CN107652588B - Ferroelectric polymer based dielectric film, preparation method and application thereof - Google Patents
Ferroelectric polymer based dielectric film, preparation method and application thereof Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/20—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06
- H01G4/206—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06 inorganic and synthetic material
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention relates to a ferroelectric polymer-based dielectric film, a preparation method and application thereof. The ferroelectric polymer-based dielectric film contains vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) and inorganic matter AlOOH, wherein the proportion of the VDF-co-HFP-x% AlOOH is (100-x)% P (VDF-co-HFP) -x% AlOOH in volume percentage, and x is less than or equal to 0 and less than or equal to 10. The ferroelectric polymer-based dielectric film has high breakdown field strength, high energy storage density, high energy storage efficiency, no lead, environmental protection and excellent energy storage performance, and is suitable for the field of high-density energy storage.
Description
Technical Field
The invention relates to a ferroelectric polymer-based dielectric film, a preparation method and application thereof, belonging to the field of dielectric materials.
Background
The dielectric capacitor is a main passive energy storage device, has high charging and discharging speed and ultrahigh power density, is widely applied to electronic circuits, and can realize the functions of direct connection isolation, direct connection, coupling, bypass, filtering, tuning loop, energy conversion and the like. However, its lower energy storage density is a bottleneck for its further development and application. The energy storage density of current commercial polymer-based dielectric materials such as BOPP is only 2J/cm3One to two orders of magnitude lower than electrochemical capacitors or batteries. Therefore, the search for dielectric materials with high energy storage density has been a research focus in the field.
The ceramic dielectric medium has large dielectric constant and higher breakdown field intensity, but compared with the polymer film dielectric medium, the breakdown field intensity is not high enough, and the polymer film dielectric medium has large volume and non-flexibility, so that the ceramic dielectric medium is limited in some application fields, and the polymer-based dielectric medium film has the characteristics of flexibility, small volume and the like, and can meet the requirements of miniaturization, integration and the like of future devices.
Greater than 2J/cm for commercial BOPP films have been achieved in polymer-based dielectric films3The energy storage density of (1). Representative materials are: the material has the energy storage density of about 7-10J/cm under the field strength of 400MV/m3M.R.Gadinski and B.Chu et al respectively increase the breakdown field strength of such films to 600-700 MV/m by uniaxial tension method, and increase the energy storage density to 20J/cm3Left and right. However, the solution method adopted in the preparation process of the materials is not suitable for being applied to large-scale production. Therefore, the development of polymer-based dielectric thin film dielectric materials having high breakdown field strength, high energy storage density, and easy production is currently an urgent task in the art.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a ferroelectric polymer-based dielectric film, and a preparation method and application thereof. The ferroelectric polymer-based dielectric film has high breakdown field strength, high energy storage density and high energy storage efficiency, and the preparation method is simple and feasible and is convenient to produce.
Means for solving the problems
The invention provides a ferroelectric polymer-based dielectric film, which contains vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) and inorganic matter AlOOH, wherein the proportion of the VDF-co-HFP-x% AlOOH is (100-x)% P (VDF-co-HFP) -x% AlOOH in volume percentage, and x is more than 0 and less than or equal to 10.
According to the ferroelectric polymer-based dielectric thin film, the thickness of the thin film is 5-30 μm, and preferably 6-20 μm.
According to the ferroelectric polymer-based dielectric thin film, the morphology of the inorganic matter AlOOH is two-dimensional layered.
The present invention also provides a method for preparing a ferroelectric polymer-based dielectric thin film according to the present invention, characterized by comprising the steps of:
step 1), carrying out hydrothermal reaction on an alkaline solution containing Al salt to obtain an inorganic AlOOH;
step 2), mixing the inorganic matter AlOOH and the vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) in an organic solvent according to a ratio to obtain an electrostatic spinning solution;
step 3), carrying out high-voltage electrostatic spinning on the electrostatic spinning solution to obtain a non-woven fabric-shaped spinning body;
and 4), carrying out hot pressing on the non-woven fabric-shaped spinning body, naturally cooling to room temperature, and then carrying out cold quenching to obtain the ferroelectric polymer-based dielectric film.
