CN113061341B - Preparation of surface-modified inorganic filling phase/polyether sulfone-based composite dielectric - Google Patents

Preparation of surface-modified inorganic filling phase/polyether sulfone-based composite dielectric Download PDF

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CN113061341B
CN113061341B CN202110514356.7A CN202110514356A CN113061341B CN 113061341 B CN113061341 B CN 113061341B CN 202110514356 A CN202110514356 A CN 202110514356A CN 113061341 B CN113061341 B CN 113061341B
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CN113061341A (en
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张月
丛秀纯
迟庆国
张天栋
王暄
雷清泉
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Harbin University of Science and Technology
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    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Abstract

The invention relates to preparation of a surface-modified inorganic filling phase/polyether sulfone-based composite dielectric, belonging to the technical field of composite dielectric energy storage materials. In order to solve the problems of low dielectric constant, low energy storage density and low efficiency of the existing polymer-based dielectric material, the invention adopts an electrostatic spinning technology to prepare barium calcium zirconate titanate inorganic fiber, uses a hydrothermal method to wrap the barium calcium zirconate titanate inorganic fiber with bismuth ferrite-strontium titanate, compounds the barium calcium zirconate titanate inorganic fiber with a linear polymer PESU, and prepares a compact and uniform composite film through a heat treatment technology. The doping amount of the filling phase is 0-7 wt% of the composite material. When the content of the inorganic filling phase is 2wt.%, the energy storage density can reach 10.5J/cm under an electric field of 500kV/mm 3 The efficiency is as high as 84.2%. The preparation process is simple and convenient, has excellent dielectric and energy storage properties, and is easy to popularize and implement.

Description

Preparation of surface-modified inorganic filling phase/polyether sulfone-based composite dielectric
Technical Field
The invention belongs to the field of dielectric capacitors, and relates to a method for preparing a surface-modified inorganic filling phase/polyether sulfone-based composite dielectric.
Background
The dielectric capacitor has wide application prospect in the fields of hybrid electric vehicles, solar energy converters and the like. In the energy storage device, the fuel cell has strong energy storage capacity, but because of polarization limitation during working, the carrier moves slowly, and the power output is limited; in electrochemical energy storage, the ratio of the lithium ion battery is the largest, but the lithium ion battery has the danger of safety; the service life of the super capacitor is long, but the electrolyte is easy to leak and expensive, so that the development of the super capacitor is limited; dielectric capacitors have been widely studied for their advantages of long life cycle, good temperature stability, and high power density, but have limited energy storage density. This means that the dielectric capacitor occupies a large space as an energy storage device, which greatly limits the development in the modern power electronics field, and restricts the application of the dielectric capacitor in converters, inverters, high-power microwave devices, and the like.
Disclosure of Invention
The invention aims to solve the problems of low dielectric constant, low energy storage density and low efficiency of a dielectric medium. The invention relates to a method for preparing a surface-modified inorganic filling phase/polyether sulfone-based composite dielectric.
The technical scheme of the experiment is as follows:
the inorganic filling phase/polyether sulfone-based composite dielectric with the surface modification is characterized in that the inorganic filling phase/polyether sulfone-based composite dielectric with the surface modification contains barium calcium zirconate titanate @ bismuth ferrite-strontium titanate nano fibers (BZCT @ BFSTO NFs), the BZCT @ BFSTO NFs is of a core-shell fiber structure, and a core layer is barium calcium zirconate titanate (0.5 Ba (Zr) 0.2 Ti 0.8 )O 3 -0.5(Ba 0.7 Ca 0.3 )TiO 3 ) The shell layer is bismuth ferrite-strontium titanate. The polymer matrix is Polyethersulfone (PESU).
Further, the preparation method of the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric is characterized in that the mass percentage of the inorganic filling phase in the composite film is 1wt.%, 2wt.%, 3wt.%, 5wt.% and 7wt.%.
Further, the preparation method of the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric is characterized in that the thickness of the composite film is 8-20 mu m.
A method for preparing a surface-modified inorganic filling phase/polyether sulfone-based composite dielectric comprises the following steps:
the method comprises the following steps:
acetic acid is used as a solvent and acetylacetone is used as a stabilizer. Barium hydroxide octahydrate, calcium hydroxide and zirconium acetylacetonate as solid solutes and tetrabutyl titanate as a liquid solute. Firstly, barium hydroxide octahydrate and calcium hydroxide are added into an acetic acid solvent for heating and stirring, and the heating is stopped after the solution is clarified. Secondly, acetylacetone and acetylacetone zirconium powder are added, and a certain amount of tetrabutyl titanate solution is added after the solution is clarified. Finally, polyvinylpyrrolidone powder was added to the clear solution and stirred vigorously. And finally, aging at room temperature to form a stable barium calcium zirconate titanate precursor solution.
