CN115403800A - Preparation method of polyimide/three-dimensional graphene composite film with high dielectric constant - Google Patents
Preparation method of polyimide/three-dimensional graphene composite film with high dielectric constant Download PDFInfo
- Publication number
- CN115403800A CN115403800A CN202211190971.8A CN202211190971A CN115403800A CN 115403800 A CN115403800 A CN 115403800A CN 202211190971 A CN202211190971 A CN 202211190971A CN 115403800 A CN115403800 A CN 115403800A
- Authority
- CN
- China
- Prior art keywords
- dimensional graphene
- polyimide
- composite film
- heating
- dielectric constant
- 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 177
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 168
- 229920001721 polyimide Polymers 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 239000004642 Polyimide Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000013329 compounding Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 70
- 238000010438 heat treatment Methods 0.000 claims description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 229910052759 nickel Inorganic materials 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- 239000006260 foam Substances 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 claims description 9
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 17
- 239000003990 capacitor Substances 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 25
- 239000011159 matrix material Substances 0.000 description 13
- 230000005684 electric field Effects 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005325 percolation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A preparation method of a polyimide/three-dimensional graphene composite film with a high dielectric constant relates to a preparation method of a composite film. The invention aims to solve the problems that the strong pi-pi interaction exists between the existing graphene sheets, so that the sheets have strong aggregation tendency, the enhancement effect of graphene in a polymer composite material is difficult to realize, and the electrical and mechanical properties of a graphene-based polymer are poor. The method comprises the following steps: 1. preparing three-dimensional graphene; 2. and compounding to obtain the polyimide/three-dimensional graphene composite film with the high dielectric constant. According to the invention, the three-dimensional graphene and the polyimide substrate can be tightly connected, and can act together with the polyimide substrate to form a plurality of micro-capacitors, so that the electrical property advantage of the graphene can be better played, and the dielectric property of the film can be improved. The invention can obtain the polyimide/three-dimensional graphene composite film with high dielectric constant.
Description
Technical Field
The invention relates to a preparation method of a composite film.
Background
The graphene is a two-dimensional carbon nano material with single atom thickness, has excellent optical, electrical, thermal and mechanical properties, and can obviously improve the mechanical property, the thermal property and the dielectric property of the polymer matrix composite material. The graphene/polymer composite material is used as a novel flexible, high-strength and light high-performance dielectric material, and has a good application prospect in the fields of film capacitors, ultra-large scale integrated circuits, electrode materials and the like. However, the graphene surface lacks active groups, so that strong interaction is difficult to form directly between polymer interfaces, the enhancement effect of graphene in a polymer composite material is difficult to realize, and meanwhile, strong pi-pi interaction exists between graphene lamellar layers, so that the lamellar layers have strong aggregation tendency, and the graphene-enhanced polymer has poor electrical and mechanical properties.
Disclosure of Invention
The invention aims to solve the problems that the strong pi-pi interaction exists between the existing graphene sheets, so that the sheets have strong aggregation tendency, the enhancement effect of graphene in a polymer composite material is difficult to realize, and the electrical and mechanical properties of a graphene-based polymer are poor, and provides a preparation method of a high-dielectric-constant polyimide/three-dimensional graphene composite film.
A preparation method of a polyimide/three-dimensional graphene composite film with a high dielectric constant is specifically completed according to the following steps:
1. preparing three-dimensional graphene:
(1) cleaning the foamed nickel, and drying to obtain cleaned foamed nickel;
(2) putting the cleaned foamed nickel into a quartz boat, putting the quartz boat into a heating area of a CVD tubular furnace body, introducing nitrogen into the CVD tubular furnace, heating the CVD tubular furnace to 900-950 ℃ under the protection of the nitrogen, preserving the heat at 900-950 ℃, introducing the nitrogen into the CVD tubular furnace and introducing absolute ethyl alcohol, preserving the heat at 900-950 ℃ and introducing the absolute ethyl alcohol, stopping introducing the absolute ethyl alcohol and stopping heating, introducing the nitrogen, and naturally cooling the CVD tubular furnace to below 40 ℃ under the protection of the nitrogen to obtain the foamed nickel for growing the three-dimensional graphene;
2. compounding:
(1) soaking foam nickel for growing three-dimensional graphene in FeCl 3 Removing foam nickel in the solution to obtain three-dimensional graphene;
(2) adding 4, 4-diaminodiphenyl ether into N, N-dimethylacetamide, and then adding pyromellitic dianhydride in batches to obtain a PAA solution;
(3) and placing the three-dimensional graphene on a glass sheet, then covering the glass sheet with PAA solution, performing gradient heating for imidization treatment, soaking the glass sheet in hot water, stripping the film from the glass sheet, taking out the film, and drying to obtain the high-dielectric-constant polyimide/three-dimensional graphene composite film.
