CN111547707A - Graphene bubble film and preparation method and application thereof - Google Patents
Graphene bubble film and preparation method and application thereof Download PDFInfo
- Publication number
- CN111547707A CN111547707A CN202010334109.4A CN202010334109A CN111547707A CN 111547707 A CN111547707 A CN 111547707A CN 202010334109 A CN202010334109 A CN 202010334109A CN 111547707 A CN111547707 A CN 111547707A
- Authority
- CN
- China
- Prior art keywords
- bubble film
- graphene
- graphene bubble
- film
- air holes
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims description 35
- 239000000725 suspension Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000004793 Polystyrene Substances 0.000 claims description 20
- 229920002223 polystyrene Polymers 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000007581 slurry coating method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000006194 liquid suspension Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000012528 membrane Substances 0.000 description 31
- 239000002131 composite material Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 241000446313 Lamella Species 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- 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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention belongs to the technical field of electromagnetic shielding materials, and particularly relates to a graphene bubble film and a preparation method and application thereof. The invention provides a graphene bubble film, which contains closed air holes, wherein the average diameter of the air holes is 5-30 mu m; the thickness of the graphene bubble film is 60-200 mu m; the volume density of the graphene bubble film is 0.1-0.3 g/cm3(ii) a The closed pore rate of the graphene bubble film is greater than 50%. According to the invention, the graphene with good electrical conductivity and thermal conductivity is directly used as the matrix, so that the electrical conductivity and thermal conductivity of the graphene bubble film are ensured; the graphene bubble film contains closed air holes, and when electromagnetic waves enter the closed air holes, the electromagnetic waves are reflected back and forth in the closed air holes until the electromagnetic waves are exhausted, so that the electromagnetic waves are realizedAnd (4) shielding.
Description
Technical Field
The invention belongs to the technical field of electromagnetic shielding materials, and particularly relates to a graphene bubble film and a preparation method and application thereof.
Background
Electromagnetic compatibility and heat dissipation are two key issues in the field of electronic devices. With the development of communication technology, the electronic devices in the communication field generate high-frequency electromagnetic waves, so that the risks of crosstalk and common mode between adjacent devices are increased, and higher requirements on electromagnetic compatibility are provided; at the same time, the electronic device operates faster, which means that the heat generation of the electronic device is more obvious, and therefore, the heat dissipation design also has obvious challenges.
The core of the electromagnetic compatibility design is to shield the electromagnetic wave emitted by the device, and the shielding mechanism can be divided into a reflection type and an absorption type. Most of the existing metallic electromagnetic field shielding materials belong to reflection type shielding materials, and the materials have the characteristics of excellent conductivity, obvious reflection occurs when electromagnetic waves enter the surfaces of the materials, but the reflected electromagnetic waves can generate crosstalk to adjacent electronic devices, so that the normal operation of the adjacent electronic devices is influenced.
The design idea of the absorption electromagnetic shielding material is to construct a closed conductive cavity, and when electromagnetic waves are incident on the conductive cavity, the electromagnetic waves are reflected back and forth on the inner wall of the cavity until the electromagnetic waves are exhausted. The absorption type electromagnetic shielding material can overcome the defects of a reflection type shielding material. Silver is plated on the surface of the hollow glass microsphere by Wangyman university, and the like to form a closed conductive cavity, and then the conductive cavity is compounded with a resin matrix to obtain the high-absorption shielding material (preparation and performance of the silver-coated glass microsphere core-shell particle for the electromagnetic shielding material, silicate science and report 2008,36(3): 301-305). However, the diameter of the hollow glass beads is generally 20-200 μm, the thickness of the hollow glass beads after being compounded with the resin matrix is generally 1-3 mm, the thickness of the high-absorption shielding material exceeds the design requirements of most electronic equipment, and the high-absorption shielding material has poor heat conductivity and is difficult to be applied to 5G electronic equipment.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the graphene bubble film with excellent electromagnetic shielding function and good thermal conductivity, the graphene bubble film provided by the invention takes graphene as a matrix, and the thermal conductivity can reach 400W/mK; the electromagnetic shielding effectiveness of the graphene bubble film can reach 54dB, and the thickness of the graphene bubble film is 60-200 mu m.