Step two:
and (4) sucking the barium zirconate titanate calcium precursor solution obtained in the step one into an injector to prepare for spinning. The injector is ensured to be arranged at a certain advancing speed, the rotating speed of the receiver is arranged at a proper value, the distance from the injector to the receiver is fixed, and the injector and the receiver apply voltage simultaneously. And (3) calcining the precursor fiber obtained by spinning in a muffle furnace, and fully grinding the calcined fiber to obtain barium calcium zirconate titanate (BZCT NFs).
Step three:
adding bismuth nitrate pentahydrate [ Bi (NO) 3 ) 3 ·5H 2 O]Ferric nitrate nonahydrate [ Fe (NO) 3 ) 3 ·9H 2 O]Dissolving in liquid solvent acetic acid to prepare bismuth ferrite solution. Dissolving strontium acetate in acetic acid in another beaker, clarifying the solution, adding acetylacetone as a stabilizer, and adding tetrabutyl titanate to obtain a strontium titanate solution. Mixing the prepared bismuth ferrite solution with the strontium titanate solution to prepare 0.25BiFeO 3 -0.75SrTiO 3 And (3) solution. Ethanolamine solution was added to clarify the solution. Adding a certain amount of BZCT NFs into a mixed solution of bismuth ferrite and strontium titanate, and ultrasonically dispersing. Pouring the mixed solution into a reaction kettle, and reacting under the condition of proper temperature. After the reaction is finished, the modified powder is collected by centrifugal washing and washed with deionized water and ethanol to a proper pH value. Finally, the sample is transferred to a drying box for drying.
Step four:
and C, dispersing the BZCT @ BFSTO NFs filling phase obtained in the step three in an N-methylpyrrolidone solution according to a certain mass, and performing ultrasonic dispersion under proper power. Adding polyether sulfone (PESU) particles into the solution, stirring on a stirrer, and then placing the BZCT @ BFSTO NFs/PESU composite solution into a vacuum box for vacuumizing, standing and air bubble discharging to obtain the BZCT @ BFSTO NFs/PESU precursor solution.
Step five:
and D, performing film coating treatment on the BZCT @ BFSTO NFs/PESU precursor obtained in the step four. Before coating, the film-pushing speed of the coating film and the number of the blade revolution needs to be controlled. And (3) placing the coated film in a vacuum oven, carrying out heat treatment on the BZCT @ BFSTO NFs/PESU film, and removing the organic solvent to obtain the BZCT @ BFSTO NFs/PESU film.
Then, in the first step, 1-16 g of barium hydroxide octahydrate and 0.2-0.9 g of calcium hydroxide are added into 10-65 mL of acetic acid solvent for stirring, 1-18 mL of acetylacetone and 0.1-4 g of zirconium acetylacetonate powder are added after the solution is clarified, and 0.8-20 mL of tetrabutyl titanate solution is added after the solution is clarified. Then 0.5-3.5 g polyvinylpyrrolidone powder is added into the transparent solution and stirred vigorously. After clarification, aging is carried out for 8-10 hours to form stable barium calcium zirconate titanate precursor solution. The chemical raw materials Ba, ca, zr and Ti are controlled to have the stoichiometric ratio of 0.85 to 0.15.
And further, the obtained barium calcium zirconate titanate precursor solution is sucked into an injector to prepare for spinning. The advancing speed of the injector is set to be 0.1-0.3 mm/min, the rotating speed of the receiver is set to be 90-150 r/min, the distance from the injector to the receiver is 10-20 cm, and the injector and the receiver apply positive and negative 15-20V voltage simultaneously. And after spinning is finished, sintering the precursor fiber in a muffle furnace at the temperature of 500-850 ℃ for 2-6 h. Finally obtaining barium calcium zirconate titanate nano fibers (BZCT NFs).