The principle of the invention is as follows:
according to the invention, the three-dimensional graphene is prepared by using a chemical vapor deposition method, and then the polyimide/three-dimensional graphene composite film with the high dielectric constant is prepared by using an in-situ polymerization method, in the preparation process of the composite film, the three-dimensional graphene and a polyimide matrix can be tightly connected, and a plurality of micro-capacitors are formed under the combined action of the three-dimensional graphene and the polyimide matrix, so that the electrical property advantage of the graphene can be better played, and the dielectric property of the film can be improved.
The invention has the advantages that:
1. the three-dimensional graphene has larger specific surface area, and the fibers of the three-dimensional graphene are connected with each other, so that a good network can be formed in a polymer matrix, and the three-dimensional graphene has excellent electrical and mechanical properties; the composite film is doped in the composite film, the three-dimensional graphene and the graphene oxide powder are used as dopants to form chemical bonds in a matrix interface, the mechanical property, the dielectric property and the like of the composite film are improved, and when the three-dimensional graphene is used as the dopant composite film, the composite film has excellent comprehensive properties;
2. the high-dielectric-constant polyimide/three-dimensional graphene composite film prepared by the invention has the dielectric constant of 8.03 and the tensile strength of 116.6MPa under the frequency of 1 Hz.
The invention can obtain the polyimide/three-dimensional graphene composite film with high dielectric constant.
Drawings
FIG. 1 is a SEM photograph showing a polyimide film prepared in comparative example 1, b showing three-dimensional graphene prepared in step one of example 1, and c showing graphene oxide;
fig. 2 is a raman chart, in which 1 is graphene oxide, and 2 is three-dimensional graphene prepared in step one of example 1;
fig. 3 is an infrared spectrum diagram in which 1 is a polyimide/graphene oxide composite film prepared in comparative example 2, and 2 is a high dielectric constant polyimide/three-dimensional graphene composite film prepared in example 1;
FIG. 4 is an SEM photograph of a film in which a and b are polyimide/graphene oxide composite films prepared in comparative example 2, and c and d are high dielectric constant polyimide/three-dimensional graphene composite films prepared in example 1;
fig. 5 is a graph showing the relationship between the dielectric constant and the dielectric loss of the film at room temperature and the frequency of an applied electric field, in which a is a graph showing the relationship between the dielectric constant and the frequency of the applied electric field, b is a graph showing the relationship between the dielectric loss and the frequency of the applied electric field, 1 of a and b is the polyimide film prepared in comparative example 1, 2 is the polyimide/graphene oxide composite film prepared in comparative example 2, and 3 is the polyimide/graphene oxide composite film prepared in comparative example 3;
FIG. 6 is a graph showing the relationship between the dielectric constant and the dielectric loss of the high-k polyimide/three-dimensional graphene composite film prepared in example 1 at room temperature and the variation of the frequency of an applied electric field;
fig. 7 is a graph showing tensile strength of the composite material, in which PI is the polyimide film prepared in comparative example 1, PI/Go-1 is the polyimide/Graphene oxide composite film prepared in comparative example 3, PI/Go-2 is the polyimide/Graphene oxide composite film prepared in comparative example 2, and PI/3D Graphene is the high dielectric constant polyimide/three-dimensional Graphene composite film prepared in example 1.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting thereof. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment of the invention relates to a preparation method of a high-dielectric-constant polyimide/three-dimensional graphene composite film, which is specifically completed according to the following steps:
1. preparing three-dimensional graphene:
(1) cleaning the foamed nickel, and drying to obtain cleaned foamed nickel;
(2) putting the cleaned foamed nickel into a quartz boat, putting the quartz boat into a heating area of a CVD tubular furnace body, introducing nitrogen into the CVD tubular furnace, heating the CVD tubular furnace to 900-950 ℃ under the protection of the nitrogen, preserving the heat at 900-950 ℃, introducing the nitrogen into the CVD tubular furnace and introducing absolute ethyl alcohol, preserving the heat at 900-950 ℃ and introducing the absolute ethyl alcohol, stopping introducing the absolute ethyl alcohol and stopping heating, introducing the nitrogen, and naturally cooling the CVD tubular furnace to below 40 ℃ under the protection of the nitrogen to obtain the foamed nickel for growing the three-dimensional graphene;
2. compounding:
(1) soaking foam nickel for growing three-dimensional graphene in FeCl 3 Removing foam nickel in the solution to obtain three-dimensional graphene;
(2) adding 4, 4-diaminodiphenyl ether into N, N-dimethylacetamide, and then adding pyromellitic dianhydride in batches to obtain a PAA solution;