The invention is realized by the following technical scheme.
A graphene bubble film is characterized in that: the graphene bubble film contains closed air holes, and the average diameter of the air holes is 5-30 mu m; the thickness of the graphene bubble film is 60-200 mu m, and the volume density of the graphene bubble film is 0.1-0.3 g/cm3The closed porosity of the graphene bubble film is larger than 50%, so that the graphene bubble film has good electrical conductivity and thermal conductivity, and meanwhile, enough closed air holes can be guaranteed to completely consume incident electromagnetic waves.
According to the invention, the graphene with good conductivity is directly used as a matrix, so that the conductivity and the thermal conductivity of the graphene bubble film are ensured; the graphene bubble film contains closed air holes, and when electromagnetic waves enter the closed air holes, the electromagnetic waves are reflected back and forth in the closed air holes until the electromagnetic waves are exhausted, so that electromagnetic shielding is realized.
The invention also provides a preparation method of the graphene bubble film in the technical scheme, which comprises the following steps:
s1, mixing the graphene oxide hydrosol and the pore-forming agent in a mass ratio of 10: 1-7, and carrying out ultrasonic treatment on the mixed solution with ultrasonic intensity of 200-500W for 0.5-5 h to obtain a blended suspension; the graphene oxide lamella can be separated by ultrasonic treatment to obtain a thin graphene oxide lamella, so that graphene is fully utilized; meanwhile, the graphene oxide and the pore-forming agent are fully mixed through ultrasonic treatment, so that the pore-forming agent is uniformly dispersed in the graphene oxide film;
s2, after the film is formed by the blending suspension liquid prepared in the step S1, heating treatment is carried out, wherein the heating rate is 1-10 ℃/min, the heating temperature is 600-3000 ℃, and the time is 30-120 min, so that the graphene bubble film is prepared; the graphene oxide is reduced at high temperature after heating treatment, most non-carbon elements are removed, the electric conductivity and the heat conductivity of the graphene are improved, and meanwhile, the pore-forming agent is cracked at high temperature in the heating treatment process to form closed conductive pores, so that absorption type shielding can be performed on electromagnetic waves.
Further, the pore-forming agent is polystyrene balls and/or polymethyl methacrylate balls.
Further, the average diameter of the pore-forming agent is 5-30 μm.
Further, the mass concentration of the graphene oxide in the graphene oxide hydrosol is 0.5-10 mg/mL.
Further, the manner of co-suspending the suspension liquid to form a film in step S2 is suction filtration or slurry coating.
The invention also provides the application of the graphene bubble film prepared by the technical scheme or the preparation method of the technical scheme as an electromagnetic shielding material in an electronic device.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the graphene with good electrical conductivity and thermal conductivity is directly used as the matrix, so that the electrical conductivity and thermal conductivity of the graphene bubble film are ensured; the graphene bubble film contains closed air holes, and when electromagnetic waves are incident into the closed air holes, the electromagnetic waves are reflected back and forth in the closed air holes until the electromagnetic waves are exhausted, so that electromagnetic shielding is realized.
Drawings
Fig. 1 is a process flow diagram for preparing a graphene bubble film;
fig. 2 is a microscopic morphology image of the graphene bubble film prepared in example 2 by an SEM scanning electron microscope.
Fig. 3 is a partially enlarged SEM scanning electron microscope of the graphene bubble film prepared in example 2.
Detailed Description
The invention provides a graphene bubble film, which is characterized in that: the graphene bubble film contains closed air holes, and the average diameter of the air holes is 5-30 mu m; the thickness of the graphene bubble film is 60-200 mu m, and the volume density of the graphene bubble film is 0.1-0.3 g/cm3And the closed pore rate of the graphene bubble film is more than 50%.
According to the invention, the graphene with good electrical conductivity and thermal conductivity is directly used as the matrix, so that the electrical conductivity and thermal conductivity of the graphene bubble film are ensured; the embodiment results show that the graphene bubble film provided by the invention has the electrical conductivity of 400-6000S/m and the thermal conductivity of 220.3-400W/mK.
