CN111995779A - Preparation method of all-organic PVDF-based dielectric film with high dielectric and high breakdown strength - Google Patents
Preparation method of all-organic PVDF-based dielectric film with high dielectric and high breakdown strength Download PDFInfo
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 250
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 246
- 230000015556 catabolic process Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 96
- 238000003756 stirring Methods 0.000 claims description 41
- 239000000376 reactant Substances 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 32
- 238000001291 vacuum drying Methods 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000010008 shearing Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- -1 DMF Chemical compound 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 53
- 238000012360 testing method Methods 0.000 description 13
- 239000002131 composite material Substances 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—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
- C08J2427/02—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
- C08J2427/12—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
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2439/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
Abstract
The invention discloses a preparation method of a PVDF-based dielectric film with full organic high dielectric and high breakdown strength, which comprises the following steps: s10, preparing modified polyvinylidene fluoride, namely MD-PVDF; s20, preparing cross-linked polyvinylidene fluoride, namely XL-PVDF; s30, preparing the PVDF/XL-PVDF dielectric film. The invention provides a preparation method of an all-organic dielectric film, which can improve the dielectric constant and prevent the breakdown strength from being greatly reduced.
Description
Technical Field
The invention belongs to the field of polymer film preparation, and relates to a preparation method of a PVDF-based dielectric film with all-organic high dielectric and high breakdown strength.
Background
Among a plurality of energy storage devices, the polymer-based thin film capacitor has the highest power density and the fastest charge-discharge response time, and is currently applied to the fields of renewable energy conversion storage, hybrid electric vehicles and the like. However, the lower energy storage density of the conventional polymer materials cannot meet the current requirements for miniaturization and integration of electronic devices in the development of the electronic industry. In a dielectric material, the dielectric constant and the breakdown field strength are two key physical parameters that determine its energy storage density. Attempts have been made in the past to increase the energy density of capacitors by increasing their relative dielectric constant (e.g., doping high dielectric materials, conductive materials, etc.), but such attempts have often failed because the electric field strength is reduced while fillers are added to achieve this. Failure of this attempt is evident because the storage density depends on the square of the electric field and is only linear with the dielectric constant.
Since the nano-dielectric concept was proposed by Lewis in 1994, the field of dielectric materials has made great progress, and it is gradually recognized that the internal interface structure has a decisive influence on the dielectric properties of the material. High dielectric constants are generally contradictory to high breakdown field strengths, especially when it is recognized that most of the stress under a given load is carried by the matrix polymer rather than by the high dielectric constant material. Therefore, how to ensure that the breakdown field strength is further improved (or not significantly reduced) while the dielectric constant is improved becomes a key problem for research on obtaining a dielectric material with high energy storage density.
Disclosure of Invention
In order to solve the problems, the technical scheme of the invention is a preparation method of a PVDF-based dielectric film with full organic high dielectric and high breakdown strength, which comprises the following steps:
the method comprises the following steps:
s10, preparing a modified polyvinylidene fluoride, i.e., MD-PVDF:
adding 100 parts of distilled water into a round-bottom flask, and adding 3-10 parts of sodium hydroxide for dissolving;
then adding 0.1-1 part of polyvinylpyrrolidone and 3-10 parts of polyvinylidene fluoride (PVDF), and magnetically stirring and dissolving at the rotating speed of 500-1000 rmp to obtain a clear solution;