(3) and placing the three-dimensional graphene on a glass sheet, then covering the glass sheet with PAA solution, performing gradient heating for imidization treatment, soaking the glass sheet in hot water, stripping the film from the glass sheet, taking out the film, and drying to obtain the high-dielectric-constant polyimide/three-dimensional graphene composite film.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: and step one (1), sequentially immersing the foamed nickel into deionized water, absolute ethyl alcohol and acetone for respective ultrasonic cleaning, wherein the ultrasonic cleaning time is 5-10 min each time, and drying at the temperature of 60-80 ℃ for 5-8 min to obtain the cleaned foamed nickel. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the temperature rise rate in the step one (2) is 10 ℃/min; putting the cleaned nickel foam into a quartz boat, putting the quartz boat into a heating area of a CVD tubular furnace body, introducing nitrogen into the CVD tubular furnace, heating the CVD tubular furnace to 900-950 ℃ under the protection of the nitrogen, preserving the heat for 1-2 h at 900-950 ℃, introducing the nitrogen into the CVD tubular furnace to bring absolute ethyl alcohol, preserving the heat for 20-50 min at 900-950 ℃ and under the condition of bringing the absolute ethyl alcohol, stopping introducing the absolute ethyl alcohol and stopping heating, introducing the nitrogen, and naturally cooling the CVD tubular furnace to below 40 ℃ under the protection of the nitrogen to obtain the nickel foam for growing the three-dimensional graphene. The other steps are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is: feCl described in step two (1) 3 The concentration of the solution is 0.5 mol/L-1 mol/L. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and the first to the fourth embodiments is: step two (1), soaking foam nickel for growing three-dimensional graphene in FeCl 3 The time in the solution is 36-48 h. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the first to fifth embodiments is: the mass ratio of the 4, 4-diaminodiphenyl ether to the N, N-dimethylacetamide in the step two (2) is (2-4) to (20-30); the mass ratio of the pyromellitic anhydride to the N, N-dimethylacetamide in the step two (2) is (2-4) to (20-30). The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and the first to sixth embodiments is: the mass ratio of the three-dimensional graphene to the PAA solution in the second step (3) is (20-50 mg) to (10-20 g). The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the process for imidizing by gradient heating in the step two (3) comprises the following steps: firstly, heating to 80 ℃, heating for 3-5 h at 80 ℃, heating to 120 ℃, heating for 1-2 h at 120 ℃, heating to 200 ℃, heating for 1-2 h at 200 ℃, heating to 300 ℃, and heating for 1-2 h at 300 ℃; the heating rate is 5 ℃/min. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: and in the second step (3), the glass plate is soaked in hot water at the temperature of 60-80 ℃ for 5-10 min, the film is stripped from the glass sheet, the film is taken out, and then the film is dried at the temperature of 25-35 ℃ to obtain the polyimide/three-dimensional graphene composite film with the high dielectric constant. The other steps are the same as those in the first to eighth embodiments.
The specific implementation mode is ten: the difference between this embodiment and the first to ninth embodiments is: and the thickness of the polyimide/three-dimensional graphene composite film with the high dielectric constant in the step two (3) is 70-90 μm. The other steps are the same as those in the first to ninth embodiments.
The following examples were employed to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of a polyimide/three-dimensional graphene composite film with a high dielectric constant is specifically completed according to the following steps:
1. preparing three-dimensional graphene:
(1) sequentially soaking the foamed nickel into deionized water, absolute ethyl alcohol and acetone for respective ultrasonic cleaning, wherein the ultrasonic cleaning time is 5min each time, and drying at the temperature of 70 ℃ for 8min to obtain cleaned foamed nickel;
the size of the foamed nickel in the step one (1) is 5mm multiplied by 40mm;
(2) putting the cleaned foamed nickel into a quartz boat, putting the quartz boat into a heating area of a CVD tubular furnace body, introducing nitrogen into the CVD tubular furnace, heating the CVD tubular furnace to 950 ℃ under the protection of the nitrogen, preserving the heat at 950 ℃ for 1.5h, introducing the nitrogen into the CVD tubular furnace to bring absolute ethyl alcohol, preserving the heat at 950 ℃ and the absolute ethyl alcohol for 30min, stopping bringing the absolute ethyl alcohol and stopping heating, introducing the nitrogen, naturally cooling the CVD tubular furnace to below 40 ℃ under the protection of the nitrogen, and obtaining three-dimensional graphene on the foamed nickel;
the temperature rising rate in the step one (2) is 10 ℃/min;
2. compounding:
(1) soaking the foamed nickel for growing the three-dimensional graphene in FeCl with the concentration of 0.5mol/L 3 Removing foam nickel in the solution for 40h to obtain three-dimensional graphene;
(2) adding 3g of 4, 4-diaminodiphenyl ether into 26g of N, N-dimethylacetamide, and adding 3.28g of pyromellitic dianhydride 4 times to obtain a PAA solution;
(3) placing the three-dimensional Graphene on a glass sheet, covering a PAA solution, performing imidization treatment by gradient heating, soaking the glass sheet in hot water at the temperature of 60 ℃ for 8min, stripping the film from the glass sheet, taking out the film, and drying at the temperature of 35 ℃ for 2h to obtain a high-dielectric-constant polyimide/three-dimensional Graphene composite film (PI/3D Graphene);
the mass ratio of the three-dimensional graphene to the PAA solution in the second step (3) is 77.8mg;
the process for imidizing by gradient heating in the second step (3) comprises the following steps: firstly, heating to 80 ℃, heating for 5h at 80 ℃, heating to 120 ℃, heating for 2h at 120 ℃, heating to 200 ℃, heating for 2h at 200 ℃, heating to 300 ℃ and heating for 2h at 300 ℃; the heating rate is 10 ℃/min;
and the thickness of the polyimide/three-dimensional graphene composite film with the high dielectric constant in the second step (3) is 80 micrometers.