According to the preparation method of the ferroelectric polymer-based dielectric thin film of the present invention, the pH of the alkaline solution in the step 1) is > 8.
According to the preparation method of the ferroelectric polymer-based dielectric film, in the step 1), a hydrothermal reaction is carried out at the temperature of 150-240 ℃ for 2-24 hours.
According to the preparation method of the ferroelectric polymer-based dielectric film, in the step 3), the positive-negative voltage difference of the high-voltage electrostatic spinning is more than or equal to 5kV, the rotating speed of the collecting wheel is more than or equal to 200 rpm, and the solution propelling speed is more than or equal to 1 mL/h.
According to the preparation method of the ferroelectric polymer-based dielectric film, in the step 4), the non-woven fabric-shaped spinning body is hot-pressed for 20-100 minutes at 100-500 ℃ and under the pressure of 400-600 dpi.
According to the preparation method of the ferroelectric polymer-based dielectric film, the non-woven fabric-shaped spinning body is subjected to hot pressing, naturally cooled to room temperature, kept at 150-250 ℃ for 2-20 minutes, and then subjected to cold quenching at 0 ℃.
Use of a ferroelectric polymer based dielectric thin film according to the invention in an electrical component.
ADVANTAGEOUS EFFECTS OF INVENTION
The ferroelectric polymer-based dielectric film provided by the invention has the advantages of high breakdown field strength, high energy storage density, high energy storage efficiency, no lead, environmental protection, excellent energy storage performance and suitability for high-density energy storage. Meanwhile, the ferroelectric polymer-based dielectric film provided by the invention has smaller dielectric loss, and is a material which can be applied to various electric elements, such as embedded capacitors, electrostatic energy storage components, pulse power elements and other fields.
Drawings
Fig. 1 is a schematic diagram of a polymer-based dielectric capacitor.
FIG. 2 Transmission Electron Microscopy (TEM) image of inorganic AlOOH prepared in example 1
Figure 3 XRD pattern of inorganic AlOOH prepared in example 1.
Fig. 4 energy storage densities of the polymer-based dielectric thin films prepared in example 1 and comparative example 1.
FIG. 5-1 dielectric constant of Polymer-based dielectric films prepared in example 1 and comparative example 1
Fig. 5-2 dielectric loss of the polymer-based dielectric films prepared in example 1 and comparative example 1.
Description of the reference numerals
1-dielectric capacitor, 2-electrode, 3-polymer-based dielectric thin film
Detailed Description
The invention provides a ferroelectric polymer-based dielectric film, which contains vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) and an inorganic matter AlOOH, wherein the proportion of the VDF-co-HFP-x% AlOOH is (100-x)% P (VDF-co-HFP) -x% AlOOH in volume percentage, 0< x > is less than or equal to 10, preferably 1-5, and the ferroelectric polymer has good flexibility in the range.
Compared with other ferroelectric polymers, such as PVDF and the like, P (VDF-co-HFP) generated by copolymerizing hexafluoropropylene HFP monomer and vinylidene fluoride VDF has a narrower hysteresis loop, and is an excellent substitute for PVDF which is a fluorine-containing ferroelectric polymer.
The invention improves the breakdown environment in the ferroelectric polymer by adding the inorganic matter AlOOH, and can achieve the purpose of improving the breakdown field strength of the ferroelectric polymer. The breakdown field strength of the ferroelectric polymer-based dielectric film of the present invention is 400kV/mm or more at room temperature, and when x is more preferably 1< x <3, the breakdown field strength of the ferroelectric polymer-based dielectric film of the present invention is 600kV/mm or more at room temperature.
The ferroelectric polymer-based dielectric film has the thickness of 5-30 micrometers, preferably 6-20 micrometers, and the thickness range is better matched with existing film preparation equipment and processes mature in the industry.
The ferroelectric polymer-based dielectric film disclosed by the invention has the advantages that the appearance of the inorganic AlOOH in the film is in a two-dimensional layer shape, and the appearance is favorable for improving the breakdown field strength of the film, so that the energy storage density is increased. The distribution state of inorganic AlOOH in the ferroelectric polymer can be regulated and controlled by regulating and controlling the spinning process and the hot pressing process, so that the adjustability of the energy storage density is realized.
