CN111844955B - High-dielectric composite material and preparation method thereof - Google Patents

High-dielectric composite material and preparation method thereof Download PDF

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CN111844955B
CN111844955B CN202010727521.2A CN202010727521A CN111844955B CN 111844955 B CN111844955 B CN 111844955B CN 202010727521 A CN202010727521 A CN 202010727521A CN 111844955 B CN111844955 B CN 111844955B
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graphene oxide
film
barium titanate
composite material
sandwich
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CN111844955A (en
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陈苑明
曹金东
毕建民
严丹
何为
王守绪
王美娟
谭建容
周国云
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Xinhua Haitong Xiamen Information Technology Co ltd
University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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Abstract

The invention relates to a high dielectric composite material, and belongs to the technical field of functional materials. The invention provides a high-dielectric composite material, which is characterized in that a sandwich-structure film composed of a graphene oxide film and a barium titanate film is prepared through vacuum filtration, a capacitor structure is firstly formed inside the sandwich-structure film composed of the graphene oxide film and the barium titanate film, then polyphenyl ether resin is poured to wrap the sandwich-structure film composed of the graphene oxide film and the barium titanate film, copper foils are covered on the upper surface and the lower surface of the sandwich-structure film, and a solvent is volatilized through hot pressing and heating to obtain a polyphenylene ether-based composite material, so that the sandwich-structure film composed of the graphene oxide film and the barium titanate film is compounded with polyphenyl ether, and the high-dielectric and low-loss polyphenylene ether-based composite material is obtained. The polyphenylene ether-based composite material disclosed by the invention can be used for a printed circuit embedded capacitor device, has the advantages of high dielectric constant and low loss, and is simple and efficient in preparation method.

Description

High-dielectric composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a high-dielectric composite material and a preparation method thereof.
Background
Graphene is a novel monolayer carbon material having a two-dimensional network structure of a single atomic layer formed by connecting sp2 hybridized carbon atoms. The graphene has excellent optical, electrical, mechanical and thermodynamic properties, flexibility and large specific surface area, and shows great application potential in the fields of supercapacitors, optoelectronic devices, lithium ion batteries, solar batteries and the like.
The dielectric property is an important component in the electrical property of the polymer matrix composite material, and the application of the graphene in improving the dielectric constant of the composite material and reducing the dielectric loss is a new research hotspot. The traditional dielectric material mainly takes ferroelectric ceramic as a main material, but the dielectric loss of the material is large, and the processing conditions are harsh. The graphene/polymer composite material has good molding processability and has great potential in replacing the traditional dielectric material. The preparation principle of the high dielectric polymer composite material is mainly to add conductive particles into a polymer matrix so as to achieve the purpose of enhancing the dielectric property of the composite material.
At present, the preparation of high dielectric composite materials is generally to physically mix inorganic fillers with high dielectric constant and organic resins, which combines the advantages of organic and inorganic materials and simultaneously endows the materials with a plurality of excellent performances in the aspects of mechanics, optics, and the like. The high dielectric composite material can be obtained by the method, for example, the document reports Chinese invention patent with application number CN 201610560678.4, an epoxy resin based high dielectric composite material and a preparation method thereof, epoxy resin is taken as a matrix, barium titanate which is doped with niobium pentoxide and cobaltosic oxide for modification is taken as a filler, a curing agent is added for heating and curing, and the epoxy resin based high dielectric composite material with higher dielectric constant and lower dielectric loss is obtained; the invention relates to a phenolic resin based high-temperature dielectric composite material and a preparation method thereof, which is disclosed in Chinese patent application No. CN 201611011781. X.A phenolic resin is taken as a matrix and is compounded with nano titanium dioxide, nano silicon dioxide and nano copper oxide which are treated by a coupling agent, so that the obtained composite material has high dielectric constant and high use temperature; in the invention patent of China with the application number of CN 201310226961.X, namely polyimide high-dielectric composite material and a preparation method thereof, the high-dielectric composite material is prepared by taking polyimide as a matrix and modified graphene and nano barium titanate as fillers through a solution blending method; in the above patents, all the preparation methods are blending to obtain the dielectric composite material with the filler and the resin matrix uniformly mixed, however, the dielectric loss is high. For example, in the chinese patent application No. cn201610457174.x, a polyolefin-based conductive and dielectric composite material and a preparation method thereof are prepared into a polyolefin-based composite material having a high dielectric constant by a melting method, but it requires relatively precise temperature control and process conditions are not easy to control.