Comparative example 1: the polyimide film is prepared by the following steps:
1. adding 3g of 4, 4-diaminodiphenyl ether into 26g of N, N-dimethylacetamide, and adding 3.28g of pyromellitic dianhydride 4 times to obtain a PAA solution;
2. coating a PAA solution on a glass sheet, performing gradient heating to perform imidization treatment, soaking the glass sheet in hot water at the temperature of 60 ℃ for 8min, stripping a film from the glass sheet, taking out the film, and drying at the temperature of 35 ℃ for 2h to obtain a polyimide film (PI);
the process for imidization treatment by gradient heating in the step two comprises the following steps: firstly, heating to 80 ℃, heating for 5 hours at 80 ℃, heating to 120 ℃, heating for 2 hours at 120 ℃, heating to 200 ℃, heating for 2 hours at 200 ℃, heating to 300 ℃ and heating for 2 hours at 300 ℃; the heating rate is 10 ℃/min;
and the thickness of the polyimide film in the second step is 80 μm.
Comparative example 2: the polyimide/graphene oxide composite film is prepared by the following steps:
1. preparing a graphene oxide dispersion liquid;
ultrasonically dispersing graphite oxide in DMAc for 30min to obtain graphene oxide dispersion liquid with the mass fraction of 0.48% (the mass fraction of solid components in the prepared PAA solution is about 2%);
the diameter of the graphite oxide in the step one is 0.3-2.0 μm, and the graphite oxide is purchased from Heizhou sixth element material science and technology GmbH;
2. under the protection of nitrogen atmosphere, adding 26g of graphene oxide dispersion liquid with the mass fraction of 0.48% into a flask, then adding 3g of 4, 4-diaminodiphenyl ether, adding 3.28g of pyromellitic dianhydride for 4 times, and continuously stirring for 2 hours to obtain a GO/PAA solution;
3. coating a GO/PAA solution on a glass sheet, performing gradient heating to perform imidization treatment, soaking the glass sheet in hot water at the temperature of 60 ℃ for 8min, stripping the film from the glass sheet, taking out the film, and drying at the temperature of 35 ℃ for 2h to obtain a polyimide/graphene oxide composite film (PI/GO-2).
Comparative example 3: the polyimide/graphene oxide composite film is prepared by the following steps:
1. preparing a graphene oxide dispersion liquid;
ultrasonically dispersing graphite oxide in DMAc for 30min to obtain a graphene oxide dispersion liquid with the mass fraction of 0.24% (the mass fraction of graphene oxide in the prepared PAA solution is about 1%);
the diameter of the graphite oxide in the step one is 0.3-2.0 mu m, and the graphite oxide is purchased from Heizhou sixth element material science and technology GmbH;
2. under the protection of nitrogen atmosphere, 26g of graphene oxide (accounting for about 1% of the solid components in the PAA solution) with the mass fraction of 0.24% is added into a flask, then 3g of 4, 4-diaminodiphenyl ether is added, 3.28g of pyromellitic anhydride is added for 4 times, and the mixture is continuously stirred for 2 hours to obtain a GO/PAA solution;
3. coating a GO/PAA solution on a glass sheet, performing gradient heating for imidization, soaking the glass sheet in hot water at the temperature of 60 ℃ for 8min, stripping the film from the glass sheet, taking out the film, and drying at the temperature of 35 ℃ for 2h to obtain a polyimide/graphene oxide composite film (PI/GO-1).