Subsequently, 0.9 to 2.2g of Bi (NO) described in step three 3 ) 3 ·5H 2 O, 0.7-2 g Fe (NO) 3 ) 3 ·9H 2 Dissolving O in acetic acid as liquid solvent to prepare bismuth ferrite solution. Dissolving 1.1-2.3 g of strontium acetate in acetic acid in another beaker, clarifying the solution, adding 1-2 mL of acetylacetone as a stabilizer, and then adding 1.8-3 mL of tetrabutyl titanate to obtain a strontium titanate solution. Mixing the prepared bismuth ferrite solution with the strontium titanate solution, and adding 1-2.5 mL of ethanolamine solution to clarify the solution. Adding 1-2 g of BZCT NFs into a mixed solution of bismuth ferrite and strontium titanate, and carrying out ultrasonic treatment for 3-5 min. Pouring the mixed solution into a reaction kettle, and reacting for 24 hours at the temperature of 100-150 ℃. After the reaction was completed, the modified powder was collected by centrifugal washing and washed with deionized water and ethanol to pH 7. Finally, the mixture was transferred to a drying oven and dried at 60 ℃ for 12 hours.
And fourthly, dispersing the BZCT @ BFSTO NFs filling phase into the N-methylpyrrolidone solution according to a certain mass, and performing ultrasonic dispersion for 1-2 min at the ultrasonic power of 40-60W. Adding polyether sulfone (PESU) particles into the solution, and stirring on a stirrer to obtain the BZCT @ BFSTO NFs/PESU composite solution. And then placing the BZCT @ BFSTO NFs/PESU composite solution in a vacuum box, vacuumizing for 2-8 h, standing and discharging bubbles to obtain a BZCT @ BFSTO NFs/PESU precursor solution.
And finally, performing film coating treatment on the precursor of BZCT @ BFSTO NFs/PESU in the fifth step. Before coating, the film pushing speed of the coating film is required to be controlled to be 1-3 cm/s, and the number of the grids rotated by a scraper is required to be 20-35. The coated film is put in a vacuum oven with the temperature of 60-140 ℃, and the BZCT @ BFSTO NFs/PESU film is subjected to heat treatment to remove the organic solvent. And peeling the composite film from the glass plate under the action of deionized water to finally obtain the BZCT @ BFSTO NFs/PESU composite film.
The invention has the beneficial effects that:
the BZCT NFs have a large length-diameter ratio structure, so that extension of electric branches can be effectively inhibited, the breakdown strength of a medium is further improved, a layer of BFSTO wraps the BZCT NFs, the BFSTO relieves dielectric difference between the BZCT and the PESU, and electric field distortion at an interface can be reduced. The PESU is a linear polymer with low dielectric loss. This is advantageous for the BZCT @ BFSTO NFs/PESU film to achieve large energy storage density and high efficiency.
The preparation process is simple and convenient, reduces the production cost and is suitable for large-scale production. The developed BZCT @ BFSTO NFs/PESU composite medium with the heat treatment temperature of 140 ℃ and 2wt.% has excellent dielectric property, energy storage density and efficiency. Therefore, the BZCT @ BFSTO NFs/PESU composite film medium prepared by the experiment can be applied to an energy storage device.
Drawings
FIG. 1 is an X-ray diffraction pattern of inorganic filler phases BZCT NFs and BZCT @ BFSTO NFs;
FIG. 2 is an X-ray diffraction pattern of pure PESU, composite films of different inorganic filler phase contents, and BZCT @ BFSTO NFs;
FIG. 3 is a TEM image of inorganic filler phases BZCT @ BFSTO NFs;
FIG. 4 is a scanning electron micrograph of a pure PESU and BZCT @ BFSTO NFs/PESU composite film (a) pure PESU (b) 1wt.% BZCT @ BFSTO NFs/PESU (c) 2wt.% BZCT @ BFSTO NFs/PESU (d) 3wt.% BZCT @ BFSTO NFs/PESU (e) 5wt.% BZCT @ BFSTO NFs/PESU (f) 7wt.% BZCT @ BFSTO NFs/PESU;
FIG. 5 is a graph of dielectric properties of a composite film of pure PESU and BZCT @ BFSTO NFs/PESU with different inorganic filler phase contents;
FIG. 6 is a Weibull distribution plot of breakdown field strengths of BZCT @ BFSTO NFs/PESU composite films of pure PESU and different inorganic filler phase contents;
FIG. 7 is a graph of energy storage performance of a composite film of pure PESU and BZCT @ BFSTO NFs/PESU with different inorganic filler phase contents;
Detailed Description
The technical solution of the present invention is not limited to the embodiments listed below, and includes any combination of the embodiments.