The energy storage density of the ferroelectric polymer-based dielectric film at room temperature is more than 5J/cm3Preferably 21 to 26J/cm3. Polymers with inorganic additions have higher dielectric constants than pure ferroelectric polymers while losses remain substantially unchanged.
The invention also provides a preparation method of the ferroelectric polymer-based dielectric film, which comprises the following steps:
step 1), carrying out hydrothermal reaction on an alkaline solution containing Al salt to obtain an inorganic AlOOH;
step 2), mixing the inorganic matter AlOOH and the vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) in an organic solvent according to a ratio to obtain an electrostatic spinning solution;
step 3), carrying out high-voltage electrostatic spinning on the electrostatic spinning solution to obtain a non-woven fabric-shaped spinning body;
and 4), carrying out hot pressing on the non-woven fabric-shaped spinning body, naturally cooling to room temperature, and then carrying out cold quenching to obtain the ferroelectric polymer-based dielectric film.
The preparation method of the ferroelectric polymer-based dielectric thin film of the present invention, wherein the pH of the alkaline solution in the step 1) is preferably > 8. Meanwhile, in the step 1), the hydrothermal reaction is carried out at the temperature of 150-240 ℃ for 2-24 hours.
The preparation method of the ferroelectric polymer-based dielectric film comprises the following steps of 1), washing a reaction product to be neutral after hydrothermal reaction, and drying.
The preparation method of the ferroelectric polymer-based dielectric film comprises the step 2), stirring and mixing for 12-24 hours for uniform mixing.
The preparation method of the ferroelectric polymer-based dielectric film comprises the step 2) of using acetone, N-Dimethylformamide (DMF) or N, N-Dimethylacetamide (DMA) as an organic solvent.
The preparation method of the ferroelectric polymer-based dielectric film adopts an electrostatic spinning method, which is beneficial to preparing the polymer film with a special multilayer structure, wherein in the step 3), the positive-negative voltage difference of high-voltage electrostatic spinning is more than or equal to 5kV, the rotating speed of a collecting wheel is more than or equal to 200 r/min, and the solution propelling speed is more than or equal to 1 mL/h. The ratio of the solute (g) to the solution (ml) is in the range of 1: 4.12-1: 7.83.
The preparation method of the ferroelectric polymer-based dielectric film comprises the step 4), wherein the non-woven fabric-shaped spinning body is hot-pressed for 20-100 minutes at 100-500 ℃ and under the pressure of 400-600 dpi.
The preparation method of the ferroelectric polymer-based dielectric film comprises the steps of carrying out hot pressing on the non-woven fabric-shaped spinning body, naturally cooling to room temperature, carrying out heat preservation at 150-250 ℃ for 2-20 minutes, and carrying out cold quenching at 0 ℃, so that the polymer can obtain better energy storage density.
The invention also provides the application of the ferroelectric polymer-based dielectric film in electric appliance elements. The electrical element is an embedded capacitor, an electrostatic energy storage component or a pulse power element.
Examples
Example 1
Respectively mixing AlCl3·6H2O、NaOH、NH3OH was prepared as a 1M solution in deionized water, then NaOH and NH3Gradually and slowly dropping AlCl into OH mixed solution3In the solution, the solution is transferred to a reaction kettle with a polytetrafluoroethylene lining until the pH value of the solution is 10, the solution is kept at the temperature of 200 ℃ for 17 hours, precipitates are obtained after natural cooling, the precipitates are repeatedly washed by deionized water and ethanol until the pH value is neutral, the dried precipitates are mixed according to 98.32 vol% P (VDF-co-HFP) -1.68 vol% AlOOH (x is 1.68), and acetone is used as a solvent to be stirred for 12 hours to prepare spinning solution for standby. The ratio of solute (g) to solution (ml) was in the range of 1: 5.
The uniform spinning body of the polymer nano-filament is prepared by adopting high-voltage electrostatic spinning. The parameters of the high-voltage electrostatic spinning are as follows: the positive and negative voltage difference is 6 kV; the roller speed was 300 rpm and the solution advancing speed was 1mL per hour.
