CN111619030A - Preparation method of high-energy-storage-density composite dielectric material - Google Patents

Preparation method of high-energy-storage-density composite dielectric material Download PDF

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CN111619030A
CN111619030A CN202010348702.4A CN202010348702A CN111619030A CN 111619030 A CN111619030 A CN 111619030A CN 202010348702 A CN202010348702 A CN 202010348702A CN 111619030 A CN111619030 A CN 111619030A
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赵灶生
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Abstract

The invention relates to a preparation method of a high-energy-storage-density composite dielectric material, belonging to the technical field of dielectric materials. The polyvinylidene fluoride is used as a polymer base material to prepare the high-energy-storage-density composite dielectric material, the polyvinylidene fluoride is a nonlinear dielectric polymer and has a relatively high dielectric constant, during the charge and discharge processes of the polyvinylidene fluoride, the dipoles in the material have a strong coupling effect, so that partial polarization exists even after an external electric field is removed, the polyvinylidene fluoride has good breakdown field strength and high energy storage density, the composite dielectric material prepared by using the polyvinylidene fluoride as the polymer base material has good mechanical property and electrical insulation property, and the polyvinylidene fluoride is used for preparing the dielectric material, so that the preparation and use cost of the dielectric material can be effectively reduced, the processing quality is improved, and the large-area high-quality composite dielectric material can be prepared.

Description

Preparation method of high-energy-storage-density composite dielectric material
Technical Field
The invention relates to a preparation method of a high-energy-storage-density composite dielectric material, belonging to the technical field of dielectric materials.
Background
Energy storage devices have an important position in the rapid development of modern electronic technology, and are particularly widely applied to the fields of pulse power supply devices, hybrid power systems and the like. With the change of science and technology, the requirement for the energy storage property of materials is continuously improved. Materials with high energy storage, particularly polymer-based flexible materials, have attracted more attention from researchers.
Along with the continuous increase of energy demand and the continuous consumption of traditional energy, the problems of improving the utilization efficiency of the traditional energy and expanding the practical range of the energy are increasingly highlighted. Energy storage and integration of energy sources into the power grid are important foundations for mass production of electric vehicles and continuous development of portable electronic devices. Due to the development of new energy technologies and remote electric energy transmission technologies, and the popularization of mobile devices, new energy vehicles and the like, people have higher and higher requirements on efficient energy storage technologies and equipment. Electrostatic capacitors are excellent representatives of the field of electric memory devices and power electronic systems, and there is an increasing call for improving and updating the performance and technology of electrostatic capacitors. The current electrostatic capacitor has the defects of low energy density, which is generally caused by the low energy density of the energy storage medium between the capacitors. Therefore, the improvement of the energy storage characteristic of the energy storage medium is the key point for improving the electrostatic capacitor.
The dielectric material with high energy storage density has important function in modern electronic and electric systems, especially has remarkable application prospect in the fields of pulse power, electronic packaging technology and the like, and is an important material for preparing high-performance capacitors, brakes, sensors, spacecrafts, electric stress control devices and the like.
In recent years, high-performance electronic devices have been developed in an intensive manner, and higher requirements have been placed on the energy storage density of electronic materials, and it has been desired to obtain a material system having a high dielectric constant, a low dielectric loss, a high breakdown voltage, and good overall properties such as easy processability. Traditional polymer materials such as Polyimide (PI), polyvinylidene fluoride (PVDF), epoxy resin and the like have the characteristics of small volume, easiness in processing and the like, but most of polymers have low dielectric constants and are difficult to meet the actual use requirements. For the energy storage medium, the energy storage density is in direct proportion to the square of the breakdown strength of the medium and the dielectric constant, so the energy storage performance is in direct relation to the dielectric and breakdown characteristics of the medium. High dielectric ceramics are utilized such as: the synthesis of high dielectric composite media using lead zirconate titanate (PZT), Barium Titanate (BT), etc. as the filler phase is currently common. Although the dielectric constant of the polymer matrix can be improved by using the inorganic high dielectric reinforcement, a larger filling amount is required, which inevitably causes the electrical insulation performance and the processability of the polymer matrix to be deteriorated: the dielectric loss and the conductivity are increased, the dielectric breakdown strength is reduced, the flexibility is poor and the like, and the requirements of the energy storage medium in practical application cannot be met. Therefore, the high dielectric reinforcement is compounded with the polymer matrix with excellent mechanical property, so that the excellent characteristics of two phases can be maintained, and the purposes of improving the dielectric, breakdown and processability characteristics of the composite medium can be achieved. The all-organic dielectric material becomes a flexible energy storage material with potential by virtue of the advantages of high breakdown strength, high quality factor, light weight, high flexibility and easiness in processing. However, all-organic media as high energy storage materials also have certain disadvantages: low dielectric constant, complex chemical synthesis process, high price and the like, and limit the practical application of the material.