Detailed description of the preferred embodiment 1
The preparation method of the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric comprises the following steps:
the method comprises the following steps:
1-16 g of barium hydroxide octahydrate and 0.2-0.9 g of calcium hydroxide are added into 10-65 mL of acetic acid solvent for stirring, 1-18 mL of acetylacetone and 0.1-4 g of zirconium acetylacetonate powder are added after the solution is clarified, and 0.8-20 mL of tetrabutyl titanate solution is added after the solution is clarified. Then 0.5-3.5 g polyvinylpyrrolidone powder is added into the transparent solution and stirred vigorously. After clarification, aging is carried out for 8-10 hours to form stable barium calcium zirconate titanate precursor solution. The chemical raw materials Ba, ca, zr and Ti are controlled to have the stoichiometric ratio of 0.85 to 0.15.
Step two:
and (4) sucking the barium zirconate titanate precursor solution obtained in the step one into an injector for preparing spinning. The advancing speed of the injector is set to be 0.1-0.3 mm/min, the rotating speed of the receiver is set to be 90-150 r/min, the distance from the injector to the receiver is 10-20 cm, and the injector and the receiver apply positive and negative 15-20V voltage simultaneously. And after spinning is finished, putting the precursor fiber into a muffle furnace to be sintered for 2-6 h at the temperature of 500-850 ℃. Finally obtaining barium calcium zirconate titanate nano fibers (BZCT NFs).
Step three:
0.9-2.2 g of bismuth nitrate pentahydrate [ Bi (NO) 3 ) 3 ·5H 2 O]0.7-2 g of ferric nitrate nonahydrate [ Fe (NO) 3 ) 3 ·9H 2 O]Dissolving in liquid solvent acetic acid to prepare bismuth ferrite solution. Dissolving 1.1-2.3 g of strontium acetate in acetic acid in another beaker, adding acetylacetone as a stabilizing agent after the solution is clarified, and then adding 1.8-3 mL of tetrabutyl titanate to obtain a strontium titanate solution. Mixing the prepared bismuth ferrite solution with the strontium titanate solution, and adding 1-2.5 mL of ethanolamine solution to clarify the solution. Adding 1-2 g of BZCT NFs into the mixed solution of bismuth ferrite and strontium titanate, and carrying out ultrasonic treatment for 3-5 min. Pouring the mixed solution into a reaction kettle, and reacting for 24 hours at the temperature of 100-150 ℃. After the reaction was completed, the modified powder was collected by centrifugal washing and washed with deionized water and ethanol to pH 7. Finally, the mixture was transferred to a drying oven and dried at 60 ℃ for 12 hours.
Step four:
and dispersing the BZCT @ BFSTO NFs filling phase in the step three in an N-methylpyrrolidone solution according to a certain mass, and ultrasonically dispersing for 1-2 min at the ultrasonic power of 40-60W. Polyether sulfone (PESU) particles are added into the solution and stirred on a stirrer to obtain a BZCT @ BFSTO NFs/PESU composite solution. And then placing the BZCT @ BFSTO NFs/PESU composite solution in a vacuum box, vacuumizing for 2-8 h, standing, and discharging bubbles to obtain the BZCT @ BFSTO NFs/PESU precursor solution.
Step five:
and D, performing film coating treatment on the precursor BZCT @ BFSTO NFs/PESU obtained in the step four. Before coating, the film pushing speed of the coating film is required to be controlled to be 1-3 cm/s, and the number of the grids rotated by a scraper is required to be 20-35. And (3) placing the coated film in a vacuum oven at the temperature of 60-140 ℃, and carrying out heat treatment on the BZCT @ BFSTO NFs/PESU film to remove the organic solvent. And then peeling the composite film from the glass plate under the action of deionized water to finally obtain the BZCT @ BFSTO NFs/PESU composite film.
Example 2
A preparation method of a surface-modified inorganic filling phase/polyether sulfone-based composite dielectric comprises the following steps:
the method comprises the following steps:
acetic acid is used as a solvent and acetylacetone as a stabilizer. Barium hydroxide octahydrate, calcium hydroxide and zirconium acetylacetonate as solid solutes and tetrabutyl titanate as a liquid solute. First, 5.7g of barium hydroxide octahydrate and 0.2g of calcium hydroxide were added to 47mL of acetic acid solvent, followed by stirring, after the solution was clarified, 3mL of acetylacetone and 1g of zirconium acetylacetonate powder were added, and after the solution was clarified, 6.4mL of tetrabutyl titanate solution was added. 0.8g of polyvinylpyrrolidone powder was then added to the clear solution and stirred vigorously. After clarification, the mixture is aged for 10 hours to form a stable barium calcium zirconate titanate precursor solution. Wherein the stoichiometric ratio of various chemical raw materials of Ba to Ca to Zr to Ti is controlled to be 0.85.