reacting the solution at 50-80 ℃ for 3-24 h, filtering the reactant, washing the reactant for 3-5 times by using distilled water, and drying the reactant at 100-120 ℃ for 12-24 h to obtain MD-PVDF;
s20, preparing crosslinked polyvinylidene fluoride, namely XL-PVDF:
weighing 100 parts of N, N-Dimethylformamide (DMF), namely DMF, into a round-bottom flask, adding 3-10 parts of modified polyvinylidene fluoride prepared in S10, and magnetically stirring and dissolving at the rotating speed of 500-1000 rmp to obtain a clear solution;
adding 0.1-1 part of azodiisobutyronitrile, and stirring and refluxing in an oil bath kettle at 50-100 ℃ for 8-24 hours;
after the reaction is finished, cooling to room temperature, filtering the reactant, and washing for 3-5 times by using absolute ethyl alcohol to obtain a cross-linked structure product;
drying at 100-120 ℃ for 12-24 h to obtain polyvinylidene fluoride with a cross-linked structure, namely XL-PVDF;
s30, preparing a PVDF/XL-PVDF dielectric film:
adding 0-10 parts of PVDF into a round-bottom flask, adding 1-10 parts of XL-PVDF, adding 100 parts of DMF, stirring for 3-6 h at normal temperature, and performing ultrasonic dispersion for 20-30 min;
putting the dissolved PVDF/XL-PVDF solution into a vacuum drying oven, and drying for 12-24 hours at 100-120 ℃ to prepare a vacuum drying film;
cutting the vacuum drying film, placing the cut vacuum drying film in a powder tabletting machine, setting the temperature of a template to be 160-190 ℃, setting the pressure to be 2-4 MPa, and keeping the temperature and the pressure for 1-3 hours;
and after the heat preservation and pressure preservation are finished, adjusting the temperature to 50-80 ℃, preserving the heat for 1-6 h, naturally cooling, cooling to room temperature, and taking out to obtain the PVDF/XL-PVDF dielectric film.
Preferably, the thickness of the finished PVDF/XL-PVDF dielectric film prepared in S30 is 20-40 μm.
Preferably, the modified polyvinylidene fluoride is prepared by adding 100 parts of distilled water into a round-bottom flask, and adding 3 parts of sodium hydroxide for dissolution; then adding 0.1 part of polyvinylpyrrolidone and 3 parts of PVDF, magnetically stirring and dissolving at the rotating speed of 500rmp to obtain a clear solution, reacting the solution at 50 ℃ for 3h, filtering the reactant, washing the reactant for 3 times by using distilled water, and drying the reactant at 100 ℃ for 12h to obtain modified polyvinylidene fluoride, namely MD-PVDF.
Preferably, the preparation of the cross-linked polyvinylidene fluoride comprises the steps of weighing 100 parts of DMF (dimethyl formamide) in a round-bottom flask, adding 3 parts of prepared MD-PVDF, and magnetically stirring and dissolving at the rotating speed of 500rmp to obtain a clear solution; adding 0.1 part of azodiisobutyronitrile, and stirring and refluxing for 8 hours in an oil bath kettle at 50 ℃; after the reaction is finished, cooling to room temperature, filtering the reactant, washing for 3 times by using absolute ethyl alcohol to obtain a product with a cross-linked structure, and drying at 100 ℃ for 12 hours to obtain polyvinylidene fluoride with the cross-linked structure, namely XL-PVDF.
Preferably, the PVDF/XL-PVDF dielectric film is prepared by adding 0 part of PVDF into a round-bottom flask, adding 1 part of XL-PVDF into the round-bottom flask, adding 100 parts of DMF (dimethyl formamide), stirring for 3 hours at normal temperature, and performing ultrasonic dispersion for 20 minutes; putting the dissolved PVDF/XL-PVDF solution into a vacuum drying oven, and drying for 12 hours at 10 ℃ to obtain a vacuum drying film; shearing, placing in a powder tabletting machine, setting the temperature of a template at 160 ℃, setting the pressure at 2MPa, and keeping the temperature and pressure for 1 h; and after the heat preservation and pressure preservation are finished, regulating the temperature to 50 ℃, preserving the heat for 1h, then naturally cooling, and taking out after cooling to the room temperature to obtain the PVDF/XL-PVDF dielectric film.
Preferably, the PVDF/XL-PVDF dielectric film has a thickness of 20 μm.
The invention has the following beneficial effects:
the PVDF/XL-PVDF dielectric film prepared by the method not only has high dielectric constant, but also can not greatly reduce the breakdown strength. All are organic materials, light in weight, low in cost, good in flexibility, easy to machine and form, and easy to integrate, miniaturize and miniaturize devices.
Drawings
FIG. 1 is a flow chart of the steps of a method for preparing an all-organic high dielectric, high breakdown strength PVDF-based dielectric film in accordance with an embodiment of the present invention;
FIG. 2 is a graph of the dielectric constant of a prior art PVDF film and a PVDF/XLPFFD film of an embodiment of the present invention;
FIG. 3 is a graph of breakdown strength data for prior art PVDF films and PVDF/XLPFD films of embodiments of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.
Referring to fig. 1, which is a flow chart of steps of a method for preparing an all-organic PVDF-based dielectric film with high dielectric constant and high breakdown strength according to an embodiment of the present invention, the method includes the following steps:
s10, preparing a modified polyvinylidene fluoride, i.e., MD-PVDF:
adding 100 parts of distilled water into a round-bottom flask, and adding 3-10 parts of sodium hydroxide for dissolving;
then adding 0.1-1 part of polyvinylpyrrolidone and 3-10 parts of polyvinylidene fluoride (PVDF), and magnetically stirring and dissolving at the rotating speed of 500-1000 rmp to obtain a clear solution;
reacting the solution at 50-80 ℃ for 3-24 h, filtering the reactant, washing the reactant for 3-5 times by using distilled water, and drying the reactant at 100-120 ℃ for 12-24 h to obtain MD-PVDF;
s20, preparing crosslinked polyvinylidene fluoride, namely XL-PVDF:
weighing 100 parts of N, N-Dimethylformamide (DMF), namely DMF, into a round-bottom flask, adding 3-10 parts of modified polyvinylidene fluoride prepared in S10, and magnetically stirring and dissolving at the rotating speed of 500-1000 rmp to obtain a clear solution;
adding 0.1-1 part of azodiisobutyronitrile, and stirring and refluxing in an oil bath kettle at 50-100 ℃ for 8-24 hours;
after the reaction is finished, cooling to room temperature, filtering the reactant, and washing for 3-5 times by using absolute ethyl alcohol to obtain a cross-linked structure product;
drying at 100-120 ℃ for 12-24 h to obtain polyvinylidene fluoride with a cross-linked structure, namely XL-PVDF;
s30, preparing a PVDF/XL-PVDF dielectric film:
adding 0-10 parts of PVDF into a round-bottom flask, adding 1-10 parts of XL-PVDF, adding 100 parts of DMF, stirring for 3-6 h at normal temperature, and performing ultrasonic dispersion for 20-30 min;
putting the dissolved PVDF/XL-PVDF solution into a vacuum drying oven, and drying for 12-24 hours at 100-120 ℃ to prepare a vacuum drying film;
cutting the vacuum drying film, placing the cut vacuum drying film in a powder tabletting machine, setting the temperature of a template to be 160-190 ℃, setting the pressure to be 2-4 MPa, and keeping the temperature and the pressure for 1-3 hours;
and after the heat preservation and pressure preservation are finished, adjusting the temperature to 50-80 ℃, preserving the heat for 1-6 h, naturally cooling, cooling to room temperature, and taking out to obtain the PVDF/XL-PVDF dielectric film.
The thickness of the PVDF/XL-PVDF dielectric film prepared in S30 is 20-40 μm.
Example 1
S10, preparing modified polyvinylidene fluoride, namely adding 100 parts of distilled water into a round-bottom flask, and adding 3 parts of sodium hydroxide for dissolving; then adding 0.1 part of polyvinylpyrrolidone and 3 parts of PVDF, magnetically stirring and dissolving at the rotating speed of 500rmp to obtain a clear solution, reacting the solution at 50 ℃ for 3h, filtering the reactant, washing the reactant for 3 times by using distilled water, and drying the reactant at 100 ℃ for 12h to obtain modified polyvinylidene fluoride, namely MD-PVDF.