In recent years, many studies have been focused on the preparation of high dielectric materials having a multi-layer structure, for example, chinese patent application No. CN201510511446.5, "a dielectric material" mentions that a dielectric composite material having not less than two layers is formed by combining an inorganic/polymer composite material layer with a pure polymer layer, resulting in a composite material having a high energy storage level.
There have also been many studies in recent years on dielectric composite materials prepared by filling graphene oxide and barium titanate into polymers. While Kong, et al, in the literature "preparation and performance research of graphite oxide/Barium titanate/epoxy resin three-phase composite material", prepare high dielectric composite material by solution blending method, Yang, et al, in the literature "Barium titanate coated and thermally reduced graphene oxide composites high dielectric constant and low loss of polymeric composites", prepare polyvinylidene fluoride based composite material by solution blending graphene and Barium titanate, wherein the organic resin used therein has performance defects, such as high polyimide hygroscopicity, poor epoxy resin aging resistance and moisture and heat resistance, and the dielectric composite material prepared by the above method has large dielectric loss and complicated preparation process.
Disclosure of Invention
The invention aims to solve the technical problem in the prior art and provides a high-dielectric composite material and a preparation method thereof.
In order to solve the technical problem, an embodiment of the present invention provides a high dielectric composite material, including a first copper foil, a polyphenylene ether resin, and a second copper foil, which are sequentially stacked from bottom to top;
the polyphenyl ether resin is provided with a sandwich structure film consisting of a graphene oxide film and a barium titanate film.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the preparation method of the sandwich structure film comprises the following steps:
step A1: preparing a graphene oxide aqueous solution: adding graphene oxide into pure water, and performing ultrasonic treatment to obtain a graphene oxide aqueous solution, wherein the mass concentration of the graphene oxide in the graphene oxide aqueous solution is 1.0-10.0 mg/mL;
step A2: preparing a barium titanate turbid solution: adding barium titanate into pure water, and performing ultrasonic treatment to obtain a barium titanate turbid liquid, wherein the mass ratio of barium titanate to pure water in the barium titanate turbid liquid is 1: 10-1: 100;
step A3: performing vacuum filtration treatment on 8-12 mL of the graphene oxide aqueous solution obtained in the step A1 by using a ceramic funnel to form a graphene oxide film;
step A4: pouring 3-10 mL of the barium titanate turbid solution obtained in the step A2 into the ceramic funnel covered with the graphene oxide film obtained in the step A3, and after vacuum filtration treatment, superposing a barium titanate film on the surface of the graphene oxide film;
step A5: and repeating the step A3 once, then continuously repeating the steps A4 and A3 in sequence, wherein the repetition frequency is N times (N is more than or equal to 1), and finally obtaining the thin film with a sandwich structure consisting of the graphene oxide film and the barium titanate film.
Further, the graphene oxide is any one of a single-layer graphene oxide, a double-layer graphene oxide, or a multi-layer graphene oxide.
Further, the particle size of the barium titanate is nano-scale or micro-scale.
Further, the step of forming the graphene oxide film after performing vacuum filtration treatment by using a ceramic funnel specifically comprises: the ceramic core surface of the ceramic funnel is covered with a water system microporous filter membrane, pure water of the graphene oxide aqueous solution is discharged through the funnel, and the graphene oxide is covered on the surface of the water system microporous filter membrane to form a graphene oxide membrane.
Further, the ceramic funnel has a specification of G1, G2, G3, G4 or G5.
Further, the first copper foil and the second copper foil are copper foils for manufacturing printed circuit boards, and the thickness of the copper foil is any one of 12 μm, 15 μm, 35 μm and 70 μm.
In order to solve the above technical problems, an embodiment of the present invention provides a method for preparing a high dielectric composite material, including the following steps:
step B1: dissolving polyphenyl ether resin in an organic solvent to prepare a uniform polyphenyl ether viscous solution, wherein the mass ratio of the polyphenyl ether resin to the organic solvent is 1: 5;
step B2: pouring 0.5g-4g of the polyphenyl ether viscous solution on the surface of a first copper foil, then forming a 'sandwich' structure film consisting of a graphene oxide film and a barium titanate film on the polyphenyl ether viscous solution, pouring 0.5g-4g of the polyphenyl ether viscous solution for the second time, and finally stacking a second copper foil on the polyphenyl ether viscous solution poured for the second time to obtain a composite material foundation system;
step B3: and placing the composite material basic system in an oven to volatilize the organic solvent, and hot-pressing for 24-48 hours to form the high-dielectric composite material.