Step two:
and (3) sucking the obtained barium calcium zirconate titanate precursor solution into an injector to prepare for spinning. Ensuring that the advancing speed of the injector is set to be 0.12mm/min, the rotating speed of the receiver is set to be 120r/min, the distance from the injector to the receiver is 16cm, and the injector and the receiver apply positive and negative 16V voltage simultaneously; and (3) calcining the precursor fiber obtained by spinning in a muffle furnace at the temperature of 700 ℃ for 3h, and fully grinding the calcined fiber to obtain barium calcium zirconate titanate fibers (BZCT NFs).
Step three:
0.9g of bismuth nitrate pentahydrate [ Bi (NO) ] 3 ) 3 ·5H 2 O]0.7g of iron nitrate nonahydrate [ Fe (NO) 3 ) 3 .9H 2 O]Dissolving in 7mL of acetic acid as a liquid solvent to prepare a bismuth ferrite solution. In another beaker, 1.1g strontium acetate was dissolved in 15mL acetic acid, and after the solution was clarified, 5mL acetylacetone was added as a stabilizer, and 1.8mL tetrabutyl titanate was added to obtain a strontium titanate solution. The prepared bismuth ferrite solution was mixed with the strontium titanate solution, and 2mL of ethanolamine solution was added to clarify the solution. Adding 1g of barium calcium zirconate titanate fiber into the mixed solution of bismuth ferrite and strontium titanate, carrying out ultrasonic treatment for 3 minutes, pouring the mixed solution into a reaction kettle, and reacting for 24 hours at the temperature of 150 ℃. After the reaction was completed, the modified powder was collected by centrifugal washing and washed with deionized water and ethanol to pH 7. Finally, the mixture was transferred to a drying oven and dried at 60 ℃ for 12 hours.
Step four:
and dispersing the BZCT @ BFSTO NFs filling phase obtained in the third step into an N-methylpyrrolidone solution, and performing ultrasonic dispersion for 2min at the power of 40W. Adding polyether sulfone (PESU) particles into the solution, stirring on a stirrer, and then placing the BZCT @ BFSTO NFs/PESU composite solution into a vacuum box for vacuumizing, standing and bubble discharging for 5h to obtain the BZCT @ BFSTO NFs/PESU precursor solution.
Step five:
and D, performing film coating treatment on the BZCT @ BFSTO NFs/PESU precursor solution obtained in the step four, wherein the film coating speed is controlled to be 1.8cm/s, and the number of the rotating grids of the scraper is 25. And (3) placing the coated film in a vacuum oven at 140 ℃, and carrying out heat treatment on the BZCT @ BFSTO NFs/PESU film to remove the organic solvent. And then peeling the composite film from the glass plate under the action of deionized water to finally obtain the BZCT @ BFSTO NFs/PESU composite film.
FIG. 1 is an X-ray diffraction pattern of inorganic filler phases BZCT NFs and BZCT @ BFSTO NFs. BZCT @ BFSTO can find(100) The (110), (111), (200), (210), (211), (220), (221), (310), (311), and (322) crystal planes. However, compared with BZCT NFs, the characteristic peak of BZCT @ BFSTO NFs is sharper, and the intensity is obviously enhanced. This is because bismuth ferrite and strontium titanate are both ABO 3 The perovskite structure has the characteristic peak of BFSTO and the characteristic peak of BZCT which are coincided, and the diffraction peak of BZCT and the intensity of the diffraction peak of BFSTO are superposed. Therefore, the characteristic peak of BZCT @ BFSTO is more sharp and obvious, and the crystallization is more complete.
FIG. 2 is an X-ray diffraction pattern of pure PESU, BZCT @ BFSTO NFs/PESU composite film and BZCT @ BFSTO NFs. Since the PESU is of an amorphous structure, a diffuse steamed bun peak appears at a 2 theta position equal to about 17.8 degrees, and when the content of the filling phase is 1wt.%, a characteristic peak with a 2 theta position of about 31.5 degrees can be seen, but other characteristic diffraction peaks do not appear, because the doping content is less, only a peak with the strongest intensity appears, and corresponds to a (110) diffraction crystal face. As the content of the inorganic filling phase increases, more characteristic diffraction peaks begin to be reflected, and the intensity of the diffraction peaks is gradually increased. By 7wt.% BZCT @ BFSTO NFs, characteristic diffraction peaks were evident at this time, and characteristic diffraction peaks were seen at about 31.5 °, 38.7 °, 50.8 °, and 65.8 ° in 2 θ.
