CN113429600A - Silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film and preparation method thereof - Google Patents
Silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film and preparation method thereof Download PDFInfo
- Publication number
- CN113429600A CN113429600A CN202110625568.2A CN202110625568A CN113429600A CN 113429600 A CN113429600 A CN 113429600A CN 202110625568 A CN202110625568 A CN 202110625568A CN 113429600 A CN113429600 A CN 113429600A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- silver
- polyvinylidene fluoride
- composite film
- filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种银‑二氧化钛填料掺杂聚偏氟乙烯的电介质复合薄膜及其制备方法，特点是该复合薄膜由银‑二氧化钛填料填充于聚偏氟乙烯基体中复合而成，银‑二氧化钛填料为核壳结构，其中核层为呈树皮状的表面包覆有片状二氧化钛的一维二氧化钛纳米线，壳层为修饰在片状二氧化钛表面的银纳米颗粒，其制备方法包括将制备得到的银‑二氧化钛填料分散在有机溶剂N‑N二甲基甲酰胺中，然后超声搅拌后，加入聚偏氟乙烯搅拌，采用溶液铸造法制备得到银‑二氧化钛填料体积分数为0.5‑2%的银‑二氧化钛填料掺杂聚偏氟乙烯的电介质复合薄膜的步骤；优点是在较低电场强度下，具有极高的极化、较高的充放电效率和极高的能量密度。
The invention discloses a silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film and a preparation method thereof. The filler is a core-shell structure, wherein the core layer is one-dimensional titanium dioxide nanowires with bark-like surfaces covered with flake titanium dioxide, and the shell layer is silver nanoparticles decorated on the surface of flake titanium dioxide. The silver-titanium dioxide filler was dispersed in the organic solvent N-N dimethylformamide, and after ultrasonic stirring, polyvinylidene fluoride was added to stir, and the solution casting method was used to prepare the silver-titanium dioxide filler with a volume fraction of 0.5-2% silver. ‑Steps of titanium dioxide filler doped polyvinylidene fluoride dielectric composite film; the advantage is that it has extremely high polarization, high charge-discharge efficiency and extremely high energy density at lower electric field strength.
Description
Technical Field
The invention relates to a dielectric composite film, in particular to a silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film and a preparation method thereof.
Background
With the increasing demand of countries in the world for reducing carbon dioxide emission and fossil fuel consumption, efficient electric energy storage technologies dedicated to intermittent and unstable energy sources such as solar energy and wind energy are becoming the inevitable choices for sustainable development. Dielectric capacitors are receiving attention for their wide application in the fields of electronic circuits, hybrid vehicles, renewable energy storage devices, and the like. The polymer is used as the preferred material of the film dielectric capacitor, and compared with a ceramic material, the polymer has the advantages of easy processability, mechanical flexibility, high breakdown strength and the like. However, the low energy density of polymer dielectric materials leads to excessive capacitor volumes and weights that do not meet the increasing demand for miniaturization and lightness, e.g., polymer film capacitors can only provide 1-2J/cm using BOPP as the dielectric3The energy density of (1). Therefore, how to develop a dielectric capacitor having both high discharge energy density and charge-discharge efficiency while maintaining stable performance is of great significance.
The dielectric material realizes the charge and discharge of the capacitor through the polarization and depolarization process under the applied electric field. Thus, polarize: (P) And breakdown strength: (E b) Are two decisive factors affecting the dielectric energy storage performance, among themPAnd dielectric constant: (ε) It is related. Andεdielectric ceramics having values of hundreds or even thousands, dielectric polymersεMuch lower values, low dielectric constants of these polymers: (ε<10) The energy density and thus their application is limited. Polymer-based nanocomposites which convert polymersHeight of the substrateE bWith a high degree of nanofillersεIn combination, have the potential to achieve high energy densities. To increase the dielectric constant of the nanocomposite, a high loading of ceramic particulate filler is often required, however, due to poor compatibility of the two, filler aggregation, voids and other structural defects are often generated, resulting in a substantial decrease in breakdown field strength. Small amounts of one-dimensional nanofillers (nanowires, nanorods, etc.) can increase the electric field strength by their anisotropy, but the improvement of polarization is very limited.
The polymer-based dielectric composite material used as an important constituent material in the capacitor has to have the advantages of high dielectric constant, high energy storage density, good flexibility, large operable electric field and the like, so that the traditional dielectric composite material cannot meet the current actual requirements. Conventional dielectric polymers such as biaxially oriented polypropylene (BOPP), Polyimide (PI), epoxy resin (EP), Polystyrene (PS), etc. which are commonly used, although they have an ultra-high breakdown field strength (> 500 MV/m), they cannot be applied to the high energy storage field due to their low dielectric constant (< 4). Polyvinylidene fluoride (PVDF) has high dielectric constant and flexibility, so that the PVDF is the first choice for a high-performance dielectric material matrix. However, polymer-based dielectric composites intended to achieve high energy storage density are far from adequate depending on the dielectric constant of the polymer matrix. Therefore, the addition of high dielectric fillers to polymer matrices is recognized by many researchers and is a hot spot in research.