The graphene bubble film contains closed air holes, and when electromagnetic waves enter the closed air holes, the electromagnetic waves are reflected back and forth in the closed air holes until the electromagnetic waves are exhausted, so that electromagnetic shielding is realized. In the invention, the average diameter of closed pores in the graphene bubble film is 5-30 μm, preferably 10-25 μm, and more preferably 15 μm; the volume density of the graphene bubble film is 0.1-0.3 g/cm3Preferably 0.12 to 0.15g/cm3More preferably 0.14g/cm3(ii) a The thickness of the graphene bubble film is 60-200 microns, preferably 80-120 microns, and more preferably 90-100 microns; the closed pore rate of the graphene bubble film is greater than 50%, preferably 60-90%, and more preferably 65-75%.
According to the invention, the average diameter of closed air holes, the volume density of the graphene bubble film and the closed hole rate are limited, so that the closed air holes are uniformly distributed in the graphene bubble film, the graphene bubble film has good conductivity, and meanwhile, enough closed air holes can be ensured to completely consume incident electromagnetic waves.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
As shown in fig. 1, the invention further provides a preparation method of the graphene bubble film according to the above technical scheme, which comprises the following steps:
s1, mixing the graphene oxide hydrosol with a pore-forming agent, wherein the mass ratio of the graphene oxide to the pore-forming agent is 10: 1-7, preferably 10: 2-5, and more preferably 10: 3; according to the invention, the mass ratio of the graphene oxide to the pore-forming agent is controlled within the range, so that incident electromagnetic waves can be consumed while the conductivity of the graphene bubble film is ensured;
carrying out ultrasonic treatment on the mixed solution of the graphene oxide hydrosol and the pore-forming agent, wherein the ultrasonic intensity is 200-500W, and the ultrasonic treatment time is 0.5-5 h, so as to prepare a blending suspension; the ultrasonic intensity is preferably 300W, and the ultrasonic treatment time is preferably 2-4 h, more preferably 3 h; in the invention, the ultrasonic treatment can separate graphene oxide lamella to obtain a thin graphene oxide lamella, so that graphene is fully utilized; meanwhile, the graphene oxide and the pore-forming agent are fully mixed through ultrasonic treatment, so that the pore-forming agent is uniformly dispersed in the graphene oxide film;
s2, after the film is formed by the blending suspension liquid prepared in the step S1, heating treatment is carried out, wherein the heating rate is 1-10 ℃/min, the heating temperature is 600-3000 ℃, and the time is 30-120 min, so that the graphene bubble film is prepared; the graphene oxide is reduced at high temperature after heating treatment, most non-carbon elements are removed, the electric conductivity and the heat conductivity of the graphene are improved, and meanwhile, the pore-forming agent is cracked at high temperature in the heating treatment process to form closed conductive pores, so that absorption type shielding can be performed on electromagnetic waves.
In the present invention, the heat treatment is preferably performed under a protective atmosphere, which preferably includes nitrogen or argon. In the invention, the temperature of the heating treatment is 600-3000 ℃, preferably 800-2400 ℃, and more preferably 1000-1200 ℃; the time is 30-120 min, preferably 40-60 min. In the present invention, the rate of temperature rise to the temperature of the heat treatment is preferably 1 to 10 ℃/min, more preferably 2 to 6 ℃/min, and most preferably 3 to 5 ℃/min. The present invention has no particular requirement on the apparatus used for the heat treatment, and a heat treatment apparatus known to those skilled in the art may be used. In the embodiment of the invention, a tube furnace is specifically selected. In the invention, after the heating treatment is finished, the graphene bubble film is preferably cooled to room temperature, and the cooling mode preferably includes natural cooling.
According to the invention, after the heating treatment, most non-carbon elements in the oxidized graphene are removed by high-temperature reduction, so that the electric conductivity and the heat conductivity of the graphene are improved, and meanwhile, in the heating treatment process, the pore-forming agent is cracked at high temperature to form closed conductive pores, so that the electromagnetic wave can be subjected to absorption type shielding.