FIG. 1 is an SEM photograph showing a polyimide film prepared in comparative example 1, b three-dimensional graphene prepared in step one of example 1, and c graphene oxide;
in FIG. 1c, the graphite oxide has a diameter of 0.3-2.0 μm and is available from Hexagon science and technology, inc.; as can be seen from fig. 1 a: the surface and the side surface of the polyimide film are flat and smooth, and the cleanliness of the section is higher without doping other nano materials. As can be seen from fig. 1c, the graphene oxide is relatively flat on both the surface and the side surface, and exhibits a typical layered morphology. As can be seen from fig. 1b, the surface and the side surfaces of the three-dimensional graphene are relatively flat and present a typical layered morphology, the structural skeleton of the three-dimensional graphene has a smooth surface, fewer defects and higher quality, and the three-dimensional graphene has interconnected three-dimensional skeletons.
Fig. 2 is a raman chart, in which 1 is graphene oxide, and 2 is three-dimensional graphene prepared in step one of example 1;
it can be observed from FIG. 2 that the distance is 1360cm -1 And 1610cm -1 The obvious D peak and G peak are generated. 1360cm -1 Corresponds to the internal defect condition of graphene, 1610cm -1 The G peak of (A) represents a graphene structureThe integrity of (c). The 2D peak is widened and split into 2 peaks, the peak shape is wide and blunt, and the graphene oxide and the three-dimensional graphene are not in a single-layer structure, and the number of layers is more than 5.
Fig. 3 is an infrared spectrum diagram in which 1 is a polyimide/graphene oxide composite film prepared in comparative example 2, and 2 is a high dielectric constant polyimide/three-dimensional graphene composite film prepared in example 1;
as can be seen from fig. 3: the spectra of both films showed that a C = O symmetric stretching vibration absorption peak near 1 734cm of PI, 1789cm -1 A nearby C = O asymmetric stretching vibration absorption peak, a C-N axial stretching vibration absorption peak near I369 cm, and a C = O bending vibration absorption peak near 726 cm. The infrared spectroscopic analysis results show that the polyimide/graphene oxide composite film is successfully prepared in comparative example 2, and the high-dielectric-constant polyimide/three-dimensional graphene composite film is successfully prepared in example 1.
FIG. 4 is an SEM photograph of a film in which a and b are polyimide/graphene oxide composite films prepared in comparative example 2, and c and d are high dielectric constant polyimide/three-dimensional graphene composite films prepared in example 1;
it can be seen from fig. 4a that the distribution of the three-dimensional graphene sheet layers is relatively uniform, no obvious phase separation phenomenon occurs, and the three-dimensional graphene can be tightly connected with the PI substrate and forms a plurality of micro-capacitors together with the polyimide substrate, so that the electrical property advantage of the graphene can be more favorably exerted, and the dielectric property of the film can be improved. As shown in fig. 4c, the graphene oxide and the polyimide substrate are combined to form a lamellar structure, and the graphene oxide and the polyimide substrate are combined to form such a lamellar structure, which has an obvious delamination phenomenon, and the combination is not very tight, so that the electrical performance advantage of the graphene lamellar layer cannot be exerted.
Fig. 5 is a graph showing the relationship between the dielectric constant and the dielectric loss of the film at room temperature and the frequency of an applied electric field, in which a is a graph showing the relationship between the dielectric constant and the frequency of the applied electric field, b is a graph showing the relationship between the dielectric loss and the frequency of the applied electric field, 1 of a and b is the polyimide film prepared in comparative example 1, 2 is the polyimide/graphene oxide composite film prepared in comparative example 2, and 3 is the polyimide/graphene oxide composite film prepared in comparative example 3;
the test frequency of FIG. 5 is 1-10 6 Hz. As can be seen from fig. 5a, the dielectric constant of the mass composite film increases as the content of graphene oxide increases. When the graphene oxide is increased to 1%, the dielectric constant of the composite film is 5.8 at the frequency of 1Hz, which is 1.7 times higher than that of a pure polyimide film (3.36); when the graphene oxide is further increased to 2%, the dielectric constant of the composite film is 10.6 at a frequency of 1Hz, which is 3.1 times higher than that of pure polyimide (3.36). From fig. 5b, it can be seen that the dielectric loss of the composite film increases with the content of graphene oxide. The dielectric property change of the polyimide/graphene oxide composite film can be explained by a conductor/polymer percolation threshold model. The percolation threshold theory holds that when the conductive particles are added into the insulating material, the electrical property of the polymer matrix material dominates the electrical property of the composite material when the content of the conductive particles is very small; the filler gradually forms clusters in the matrix in random distribution along with the increase of the content of the conductive particles, when the filler increases to a certain concentration, the cluster particles are more and more, the particles are connected with each other in a certain range, and the composite material begins to be converted from an insulator to a conductor. When a large-scale mutual lapping system is about to be formed and is not formed yet, the composite material has high dielectric transition. This is manifested by an increase in dielectric constant, even by orders of magnitude. The dielectric constant of such a conductive/insulating system can be characterized by the following power equation: in the formula: f. of filler And f 0 And respectively the volume fraction and the percolation threshold concentration of the filler in the polymer matrix, f 0 Closely related to the microstructure of the composite material; epsilon 0 Is the dielectric constant of the polymer matrix; q is a scale constant related to material properties, microstructure, connectivity between phases, etc. in the composite system. When the content of graphene oxide is small (1%), the change of the dielectric constant and the dielectric loss of the film is not obvious, and at the moment, a small amount of functional groups on the surface of the graphene oxide are combined with polyimide to form a lamellar structure under weak acting force, but the lamellar structure is formed from lamellar to plateThe layers are far apart from each other, an effective capacitor network is not formed, the dielectric property of the matrix is slightly influenced by the graphene oxide and is 10-10 DEG 6 Remains substantially stable in the Hz range. The reason why the dielectric constant and dielectric loss of the film begin to increase at low frequency as the content of graphene oxide further increases to 2% is that the interface polarization increases and the loss increases as the number of polyimide/three-dimensional graphene composite film sheet structures increases, but a large-scale capacitor network is not formed yet, so that the influence on the dielectric constant is still small.