Furthermore, the polyphenylene ether resin contains a crosslinkable active group end cap.
Further, the crosslinkable active group is vinyl, propenyl, allyl or acryloyl.
Further, the number average molecular weight of the polyphenylene ether resin is 1500-6000.
Further, the organic solvent is any one of N, N-dimethylformamide, tetrahydrofuran, acetone, butanone and toluene.
Further, the temperature of the oven is 40-60 ℃.
The invention has the beneficial effects that: the high-dielectric composite material formed by the polyphenyl ether resin and the sandwich-structured thin film consisting of the graphene oxide film and the barium titanate film has small moisture absorption and corrosion resistance, and compared with most resin materials, the high-dielectric composite material has high curing temperature and long curing time, the polyphenyl ether resin can be rapidly cured at a relatively low temperature, and has advantages in energy conservation and manufacturing efficiency; the preparation method of the sandwich-structure film consisting of the graphene oxide film and the barium titanate film is simple and easy to operate, has a good film forming effect and a certain tensile property, has the advantages of high dielectric and low loss when being used for preparing a composite material, and has the advantage of simple preparation method.
Drawings
FIG. 1 is a schematic structural diagram of a high dielectric composite according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a "sandwich" structure thin film composed of a graphene oxide film and a barium titanate film according to an embodiment of the present invention, where a is a perspective view and b is a cross-sectional view;
FIG. 3 is an SEM image of a high dielectric composite according to an embodiment of the present invention;
FIG. 4 is a graph of the dielectric constant of a high dielectric composite material in accordance with one embodiment of the present invention;
FIG. 5 is a graph of dielectric loss of a high dielectric composite material in accordance with an embodiment of the present invention.
In the drawings, the components represented by the respective reference numerals are listed below:
1. the film comprises a first copper foil, 2 parts of polyphenyl ether resin, 3 parts of a second copper foil, 4 parts of a graphene oxide film, 5 parts of a barium titanate film, 6 parts of a 'sandwich' structure film.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
As shown in fig. 1, a high dielectric composite material provided by the first aspect of the present invention includes a first copper foil 1, a polyphenylene ether resin 2, and a second copper foil 3, which are sequentially stacked from bottom to top;
the polyphenylene ether resin 2 has a "sandwich" structure film 6 composed of a graphene oxide film 4 and a barium titanate film 5.
Optionally, the preparation method of the "sandwich" structure film comprises the following steps:
step A1: preparing a graphene oxide aqueous solution: adding graphene oxide into pure water, and performing ultrasonic treatment to obtain a graphene oxide aqueous solution, wherein the mass concentration of the graphene oxide in the graphene oxide aqueous solution is 1.0-10.0 mg/mL;
step A2: preparing a barium titanate turbid solution: adding barium titanate into pure water, and performing ultrasonic treatment to obtain a barium titanate turbid liquid, wherein the mass ratio of barium titanate to pure water in the barium titanate turbid liquid is 1: 10-1: 100;
step A3: performing vacuum filtration treatment on 8-12 mL of the graphene oxide aqueous solution obtained in the step A1 by using a ceramic funnel to form a graphene oxide film;
step A4: pouring 3-10 mL of the barium titanate turbid solution obtained in the step A2 into the ceramic funnel covered with the graphene oxide film obtained in the step A3, and after vacuum filtration treatment, superposing a barium titanate film on the surface of the graphene oxide film;
step A5: and repeating the step A3 once, then continuously repeating the steps A4 and A3 in sequence, wherein the repetition frequency is N times (N is more than or equal to 1), and finally obtaining the thin film with a sandwich structure consisting of the graphene oxide film 4 and the barium titanate film 5.
Optionally, the graphene oxide is any one of a single-layer graphene oxide, a double-layer graphene oxide, or a multi-layer graphene oxide.
Optionally, the particle size of the barium titanate is nano-scale or micro-scale.
Optionally, the step of forming the graphene oxide film after performing vacuum filtration treatment by using a ceramic funnel specifically comprises: the ceramic core surface of the ceramic funnel is covered with a water system microporous filter membrane, pure water of the graphene oxide aqueous solution is discharged through the funnel, and the graphene oxide is covered on the surface of the water system microporous filter membrane to form a graphene oxide membrane.
Optionally, the ceramic funnel is of gauge G1, G2, G3, G4, or G5.
Optionally, the first copper foil and the second copper foil are copper foils for manufacturing printed circuit boards, and the thickness of the copper foil is any one of 12 μm, 15 μm, 35 μm and 70 μm.
The preparation method of the high dielectric composite material provided by the second aspect of the invention comprises the following steps:
step B1: dissolving polyphenyl ether resin in an organic solvent to prepare a uniform polyphenyl ether viscous solution, wherein the mass ratio of the polyphenyl ether resin to the organic solvent is 1: 5;
step B2: pouring 0.5g-4g of the polyphenyl ether viscous solution on the surface of a first copper foil 1, then forming a 'sandwich' structure film 6 consisting of a graphene oxide film 4 and a barium titanate film 5 on the polyphenyl ether viscous solution, pouring 0.5g-4g of the polyphenyl ether viscous solution for the second time, and finally stacking a second copper foil 3 on the polyphenyl ether viscous solution poured for the second time to obtain a composite material base system;
step B3: and placing the composite material basic system in an oven to volatilize the organic solvent, and hot-pressing for 24-48 hours to form the high-dielectric composite material.
Wherein, the hot pressing can enhance the bonding force of the composite material basic system.
Optionally, the polyphenylene ether resin contains a crosslinkable active group end cap.
The crosslinkable active group is terminated, so that the resin molecules are crosslinked to form a more complex crosslinking system, and a material with better thermal stability is obtained.
Optionally, the crosslinkable reactive group is vinyl, propenyl, allyl, or acryloyl.
Optionally, the number average molecular weight of the polyphenylene ether resin is 1500-6000.
Optionally, the organic solvent is any one of N, N-dimethylformamide, tetrahydrofuran, acetone, butanone, and toluene.
Optionally, the temperature of the oven is 40-60 ℃.
The present invention will be described in detail below by way of examples.
Example 1
Step A: preparing a "sandwich" structure thin film 6 composed of a graphene oxide film 4 and a barium titanate film 5:
a1: and preparing a graphene oxide aqueous solution. Adding graphene oxide into pure water, and performing ultrasonic treatment to obtain a graphene oxide aqueous solution; the mass concentration of the graphene oxide in the graphene oxide aqueous solution is 4.0mg/mL, and the graphene oxide is multilayer graphene oxide.
A2: and preparing the barium titanate turbid liquid. Adding barium titanate into pure water, and performing ultrasonic treatment to obtain a barium titanate turbid solution; the mass ratio of barium titanate to pure water in the barium titanate turbid solution is 1:20, and the particle size of barium titanate is micron-sized.
A3: carrying out vacuum filtration on 8mL of the graphene oxide aqueous solution obtained in the step A1 by using a vacuum filtration system to form a graphene oxide film; the vacuum filtration system is a ceramic funnel, and the surface of a ceramic core of the ceramic funnel is covered with a water system microporous filter membrane; discharging pure water of the graphene oxide aqueous solution through a funnel, wherein the graphene oxide covers the surface of the water system microporous filter membrane to form a graphene oxide membrane which is a first layer;
a4: pouring 10mL of the barium titanate turbid solution obtained in the step A2 into the ceramic funnel covered with the graphene oxide film obtained in the step A3, and after vacuum filtration treatment, superposing a barium titanate film on the surface of the graphene oxide film, wherein the barium titanate film is a second layer;
a5: continuously dropwise adding 8mL of graphene oxide aqueous solution on the barium titanate film obtained in the step A4, and performing vacuum filtration to form a graphene oxide film which is a third layer;
a6: pouring 10mL of barium titanate turbid solution into the ceramic funnel covered with the graphene oxide film obtained in the step A5, and after vacuum filtration, superposing a barium titanate film on the surface of the graphene oxide film, wherein the layer is a fourth layer;
a7: continuously dropwise adding 8mL of graphene oxide aqueous solution on the barium titanate film obtained in the step A6, and performing vacuum filtration to form a fifth graphene oxide film;
a8: and D, setting the graphene oxide film/barium titanate film sandwich-structured thin film obtained in the step A7 at room temperature for 8h, completely evaporating water to obtain a five-layer sandwich-structured thin film 6 consisting of a graphene oxide film 4 and a barium titanate film 5, as shown in figure 2.