Further, the pore-forming agent is a polystyrene sphere and/or a polymethyl methacrylate sphere, and is more preferably a polystyrene sphere or a polymethyl methacrylate sphere. When the pore-forming agent is a polystyrene ball and a polymethyl methacrylate ball, the invention has no special limitation on the mass ratio of the polystyrene ball to the polymethyl methacrylate ball, and the polystyrene ball and the polymethyl methacrylate ball can be mixed according to any proportion.
Further, the average diameter of the pore-forming agent is 5 to 30 μm, more preferably 10 to 25 μm, and most preferably 15 μm. In the present invention, the diameter of the closed pores in the graphene bubble film is preferably consistent with the diameter of the pore-forming agent.
Further, the manner of co-suspending the suspension liquid to form a film in step S2 is suction filtration or slurry coating.
The invention has no special limit on the suction filtration, adopts the process well known by the technicians in the field and can ensure that the filter membrane with uniform thickness is obtained; the thickness of the graphene bubble film is controlled by adjusting the using amount of the blending suspension. After the membrane is formed by suction filtration, the filter membrane is preferably dried, the drying mode has no special requirement, the conventional drying mode is adopted, and the filter membrane can be separated from the filter paper as long as the drying degree of the filter membrane has no special requirement. The invention has no special requirements on the separation mode, and only needs to adopt a conventional separation mode.
In the invention, the slurry coating is preferably carried out on a substrate to obtain a composite film with uniform thickness; the thickness of the graphene bubble film is adjusted by controlling the using amount of the blending suspension. In the present invention, the substrate preferably comprises an epoxy board, a polyester resin (PET) sheet, or a mixed fiber film. The coating is not particularly limited in the present invention as long as a composite film having a uniform thickness can be obtained. After the slurry coating is carried out to form a film, the composite film is preferably dried, the drying mode of the composite film is not specially required, the conventional drying mode is adopted, and the drying degree of the composite film is not specially required as long as the composite film can be separated from the substrate. The invention has no special requirements on the separation mode, and only needs to adopt a conventional separation mode.
The invention also provides the application of the graphene bubble film prepared by the technical scheme or the preparation method of the technical scheme as an electromagnetic shielding material in an electronic device. In the present invention, the graphene bubble film is preferably applied to an electromagnetic shielding and heat dissipation member of a portable electronic device. The graphene bubble film provided by the invention has a high-efficiency electromagnetic shielding function and good heat conduction capability, and can reduce the risks of crosstalk and common mode between adjacent electronic devices.
For further illustration of the present invention, the following examples are provided to describe the graphene bubble film and the preparation method and application thereof in detail, but not to limit the scope of the present invention. Unless otherwise specified, the examples follow conventional experimental conditions. In addition, it will be apparent to those skilled in the art that various modifications or improvements can be made to the material components and amounts in these embodiments without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1
S1, mixing 5mL of graphene oxide hydrosol with the mass concentration of 5mg/mL and 3mg of polystyrene spheres with the average diameter of 5 microns, and performing ultrasonic dispersion for 2 hours under the condition that the ultrasonic intensity is 200W to obtain a blended suspension;
s2, carrying out suction filtration on 5ml of the blended suspension to obtain a filter membrane; and naturally airing the filter membrane, separating the filter membrane from the filter paper, placing the separated filter membrane in a tubular furnace, heating to 600 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, preserving heat for 40min, and naturally cooling to room temperature to obtain the graphene bubble film with the thickness of 60 mu m and the average diameter of closed pores of 5 mu m.
Example 2
S1, mixing 60mL of graphene oxide hydrosol with the mass concentration of 0.5mg/mL and 21mg of polystyrene spheres with the average diameter of 30 microns, and performing ultrasonic dispersion for 5 hours under the condition that the ultrasonic intensity is 500W to obtain a blending suspension;
s2, carrying out suction filtration on 60mL of the blended suspension to obtain a filter membrane; and naturally airing the filter membrane, separating the filter membrane from the filter paper, placing the separated filter membrane in a tubular furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat for 60min, and naturally cooling to room temperature to obtain the graphene bubble film with the thickness of 70 mu m and the average diameter of closed pores of 30 mu m, wherein the micro-morphology of the graphene bubble film is shown in figures 2 and 3.