FIG. 6 is a graph showing the relationship between the dielectric constant and the dielectric loss of the high-k polyimide/three-dimensional graphene composite film prepared in example 1 at room temperature and the variation of the frequency of an applied electric field;
the test frequency of FIG. 6 is 1-10 6 Hz; it can be seen from fig. 6 that the dielectric constant of the Graphene sheets is significantly increased compared to that of pure polyimide (3.36) due to the formation of conductive network between the Graphene sheets. Meanwhile, when the frequency of an external electric field is increased, the response of a capacitor network cannot follow the change of the electric field due to the limitation of interface polarization time, so that the dielectric constant and the dielectric loss are both reduced along with the increase of the frequency, and the dielectric constant of the capacitor network is smaller along with the change of the frequency than that of a PI/Go composite film due to the fact that the three-dimensional graphene forms a stable network structure in a polymer matrix, so that the capacitor network has a more stable structure.
FIG. 7 is a graph showing tensile strength of a composite material, in which PI is a polyimide film prepared in comparative example 1, PI/Go-1 is a polyimide/Graphene oxide composite film prepared in comparative example 3, PI/Go-2 is a polyimide/Graphene oxide composite film prepared in comparative example 2, and PI/3D Graphene is a high dielectric constant polyimide/three-dimensional Graphene composite film prepared in example 1;
as can be seen from fig. 7, the tensile strength of all the composite materials exceeds that of the pure polyimide film, the addition of the graphene oxide and the three-dimensional graphene obviously improves the mechanical properties of the composite materials, and the strength and modulus of the composite materials increase with the increase of the addition amount of the graphene oxide, but the high-dielectric-constant polyimide/three-dimensional graphene composite film prepared in example 1 has more excellent mechanical properties. When the content of graphene oxide is 1%, the tensile strength of the polyimide/graphene oxide composite film prepared in comparative example 3 is 106.3MPa, which is increased by more than one time than that of a pure polyimide film; however, when the content of graphene oxide was 2%, the tensile strength of the polyimide/graphene oxide composite film prepared in comparative example 2 was 100.3MPa, which was lower than that of the polyimide/graphene oxide composite film prepared in comparative example 3. The reason is that the graphene has a honeycomb-shaped lattice structure of a monoatomic layer formed by connecting carbon-carbon double bonds, and the unique stable structure makes the graphene extremely hard, but when the content of the graphene is increased, agglomeration is easily formed in a polymer matrix, so that the mechanical property of the graphene is reduced. Due to the unique three-dimensional network structure of the three-dimensional graphene in the matrix polymer, the three-dimensional graphene has good dispersibility in the polymer matrix, which also becomes an important factor for improving the mechanical properties of the polyimide/three-dimensional graphene composite film with the high dielectric constant prepared in example 1.