FIG. 3 is a TEM image of inorganic filler phases BZCT @ BFSTO NFs. It can be clearly seen in transmission electron microscopy that BZCT @ BFSTO NFs are about 650nm in length and about 130nm in diameter. The surface of the BZCT fiber can be clearly seen to have a thin shell layer. The shell layer uniformly and smoothly wraps the BZCT NFs, and the BFSTO is proved to be successfully wrapped on the surface of the BZCT NFs.
FIG. 4 is the scanning electron microscope image of pure PESU and BZCT @ BFST NFs/PESU composite film. According to SEM results, the film of pure PESU has clear section, BZCT @ BFSTO NFs has good compatibility with PESU, large-area agglomeration phenomenon is not found, the section is smooth, and obvious macroscopic defects such as cracks, bubbles and the like are not observed.
FIG. 5 is a dielectric property diagram of pure PESU and BZCT @ BFSTO NFs/PESU composite film. The frequency range tested was 10 0 ～10 7 Hz, the dielectric constant is gradually increased along with the increase of the doping content, which is caused by the introduction of BZCT @ BFSTO NFsInterface polarization is brought to a certain extent, the more the filling amount of BZCT @ BFSTO NFs is, the more the interface is introduced, the consequent increase of the interface polarization and finally the promotion of the dielectric constant are brought. The dielectric constant shows a tendency to decrease with increasing frequency. This is due to the fact that as the frequency increases, the dipole turn gradually fails to follow the change in the outer field, resulting in the gradual disappearance of the portion of the polarization of the dipole turn in the polarization. Incorporation of 1wt.%, 2wt.%, 3wt.%, 5wt.%, 7wt.% of BZCT NFs into a PESU matrix relative to pure PESU polymer, with dielectric constants ranging from 5.0 to 6.0, dielectric losses ranging from 0.013 to 0.016, at a frequency of 1Hz, at 10 Hz 3 The range of dielectric constant is 4.8-5.7 and the range of dielectric loss is 0.005-0.008 under Hz frequency. At 10 5 The range of dielectric constant is 4.7-5.6 and the range of dielectric loss is 0.009-0.010 at Hz frequency. At 10 7 The range of the dielectric constant is 4.4 to 5.1 and the range of the dielectric loss is 0.020 to 0.040 in Hz frequency. The dielectric losses remain low at low frequencies. At 10 6 After Hz, the dielectric losses increase. The dielectric loss is smaller mainly under the action of BFSTO wrapping, so that the formation of a conductive path in the BZCT @ BFSTO NFs/PESU film is greatly hindered, and the migration capability of carriers is inhibited. The introduction of strontium titanate in the shell layer can inhibit the formation of oxygen vacancy, which can greatly improve the insulating property of the dielectric film and lower the dielectric loss. This will result in an optimization of the dielectric properties of the film.
FIG. 6 is a Weibull distribution plot of breakdown field strength of pure PESU and BZCT @ BFSTO NFs/PESU composite films. The range of the characteristic breakdown strength at a cumulative failure probability of 63.2% was 364-490 kV/mm when 1wt.%, 2wt.%, 3wt.%, 5wt.%, 7wt.% of BZCT NFs were introduced into the PESU matrix. At a filler phase content of 2wt.%, the value of the breakdown field is highest, up to 490kV/mm, and the value of β is also highest, up to 16.4, which is much larger than the breakdown field of pure PESU. Firstly, the electric field distribution is more reasonable due to the introduction of the fiber. And the strontium titanate exists in the coated shell layer, so that the capability of inhibiting current carriers is enhanced. And thirdly, the BFSTO shell layer relieves the dielectric difference between the BZCT and the PESU, and is beneficial to reducing the electric field distortion at the interface.