Electrostatic capacitors have become key devices for many applications in advanced electronic and power systems due to their ability to charge/discharge very quickly and very high power densities. However, the energy density of the polymer dielectric used in the capacitor is low, and the requirement of the power system for continuous development cannot be met, so that the search and development of the composite dielectric with high energy storage density is the focus and hot direction of the current research.
The existing polymer-based composite dielectric usually adopts a PVDF-based polymer matrix to utilize its high and adjustable dielectric constant (10-100) and high breakdown field strength. And ferroelectric ceramics having a high dielectric constant, such as barium titanate-based ceramic particles, are often used as the ceramic particles. Through the research in recent years, the complex system has made great progress in the field of high energy storage, such as the preparation of the complex system with high energy storage density (10-30J/cm)3) The composite dielectric material of (a); however, the composite system usually has higher energy loss due to the adoption of the PVDF-based polymer with ferroelectric property and the ferroelectric ceramic particles as components, and the energy release efficiency of the composite system is about 40-60%, which is far lower than the requirement of a high-performance energy storage capacitor. This is due to the self electric field polarization characteristics of the two-phase componentThe ferroelectric PVDF-based polymer has larger polarization relaxation loss, and the difference of the electrical properties between two phases also causes the electric field distribution in the composite dielectric medium to be uneven and the ion leakage conductance to be larger, which all result in higher loss value of the final material. High losses not only reduce the dielectric energy storage efficiency, but also can be converted to heat that destroys the dielectric and renders it ineffective.
The problems existing in the prior art are as follows:
(1) the traditional dielectric ceramic material has high dielectric constant, but has low breakdown strength and great processing difficulty.
Organic polymer dielectric materials typically have a low dielectric constant.
The current dielectric composite materials are not perfect in the aspects of electrical property, mechanical property or processing property and the like.
Therefore, it is necessary to comprehensively consider the influence factors of the dielectric constant, the dielectric loss, the breakdown strength, and the like of the polymer composite dielectric material, so that the high energy storage density is obtained and the performances in all aspects are optimally balanced to meet the practical application requirements.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problems of low breakdown strength, large processing difficulty and low dielectric constant of organic polymer dielectric materials of the traditional dielectric ceramic materials, the preparation method of the composite dielectric material with high energy storage density is provided.
In order to solve the technical problems, the invention adopts the following technical scheme:
(1) placing polyvinylidene fluoride, fluorinated graphene, nano boron nitride, glycerol, sodium stearate and an antioxidant 1010 in a high-speed stirrer, and stirring and mixing at the rotating speed of 2000-2400 r/min for 40-60 min at normal temperature to obtain a mixture;
(2) placing the mixture in a double-screw extruder, extruding and granulating at 220-260 ℃, and cooling at normal temperature to obtain composite granules;
(3) and (3) placing the composite granules into an injection molding machine for injection molding, and cooling at normal temperature to obtain the high-energy-storage-density composite dielectric material.
The polyvinylidene fluoride, the fluorinated graphene, the nano boron nitride, the glycerol, the sodium stearate and the antioxidant 1010 are 100-200 parts by weight of polyvinylidene fluoride, 20-40 parts by weight of fluorinated graphene, 8-10 parts by weight of nano boron nitride, 4-8 parts by weight of glycerol, 2-4 parts by weight of sodium stearate and 0.2-0.4 part by weight of the antioxidant 1010.
The injection molding conditions in the step (3) are that the temperature is 180-200 ℃ and the pressure is 20-40 MPa.