Example 3
S1, mixing 25mL of graphene oxide hydrosol with the mass concentration of 3mg/mL and 21mg of polystyrene spheres with the average diameter of 30 microns, and performing ultrasonic dispersion for 5 hours under the condition that the ultrasonic intensity is 200W to obtain a blending suspension;
s2, carrying out suction filtration on 25mL of the blended suspension to obtain a filter membrane; and naturally airing the filter membrane, separating the filter membrane from the filter paper, placing the separated filter membrane in a tubular furnace, heating to 1200 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, preserving heat for 120min, and naturally cooling to room temperature to obtain the graphene bubble film with the thickness of 200 mu m and the average diameter of closed pores of 30 mu m.
Example 4
S1, mixing 35mL of graphene oxide hydrosol with the mass concentration of 1mg/mL and 9mg of polymethyl methacrylate spheres with the average diameter of 15 microns, and performing ultrasonic dispersion for 3 hours under the condition that the ultrasonic intensity is 500W to obtain a blended suspension;
s2, carrying out suction filtration on 35mL of the blended suspension to obtain a filter membrane; and naturally airing the filter membrane, separating the filter membrane from the filter paper, placing the separated filter membrane in a tube furnace, heating to 2400 ℃ at a heating rate of 10 ℃/min under the protection of argon, preserving heat for 30min, and naturally cooling to room temperature to obtain the graphene bubble film with the thickness of 90 mu m and the average diameter of closed pores of 15 mu m.
Example 5
S1, mixing 20mL of graphene oxide hydrosol with the mass concentration of 2mg/mL and 12mg of polymethyl methacrylate spheres with the average diameter of 5 microns, and performing ultrasonic dispersion for 3 hours under the condition that the ultrasonic intensity is 500W to obtain a blended suspension;
s2, performing suction filtration on 20mL of the blended suspension to obtain a filter membrane; and naturally airing the filter membrane, separating the filter membrane from the filter paper, placing the separated filter membrane in a tubular furnace, heating to 1000 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, preserving heat for 60min, and naturally cooling to room temperature to obtain the graphene bubble film with the thickness of 100 mu m and the average diameter of closed pores of 5 mu m.
Example 6
S1, mixing 3mL of graphene oxide hydrosol with the mass concentration of 10mg/mL and 3mg of polystyrene spheres with the average diameter of 15 microns, and performing ultrasonic dispersion for 3 hours under the condition that the ultrasonic intensity is 500W to obtain a blended suspension;
s2, coating 3mL of the blended suspension on an epoxy plate to obtain a graphene oxide/polystyrene composite film; naturally airing the graphene oxide/polystyrene composite membrane, separating the graphene oxide/polystyrene composite membrane from the epoxy plate, placing the separated graphene oxide/polystyrene composite membrane in a tubular furnace, heating to 3000 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving heat for 30min, and naturally cooling to room temperature to obtain the graphene bubble film with the thickness of 80 mu m and the average diameter of closed pores of 15 mu m.
Example 7
S1, mixing 35mL of graphene oxide hydrosol with the mass concentration of 1mg/mL and 9mg of polystyrene spheres with the average diameter of 5 microns, and performing ultrasonic dispersion for 4 hours under the condition that the ultrasonic intensity is 300W to obtain a blended suspension;
s2, coating 35mL of the blended suspension on an epoxy plate to obtain a graphene oxide/polystyrene composite film; naturally airing the graphene oxide/polystyrene composite membrane, separating the graphene oxide/polystyrene composite membrane from the epoxy plate, placing the separated graphene oxide/polystyrene composite membrane in a tubular furnace, heating to 1200 ℃ at a heating rate of 6 ℃/min under the protection of argon, preserving heat for 60min, and naturally cooling to room temperature to obtain the graphene bubble film with the thickness of 80 mu m and the average diameter of closed pores of 5 mu m.
In the present invention, fig. 2 is obtained by observing the graphene bubble film obtained in example 2 through an SEM scanning electron microscope, and as is clear from fig. 2, the graphene bubble film in the present invention contains closed pores.