S20, preparing crosslinked polyvinylidene fluoride, namely weighing 100 parts of DMF (dimethyl formamide) in a round-bottom flask, adding 3 parts of prepared MD-PVDF, and magnetically stirring and dissolving at the rotating speed of 500rmp to obtain a clear solution; adding 0.1 part of azodiisobutyronitrile, and stirring and refluxing for 8 hours in an oil bath kettle at 50 ℃; after the reaction is finished, cooling to room temperature, filtering the reactant, washing for 3 times by using absolute ethyl alcohol to obtain a product with a cross-linked structure, and drying at 100 ℃ for 12 hours to obtain polyvinylidene fluoride with the cross-linked structure, namely XL-PVDF.
S30, preparing a PVDF/XL-PVDF dielectric film, namely adding 0 part of PVDF into a round-bottom flask, adding 1 part of XL-PVDF into the round-bottom flask, adding 100 parts of DMF (dimethyl formamide), stirring for 3 hours at normal temperature, and performing ultrasonic dispersion for 20 minutes; putting the dissolved PVDF/XL-PVDF solution into a vacuum drying oven, and drying for 12 hours at 10 ℃ to obtain a vacuum drying film; shearing, placing in a powder tabletting machine, setting the temperature of a template at 160 ℃, setting the pressure at 2MPa, and keeping the temperature and pressure for 1 h; and after the heat preservation and pressure preservation are finished, regulating the temperature to 50 ℃, preserving the heat for 1h, then naturally cooling, and taking out after cooling to room temperature to obtain the PVDF/XL-PVDF dielectric film with the thickness of 20 microns.
Example 2
S10, preparing modified polyvinylidene fluoride MD-PVDF: adding 100 parts of distilled water into a round-bottom flask, and adding 3 parts of sodium hydroxide for dissolving; then adding 0.3 part of polyvinylpyrrolidone and 3 parts of polyvinylidene fluoride (PVDF), magnetically stirring and dissolving at the rotating speed of 600rmp to obtain a clear solution, reacting the solution at 50 ℃ for 5 hours, filtering the reactant, washing the reactant for 3 times by using distilled water, and drying the reactant at 100 ℃ for 16 hours to obtain MD-PVDF;
s20, preparing cross-linked polyvinylidene fluoride XL-PVDF: weighing 100 parts of DMF (N, N-dimethylformamide) in a round-bottom flask, adding 4 parts of modified polyvinylidene fluoride prepared in the step, and magnetically stirring and dissolving at the rotating speed of 800rmp to obtain a clear solution; adding 0.2 part of azodiisobutyronitrile, stirring and refluxing for 8 hours in a 50 ℃ oil bath kettle, cooling to room temperature after the reaction is finished, filtering the reactant, washing for 4 times by using absolute ethyl alcohol to obtain a cross-linked structure product, and drying for 12 hours at 105 ℃ to obtain polyvinylidene fluoride with a cross-linked structure, namely XL-PVDF;
s30, preparing a PVDF/XL-PVDF dielectric film: adding 1 part of PVDF into a round-bottom flask, adding 1 part of XL-PVDF, adding 100 parts of DMF (N, N-dimethylformamide), stirring for 3 hours at normal temperature, and performing ultrasonic dispersion for 25 minutes; putting the dissolved PVDF/XL-PVDF solution into a vacuum drying oven, and drying for 12 hours at 100 ℃; and shearing the vacuum dried film, placing the film in a powder tabletting machine, setting the temperature of a template at 160 ℃, adjusting the pressure to 2MPa, and keeping the temperature and the pressure for 1 h. And after the pressure maintaining is finished, adjusting the temperature to 55 ℃, preserving the temperature for 3h, then naturally cooling, and taking out after cooling to room temperature to obtain the PVDF/XL-PVDF dielectric film with the thickness of about 25 mu m.