The energy storage performance of the composite film is mainly represented by energy storage density and charge-discharge efficiency. The magnitude of the energy storage density is determined by the dielectric constant of the composite material and the breakdown electric field intensity, and the charge-discharge efficiency is the ratio of the discharge energy density to the total energy density. At present, the method for improving the dielectric property of the composite material mainly fills the insulating ceramic filler with high dielectric constant into the polymer matrix or simultaneously adds the conductive and insulating ceramic nano filler. Due to the addition of the high-dielectric ceramic nano filler, the dielectric property of the composite material is obviously improved, the energy storage density is improved, but with the increase of the content of the filler, the dispersibility of the filler in a matrix is reduced, and the phenomena of defects and agglomeration are also increased, so that the breakdown field strength is reduced sharply, and the flexibility of the material is damaged. Although the composite material prepared by utilizing the advantages of various materials can improve the energy storage density, the biggest defect is that the charge-discharge efficiency is low, because the various fillers are difficult to realize uniform dispersion in a polymer matrix and are easy to agglomerate and intertwine, the loss and the leakage current of the composite material are increased, and the energy storage efficiency is obviously reduced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film with extremely high polarization, high charge-discharge efficiency and extremely high energy density under the condition of lower electric field intensity and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the composite film is formed by filling silver-titanium dioxide (Ag @ TO @ TO) filler into a polyvinylidene fluoride substrate and compounding, wherein the silver-titanium dioxide filler is of a core-shell structure, a core layer is a bark-shaped one-dimensional titanium dioxide nanowire (TO NWs) with flaky titanium dioxide (p-TO) coated on the surface, and a shell layer is silver nanoparticles (Ag NPs) modified on the surface of the flaky titanium dioxide.
Preferably, the filling volume of the silver-titanium dioxide filler in the polyvinylidene fluoride matrix is 0.5-2%.
Preferably, the filling volume of the silver-titanium dioxide filler in the polyvinylidene fluoride matrix is 1.5%.
Preferably, the diameter of the core layer is 225-950 nm, the diameter of the one-dimensional titanium dioxide nanowire is 62-550 nm, and the average particle diameter of the silver nanoparticle is 20-30 nm.
The preparation method of the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film comprises the following steps:
(1) synthesizing titanium dioxide nano powder into titanium dioxide nano wires (TO NWs) by a hydrothermal method, and drying for later use;
(2) preparation of bark-like titanium dioxide
Dissolving titanium dioxide nanowires (TO NWs) in isopropanol, magnetically stirring, adding a Diethylenetriamine (DETA) solution, dropwise adding a mixed solution consisting of isopropyl Titanate (TIP) and isopropanol in a volume ratio of 1:5, uniformly mixing, transferring TO a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 24 hours, centrifuging, collecting precipitate, and drying TO obtain bark-shaped one-dimensional titanium dioxide nanowires with surfaces coated with flaky titanium dioxide;
(3) preparation of silver-titanium dioxide fillers
Dissolving bark-shaped titanium dioxide in ethylene glycol, placing into a flask, carrying out ultrasonic treatment for 2 minutes, adding polyvinylpyrrolidone (PVP) and stirring for dissolving for 30 min; fully immersing the flask into an oil bath kettle, and when the temperature rises to 140 ℃, adding AgNO3Slowly dripping ethylene glycol solution into the flask, keeping the oil bath at 140 ℃ for 25 min, simultaneously keeping low-speed stirring, cooling to room temperature, alternately centrifugally cleaning for 4 times by using deionized water and ethanol, and drying to obtain the silver-titanium dioxide filler; too long time or no stirring can result in too large silver particle size (up to 500 nm at maximum) to achieve the desired energy storage performance;
(4) preparation of dielectric composite film
Dispersing 0.00615-0.02461 g of silver-titanium dioxide filler in 3.5 mL of organic solvent N-N Dimethylformamide (DMF), then carrying out ultrasonic treatment for 1 h, stirring for 2 h, adding 0.5 g of polyvinylidene fluoride (PVDF), stirring for 24 h, and preparing the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film with the silver-titanium dioxide filler volume fraction of 0.5-2% by adopting a solution casting method.