After spinning, the film is hot pressed for 60 minutes at 200 ℃ and 500dpi, and then is naturally cooled to room temperature. And (3) keeping the temperature of the hot-pressed film at 240 ℃ for 10 minutes, and then performing cold quenching at 0 ℃ to obtain the ferroelectric polymer based dielectric film, which is marked as film-1.
The thickness of the obtained film-1 was about 10 μm, and the properties of the polymer-based dielectric film at 25 ℃ were: under 1KHz, the dielectric constant and dielectric loss are respectively 10 and 0.04, the breakdown field strength is 615kV/mm, and the energy storage density is 24J/cm3。
Example 2
Respectively mixing AlCl3·6H2O、NaOH、NH3OH was prepared as a 1M solution in deionized water, then NaOH and NH3Gradually and slowly dropping AlCl into OH mixed solution3In the solution, the solution is transferred to a reaction kettle with a polytetrafluoroethylene lining until the pH value of the solution is 10, the solution is kept at the temperature of 200 ℃ for 17 hours, precipitates are obtained after natural cooling, the precipitates are repeatedly washed by deionized water and ethanol until the pH value is neutral, the dried precipitates are mixed according to 90 vol% P (VDF-co-HFP) -10 vol% AlOOH (x is 10), and the mixture is stirred for 12 hours by taking acetone as a solvent to prepare spinning solution for standby. The ratio of solute (g) to solution (ml) was in the range of 1: 5.
The uniform spinning body of the polymer nano-filament is prepared by adopting high-voltage electrostatic spinning. The parameters of the high-voltage electrostatic spinning are as follows: the positive and negative voltage difference is 6 kV; the roller speed was 300 rpm and the solution advancing speed was 1mL per hour. After spinning, the film is hot pressed for 60 minutes at 200 ℃ and 500dpi pressure, and then naturally cooled to room temperature. And (3) keeping the temperature of the hot-pressed film at 240 ℃ for 10 minutes, and then performing cold quenching at 0 ℃ to obtain the ferroelectric polymer based dielectric film, which is marked as film-2.
The thickness of the resulting film-2 was about 9.8 μm, and the properties of the polymer-based dielectric film at 25 ℃ were: at 1KHz, the dielectric constant and dielectric loss were 16 and0.047, breakdown field strength of 620kV/mm, and energy storage density of 13J/cm3。
Example 3
Respectively mixing AlCl3·6H2O、NaOH、NH3OH was prepared as a 1M solution in deionized water, then NaOH and NH3Gradually and slowly dropping AlCl into OH mixed solution3In the solution, the solution is transferred to a reaction kettle with a polytetrafluoroethylene lining until the pH value of the solution is 10, the solution is kept at the temperature of 200 ℃ for 17 hours in an oven, precipitates are obtained after natural cooling, the precipitates are repeatedly washed by deionized water and ethanol until the pH value is neutral, the dried precipitates are mixed according to 93 vol% P (VDF-co-HFP) -7 vol% AlOOH (x is 7), and the mixture is stirred for 12 hours by taking acetone as a solvent to prepare spinning solution for standby. The ratio of solute (g) to solution (ml) was in the range of 1: 5.
The uniform spinning body of the polymer nano-filament is prepared by adopting high-voltage electrostatic spinning. The parameters of the high-voltage electrostatic spinning are as follows: the positive and negative voltage difference is 6 kV; the rotating speed of the roller is 300 r/min, after the spinning of 1mL of solution per hour is finished, the film is hot-pressed for 60 minutes at 200 ℃ and 500dpi pressure, and then the temperature is naturally reduced to the room temperature. And (3) keeping the temperature of the hot-pressed film at 240 ℃ for 10 minutes, and then performing cold quenching at 0 ℃ to obtain the ferroelectric polymer based dielectric film, which is marked as film-3.