Example 3
S10, preparing modified polyvinylidene fluoride MD-PVDF: adding 100 parts of distilled water into a round-bottom flask, and adding 5 parts of sodium hydroxide for dissolving; then adding 0.3 part of polyvinylpyrrolidone and 4 parts of polyvinylidene fluoride (PVDF), magnetically stirring and dissolving at the rotating speed of 800rmp to obtain a clear solution, reacting the solution at 60 ℃ for 8 hours, filtering the reactant, washing with distilled water for 3 times, and drying at 110 ℃ for 16 hours to obtain MD-PVDF;
s20, preparing cross-linked polyvinylidene fluoride XL-PVDF: weighing 100 parts of DMF (N, N-dimethylformamide) in a round-bottom flask, adding 5 parts of modified polyvinylidene fluoride prepared in S20, and magnetically stirring and dissolving at the rotating speed of 600rmp to obtain a clear solution; adding 0.4 part of azodiisobutyronitrile, stirring and refluxing for 10 hours in an oil bath kettle at 70 ℃, cooling to room temperature after the reaction is finished, filtering, washing for 3-5 times by using absolute ethyl alcohol to obtain a cross-linked structure product, and drying for 16 hours at 105 ℃ to obtain polyvinylidene fluoride with a cross-linked structure, namely XL-PVDF;
s30, preparing a PVDF/XL-PVDF dielectric film: adding 5 parts of PVDF into a round-bottom flask, adding 2 parts of XL-PVDF, adding 100 parts of DMF (N, N-dimethylformamide), stirring for 5 hours at normal temperature, and performing ultrasonic dispersion for 20 minutes; putting the dissolved PVDF/XL-PVDF solution into a vacuum drying oven, and drying for 15 hours at 110 ℃; cutting the vacuum dried film, placing in a powder tabletting machine, setting the temperature of a template at 170 ℃, adjusting the pressure to 2.5MPa, and keeping the temperature and pressure for 2 h. And after the pressure maintaining is finished, adjusting the temperature to 65 ℃, preserving the temperature for 3h, then naturally cooling, and taking out after cooling to room temperature to obtain the PVDF/XL-PVDF dielectric film with the thickness of about 30 microns.
Example 4
S10, preparing modified polyvinylidene fluoride MD-PVDF: adding 100 parts of distilled water into a round-bottom flask, and adding 6 parts of sodium hydroxide for dissolution; then adding 0.6 part of polyvinylpyrrolidone and 6 parts of polyvinylidene fluoride (PVDF), magnetically stirring and dissolving at the rotating speed of 600rmp to obtain a clear solution, reacting the solution at 60 ℃ for 15 hours, filtering the reactant, washing the reactant for 5 times by using distilled water, and drying the reactant at 110 ℃ for 18 hours to obtain MD-PVDF;
s20, preparing cross-linked polyvinylidene fluoride XL-PVDF: weighing 100 parts of DMF (N, N-dimethylformamide) in a round-bottom flask, adding 6 parts of modified polyvinylidene fluoride prepared by S20, and magnetically stirring and dissolving at the rotating speed of 600rmp to obtain a clear solution; adding 0.1-1 part of azodiisobutyronitrile, and stirring and refluxing in an oil bath kettle at 60 ℃ for 12 hours; after the reaction is finished, cooling to room temperature, filtering, washing for 4 times by using absolute ethyl alcohol to obtain a cross-linked structure product, and drying for 16 hours at 110 ℃ to obtain polyvinylidene fluoride with a cross-linked structure, namely XL-PVDF.
S30, preparing a PVDF/XL-PVDF dielectric film: 6 parts of PVDF were placed in a round-bottomed flask, 6 parts of XLPPVDF were added, 100 parts of DMF (N, N-dimethylformamide) were added, stirring was carried out at normal temperature for 5 hours, ultrasonic dispersion was carried out for 26min, and the dissolved PVDF/XL-PVDF solution was placed in a vacuum drying oven and dried at 110 ℃ for 16 hours. And (3) shearing the vacuum-dried film, placing the film in a powder tabletting machine, setting the temperature of a template at 170 ℃, adjusting the pressure to 3MPa, and keeping the temperature and the pressure for 2 hours. And after the pressure maintaining is finished, adjusting the temperature to 70 ℃, preserving the temperature for 4h, then naturally cooling, and taking out after cooling to room temperature to obtain the PVDF/XL-PVDF dielectric film with the thickness of about 30 microns.