Claims (10)
1. A preparation method of a polyimide/three-dimensional graphene composite film with a high dielectric constant is characterized by comprising the following steps:
1. preparing three-dimensional graphene:
(1) cleaning the foamed nickel, and drying to obtain cleaned foamed nickel;
(2) putting the cleaned foamed nickel into a quartz boat, putting the quartz boat into a heating area of a CVD tubular furnace body, introducing nitrogen into the CVD tubular furnace, heating the CVD tubular furnace to 900-950 ℃ under the protection of the nitrogen, preserving the heat at 900-950 ℃, introducing the nitrogen into the CVD tubular furnace and introducing absolute ethyl alcohol, preserving the heat at 900-950 ℃ under the condition of introducing the absolute ethyl alcohol, stopping introducing the absolute ethyl alcohol and stopping heating, introducing the nitrogen, and naturally cooling the CVD tubular furnace to below 40 ℃ under the protection of the nitrogen to obtain the foamed nickel for growing the three-dimensional graphene;
2. compounding:
(1) soaking foam nickel for growing three-dimensional graphene in FeCl 3 In the solution, the foam nickel is removed,obtaining three-dimensional graphene;
(2) adding 4, 4-diaminodiphenyl ether into N, N-dimethylacetamide, and then adding pyromellitic dianhydride in batches to obtain a PAA solution;
(3) and placing the three-dimensional graphene on a glass sheet, then covering the glass sheet with PAA solution, performing gradient heating for imidization treatment, soaking the glass sheet in hot water, stripping the film from the glass sheet, taking out the film, and drying to obtain the high-dielectric-constant polyimide/three-dimensional graphene composite film.
2. The preparation method of the high dielectric constant polyimide/three-dimensional graphene composite film according to claim 1, wherein in the step one (1), the foamed nickel is sequentially immersed into deionized water, absolute ethyl alcohol and acetone for respective ultrasonic cleaning, the ultrasonic cleaning time is 5min to 10min each time, and then the cleaned foamed nickel is obtained by drying at 60 ℃ to 80 ℃ for 5min to 8 min.
3. The method for preparing a polyimide/three-dimensional graphene composite film with a high dielectric constant according to claim 1, wherein the temperature rise rate in the step one (2) is 10 ℃/min; putting the cleaned nickel foam into a quartz boat, putting the quartz boat into a heating area of a CVD tubular furnace body, introducing nitrogen into the CVD tubular furnace, heating the CVD tubular furnace to 900-950 ℃ under the protection of the nitrogen, preserving the heat for 1-2 h at 900-950 ℃, introducing the nitrogen into the CVD tubular furnace to bring absolute ethyl alcohol, preserving the heat for 20-50 min at 900-950 ℃ and under the condition of bringing the absolute ethyl alcohol, stopping introducing the absolute ethyl alcohol and stopping heating, introducing the nitrogen, and naturally cooling the CVD tubular furnace to below 40 ℃ under the protection of the nitrogen to obtain the nickel foam for growing the three-dimensional graphene.
4. The method for preparing a high dielectric constant polyimide/three-dimensional graphene composite film according to claim 1, wherein the FeCl in the step two (1) 3 The concentration of the solution is 0.5 mol/L-1 mol/L.
5. The method for preparing the polyimide/three-dimensional graphene composite film with the high dielectric constant according to claim 1, wherein in the second step (1), the foamed nickel for growing the three-dimensional graphene is soaked in FeCl 3 The time in the solution is 36-48 h.
6. The method for preparing a high dielectric constant polyimide/three-dimensional graphene composite film according to claim 1, wherein the mass ratio of 4, 4-diaminodiphenyl ether to N, N-dimethylacetamide in the step two (2) is (2-4) to (20-30); the mass ratio of the pyromellitic dianhydride to the N, N-dimethylacetamide in the step two (2) is (2-4) to (20-30).
7. The method for preparing a high dielectric constant polyimide/three-dimensional graphene composite film according to claim 1, wherein the mass ratio of the three-dimensional graphene to the PAA solution in the step two (3) is (50 mg-80 mg) to (10 g-20 g).
8. The method for preparing a polyimide/three-dimensional graphene composite film with a high dielectric constant according to claim 1, wherein the step two (3) comprises the following steps: firstly, heating to 80 ℃, heating for 3-5 h at 80 ℃, heating to 120 ℃, heating for 1-2 h at 120 ℃, heating to 200 ℃, heating for 1-2 h at 200 ℃, heating to 300 ℃, and heating for 1-2 h at 300 ℃; the heating rate is 5 ℃/min.
9. The method for preparing a high dielectric constant polyimide/three-dimensional graphene composite film according to claim 1, wherein in the second step (3), the glass plate is soaked in hot water at a temperature of 60-80 ℃ for 5-10 min, the film is peeled from the glass plate, the film is taken out, and then dried at a temperature of 25-35 ℃ to obtain the high dielectric constant polyimide/three-dimensional graphene composite film.