The specific preparation steps of the fluorinated graphene in the step (1) are as follows:
(1) placing the graphene powder and the xenon difluoride powder in a high-speed stirrer, and stirring and mixing at the normal temperature at the rotating speed of 1600-1800 r/min for 30-40 min to obtain mixed powder;
(2) and placing the mixed powder in a tubular atmosphere furnace, introducing nitrogen for protection, calcining for 20-24 hours at 180-200 ℃, and cooling to room temperature along with the furnace to obtain the fluorinated graphene.
The graphene powder and the xenon difluoride powder are 10-20 parts by weight of graphene powder and 20-40 parts by weight of xenon difluoride powder.
And (3) introducing the nitrogen in the step (2) at a speed of 120-160 mL/min.
The specific preparation steps of the graphene powder in the step (1) are
(1) Slowly adding sulfuric acid into a container filled with graphite flakes at a speed of 40-60 mL/min, and stirring at a rotating speed of 120-160 r/min for 10-15 min at a temperature of 0-4 ℃ to obtain a graphite flake sulfuric acid mixed solution;
(2) slowly adding potassium permanganate powder into the graphite flake sulfuric acid mixed solution for 60-90 min, and stirring and oxidizing for 2-4 h at 180-200 r/min under the condition of water bath at 40-50 ℃ to obtain a reaction solution;
(3) slowly adding deionized water into the reaction solution at the speed of 80-100 mL/min, placing the reaction solution at the temperature of 0-4 ℃, adding hydrogen peroxide, placing the reaction solution in a centrifuge, centrifugally separating the reaction solution at the rotating speed of 4500-5500 r/min for 10min, taking lower-layer solid, washing the lower-layer solid to be neutral by using the deionized water, and drying the lower-layer solid in the shade at normal temperature to obtain graphene oxide;
(4) placing graphene oxide in a tubular atmosphere furnace, introducing argon for protection, calcining for 1-2 hours at 1000-1100 ℃, and cooling to room temperature along with the furnace to obtain graphene powder;
the graphite flake, the sulfuric acid, the potassium permanganate powder, the hydrogen peroxide and the deionized water are 10-20 parts by weight of the graphite flake, 40-80 parts by weight of 10% sulfuric acid, 15-30 parts by weight of the potassium permanganate powder, 20-40 parts by weight of the hydrogen peroxide and 400-800 parts by weight of the deionized water.
And (4) introducing the argon at a rate of 180-200 mL/min.
Compared with other methods, the method has the beneficial technical effects that:
(1) the invention takes polyvinylidene fluoride as a polymer base material to prepare a high energy storage density composite dielectric material, the polyvinylidene fluoride is a nonlinear dielectric polymer and has relatively high dielectric constant, in the charging and discharging process of the polyvinylidene fluoride, strong coupling action exists between dipoles in the material, so that partial polarization exists even after an external electric field is removed, the polyvinylidene fluoride has good breakdown field strength and higher energy storage density, the composite dielectric material prepared by taking the polyvinylidene fluoride as the polymer base material has good mechanical property and electrical insulation property, and the preparation of the dielectric material by adopting the polyvinylidene fluoride can effectively reduce the preparation and use cost of the dielectric material, improve the processing quality, the processing property of the polyvinylidene fluoride is excellent, and the composite dielectric material with large area, small area, high energy storage density and high energy storage density can be prepared, The composite dielectric material with high quality is used for production, and the unique self-healing behavior of the polyvinylidene fluoride can avoid short circuit caused by local dielectric breakdown on a large-area capacitor film, so that the practicability and safety of the composite dielectric material with high energy storage density are effectively improved;
(2) the invention takes fluorinated graphene as an energy storage filler and is added with high dielectric material nano boron nitride to prepare the high energy storage density composite dielectric material, wherein the graphene is prepared by leading valence electrons of carbon atoms to pass through sp2The graphene has a large specific surface area, and the theoretical specific capacitance energy storage density can reach 550 Fg−1Has higher energy storage densityThe degree, the addition of graphite alkene can effectively improve composite dielectric material's energy storage density, fluorinate graphite alkene through xenon dioxide, can effectively reduce its electric conductivity, it has good heat conductivity and thermal stability to fluorinate graphite alkene, when composite dielectric material is under the electric field, the inside heat that can produce of dielectric, these heats can be through the inside graphite alkene homodisperse that fluorinates of material, prevent that polyvinylidene fluoride in the material from producing the aperture because of inside is heated inequality, thereby reduce composite dielectric material's inside conductive channel's formation, improve close breakdown strength, nanometer boron nitride itself has excellent thermal conductivity, add nanometer boron nitride and can effectively improve composite dielectric material's thermal conductivity, reduce the leakage conduction current in the composite material, improve material's insulating nature, reinforcing breakdown strength.
Detailed Description
Respectively weighing 10-20 parts of graphite flakes, 40-80 parts of sulfuric acid with the mass fraction of 10%, 15-30 parts of potassium permanganate powder, 20-40 parts of hydrogen peroxide and 400-800 parts of deionized water according to parts by weight, slowly adding the sulfuric acid into a container filled with the graphite flakes at the speed of 40-60 mL/min, stirring at the speed of 120-160 r/min for 10-15 min at the temperature of 0-4 ℃ to obtain a graphite flake sulfuric acid mixed solution, slowly adding the potassium permanganate powder into the graphite flake sulfuric acid mixed solution, adding for 60-90 min, stirring and oxidizing at the speed of 180-200 r/min for 2-4 h under the water bath condition of 40-50 ℃ to obtain a reaction solution, slowly adding the deionized water into the reaction solution at the speed of 80-100 mL/min, adding the hydrogen peroxide at the temperature of 0-4 ℃, placing into a centrifuge, centrifuging and separating at the speed of 4500-5500 r/min for 10min, taking the lower-layer solid, washing the lower-layer solid with deionized water to be neutral, drying the lower-layer solid in the shade at normal temperature to obtain graphene oxide, placing the graphene oxide in a tubular atmosphere furnace, introducing argon at the speed of 180-200 mL/min for protection, calcining the graphene oxide for 1-2 hours at the temperature of 1000-1100 ℃, and cooling the graphene oxide to the room temperature along with the furnace to obtain graphene powder; respectively weighing 10-20 parts of graphene powder and 20-40 parts of xenon difluoride powder according to parts by weight, placing the graphene powder and the xenon difluoride powder in a high-speed stirrer, stirring and mixing at a rotating speed of 1600-1800 r/min for 30-40 min at normal temperature to obtain mixed powder, placing the mixed powder in a tubular atmosphere furnace, introducing nitrogen at a speed of 120-160 mL/min for protection, calcining for 20-24 h at the temperature of 180-200 ℃, and cooling to room temperature along with the furnace to obtain fluorinated graphene; and then, respectively weighing 100-200 parts by weight of polyvinylidene fluoride, 20-40 parts by weight of fluorinated graphene, 8-10 parts by weight of nano boron nitride, 4-8 parts by weight of glycerol, 2-4 parts by weight of sodium stearate and 0.2-0.4 part by weight of antioxidant 1010, placing the polyvinylidene fluoride, the fluorinated graphene, the nano boron nitride, the glycerol, the sodium stearate and the antioxidant 1010 in a high-speed stirrer, stirring and mixing at the rotating speed of 2000-2400 r/min for 40-60 min at normal temperature to obtain a mixture, placing the mixture in a double-screw extruder, extruding and granulating at the temperature of 220-260 ℃, cooling at the normal temperature to obtain composite granules, placing the composite granules in an injection molding machine, performing injection molding at the temperature of 180-200 ℃ and under the pressure of 20-40 MPa, and cooling at the normal temperature to obtain the high energy storage density composite dielectric material.
