114561805B (en) | 2023-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yi et al. | Regulating pyrolysis strategy to construct CNTs-linked porous cubic Prussian blue analogue derivatives for lightweight and broadband microwave absorption | |
| CN114561805B (en) | Flexible electromagnetic shielding material and preparation method thereof | |
| Wang et al. | Construction of 1D heterostructure NiCo@ C/ZnO nanorod with enhanced microwave absorption | |
| Zeng et al. | Construction of 0D/1D/2D MXene nanoribbons-NiCo@ NC hierarchical network and their coupling effect on electromagnetic wave absorption | |
| CN109252359B (en) | Preparation method of carbon nanotube modified carbon fiber reinforced resin-based electromagnetic shielding composite material for in-situ growth of solid carbon source | |
| CN115491177B (en) | MOF-derived carbon-based magnetic nano composite electromagnetic wave absorbing material and preparation method thereof | |
| CN112980390B (en) | Preparation method of bimetal organic framework derived magnetic carbon composite wave-absorbing material | |
| CN113079684B (en) | Preparation method and application of three-dimensional graphene-based composite material | |
| CN113271758B (en) | Electromagnetic wave shielding breathable porous carbon composite material and preparation method and application thereof | |
| CN107934945A (en) | A kind of method for preparing magnetic graphene using molysite gas phase intercalation and microwave technology | |
| Zhang et al. | Three-dimensional carbon foam modified with starlike-ZnO@ reduced graphene oxide for microwave absorption with low filler content | |
| Xu et al. | Monodisperse branched nickel carbide nanoparticles in situ grown on reduced graphene oxide with excellent electromagnetic absorption properties | |
| CN114349060B (en) | Preparation method of carbon-coated magnetic nanoparticle nitrogen-doped magnetic graphene | |
| CN109652013B (en) | Composite microwave absorbent | |
| Jiang et al. | Controlled growth of highly active NiMoN (100)-decorated porous N-doped carbon nanotubes on carbon cloth as efficient electrodes for alkaline media and seawater electrolysis | |
| Shen et al. | Promoting Electromagnetic Wave Absorption Performance by Integrating MoS2@ Gd2O3/MXene Multiple Hetero‐Interfaces in Wood‐Derived Carbon Aerogels | |
| CN111962090B (en) | Ti3C2-MXene modified alpha-iron oxide photoelectrode and preparation method thereof | |
| CN110026220B (en) | Transition metal carbide/graphitized carbon-like composite powder and preparation method thereof | |
| CN114804218B (en) | Multistage heterostructure microwave absorbing material and preparation method thereof | |
| CN111573745A (en) | Preparation method of nickel-cobalt sulfide and graphene composite material rich in elemental sulfur | |
| CN108640165B (en) | Metal oxide nano-structure composite material and preparation method thereof | |
| CN114573037B (en) | Method for rapidly preparing wave-absorbing material by laser irradiation | |
| CN111115617A (en) | Large-scale preparation method of high-purity hollow carbon nano-onion | |
| CN113480973B (en) | Boron/nitrogen double-doped carbon nanotube-carbon nanosheet composite material and preparation method thereof | |
| CN114614272A (en) | MXene/Co/C composite wave-absorbing material derived from MOF and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |