CN108878145B - Preparation method of dielectric material for high-energy-storage capacitor - Google Patents
Preparation method of dielectric material for high-energy-storage capacitor Download PDFInfo
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- CN108878145B CN108878145B CN201810557674.XA CN201810557674A CN108878145B CN 108878145 B CN108878145 B CN 108878145B CN 201810557674 A CN201810557674 A CN 201810557674A CN 108878145 B CN108878145 B CN 108878145B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/16—Organic dielectrics of fibrous material, e.g. paper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
Abstract
The invention discloses a preparation method of a dielectric material for a high energy storage capacitor, which relates to the technical field of dielectric materials, and the preparation method comprises the steps of taking polyaniline coated with inorganic nano particles as a filler, taking polyvinylidene fluoride as a polymer matrix, taking metal Ni as a load, firstly carrying out surface modification on the inorganic nano particles by adopting a method of combining physical ball milling and a chemical surfactant, then coating the polyaniline on the surfaces of the inorganic nano particles by adopting a supercritical fluid reaction to prepare a composite filler, spinning the composite filler and the polyvinylidene fluoride into a fiber membrane by adopting melt electrostatic spinning, and finally loading the metal Ni on the composite fiber membrane with the polyvinylidene fluoride by adopting magnetron sputtering, wherein the loading of the metal Ni is not only beneficial to filling the higher porosity of the fiber membrane prepared by the electrostatic spinning method, but also beneficial to keeping the higher breakdown field intensity and energy storage density of the dielectric material, the dielectric constant is improved, the dielectric loss is reduced, and the prepared composite dielectric material has high energy storage performance.
Description
Technical Field
The invention belongs to the technical field of dielectric materials, relates to the technical field of dielectric materials for high energy storage capacitors, and particularly relates to a preparation method of a dielectric material for a high energy storage capacitor.
Background
Dielectric materials store energy in the form of static electricity and have very important applications in the information, electronics and power industries. With the rapid development of the electronic industry, the research and development and application of polymer-based composite materials with high dielectric constant, low dielectric loss, low cost and easy processing are receiving more and more attention. In the field of electrical engineering, the polymer-based composite material can be used as a dielectric material for a high energy storage density capacitor; in the field of microelectronics, by selecting a proper polymer matrix, a high-capacitance embedded micro-capacitor can be prepared on a large scale, so that the high-speed and safe operation of an integrated circuit is ensured. However, the polymer dielectric material has the defects of lower dielectric constant and lower breakdown strength than a ceramic material, and can be widely applied only by preparing a polymer-based composite dielectric material by matching dielectric fillers.
The inorganic ceramic material has high dielectric constant and high thermal stability, but the application of the inorganic ceramic material is limited by the defects of complex preparation process, brittleness, large dielectric loss, poor compatibility with the current circuit integrated processing technology and the like. However, the dielectric constant of the polymer dielectric material can be effectively improved by adding the ceramic material into the polymer dielectric material and utilizing the interfacial polarization between the ceramic alloy and the polymer. The metal ions have good conductivity, the dielectric property of the polymer dielectric material can be effectively improved by adding a small amount of conductive particles into the polymer dielectric material, the conductivity of the carbon material particles is higher, the dielectric constant of the polymer can be greatly improved by using a lower amount of the conductive particles, but the inorganic ceramic material, the metal particles or the carbon material particles have the defect of easy agglomeration in a matrix, so that the improvement of the compatibility of the filler and the polymer is the key point of the research of the polymer-based dielectric material at present.
Disclosure of Invention
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a dielectric material for a high energy storage capacitor comprises the following specific steps:
1) placing the inorganic nanoparticles and surfactant in a high-speed ball mill, ball-milling for modification for 15-25min, adding the modified inorganic nanoparticles, aniline and initiator into a high-pressure reaction kettle, and adopting supercritical CO2Carrying out polymerization reaction by a fluid technology to obtain a composite filler;
2) vacuum drying the composite filler and polyvinylidene fluoride at 60-70 ℃ for 80-90min, and preparing the polyvinylidene fluoride composite fiber membrane by adopting a melt electrostatic spinning method after drying;
3) and loading metal Ni on the surface of the prepared vinylidene fluoride composite fiber film by adopting a magnetron sputtering method.