Example 1
Respectively weighing 10-20 parts of graphite flakes, 40-80 parts of sulfuric acid with the mass fraction of 10%, 15-30 parts of potassium permanganate powder, 20-40 parts of hydrogen peroxide and 400-800 parts of deionized water according to parts by weight, slowly adding the sulfuric acid into a container filled with the graphite flakes at the speed of 40-60 mL/min, stirring at the rotating speed of 120r/min for 10min at the temperature of 0-4 ℃ to obtain a graphite flake sulfuric acid mixed solution, slowly adding the potassium permanganate powder into the graphite flake sulfuric acid mixed solution, adding the mixture for 60min, stirring and oxidizing at the water bath condition of 40 ℃ for 2h at the rotating speed of 180r/min to obtain a reaction solution, slowly adding the deionized water into the reaction solution at the speed of 80mL/min, adding the hydrogen peroxide at the temperature of 0 ℃, placing the reaction solution into a centrifuge, centrifugally separating at the rotating speed of 4500r/min for 10min, taking a lower-layer solid, washing the lower-layer solid to be neutral by using deionized water, drying in the shade at normal temperature to obtain graphene oxide, placing the graphene oxide in a tubular atmosphere furnace, introducing argon at the rate of 180mL/min for protection, calcining for 1h at the temperature of 1000 ℃, and cooling to room temperature along with the furnace to obtain graphene powder; respectively weighing 10 parts of graphene powder and 20 parts of xenon difluoride powder according to parts by weight, placing the graphene powder and the xenon difluoride powder in a high-speed stirrer, stirring and mixing at the normal temperature at the rotating speed of 1600r/min for 30min to obtain mixed powder, placing the mixed powder in a tubular atmosphere furnace, introducing nitrogen at the speed of 120mL/min for protection, calcining for 20h at the temperature of 180 ℃, and cooling to the room temperature along with the furnace to obtain fluorinated graphene; and then, respectively weighing 100 parts of polyvinylidene fluoride, 20 parts of fluorinated graphene, 8 parts of nano boron nitride, 4 parts of glycerol, 2 parts of sodium stearate and 0.2 part of antioxidant 1010 according to parts by weight, placing the polyvinylidene fluoride, the fluorinated graphene, the nano boron nitride, the glycerol, the sodium stearate and the antioxidant 1010 in a high-speed mixer, stirring and mixing at the rotating speed of 2000r/min for 40min at normal temperature to obtain a mixture, placing the mixture in a double-screw extruder, extruding and granulating at the temperature of 220 ℃, cooling at the normal temperature to obtain composite granules, placing the composite granules in an injection molding machine, performing injection molding at the temperature of 180 ℃ and the pressure of 20MPa, and cooling at the normal temperature to obtain the high-energy-storage-density composite dielectric material.
Example 2
Respectively weighing 15 parts of graphite flake, 60 parts of sulfuric acid with the mass fraction of 10%, 22 parts of potassium permanganate powder, 30 parts of hydrogen peroxide and 600 parts of deionized water according to parts by weight, slowly adding the sulfuric acid into a container filled with the graphite flake at the speed of 50mL/min, stirring at the rotating speed of 140r/min for 13min at the temperature of 2 ℃ to obtain graphite flake sulfuric acid mixed solution, slowly adding the potassium permanganate powder into the graphite flake sulfuric acid mixed solution, adding the mixture for 75min, stirring and oxidizing at the speed of 190r/min for 3h under the water bath condition of 45 ℃ to obtain reaction liquid, slowly adding the deionized water into the reaction liquid at the speed of 90mL/min, adding the hydrogen peroxide at the temperature of 2 ℃, placing the reaction liquid into a centrifuge, centrifugally separating at the rotating speed of 5000r/min for 10min, taking lower-layer solid, washing with the deionized water to be neutral, drying at normal temperature in the shade to obtain graphene oxide, placing graphene oxide in a tubular atmosphere furnace, introducing argon at the rate of 190mL/min for protection, calcining at 1050 ℃ for 1.5h, and cooling to room temperature along with the furnace to obtain graphene powder; respectively weighing 15 parts of graphene powder and 30 parts of xenon difluoride powder according to parts by weight, placing the graphene powder and the xenon difluoride powder in a high-speed stirrer, stirring and mixing at the normal temperature at the rotating speed of 1700r/min for 35min to obtain mixed powder, placing the mixed powder in a tubular atmosphere furnace, introducing nitrogen at the speed of 140mL/min for protection, calcining for 22h at the temperature of 190 ℃, and cooling to the room temperature along with the furnace to obtain fluorinated graphene; respectively weighing 150 parts of polyvinylidene fluoride, 30 parts of fluorinated graphene, 9 parts of nano boron nitride, 6 parts of glycerol, 3 parts of sodium stearate and 0.3 part of antioxidant 1010 according to parts by weight, placing the polyvinylidene fluoride, the fluorinated graphene, the nano boron nitride, the glycerol, the sodium stearate and the antioxidant 1010 in a high-speed mixer, stirring and mixing at the rotating speed of 2200r/min for 50min at normal temperature to obtain a mixture, placing the mixture in a double-screw extruder, extruding and granulating at 240 ℃, cooling at normal temperature to obtain composite granules, placing the composite granules in an injection molding machine, performing injection molding at the temperature of 190 ℃ and the pressure of 30MPa, and cooling at normal temperature to obtain the high-energy-storage-density composite dielectric material.