Example 5
S10, preparing modified polyvinylidene fluoride MD-PVDF: adding 100 parts of distilled water into a round-bottom flask, and adding 8 parts of sodium hydroxide for dissolution; then 0.7 part of polyvinylpyrrolidone and 7 parts of polyvinylidene fluoride (PVDF) are added and are magnetically stirred and dissolved at the rotating speed of 700rmp to obtain a clear solution. The solution was reacted at 70 ℃ for 16 h. Filtering the reactant, washing the reactant for 4 times by using distilled water, and drying the reactant for 20 hours at 115 ℃ to obtain MD-PVDF;
s20, preparing cross-linked polyvinylidene fluoride XL-PVDF: weighing 100 parts of DMF (N, N-dimethylformamide) in a round-bottom flask, adding 8 parts of modified polyvinylidene fluoride prepared by S20, and magnetically stirring and dissolving at the rotating speed of 1000rmp to obtain a clear solution; adding 0.8 part of azodiisobutyronitrile, stirring and refluxing for 18h in an oil bath kettle at 70 ℃, cooling to room temperature after the reaction is finished, filtering, washing for 5 times by using absolute ethyl alcohol to obtain a cross-linked structure product, and drying for 20h at 120 ℃ to obtain polyvinylidene fluoride with a cross-linked structure, namely XL-PVDF.
S30, preparing a PVDF/XL-PVDF dielectric film: 8 parts of PVDF was put in a round-bottom flask, 9 parts of XL-PVDF was added, 100 parts of DMF (N, N-dimethylformamide) was added, stirring was carried out at normal temperature for 6 hours, and ultrasonic dispersion was carried out for 30 minutes. And (3) placing the dissolved PVDF/XL-PVDF solution in a vacuum drying oven, drying for 18h at 120 ℃, shearing the vacuum dried film, placing the vacuum dried film in a powder tabletting machine, setting the temperature of a template at 170 ℃, adjusting the pressure to 3.5MPa, and keeping the temperature and pressure for 2.5 h. And after the pressure maintaining is finished, adjusting the temperature to 75 ℃, preserving the temperature for 5h, then naturally cooling, and taking out after cooling to room temperature to obtain the PVDF/XL-PVDF dielectric film with the thickness of 35 microns.
Example 6
S10, preparing modified polyvinylidene fluoride MD-PVDF: adding 100 parts of distilled water into a round-bottom flask, and adding 10 parts of sodium hydroxide for dissolving; then 1 part of polyvinylpyrrolidone and 10 parts of polyvinylidene fluoride (PVDF) are added and are magnetically stirred and dissolved at the rotating speed of 1000rmp to obtain a clear solution. The solution was reacted at 80 ℃ for 24 h. Filtering the reactant, washing the reactant for 5 times by using distilled water, and drying the reactant for 24 hours at 120 ℃ to obtain MD-PVDF;
s20, preparing cross-linked polyvinylidene fluoride XL-PVDF: weighing 100 parts of DMF (N, N-dimethylformamide) in a round-bottom flask, adding 10 parts of modified polyvinylidene fluoride prepared by S20, and magnetically stirring and dissolving at the rotating speed of 1000rmp to obtain a clear solution; adding 1 part of azodiisobutyronitrile, and stirring and refluxing for 24 hours in an oil bath kettle at the temperature of 100 ℃; and after the reaction is finished, cooling to room temperature, filtering, washing for 3-5 times by using absolute ethyl alcohol to obtain a cross-linked structure product, and drying for 24 hours at 120 ℃ to obtain polyvinylidene fluoride with a cross-linked structure, namely XL-PVDF.