2. The method for preparing the dielectric material for high energy storage capacitor as claimed in claim 1, wherein the nano inorganic particles are ZnO and Al2O3Any one of AlN, graphene, or carbon nanotubes.
Preferably, the surfactant is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate, the addition method adopts an atomization spraying method, and the addition amount is 0.8-1.5% of the mass of the nano inorganic particles.
Preferably, the rotation speed of the ball milling is 4000-.
Preferably, the mass ratio of the inorganic nanoparticles to the aniline to the initiator in the composite filler is 0.15-0.35:1: 0.01-0.015.
Preferably, the supercritical CO2The conditions of the fluid technology are that the reaction pressure is 5-10MPa, the temperature is 50-65 ℃, and the reaction time is 3.5-4 h.
Preferably, the melt electrostatic spinning conditions are that the temperature is 280-350 ℃, the advancing speed is 0.3-0.8mm/min, the rotating speed of the roller is 100-130r/min, the vertical distance between the spray head and the flat plate receiver is 10-18cm, the diameter of the spray head is 0.3-0.5mm, and the applied voltage is 10-15 kV.
Preferably, the magnetron sputtering is performed under the condition that the vacuum degree is 5 × 10-4-8×10-4Pa, 99.999 percent of argon as working gas, 8-17mL/min of gas flow, 0.6-0.9Pa of working pressure, 50-75w of sputtering power and 80-100s of sputtering time.
Preferably, the dielectric material for the high energy storage capacitor comprises the following components in parts by weight: 5-15 parts of composite filler, 100 parts of polyvinylidene fluoride and 10-18 parts of metal Ni.
Preferably, the dielectric material for the high energy storage capacitor comprises the following components in parts by weight: 10 parts of composite filler, 100 parts of polyvinylidene fluoride and 15 parts of metal Ni.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts physical ball milling and chemical surfactant to modify the surface of the inorganic nanoparticles, improves the surface activity of the inorganic nanoparticles, improves the dispersibility of the inorganic nanoparticles, meanwhile, trims the shape and the size of the inorganic nanoparticles to ensure that the particles are more uniform, and adopts supercritical fluid technology to perform repolymerization on the inorganic nanoparticles by aniline, thereby being beneficial to increasing the polymer phase interface, improving the dielectric constant, shortening the polymerization reaction time and improving the production efficiency.
2. The method adopts a magnetron sputtering method to load metal Ni on the vinylidene fluoride composite fiber membrane, the magnetron sputtering has directionality, the adhesion of the Ni on the vinylidene fluoride composite fiber membrane can be increased, the equipment is simple and easy to control, no chemical reagent is used, and the method is green, environment-friendly and pollution-free.
3. The dielectric material prepared by the invention adopts the polyvinylidene fluoride filled with the composite filler prepared by melt electrostatic spinning, the nanofiber membrane prepared by the electrostatic spinning method has the advantages of simple equipment, low cost, easy operation, high efficiency and the like, and Ni is loaded on the vinylidene fluoride composite fiber membrane by adopting a magnetron sputtering mode, so that the higher porosity of the fiber membrane prepared by the electrostatic spinning method is favorably filled, the higher breakdown field intensity and the energy storage density of the dielectric material are favorably maintained, the dielectric constant is improved, and the dielectric loss is reduced.
Detailed Description
The following embodiments are described in further detail to help those skilled in the art to more fully, accurately and deeply understand the inventive concept and technical solutions of the present invention.