Example 3
Respectively weighing 20 parts of graphite flake, 80 parts of sulfuric acid with the mass fraction of 10%, 30 parts of potassium permanganate powder, 40 parts of hydrogen peroxide and 800 parts of deionized water according to parts by weight, slowly adding the sulfuric acid into a container filled with the graphite flake at the speed of 60mL/min, stirring for 15min at the rotating speed of 160r/min at the temperature of 4 ℃ to obtain graphite flake sulfuric acid mixed solution, slowly adding the potassium permanganate powder into the graphite flake sulfuric acid mixed solution, adding the mixture for 90min, stirring and oxidizing for 4h at the water bath condition of 50 ℃ at the speed of 200r/min to obtain reaction liquid, slowly adding the deionized water into the reaction liquid at the speed of 100mL/min, adding the hydrogen peroxide at the temperature of 4 ℃, placing the reaction liquid into a centrifuge, centrifugally separating for 10min at the rotating speed of 5500r/min, taking lower-layer solid, washing with the deionized water to be neutral, drying at normal temperature in the shade to obtain graphene oxide, placing graphene oxide in a tubular atmosphere furnace, introducing argon at the rate of 200mL/min for protection, calcining for 2 hours at the temperature of 1100 ℃, and cooling to room temperature along with the furnace to obtain graphene powder; respectively weighing 20 parts of graphene powder and 40 parts of xenon difluoride powder according to parts by weight, placing the graphene powder and the xenon difluoride powder in a high-speed stirrer, stirring and mixing at the normal temperature at the rotating speed of 1800r/min for 40min to obtain mixed powder, placing the mixed powder in a tubular atmosphere furnace, introducing nitrogen at the speed of 160mL/min for protection, calcining for 24h at the temperature of 200 ℃, and cooling to the room temperature along with the furnace to obtain fluorinated graphene; and respectively weighing 200 parts of polyvinylidene fluoride, 40 parts of fluorinated graphene, 10 parts of nano boron nitride, 8 parts of glycerol, 4 parts of sodium stearate and 0.4 part of antioxidant 1010 according to parts by weight, placing the polyvinylidene fluoride, the fluorinated graphene, the nano boron nitride, the glycerol, the sodium stearate and the antioxidant 1010 in a high-speed stirrer, stirring and mixing at the rotating speed of 2400r/min for 60min at normal temperature to obtain a mixture, placing the mixture in a double-screw extruder, extruding and granulating at the temperature of 260 ℃, cooling at the normal temperature to obtain composite granules, placing the composite granules in an injection molding machine, performing injection molding at the temperature of 200 ℃ and the pressure of 40MPa, and cooling at the normal temperature to obtain the high-energy-storage-density composite dielectric material.
The high energy storage density composite dielectric material prepared by the invention and the traditional dielectric ceramic material are subjected to performance tests, and specific detection results are shown in the following table 1.
The test method comprises the following steps:
(1) dielectric property test (AC test signal: frequency 20 Hz-1 MHz, voltage 1V)
Testing the capacitance C and the loss tan of the sample by using a TH2828S 1MHz glowing precise LCR digital bridge, and calculating the dielectric constant of the sample;
(2) testing the electric hysteresis loop of the aixACCT TF1000 ferroelectric workstation at 10Hz, and calculating the energy storage density according to the electric hysteresis loop:
TABLE 1 characterization of high energy storage density composite dielectric material properties
Figure 383323DEST_PATH_IMAGE001
As can be seen from Table 1, the high energy storage density composite dielectric material prepared by the invention effectively solves the problems of low breakdown strength, low dielectric constant and low energy storage density of the traditional dielectric ceramic material.