S30, preparing a PVDF/XL-PVDF dielectric film: adding 10 parts of PVDF into a round-bottom flask, adding 10 parts of XL-PVDF, adding 100 parts of DMF (N, N-dimethylformamide), stirring for 6 hours at normal temperature, and performing ultrasonic dispersion for 30 minutes; putting the dissolved PVDF/XL-PVDF solution into a vacuum drying oven, and drying for 24 hours at 120 ℃; shearing the vacuum dried film, placing the film in a powder tabletting machine, setting the temperature of a template at 190 ℃, adjusting the pressure to 4MPa, and keeping the temperature and the pressure for 3 hours; and after the pressure maintaining is finished, adjusting the temperature to 80 ℃, keeping the temperature for 6h, then naturally cooling, and taking out after cooling to room temperature to obtain the PVDF/XL-PVDF dielectric film with the thickness of 40 μm.
Comparing with the dielectric constant data of the prior art film, referring to fig. 2, the PVDF and the PVDF/XL-PVDF composite dielectric films of the embodiments of the invention with different contents are subjected to dielectric property test, the dielectric constant is slowly reduced along with the increase of frequency, and the frequency is 105The decrease after Hz is more pronounced due to the relaxation of the PVDF amorphous dipole. At 102At Hz, the dielectric constant of pure PVDF is about 8.5, PVDF/XL-PVDF19.5, PVDF/XL-PVDF29.9 of PVDF/XL-PVDF311.8, PVDF/XL-PVDF4Was 12.6. It can be seen that with the addition of XL-PVDF, the dielectric constant of the composite material is remarkably improved compared with that of pure PVDF.
Comparison of the breakdown strength data with the prior art film referring to fig. 3, the average of the data obtained is typically used in the breakdown strength test. Generally, the breakdown strength test results are calculated using a weber distribution. To ensure the accuracy of the results obtained, the breakdown strength test was performed at as many points as possible (17 points in this experiment) in the sample during the test, and the measured data were arranged according to equation 1.1.
E1≤E2≤E3≤...≤Ei≤...E17 (1.1)
The probability Pi corresponding to each test result is represented by formula 1.2
Where i is the number of test dot arrangements and n is the total number of sample test dots (17). The breakdown strength test result of the Weber distribution process is shown in the following formula 1.3
Two sides simultaneously take logarithm to become formula 1.4
Ln[-Ln(1-P)]＝βLnEi-βLnE0 (1.4)
Where Ei is the breakdown strength test result, α is the scale factor and β is the shape factor. The characteristic breakdown strength of the composite material is obtained when the breakdown probability in the test result is 63.2% after the drawing is carried out according to the formula 1.4 and linear fitting is carried out.
The breakdown strength and the energy storage density are closely related, and in order to represent the breakdown performance of PVDF and PVDF/XL-PVDF composite films with different addition amounts of XL-PVDF, breakdown strength resistance tests are carried out on the PVDF/XL-PVDF composite films. And (4) drawing the data obtained by testing by using the Weber distribution and performing linear fitting to finally obtain the characteristic breakdown value of the composite material. 17 breakdown points were tested for each sample and it can be seen that the pure PVDF matrix has a characteristic breakdown value of 260MV/m, PVDF/XLPPVDF1300MV/m, PVDF/XLPPVDF2216MV/m, PVDF/XLPPVDF3195MV/m, PVDF/XLPPVDF4Is 189 MV/m. After XL-PVDF is added to a PVDF matrix as a filler, the content of XL-PVDF gradually increases within a certain proportion range.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A preparation method of a PVDF-based dielectric film with all-organic high dielectric and high breakdown strength is characterized by comprising the following steps:
s10, preparing a modified polyvinylidene fluoride, i.e., MD-PVDF:
adding 100 parts of distilled water into a round-bottom flask, and adding 3-10 parts of sodium hydroxide for dissolving;
then adding 0.1-1 part of polyvinylpyrrolidone and 3-10 parts of polyvinylidene fluoride (PVDF), and magnetically stirring and dissolving at the rotating speed of 500-1000 rmp to obtain a clear solution;