Example 1
The preparation method of the dielectric material for the high energy storage capacitor in the embodiment comprises the following specific steps:
1) placing nano ZnO particles in a high-speed ball mill, dissolving sodium dodecyl benzene sulfonate with the addition of 1.25 percent of the mass of the nano ZnO particles in deionized water with the volume of 2 times of the mass of the nano ZnO particles, stirring the mixture till the mixture is completely dissolved, putting the mixture into an atomizer, firstly adjusting the high-speed ball mill to a low rotating speed of 100r/min, spraying a sodium dodecyl benzene sulfonate solution on the surfaces of the nano ZnO particles under the condition of rotating the ball mill, then adjusting the rotating speed of the high-speed ball mill to 4500r/min for ball milling pretreatment for 20min, naturally ventilating and drying, then adding the modified nano ZnO particles, aniline and ammonium persulfate initiator into a high-pressure reaction kettle, firstly introducing a small amount of CO, and then introducing a small amount2Discharging internal air, pumping CO into high pressure metering pump2When the pressure is 7.5MPa, the air inlet valve is closed, the magnetic stirrer is started, and the temperature is raised to 60 ℃ at the same time, and supercritical CO is carried out2Reacting the fluid for 4 hours to obtain the composite filler, wherein the mass ratio of the nano ZnO particles to the aniline to the ammonium persulfate is 0.2:1: 0.012;
2) vacuum drying the composite filler prepared in the step (1) and polyvinylidene fluoride at 65 ℃ for 85min, placing 10 parts of composite filler and 100 parts of polyvinylidene fluoride into a charging barrel of a melt electrostatic spinning instrument after drying, taking tinfoil as a receiving electrode, meanwhile, the tinfoil is placed on an aluminum plate which plays a supporting role to form a flat plate receiver, during spinning, when the temperature of a heating instrument is 330 ℃, feeding is started, the advancing speed of the feeding is 0.5mm/min, the rotating speed of a roller is 110r/min, the diameter of a spray head is 0.4mm, the vertical distance between the spinning spray head and the flat plate receiver is 13cm, applying voltage 12kV between the spray head and the flat plate receiver, respectively connecting the positive and negative electrodes of the power supply to the spray head and the flat plate receiver, spinning for 1.5h, after spinning, placing the vinylidene fluoride composite fiber membrane in a vacuum drying oven, and carrying out heat treatment for 10 hours at the temperature of 60 ℃ to obtain the vinylidene fluoride composite fiber membrane with the thickness of about 15 mu m;
3) putting the vinylidene fluoride composite fiber film with the thickness of 15 mu m prepared in the step (2) into a sample vacuum sputtering chamber, and pumping the pressure in the vacuum sputtering chamber to 7 x 10 by using a vacuum pump-4Pa, flushing argon with the purity of 99.999 percent into the vacuum sputtering chamber at the flow rate of 10mL/min, keeping the pressure in the vacuum sputtering chamber at 0.75Pa, enabling 15 parts of Ni metal to be positioned at the position of the target surface right above the sample container, enabling the direct-current sputtering power to be 60w, carrying out single-side Ni sputtering for 100s in the environment, finishing the sputtering, standing for 20min, and taking out the Ni-loaded vinylidene fluoride composite fiber membrane.
Example 2
This example is the same as example 1, except that the inorganic nanoparticles in this example are Al2O3The surfactant is sodium dodecyl sulfate, the addition amount is 0.8 percent of the mass of the nano ceramic particles, and the magnetron sputtering condition is that the vacuum degree is 5 multiplied by 10- 4Pa, gas flow rate of 8mL/min, working pressure of 0.6Pa, sputtering power of 50w and sputtering time of 80 s.
Example 3
This example is the same as example 1, except that in this example, the amount of the added surfactant is 1.5% of the mass of the nano-ceramic particles, the mass ratio of the nano-inorganic particles, the aniline, and the initiator is 0.35:1:0.015, and the magnetron sputtering condition is a vacuum degree of 8 × 10-4Pa, gas flow rate of 17mL/min, working pressure of 0.9Pa, sputtering power of 75w and sputtering time of 100 s.
Example 4
This example is the same as example 1 except that the electrostatic spinning conditions in this example were 350 ℃, a forwarding speed of 0.8mm/min, a drum rotation speed of 130r/min, a vertical distance between the nozzle and the plate receiver of 18cm, a nozzle diameter of 0.3mm, and an applied voltage of 15 kV.