And B: preparing a high dielectric composite material;
b1: dissolving 2.0g of polyphenyl ether resin in 10mL of tetrahydrofuran to prepare a uniform polyphenyl ether viscous solution;
b2: pouring 1g of the polyphenyl ether viscous solution prepared in the step B1 on a copper foil rough surface with the thickness of 15 microns, forming a five-layer 'sandwich' structure film 6 consisting of a graphene oxide film 4 and a barium titanate film 5 on the polyphenyl ether viscous solution, pouring 1g of the polyphenyl ether viscous solution for the second time, embedding the five-layer 'sandwich' structure film in the polyphenyl ether viscous solution by a pouring method, and combining the other copper foil rough surface with the thickness of 15 microns and the upper layer of the polyphenyl ether viscous solution to obtain a composite material base system;
b3: and C, placing the composite material base system prepared in the step B2 in a 50 ℃ oven to volatilize tetrahydrofuran, applying a certain pressure to form a blocky structure, and performing hot pressing for 24-48 hours to obtain the high-dielectric composite material, wherein the high-dielectric composite material is shown in figure 1.
Fig. 3 is an SEM image of the five-layer "sandwich" structure film prepared in example 1, which can be clearly observed that the five layers of graphene oxide, barium titanate, graphene oxide, barium titanate and graphene oxide are distributed from bottom to top in the film, barium titanate particles are well dispersed on the graphene oxide film, and a rugged and uneven small peak is also observed on the graphene oxide film, mainly because the surface of the barium titanate particles is not smooth, a mark of barium titanate is left on the graphene oxide film by the vacuum filtration, and this interesting structure can further increase the surface area of the graphene oxide. According to the definition of the plate capacitance, the capacitance of a plate capacitor is proportional to the area S of the plates and inversely proportional to the distance d between the plates.
Figure BDA0002602306150000081
In formula (1), C is the capacitance value of the plate capacitor; q is the amount of charge in the plate capacitor; s is the positive area of the two polar plates; epsilon is dielectric permittivity; k is an electrostatic constant of 8.987551 × 109N·m2/C2(ii) a d is the vertical distance between two polar plates. The volume fraction and the specific surface area of the graphene oxide are large, the micro-capacitor formed in the composite material also has a larger polar plate area (S) and a smaller polar plate distance (d), the graphene oxide belongs to a conductive phase, the graphene oxide can be used as two poles of the micro-capacitor, barium titanate particles are used as a medium between the two poles, and the dielectric constant of the composite material can be greatly improved.
When the polyphenyl ether, the thin film with a sandwich structure consisting of the graphene oxide film and the barium titanate film and the polyphenyl ether are stacked together, each two layers can be regarded as a simple flat capacitor, the whole polyphenyl ether composite material with the sandwich structure can be regarded as a polyphenyl ether composite material, the three flat capacitors are equal to one in total, and the three layers are stacked together and are equivalent to the three capacitors which are connected in series. According to the relation between the capacitance and the dielectric constant, the dielectric constant of the polyphenyl ether composite material with the sandwich structure can be obtained, impedance analysis and test are carried out on the polyphenyl ether composite material with the sandwich structure, as shown in fig. 4, the constructed polyphenyl ether composite material with the sandwich structure is beneficial to improving the dielectric constant, but has strong dependence on frequency, and the dielectric constant is sharply reduced along with the increase of the frequency. As shown in fig. 4 and 5, at a frequency of 1MHz, the dielectric constant and the dielectric loss of the pure polyphenylene ether resin are respectively 3.18 and 0.021, the dielectric constant and the dielectric loss of the polyphenylene ether composite material of the "sandwich" structure prepared by the present invention are respectively 141.91 and 0.038, the reason that the dielectric constant of the polyphenylene ether composite material of the "sandwich" structure is higher is that the dielectric constant of the intermediate layer is higher, and because the dielectric difference exists between the intermediate layers of the polyphenylene ether composite material of the "sandwich" structure, under the action of an applied electric field, not only the interface polarization may occur inside each layer, but also the interface polarization may occur between each layer, thereby it can be shown that the connection between the three layers is not simply overlapped together, and a certain interface interaction may also occur. Because three capacitors connected in series are formed in the polyphenyl ether composite material with the sandwich structure, the micro-morphology of the thin film with the sandwich structure consisting of the graphene oxide film and the barium titanate film can be known, the graphene oxide layer has a plurality of convex parts, the area of two electrode plates of the capacitors in the thin film is indirectly increased, and the dielectric constant of the composite material is higher. The reason why the dielectric loss of the high-dielectric composite material prepared by the invention is low is that the middle layer also has a sandwich structure, and the barium titanate layer separates the graphene oxide layer from the graphene oxide layer, so that a complete conductive network cannot be effectively formed, and the dielectric loss of the high-dielectric composite material is low.