reacting the solution at 50-80 ℃ for 3-24 h, filtering the reactant, washing the reactant for 3-5 times by using distilled water, and drying the reactant at 100-120 ℃ for 12-24 h to obtain MD-PVDF;
s20, preparing crosslinked polyvinylidene fluoride, namely XL-PVDF:
weighing 100 parts of N, N-Dimethylformamide (DMF), namely DMF, into a round-bottom flask, adding 3-10 parts of modified polyvinylidene fluoride prepared in S10, and magnetically stirring and dissolving at the rotating speed of 500-1000 rmp to obtain a clear solution;
adding 0.1-1 part of azodiisobutyronitrile, and stirring and refluxing in an oil bath kettle at 50-100 ℃ for 8-24 hours;
after the reaction is finished, cooling to room temperature, filtering the reactant, and washing for 3-5 times by using absolute ethyl alcohol to obtain a cross-linked structure product;
drying at 100-120 ℃ for 12-24 h to obtain polyvinylidene fluoride with a cross-linked structure, namely XL-PVDF;
s30, preparing a PVDF/XL-PVDF dielectric film:
adding 0-10 parts of PVDF into a round-bottom flask, adding 1-10 parts of XL-PVDF, adding 100 parts of DMF, stirring for 3-6 h at normal temperature, and performing ultrasonic dispersion for 20-30 min;
putting the dissolved PVDF/XL-PVDF solution into a vacuum drying oven, and drying for 12-24 hours at 100-120 ℃ to prepare a vacuum drying film;
cutting the vacuum drying film, placing the cut vacuum drying film in a powder tabletting machine, setting the temperature of a template to be 160-190 ℃, setting the pressure to be 2-4 MPa, and keeping the temperature and the pressure for 1-3 hours;
and after the heat preservation and pressure preservation are finished, adjusting the temperature to 50-80 ℃, preserving the heat for 1-6 h, naturally cooling, cooling to room temperature, and taking out to obtain the PVDF/XL-PVDF dielectric film.
2. The method of claim 1, wherein the thickness of the finished PVDF/XL-PVDF dielectric film prepared in S30 is 20-40 μm.
3. The method of claim 1, wherein the modified polyvinylidene fluoride is prepared by adding 100 parts of distilled water into a round-bottom flask, adding 3 parts of sodium hydroxide for dissolution; then adding 0.1 part of polyvinylpyrrolidone and 3 parts of PVDF, magnetically stirring and dissolving at the rotating speed of 500rmp to obtain a clear solution, reacting the solution at 50 ℃ for 3h, filtering the reactant, washing the reactant for 3 times by using distilled water, and drying the reactant at 100 ℃ for 12h to obtain modified polyvinylidene fluoride, namely MD-PVDF.
4. The method as claimed in claim 1, wherein the preparation of cross-linked polyvinylidene fluoride comprises weighing 100 parts of DMF in a round bottom flask, adding 3 parts of prepared MD-PVDF, and dissolving by magnetic stirring at 500rmp to obtain a clear solution; adding 0.1 part of azodiisobutyronitrile, and stirring and refluxing for 8 hours in an oil bath kettle at 50 ℃; after the reaction is finished, cooling to room temperature, filtering the reactant, washing for 3 times by using absolute ethyl alcohol to obtain a product with a cross-linked structure, and drying at 100 ℃ for 12 hours to obtain polyvinylidene fluoride with the cross-linked structure, namely XL-PVDF.
5. The method of claim 1, wherein the PVDF/XL-PVDF dielectric film is prepared by adding 0 part of PVDF to a round-bottomed flask, adding 1 part of XL-PVDF, adding 100 parts of DMF, stirring at normal temperature for 3 hours, and performing ultrasonic dispersion for 20 minutes; putting the dissolved PVDF/XL-PVDF solution into a vacuum drying oven, and drying for 12 hours at 10 ℃ to obtain a vacuum drying film; shearing, placing in a powder tabletting machine, setting the temperature of a template at 160 ℃, setting the pressure at 2MPa, and keeping the temperature and pressure for 1 h; and after the heat preservation and pressure preservation are finished, regulating the temperature to 50 ℃, preserving the heat for 1h, then naturally cooling, and taking out after cooling to the room temperature to obtain the PVDF/XL-PVDF dielectric film.
6. The method of claim 5, wherein the PVDF/XL-PVDF dielectric film has a thickness of 20 μm.
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