The volume density rho of the graphene bubble film obtained in the embodiments 1-7 is determined according to GB/T245728-Constant pressure specific heat capacity C of filmpDetermining the thermal diffusion coefficient α of the graphene bubble film obtained in the examples 1-7 according to GB/T22588-pα, the present invention lists the results of the assay in table 1.
The results in table 1 show that the graphene bubble film provided by the invention has high-efficiency electromagnetic shielding effectiveness and good heat conductivity, and can well solve the problems of electromagnetic compatibility and heat management when being applied to electronic devices.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. A graphene bubble film is characterized in that: the graphene bubble film contains closed air holes, and the average diameter of the air holes is 5-30 mu m; the thickness of the graphene bubble film is 60-200 mu m, and the volume density of the graphene bubble film is 0.1-0.3 g/cm3And the closed pore rate of the graphene bubble film is more than 50%.
2. The method for preparing the graphene bubble film according to claim 1, which is characterized by comprising the following steps:
s1, mixing the graphene oxide hydrosol and the pore-forming agent in a mass ratio of 10: 1-7, and carrying out ultrasonic treatment on the mixed solution with ultrasonic intensity of 200-500W for 0.5-5 h to obtain a blended suspension;
and S2, after the film is formed by the blending suspension prepared in the step S1, heating the film at the heating rate of 1-10 ℃/min at the heating temperature of 600-3000 ℃ for 30-120 min to prepare the graphene bubble film.
3. The method for preparing the graphene bubble film according to claim 2, wherein the method comprises the following steps: the pore-forming agent is polystyrene balls and/or polymethyl methacrylate balls.
4. The method for preparing the graphene bubble film according to claim 3, wherein the method comprises the following steps: the average diameter of the pore-forming agent is 5-30 mu m.
5. The method for preparing the graphene bubble film according to claim 2, wherein the method comprises the following steps: the mass concentration of the graphene oxide in the graphene oxide hydrosol is 0.5-10 mg/mL.
6. The method for preparing the graphene bubble film according to claim 2, wherein the method comprises the following steps: the mode of the co-suspension liquid suspension film forming in the step S2 is suction filtration or slurry coating.
7. The graphene bubble film according to claim 1 or the graphene bubble film prepared by the preparation method according to any one of claims 2 to 6 is applied to an electromagnetic shielding material in an electronic device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010334109.4A CN111547707A (en) | 2020-04-24 | 2020-04-24 | Graphene bubble film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010334109.4A CN111547707A (en) | 2020-04-24 | 2020-04-24 | Graphene bubble film and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111547707A true CN111547707A (en) | 2020-08-18 |
Family
ID=71996458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010334109.4A Pending CN111547707A (en) | 2020-04-24 | 2020-04-24 | Graphene bubble film and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111547707A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651317A (en) * | 2021-07-29 | 2021-11-16 | 南昌大学 | Method for preparing graphene foam film capable of shielding terahertz waves by polystyrene microspheres |
| WO2022086402A1 (en) * | 2020-10-19 | 2022-04-28 | Sht Smart High-Tech Ab | Graphene film reinforced thermal conductive composite film and preparation method and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103903879A (en) * | 2014-02-19 | 2014-07-02 | 国家纳米科学中心 | Porous grapheme/ MnO2 composite film and preparation method and application thereof |
| CN106395802A (en) * | 2016-09-08 | 2017-02-15 | 山东理工大学 | Method for preparing graphene porous membrane |
| CN107689271A (en) * | 2017-08-22 | 2018-02-13 | 京东方科技集团股份有限公司 | Preparation method, porous graphene film and the electronic product of porous graphene film |
| CN108530073A (en) * | 2017-10-08 | 2018-09-14 | 北京化工大学 | A kind of preparation method of the three-dimensional porous graphene film of flexible self-supporting |
-
2020
- 2020-04-24 CN CN202010334109.4A patent/CN111547707A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103903879A (en) * | 2014-02-19 | 2014-07-02 | 国家纳米科学中心 | Porous grapheme/ MnO2 composite film and preparation method and application thereof |