Example 2
Step A: preparing a "sandwich" structure thin film 6 composed of a graphene oxide film 4 and a barium titanate film 5:
a1: and preparing a graphene oxide aqueous solution. Adding graphene oxide into pure water, and performing ultrasonic treatment to obtain a graphene oxide aqueous solution; the mass concentration of the graphene oxide in the graphene oxide aqueous solution is 4.0mg/mL, and the graphene oxide is multilayer graphene oxide.
A2: and preparing the barium titanate turbid liquid. Adding barium titanate into pure water, and performing ultrasonic treatment to obtain a barium titanate turbid solution; the mass ratio of barium titanate to pure water in the barium titanate turbid solution is 1:20, and the particle size of barium titanate is micron-sized.
A3: carrying out vacuum filtration on 8mL of the graphene oxide aqueous solution obtained in the step A1 by using a vacuum filtration system to form a graphene oxide film; the vacuum filtration system is a ceramic funnel, and the surface of a ceramic core of the ceramic funnel is covered with a water system microporous filter membrane; discharging pure water of the graphene oxide aqueous solution through a funnel, wherein the graphene oxide covers the surface of the water system microporous filter membrane to form a graphene oxide membrane which is a first layer;
a4: pouring 10mL of the barium titanate turbid solution obtained in the step A2 into the ceramic funnel covered with the graphene oxide film obtained in the step A3, and after vacuum filtration treatment, superposing a barium titanate film on the surface of the graphene oxide film, wherein the barium titanate film is a second layer;
a5: continuously dropwise adding 8mL of graphene oxide aqueous solution on the barium titanate film obtained in the step A4, and performing vacuum filtration to form a graphene oxide film which is a third layer;
a6: pouring 10mL of barium titanate turbid solution into the ceramic funnel covered with the graphene oxide film obtained in the step A5, and after vacuum filtration, superposing a barium titanate film on the surface of the graphene oxide film, wherein the layer is a fourth layer;
a7: continuously dropwise adding 8mL of graphene oxide aqueous solution on the barium titanate film obtained in the step A6, and performing vacuum filtration to form a fifth graphene oxide film;
a8: pouring 10mL of barium titanate turbid solution into the ceramic funnel covered with the graphene oxide film obtained in the step A7, and after vacuum filtration, superposing a barium titanate film on the surface of the graphene oxide film, namely a sixth layer;
a9: continuously dropwise adding 8mL of graphene oxide aqueous solution on the barium titanate film obtained in the step A8, and performing vacuum filtration to form a graphene oxide film which is a seventh layer;
a10: and D, placing the graphene oxide film/barium titanate film sandwich-structured thin film obtained in the step A9 at room temperature for 8h, completely evaporating water, and obtaining a seven-layer sandwich-structured thin film 6 consisting of a graphene oxide film 4 and a barium titanate film 5.
And B: preparing a high dielectric composite material;
in the above examples, the preparation method of step B was the same as in example 1.