10. The method for preparing the polyimide/three-dimensional graphene composite film with the high dielectric constant according to claim 1, wherein the thickness of the polyimide/three-dimensional graphene composite film with the high dielectric constant in the step two (3) is 70-90 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211190971.8A CN115403800A (en) | 2022-09-28 | 2022-09-28 | Preparation method of polyimide/three-dimensional graphene composite film with high dielectric constant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211190971.8A CN115403800A (en) | 2022-09-28 | 2022-09-28 | Preparation method of polyimide/three-dimensional graphene composite film with high dielectric constant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115403800A true CN115403800A (en) | 2022-11-29 |
Family
ID=84168877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211190971.8A Pending CN115403800A (en) | 2022-09-28 | 2022-09-28 | Preparation method of polyimide/three-dimensional graphene composite film with high dielectric constant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115403800A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474461A (en) * | 2016-06-08 | 2017-12-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene/polymer three-dimensional foam base plate, its preparation method and application |
| CN108530676A (en) * | 2018-05-10 | 2018-09-14 | 桂林电子科技大学 | Three-dimensional netted carbon material/high molecular functional composite material and preparation method based on template |
| CN110357080A (en) * | 2019-08-27 | 2019-10-22 | 信阳学院 | A kind of three-dimensional grapheme and preparation method thereof |
| US20200071487A1 (en) * | 2016-12-15 | 2020-03-05 | Sabic Global Technologies B.V. | Thermally conductive three-dimensional (3-d) graphene polymer composite materials, methods of making, and uses thereof |
-
2022
- 2022-09-28 CN CN202211190971.8A patent/CN115403800A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474461A (en) * | 2016-06-08 | 2017-12-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene/polymer three-dimensional foam base plate, its preparation method and application |
| US20200071487A1 (en) * | 2016-12-15 | 2020-03-05 | Sabic Global Technologies B.V. | Thermally conductive three-dimensional (3-d) graphene polymer composite materials, methods of making, and uses thereof |
| CN108530676A (en) * | 2018-05-10 | 2018-09-14 | 桂林电子科技大学 | Three-dimensional netted carbon material/high molecular functional composite material and preparation method based on template |
| CN110357080A (en) * | 2019-08-27 | 2019-10-22 | 信阳学院 | A kind of three-dimensional grapheme and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 许博皓 等: "功能性石墨烯改善聚合物介电性能的研究进展", 包装工程, vol. 38, no. 01, pages 7 - 12 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qu et al. | Low-temperature sintering Graphene/CaCu3Ti4O12 nanocomposites with tunable negative permittivity | |
| CN108530676B (en) | Template-based three-dimensional reticular carbon material/high-molecular functional composite material and preparation method thereof | |
| Li et al. | Dielectric properties of binary polyvinylidene fluoride/barium titanate nanocomposites and their nanographite doped hybrids. | |
| CN110872193B (en) | Preparation method of high-thermal-conductivity graphene/chopped carbon fiber composite material | |
| Guo et al. | Methylene blue adsorption derived thermal insulating N, S-co-doped TiC/carbon hybrid aerogel for high-efficient absorption-dominant electromagnetic interference shielding | |
| CN108997754B (en) | Polyimide high-temperature dielectric composite film and preparation method thereof | |
| Zhang et al. | Mechanical, dielectric and thermal properties of polyimide films with sandwich structure | |
| KR20170019721A (en) | Graphene oxide-polyimide composite material and method for manufacturing the same | |
| CN111218112A (en) | rGO/polyimide composite aerogel and preparation method and application thereof | |
| CN108658064B (en) | Nitrogen-doped graphene and preparation method thereof | |
| Gao et al. | Purified nitrogen-doped reduced graphene oxide hydrogels for high-performance supercapacitors | |
| CN102009976A (en) | Method for preparing graphene film | |
| Wu et al. | Dielectric properties and thermal conductivity of polyvinylidene fluoride synergistically enhanced with silica@ multi-walled carbon nanotubes and boron nitride | |
| CN110564083B (en) | Graphite phase carbon nitride/polymer composite material, preparation method and energy storage material | |
| CN101993536B (en) | Polyimide/graphite hybrid material with high dielectric constant and preparation method thereof | |
| KR101173629B1 (en) | Method for producing nano-scaled graphene plates and the nano-scaled grapene plates | |
| CN113233453B (en) | High-electric-conductivity heat-conduction graphite material and preparation method thereof | |
| CN105603393B (en) | A kind of magnesium alloy with graphene diaphragm and preparation method thereof | |
| Liang et al. | Porous Ti3C2Tx MXene nanosheets sandwiched between polyimide fiber mats for electromagnetic interference shielding | |
| Ye et al. | Super-flexible and highly conductive H-Ti3C2Tx MXene composite films with 3D macro-assemblies for electromagnetic interference shielding | |
| CN115403800A (en) | Preparation method of polyimide/three-dimensional graphene composite film with high dielectric constant | |
| KR101319559B1 (en) | Manufacturing method for coating layer having graphene | |
| CN115231557B (en) | Graphene film and preparation method thereof | |
| CN112206725A (en) | Preparation method of titanium dioxide nanofiber aerogel | |
| KR101585294B1 (en) | Porous graphene/carbon complex and method for preparing the same |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20221129 |
|
| WD01 | Invention patent application deemed withdrawn after publication |