FIG. 7 is a graph of energy storage performance of pure PESU and BZCT @ BFST NFs/PESU composite film. Compared with pure PESU, 1wt.%, 2wt.%, 3wt.%, 5wt.%, and 7wt.% of BZCT NFs are introduced into the PESU matrix, and the electric energy density is 1.3-1.8J/cm under the electric field strength of 200kV/mm 3 The range of the charge and discharge efficiency is 95 to 97%. The discharge energy density range is 4.3-5.5J/cm under the electric field strength of 360kV/mm 3 The range of the charge and discharge efficiency is 88 to 92%.2wt.% BZCT @ BFSTO NFs/PESU has the optimal comprehensive performance, and the energy storage density can reach 10.5J/cm under the electric field of 500kV/mm 3 The efficiency is as high as 84.2%, which is far superior to the energy storage performance of pure PESU. The film can still maintain higher efficiency on the basis of excellent dielectric and breakdown field resistance.
It can be seen from fig. 5, fig. 6 and fig. 7 that the surface-modified inorganic filling phase-polymer matrix composite medium prepared by the method has excellent dielectric constant, lower dielectric loss and higher breakdown-resistant electric field strength.

Claims (7)

1. A preparation method of a surface-modified inorganic filling phase/polyether sulfone-based composite dielectric is characterized in that the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric contains BZCT @ BFSTO NFs and a polymer matrix, wherein the BZCT @ BFSTO NFs is of a core-shell fiber structure, a core layer is barium calcium zirconate titanate, a shell layer is bismuth ferrite-strontium titanate, and the polymer matrix is polyether sulfone;
the preparation method of the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric is completed according to the following steps:
step one, preparing barium calcium zirconate titanate precursor solution:
acetic acid is used as a solvent, acetylacetone is used as a stabilizer, barium hydroxide octahydrate, calcium hydroxide and zirconium acetylacetonate are used as solid solutes, and tetrabutyl titanate is used as a liquid solute; firstly, adding barium hydroxide octahydrate and calcium hydroxide into an acetic acid solvent for heating and stirring, and stopping heating after a solution is clarified; secondly, adding acetylacetone and acetylacetone zirconium powder, and adding a certain amount of tetrabutyl titanate solution after the solution is clarified; finally, adding polyvinylpyrrolidone powder into the transparent solution, violently stirring, clarifying, and aging at room temperature to form a stable barium calcium zirconate titanate precursor solution;
step two, preparing barium calcium zirconate titanate fibers:
sucking the barium calcium zirconate titanate precursor solution obtained in the step one into an injector for preparing spinning; ensuring that the advancing speed of the injector is set to a certain value, the rotating speed of the receiver is set to a proper value, the distance from the injector to the receiver is certain, and the injector and the receiver apply voltage simultaneously; then, putting the precursor fiber obtained by spinning in a muffle furnace for calcining, and fully grinding the calcined fiber to obtain BZCT NFs;
step three, preparing a BZCT @ BFSTO NFs core-shell structure:
dissolving bismuth nitrate pentahydrate and ferric nitrate nonahydrate in a liquid solvent acetic acid to prepare a bismuth ferrite solution; dissolving strontium acetate in acetic acid in another beaker, clarifying the solution, adding acetylacetone as a stabilizer, and adding tetrabutyl titanate to obtain a strontium titanate solution; mixing the prepared bismuth ferrite solution with the strontium titanate solution to prepare 0.25BiFeO 3 -0.75SrTiO 3 A solution; adding an ethanolamine solution to clarify the solution; adding a certain amount of barium calcium zirconate titanate fibers into a mixed solution of bismuth ferrite and strontium titanate, and performing ultrasonic treatment to ensure that BZCT NFs are uniformly dispersed in the mixed solution; pouring the mixed solution into a reaction kettle, reacting at a proper temperature, after the reaction is finished, collecting the modified powder by centrifugal cleaning, washing the modified powder to a proper pH value by deionized water and ethanol, and finally transferring the modified powder to a drying oven for drying to obtain BZCT @ BFSTO NFs;
step four, preparing a BZCT @ BFSTO NFs/PESU precursor solution:
dispersing the BZCT @ BFSTO NFs filling phase obtained in the step three in an N-methylpyrrolidone solution according to a certain mass, ultrasonically dispersing under proper power, adding polyether sulfone particles into the solution, stirring on a stirrer, then placing the BZCT @ BFSTO NFs/PESU composite solution in a vacuum box for vacuumizing, standing and air bubble discharging to obtain a BZCT @ BFSTO NFs/PESU precursor solution;
step five, preparing the barium calcium zirconate titanate fiber/polyether sulfone composite film:
coating the BZCT @ BFSTO NFs/PESU precursor solution obtained in the step four; before coating, the film pushing speed of the coating and the number of rotating grids of a scraper need to be controlled; placing the coated film in a vacuum oven, carrying out heat treatment on the BZCT @ BFSTO NFs/PESU film, and removing the organic solvent to obtain the BZCT @ BFSTO NFs/PESU film;
the mass percentage of BZCT @ BFSTO NFs in the BZCT @ BFSTO NFs/PESU film is 2 wt.%;
the thickness of the BZCT @ BFSTO NFs/PESU film is 8-20 μm.