The invention provides a high-dielectric composite material, which is characterized in that a sandwich-structure film composed of a graphene oxide film and a barium titanate film is prepared through vacuum filtration, a capacitor structure is firstly formed inside the sandwich-structure film composed of the graphene oxide film and the barium titanate film, then polyphenyl ether resin is poured to wrap the sandwich-structure film composed of the graphene oxide film and the barium titanate film, copper foils are covered on the upper surface and the lower surface of the sandwich-structure film, and a solvent is volatilized through hot pressing and heating to obtain a polyphenylene ether-based composite material, so that the sandwich-structure film composed of the graphene oxide film and the barium titanate film is compounded with polyphenyl ether, and the high-dielectric and low-loss polyphenylene ether-based composite material is obtained. The polyphenylene ether-based composite material disclosed by the invention can be used for a printed circuit embedded capacitor device, has the advantages of high dielectric constant and low loss, and is simple and efficient in preparation method.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A high-dielectric composite material comprises a first copper foil (1), a polyphenylene oxide resin (2) and a second copper foil (3) which are sequentially stacked from bottom to top;
the polyphenylene ether resin (2) is characterized by having a thin film (6) of a sandwich structure composed of a graphene oxide film (4) and a barium titanate film (5).
2. The high dielectric composite material of claim 1, wherein the method for preparing the "sandwich" structure film comprises the following steps:
step A1: preparing a graphene oxide aqueous solution: adding graphene oxide into pure water, and performing ultrasonic treatment to obtain a graphene oxide aqueous solution, wherein the mass concentration of the graphene oxide in the graphene oxide aqueous solution is 1.0-10.0 mg/mL;
step A2: preparing a barium titanate turbid solution: adding barium titanate into pure water, and performing ultrasonic treatment to obtain a barium titanate turbid liquid, wherein the mass ratio of barium titanate to pure water in the barium titanate turbid liquid is 1: 10-1: 100;
step A3: performing vacuum filtration treatment on 8-12 mL of the graphene oxide aqueous solution obtained in the step A1 by using a ceramic funnel to form a graphene oxide film;
step A4: pouring 3-10 mL of the barium titanate turbid solution obtained in the step A2 into the ceramic funnel covered with the graphene oxide film obtained in the step A3, and after vacuum filtration treatment, superposing a barium titanate film on the surface of the graphene oxide film;
step A5: and repeating the step A3 once, then continuously repeating the steps A4 and A3 in sequence, wherein the repetition frequency is N times (N is more than or equal to 1), and finally obtaining the thin film with a sandwich structure consisting of the graphene oxide film (4) and the barium titanate film (5).
3. The high dielectric composite material as claimed in claim 2, wherein the graphene oxide is any one of a single layer graphene oxide, a double layer graphene oxide or a multi-layer graphene oxide.
4. The high dielectric composite material of claim 2, wherein the barium titanate has a particle size of nano-or micro-scale.
5. The high-dielectric composite material of claim 2, wherein the step of forming the graphene oxide film after performing vacuum filtration treatment by using a ceramic funnel comprises: the ceramic core surface of the ceramic funnel is covered with a water system microporous filter membrane, pure water of the graphene oxide aqueous solution is discharged through the funnel, and the graphene oxide is covered on the surface of the water system microporous filter membrane to form a graphene oxide membrane.
6. The preparation method of the high dielectric composite material is characterized by comprising the following steps of:
step B1: dissolving polyphenyl ether resin in an organic solvent to prepare a uniform polyphenyl ether viscous solution, wherein the mass ratio of the polyphenyl ether resin to the organic solvent is 1: 5;
step B2: pouring 0.5g-4g of the polyphenyl ether viscous solution on the surface of a first copper foil (1), then forming a 'sandwich' structure film (6) consisting of a graphene oxide film (4) and a barium titanate film (5) on the polyphenyl ether viscous solution, pouring 0.5g-4g of the polyphenyl ether viscous solution for the second time, and finally stacking a second copper foil (3) on the polyphenyl ether viscous solution poured for the second time to obtain a composite material base system;
step B3: and placing the composite material basic system in an oven to volatilize the organic solvent, and hot-pressing for 24-48 hours to form the high-dielectric composite material.
7. The method of claim 6, wherein the polyphenylene ether resin contains a crosslinkable active group end cap.
8. The method of claim 7, wherein the crosslinkable group is vinyl, propenyl, allyl, or acryloyl.
9. The method of claim 6, wherein the organic solvent is one of N, N-dimethylformamide, tetrahydrofuran, acetone, methyl ethyl ketone and toluene.
10. The method for preparing a high dielectric composite material as claimed in claim 6, wherein the temperature of the oven is 40-60 ℃.
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