Preferably, the step (1) is specifically as follows: uniformly dispersing titanium dioxide nanopowder in 10M sodium hydroxide aqueous solution, performing ultrasonic dispersion for 30min, magnetically stirring for 12H, transferring the mixture into a reaction kettle, heating at 200 deg.C for 24H in a forced air drying oven, taking out, naturally cooling, washing with deionized water to neutrality, soaking in 0.2M hydrochloric acid solution for 4H to obtain H2Ti3O7Hydration ofWashing the product with deionized water to be neutral, drying, and then carrying out heat treatment at 400 ℃ for 3 h to obtain the titanium dioxide nanowire, wherein the mass volume ratio of the titanium dioxide nanowire powder to the sodium hydroxide aqueous solution is 1.15 g: 65 ml. The sodium titanate nanowire is centrifugally washed by deionized water to be neutral and then is directly soaked in hydrochloric acid solution, so that the grown nanowire is smoother and has larger length-diameter ratio.
Preferably, the step (2) is specifically as follows: dissolving 0.08 g of titanium dioxide nanowires (TO NWs) in 40 mL of isopropanol, magnetically stirring for 0.5 h, adding 0.06 mL of Diethylenetriamine (DETA) solution, dropwise adding a mixed solution consisting of 4 mL of isopropyl Titanate (TIP) solution and 20 mL of isopropanol at the speed of 1 mL/min, uniformly mixing, transferring TO a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 24 h, centrifugally collecting precipitates, and drying TO obtain bark-shaped one-dimensional titanium dioxide nanowires with the surfaces coated with platy titanium dioxide, wherein the rotational speed of centrifugal collection is 4000-5000 r/min. The effect of the diethylenetriamine solution is to enable the titanium dioxide to grow along a certain direction, the adding amount is accurately controlled to be 0.06 mL, the roughness of a shell layer, namely the interface area, can be influenced, and meanwhile, if the adding amount is excessive, a modifier on the surface of the filler can be formed, so that under a high electric field, the modifier in the composite film can ionize to form ions, the development of a breakdown path is promoted, and the improvement of the energy storage performance is not facilitated. The isopropyl titanate solution provides a titanium source, and if the dropping speed is too high in the process of dropping into the flask drop by drop, micron-sized large spherical titanium dioxide is generated, and the influence on the later-stage preparation of a film is great, which is very important.
Preferably, the isopropyl titanate and the isopropanol are uniformly stirred at the speed of 150-200 r/min under the sealing condition, and the stirring time is controlled to be 3 minutes.
Preferably, the step (3) is specifically: dissolving 0.1g of bark-shaped titanium dioxide in 40 mL of ethylene glycol, putting the mixture into a flask, carrying out ultrasonic treatment for 2 minutes, adding 0.001 g of polyvinylpyrrolidone (PVP), and stirring to dissolve for 30 min; fully immersing the flask into an oil bath kettle, and when the temperature rises to 140 ℃, adding AgNO3The ethylene glycol solution is slowly dropped into the flask, the oil bath is kept at 140 ℃,stirring at low speed for 25 min, cooling to room temperature, alternately centrifuging with deionized water and ethanol for 4 times, and oven drying to obtain silver-titanium dioxide filler, wherein AgNO3The ethylene glycol solution is prepared by mixing 0.0016 g AgNO3Dissolving in 20 mL of ethylene glycol and uniformly stirring to obtain the product.
Preferably, step (4) is specifically carried out by dispersing 0.00615-0.02461 g of silver-titanium dioxide filler (Ag @ TO @ TO filler) in 3.5 mL of an organic solvent, N-N Dimethylformamide (DMF), then carrying out ultrasonic treatment for 1 h, stirring for 2 h, adding 0.5 g of polyvinylidene fluoride (PVDF), stirring for 24 h, firstly carrying out vacuum treatment on the mixed solution to remove bubbles, taking 1-2 ml of the mixed solution to be dropped on a conductive surface of conductive glass and immediately paving the conductive surface by using a scraper, quickly putting the mixed solution into a 60 ℃ oven for vacuum drying for 6 h, continuously heating to 200 ℃ after completely evaporating redundant solvent DMF, preserving heat for 10 min, quickly putting the taken composite film into ice water for quenching, cleaning and drying, and obtaining the dielectric composite film of polyvinylidene fluoride doped with the silver-titanium dioxide filler, wherein the volume fraction of the silver-titanium dioxide filler is 0.5-2%.
Compared with the prior art, the invention has the advantages that: the invention relates TO a composite film of a silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film and a preparation method thereof. The PVDF polymer is used as a matrix (the PVDF polymer has higher dielectric constant in the polymer matrix), and the Ag @ TO @ TO is used as a filler, so that the field strength and the polarization are improved at the same time. The reason is as follows: first, a low content of TO NWs, by virtue of its dielectric anisotropy, can prevent distortion of local electric field and can improve electric field intensity. Second, the TO @ TO rough shell greatly increases the interfacial area and interfacial polarization. Finally, the breakdown field intensity is improved by utilizing the coulomb blocking effect of the metal silver particles, and meanwhile, the interface area is increased by the metal silver particles with small particle size, so that the interface polarization is improved.