Claims (8)

1. A preparation method of a high energy storage density composite dielectric material is characterized by comprising the following specific preparation steps:
(1) placing polyvinylidene fluoride, fluorinated graphene, nano boron nitride, glycerol, sodium stearate and an antioxidant 1010 in a high-speed stirrer, and stirring and mixing at the rotating speed of 2000-2400 r/min for 40-60 min at normal temperature to obtain a mixture;
(2) placing the mixture in a double-screw extruder, extruding and granulating at 220-260 ℃, and cooling at normal temperature to obtain composite granules;
(3) and (3) placing the composite granules into an injection molding machine for injection molding, and cooling at normal temperature to obtain the high-energy-storage-density composite dielectric material.
2. The method for preparing a composite dielectric material with high energy storage density according to claim 1, wherein the polyvinylidene fluoride, the fluorinated graphene, the nano boron nitride, the glycerol, the sodium stearate and the antioxidant 1010 are 100-200 parts by weight of polyvinylidene fluoride, 20-40 parts by weight of fluorinated graphene, 8-10 parts by weight of nano boron nitride, 4-8 parts by weight of glycerol, 2-4 parts by weight of sodium stearate and 0.2-0.4 part by weight of the antioxidant 1010.
3. The method for preparing a composite dielectric material with high energy storage density according to claim 1, wherein the injection molding in the step (3) is performed under the conditions of temperature 180-200 ℃ and pressure 20-40 MPa.
4. The method for preparing the composite dielectric material with high energy storage density according to claim 1, wherein the specific preparation steps of the fluorinated graphene in the step (1) are as follows:
(1) placing the graphene powder and the xenon difluoride powder in a high-speed stirrer, and stirring and mixing at the normal temperature at the rotating speed of 1600-1800 r/min for 30-40 min to obtain mixed powder;
(2) and placing the mixed powder in a tubular atmosphere furnace, introducing nitrogen for protection, calcining for 20-24 hours at 180-200 ℃, and cooling to room temperature along with the furnace to obtain the fluorinated graphene.
5. The method for preparing the high energy storage density composite dielectric material according to claim 4, wherein the graphene powder and the xenon difluoride powder are 10-20 parts by weight and 20-40 parts by weight.
6. The method for preparing a composite dielectric material with high energy storage density according to claim 4, wherein the nitrogen gas in the step (2) is introduced at a rate of 120-160 mL/min.
7. The method for preparing the composite dielectric material with high energy storage density according to claim 4, wherein the specific preparation steps of the graphene powder are as follows:
(1) slowly adding sulfuric acid into a container filled with graphite flakes at a speed of 40-60 mL/min, and stirring at a rotating speed of 120-160 r/min for 10-15 min at a temperature of 0-4 ℃ to obtain a graphite flake sulfuric acid mixed solution;
(2) slowly adding potassium permanganate powder into the graphite flake sulfuric acid mixed solution for 60-90 min, and stirring and oxidizing for 2-4 h at 180-200 r/min under the condition of water bath at 40-50 ℃ to obtain a reaction solution;
(3) slowly adding deionized water into the reaction solution at the speed of 80-100 mL/min, placing the reaction solution at the temperature of 0-4 ℃, adding hydrogen peroxide, placing the reaction solution in a centrifuge, centrifugally separating the reaction solution at the rotating speed of 4500-5500 r/min for 10min, taking lower-layer solid, washing the lower-layer solid to be neutral by using the deionized water, and drying the lower-layer solid in the shade at normal temperature to obtain graphene oxide;
(4) placing graphene oxide in a tubular atmosphere furnace, introducing argon for protection, calcining for 1-2 hours at 1000-1100 ℃, and cooling to room temperature along with the furnace to obtain graphene powder.
8. The method according to claim 7, wherein the method comprises the following steps:
(1) the graphite flake, the sulfuric acid, the potassium permanganate powder, the hydrogen peroxide and the deionized water are 10-20 parts by weight of the graphite flake, 40-80 parts by weight of 10% sulfuric acid, 15-30 parts by weight of the potassium permanganate powder, 20-40 parts by weight of the hydrogen peroxide and 400-800 parts by weight of the deionized water;
(2) and (4) introducing the argon at a rate of 180-200 mL/min.
CN202010348702.4A 2020-04-28 2020-04-28 Preparation method of high-energy-storage-density composite dielectric material Pending CN111619030A (en)

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