2. The method for preparing the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric as claimed in claim 1, wherein the method comprises the following steps: adding solutes in a certain order in the first step; firstly, adding 1 to 16g of barium hydroxide octahydrate and 0.2 to 0.9g of calcium hydroxide into 10 to 65mL of acetic acid solvent, stirring, adding 1 to 18mL of acetylacetone and 0.1 to 4g of zirconium acetylacetonate powder after the solution is clarified, and adding 0.8 to 20mL of tetrabutyl titanate solution after the solution is clarified; then 0.5 to 3.5g of polyvinylpyrrolidone powder is added into the transparent solution and stirred vigorously; after clarification, aging for 8 to 10 hours to form a stable barium calcium zirconate titanate precursor solution; the chemical raw materials Ba, ca, zr and Ti are controlled to have the stoichiometric ratio of 0.85 to 0.15.
3. The method for preparing the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric according to claim 2, wherein the method comprises the following steps: ensuring that the propelling speed of the injector is set to be 0.1-0.3 mm/min, the rotating speed of the receiver is set to be 90-150 r/min, the distance from the injector to the receiver is 10-20 cm, and simultaneously applying voltages of plus and minus 15-20V to the injector and the receiver; after spinning is finished, putting the precursor fiber in a muffle furnace to be sintered for 2-6 h at the temperature of 500-850 ℃; finally obtaining BZCT NFs.
4. The method for preparing the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric according to claim 3, wherein the method comprises the following steps: in the third step, 0.9 to 2.2g of bismuth nitrate [ Bi (NO) pentahydrate 3 ) 3 ·5H 2 O]0.7 to 2g of ferric nitrate nonahydrate [ Fe (NO) 3 ) 3 ·9H 2 O]Dissolving in liquid solvent acetic acid to prepare bismuth ferrite solution; dissolving 1.1 to 2.3g of strontium acetate in acetic acid in another beaker, adding acetylacetone as a stabilizer after the solution is clarified, and then adding 1.8 to 3mL of tetrabutyl titanate to obtain a strontium titanate solution; mixing the prepared bismuth ferrite solution with the strontium titanate solution, and adding 1-2.5 mL of ethanolamine solution to clarify the solution; adding 1-2 g of BZCT NFs into a mixed solution of bismuth ferrite and strontium titanate, carrying out ultrasonic treatment for 3-5 min to ensure that barium calcium zirconate titanate fibers are uniformly dispersed in the mixed solution, pouring the mixed solution into a reaction kettle, and reacting for 24h under the conditions of 100-150 ℃; after the reaction was completed, the modified powder was collected by centrifugal washing, washed with deionized water and ethanol to pH 7, and finally transferred to a drying oven for drying at 60 ℃ for 12 hours.
5. The method for preparing the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric according to claim 4, wherein the method comprises the following steps: in the fourth step, a BZCT @ BFSTO NFs filling phase is dispersed in an N-methylpyrrolidone solution, and ultrasonic dispersion is carried out for 1 to 2min, wherein the ultrasonic power is 40 to 60W.
6. The method for preparing the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric according to claim 5, wherein the method comprises the following steps: adding polyether sulfone particles into the solution in the fourth step, and stirring on a stirrer to obtain a BZCT @ BFSTO NFs/PESU composite solution; and then placing the BZCT @ BFSTO NFs/PESU composite solution in a vacuum box for vacuumizing for 2-8 h, standing and discharging air bubbles to obtain a BZCT @ BFSTO NFs/PESU precursor solution.
7. The method for preparing the surface-modified inorganic filling phase/polyether sulfone-based composite dielectric as claimed in claim 6, wherein the method comprises the following steps: before coating, controlling the film pushing speed of the coating film to be 1-3cm/s and the grid number of scraper rotation to be 20-35 grids; placing the coated film in a vacuum oven at the temperature of 60-140 ℃, and carrying out heat treatment on the BZCT @ BFSTO NFs/PESU film to remove the organic solvent; and peeling the composite film from the glass plate under the action of deionized water to finally obtain the BZCT @ BFSTO NFs/PESU composite film.
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