The present invention has been described in connection with the embodiments, and it is to be understood that the invention is not limited to the specific embodiments described above, and that various insubstantial modifications of the inventive concepts and solutions, or their direct application to other applications without modification, are intended to be covered by the scope of the invention. The protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (8)
1. A preparation method of a dielectric material for a high energy storage capacitor is characterized by comprising the following specific steps:
1) placing the inorganic nanoparticles and surfactant in a high-speed ball mill, ball-milling for modification for 15-25min, adding the modified inorganic nanoparticles, aniline and initiator into a high-pressure reaction kettle, and adopting supercritical CO2Carrying out polymerization reaction by a fluid technology to obtain a composite filler;
2) vacuum drying the composite filler and polyvinylidene fluoride at 60-70 ℃ for 80-90min, and preparing the polyvinylidene fluoride composite fiber membrane by adopting a melt electrostatic spinning method after drying;
3) loading metal Ni on the surface of the prepared vinylidene fluoride composite fiber membrane by adopting a magnetron sputtering method, wherein the melt electrostatic spinning condition is that the temperature is 280-350 ℃, the propelling speed is 0.3-0.8mm/min, the rotating speed of a roller is 100-130r/min, the vertical distance between a spray head and a flat plate receiver is 10-18cm, the diameter of the spray head is 0.3-0.5mm, and the applied voltage is 10-15 kV;
the magnetron sputtering condition is that the vacuum degree is 5 multiplied by 10-4-8×10-4Pa, 99.999 percent of argon as working gas, 8-17mL/min of gas flow, 0.6-0.9Pa of working pressure, 50-75w of sputtering power and 80-100s of sputtering time.
2. The method for preparing the dielectric material for high energy storage capacitor as claimed in claim 1, wherein the nano inorganic particles are ZnO and Al2O3Any one of AlN, graphene, or carbon nanotubes.
3. The method for preparing the dielectric material for the high energy storage capacitor as claimed in claim 1, wherein the surfactant is sodium dodecylbenzene sulfonate or sodium dodecylbenzene sulfonate, the addition method is an atomized spraying method, and the addition amount is 0.8-1.5% of the mass of the inorganic nanoparticles.
4. The method as claimed in claim 1, wherein the ball milling speed is 4000-.
5. The method for preparing the dielectric material for the high energy storage capacitor as claimed in claim 1, wherein the mass ratio of the inorganic nanoparticles, aniline and initiator in the composite filler is 0.15-0.35:1: 0.01-0.015.
6. The method for preparing a dielectric material for high energy storage capacitors as claimed in claim 1, wherein the supercritical CO is2The conditions of the fluid technology are that the reaction pressure is 5-10MPa, the temperature is 50-65 ℃, and the reaction time is 3.5-4 h.
7. The method for preparing the dielectric material for the high energy storage capacitor as claimed in claim 1, wherein the dielectric material for the high energy storage capacitor comprises the following components in parts by weight: 5-15 parts of composite filler, 100 parts of polyvinylidene fluoride and 10-18 parts of metal Ni.
8. The method for preparing the dielectric material for the high energy storage capacitor as claimed in claim 1, wherein the dielectric material for the high energy storage capacitor comprises the following components in parts by weight: 10 parts of composite filler, 100 parts of polyvinylidene fluoride and 15 parts of metal Ni.
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| CN113471399B (en) * | 2021-06-24 | 2022-11-01 | 湖北工程学院 | Preparation method and application of high-conductivity Si/C nano-film |
| CN114163815B (en) * | 2021-12-24 | 2024-01-23 | 上海海事大学 | Composite material and preparation method thereof |
| CN115521605A (en) * | 2022-09-29 | 2022-12-27 | 五邑大学 | Porous dielectric material, preparation method and light capacitive pressure sensor |
| CN116333434B (en) * | 2023-03-17 | 2023-10-27 | 中国海洋大学 | Polyvinylidene fluoride dielectric composite material based on gold/glass fiber cloth |
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| JPH01200509A (en) * | 1988-02-03 | 1989-08-11 | Matsushita Electric Ind Co Ltd | High dielectric material and capacitor using high dielectric material |
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