The thickness of the resulting film-3 was about 10.65 μm, and the properties of the polymer-based dielectric film at 25 ℃ were: under 1KHz, the dielectric constant and dielectric loss are respectively 21 and 0.04, the breakdown field strength is 469kV/mm, and the energy storage density is 9.7J/cm3。
Comparative example 1
After mixing the purchased P (VDF-co-HFP) powder with 5 ml of a mixed organic solvent (a mixture of acetone and Dimethylformamide (DMF)) per gram of solute, it was stirred at room temperature for 12 to 24 hours to be sufficiently dissolved. The uniform spinning body of the polymer nano-filament is prepared by adopting high-voltage electrostatic spinning. The parameters of the high-voltage electrostatic spinning are as follows: the positive and negative voltage difference is 6 kV; the roller speed was 300 rpm and the solution advancing speed was 1mL per hour. After spinning, the film is hot pressed for 60 minutes at 200 ℃ and 500dpi pressure, and then naturally cooled to room temperature. And (3) keeping the temperature of the hot-pressed film at 240 ℃ for 10 minutes, and then performing cold quenching at 0 ℃ to obtain the ferroelectric polymer based dielectric film, which is marked as film-4.
The thickness of the obtained film-4 was about 10 μm, and the properties of the polymer-based dielectric film at 25 ℃ were: under 1KHz, dielectric constant and dielectric loss are respectively 9 and 0.03, breakdown field strength is about 400kV/mm, and energy storage density is 7.8J/cm3。
Performance testing
Preparing a metal round electrode on the sample film-1-4 by a vacuum evaporation method, and testing each performance of the metal round electrode.
Dielectric properties: the test was performed using an impedance analyzer (agilent, E4990A, usa).
Breakdown field strength and ferroelectric hysteresis loop: the test is performed by using a ferroelectric tester (radiation tech., Precision premieri), and the energy storage density and the energy storage efficiency are calculated by an electric hysteresis loop.
Claims (9)
1. The ferroelectric polymer-based dielectric film is characterized by comprising vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) and an inorganic matter AlOOH, wherein the proportion of the VDF-co-HFP-x% AlOOH is (100-x)% P (VDF-co-HFP) -x% AlOOH, x is less than or equal to 0 and less than or equal to 10 in percentage by volume, and the thickness of the film is 5-30 mu m; the breakdown field strength of the ferroelectric polymer-based dielectric film at room temperature is more than or equal to 400 kV/mm; the appearance of the inorganic matter AlOOH is two-dimensional layered.
2. A ferroelectric polymer-based dielectric thin film as defined in claim 1, wherein the thin film has a thickness of 6 to 20 μm.
3. A method for preparing a ferroelectric polymer-based dielectric thin film according to claim 1 or 2, comprising the steps of: step 1), carrying out hydrothermal reaction on an alkaline solution containing Al salt to obtain an inorganic AlOOH;
step 2), mixing the inorganic matter AlOOH and the vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) in an organic solvent according to a ratio to obtain an electrostatic spinning solution;
step 3), carrying out high-voltage electrostatic spinning on the electrostatic spinning solution to obtain a non-woven fabric-shaped spinning body;
and 4), carrying out hot pressing on the non-woven fabric-shaped spinning body, naturally cooling to room temperature, and then carrying out cold quenching to obtain the ferroelectric polymer-based dielectric film.
4. A method for preparing a ferroelectric polymer-based dielectric thin film as in claim 3, wherein the pH of the alkaline solution in said step 1) is > 8.
5. A method for preparing a ferroelectric polymer-based dielectric thin film as in claim 3 or 4, wherein in said step 1), the hydrothermal reaction is carried out at 150 to 240 ℃ for 2 to 24 hours.
6. The method for preparing a ferroelectric polymer-based dielectric thin film as claimed in claim 3 or 4, wherein in the step 3), the voltage difference between positive and negative of the high voltage electrostatic spinning is not less than 5kV, the rotation speed of the collecting wheel is not less than 200 rpm, and the solution propelling speed is not less than 1 mL/h.
7. A method for preparing a ferroelectric polymer-based dielectric thin film as in claim 3 or 4, wherein in said step 4), said thin film is hot-pressed at 100 to 500 ℃ under a pressure of 400 to 600dpi for 20 to 100 minutes.
8. A method for manufacturing a ferroelectric polymer-based dielectric thin film as in claim 3 or 4, wherein said nonwoven fabric-like filament is hot-pressed, naturally cooled to room temperature, and then kept at 150 to 250 ℃ for 2 to 20 minutes, followed by cold quenching at 0 ℃.
9. Use of a ferroelectric polymer based dielectric thin film according to claim 1 or 2 in an electrical component.
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