| CN106395802A (en) * | 2016-09-08 | 2017-02-15 | 山东理工大学 | Method for preparing graphene porous membrane |
| CN107689271A (en) * | 2017-08-22 | 2018-02-13 | 京东方科技集团股份有限公司 | Preparation method, porous graphene film and the electronic product of porous graphene film |
| CN108530073A (en) * | 2017-10-08 | 2018-09-14 | 北京化工大学 | A kind of preparation method of the three-dimensional porous graphene film of flexible self-supporting |
Non-Patent Citations (1)
| Title |
|---|
| CHENG-MENG CHEN等: ""Macroporous "bubble" grapheme film via template-directed ordered-assembly for high rate supeicapacitors"", 《CHEM. COMUN.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022086402A1 (en) * | 2020-10-19 | 2022-04-28 | Sht Smart High-Tech Ab | Graphene film reinforced thermal conductive composite film and preparation method and use thereof |
| CN113651317A (en) * | 2021-07-29 | 2021-11-16 | 南昌大学 | Method for preparing graphene foam film capable of shielding terahertz waves by polystyrene microspheres |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111547707A (en) | Graphene bubble film and preparation method and application thereof | |
| US11183677B2 (en) | Preparation method and product of lithium-ion battery electrode sheet with vertical vent structures | |
| CN108735953B (en) | SiO (silicon dioxide)2-PS core-shell structure ceramic coating diaphragm and preparation method and application thereof | |
| CN110819302A (en) | Preparation method of silicon carbide/carbon hollow porous microsphere wave-absorbing material | |
| CN107293700A (en) | A kind of lithium ion battery anode active material and preparation method thereof, negative pole and battery | |
| CN107627678B (en) | The electromagnetic shielding material and preparation method thereof of the low reflection of high-selenium corn | |
| CN113663611B (en) | High-temperature-resistant composite nanofiber aerogel material and preparation method thereof | |
| CN108342036A (en) | A kind of magnetism Mxenes polymer composite wave-suction materials and preparation method thereof | |
| KR20050074307A (en) | Mixed metal oxide layer and method of manufacture | |
| TW202030337A (en) | Silver powder, production method thereof, and conductive paste | |
| CN109093108A (en) | High starch breeding alkene-carbon nanotube mixing Cu-base composites and preparation method thereof | |
| CN113745535A (en) | Method for producing gas diffusion layer, membrane electrode, and fuel cell | |
| CN113683471A (en) | Polyvinylidene fluoride coated micron aluminum composite powder and preparation method thereof | |
| CN111302332B (en) | Ultrahigh-thermal-conductivity graphene thick film and preparation method thereof | |
| CN113501701B (en) | Energy-saving, flame-retardant, waterproof and sound-insulating gypsum board and preparation method thereof | |
| CN112300529A (en) | Metallized porous conductive polymer composite material and preparation method and application thereof | |
| CN113648940B (en) | Ultra-light high-elasticity anti-radiation nanofiber aerogel material and preparation method thereof | |
| CN114374055A (en) | Battery separator with high mechanical strength, high flame retardance and high adhesion and preparation method thereof | |
| CN112751041B (en) | Method for preparing NiO/apatite lanthanum silicate submicron-nano porous anode functional layer | |
| CN112357915A (en) | Graphene film with high heat conductivity and good buffering property for liquid crystal screen and preparation method thereof | |
| CN113163698A (en) | Honeycomb composite material and preparation method thereof | |
| CN111615318A (en) | Preparation method and application of graphene/carbon nanotube composite porous membrane | |
| CN115101756A (en) | Microporous layer slurry and preparation method thereof, microporous layer and gas diffusion layer | |
| CN212704360U (en) | Capillary structure | |
| CN115104765A (en) | Atomizing core, preparation method of composite porous ceramic matrix for atomizing core and electronic atomizing device |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221116 Address after: Room 4016, 4th Floor, Management Committee of Shandong Daiyue Economic Development Zone, No. 22 Qinglongshan Road, Tianping Street, Tai'an City, Shandong Province, 271021 Applicant after: Shandong Rekun New Materials Co.,Ltd. Address before: 030001 No. 27 Taoyuan South Road, Shanxi, Taiyuan Applicant before: INSTITUTE OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200818 |
|
| RJ01 | Rejection of invention patent application after publication |