In summary, the composite film of the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film and the composite filmThe composite film has high breakdown field strength, extremely high polarization strength and high charge-discharge efficiency, and utilizes the dielectric anisotropy of the one-dimensional nanowires, the coulomb blockade effect of the metal particles and the bark-shaped TiO2The dielectric property and the energy storage property of the dielectric composite material are improved due to the large interface area of the filler and the interface polarization caused by the metal silver nanoparticles with smaller sizes, the filling amount of the filler is only 1.5 vol.% while the excellent energy storage property is realized, and the low filling amount is beneficial to maintaining the flexibility of the composite film. The results of the study showed that 1.5 vol.% Ag @ TO @ TO/PVDF nanocomposites had the highest when the electric field strength was 376 MV/mU dThe value is 16.5J/cm3，ηThe content was 78%.
Drawings
FIG. 1 is an SEM image of how many titration rates a core layer of silver-titanium dioxide filler is formed at
FIG. 2 is an XRD plot of (a) Ag @ TO @ TO, (b) SEM images of TO @ TO and (c) Ag @ TO @ TO, (d-f) energy spectrum analysis plot (EDS) of Ag @ TO @ TO;
FIG. 3 is a statistical representation of the core-layer size distribution of silver-titanium dioxide fillers, where (a) is one-dimensional titanium dioxide nanowires (TO NWs); (b) is a one-dimensional titanium dioxide nanowire with a bark-shaped surface coated with flaky titanium dioxide (p-TO),
FIG. 4 is a drawing showingx(ii) discharge energy density and charge-discharge efficiency of vol.% Ag @ TO @ TO/PVDF composite film, whereinxRepresents the volume fraction of Ag particles in Ag @ TO @ TO;
FIG. 5 is a graph of the dielectric constant of Ag @ TO @ TO/PVDF composite films prepared with different volume fractions of filler as a function of frequency;
FIG. 6 is a graph of the loss of Ag @ TO @ TO/PVDF composite films made with different volume fractions of filler as a function of frequency;
FIG. 7 is a graph of breakdown field strength for Ag @ TO @ TO/PVDF composite films prepared with different volume fractions of filler;
FIG. 8 is a graph of the discharge energy density and the charge-discharge efficiency of Ag @ TO @ TO/PVDF composite films prepared with different volume fractions of fillers.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Detailed description of the preferred embodiments
Example 1
A silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film is formed by filling a silver-titanium dioxide (Ag @ TO @ TO) filler into a polyvinylidene fluoride substrate and compounding, wherein the silver-titanium dioxide filler is of a core-shell structure, a core layer is a one-dimensional titanium dioxide nanowire (TO NWs) with the surface coated with bark-shaped flaky titanium dioxide (p-TO), a shell layer is silver nanoparticles (Ag NPs) modified on the surface of the flaky titanium dioxide, and the preparation process is as follows:
1. synthesizing titanium dioxide nano powder into titanium dioxide nanowires (TO NWs) by a hydrothermal method, and drying for later use, wherein the method comprises the following steps: uniformly dispersing titanium dioxide nanopowder in 10M sodium hydroxide aqueous solution, performing ultrasonic dispersion for 30min, magnetically stirring for 12H, transferring the mixture into a reaction kettle, heating in a forced air drying oven at 200 deg.C for 24H, taking out, naturally cooling, washing with deionized water to neutrality, soaking in 0.2M hydrochloric acid solution for 4H to obtain H2Ti3O7Washing the hydrate with deionized water to be neutral, drying, placing the hydrate in an alumina crucible, and carrying out heat treatment at 400 ℃ for 3 h to obtain the titanium dioxide nanowire, wherein the mass-to-volume ratio of the titanium dioxide nanopowder to the sodium hydroxide aqueous solution is 1.15 g: 65 ml;
2. preparation of bark-like titanium dioxide
Dissolving 0.08 g of titanium dioxide nanowires (TO NWs) in 40 mL of isopropanol, magnetically stirring for 0.5 h, adding 0.06 mL of Diethylenetriamine (DETA) solution, dropwise adding a mixed solution consisting of 4 mL of isopropyl Titanate (TIP) solution and 20 mL of isopropanol at the speed of 1 mL/min, uniformly mixing, transferring TO a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 24 h, centrifugally collecting precipitate, and drying TO obtain bark-shaped one-dimensional titanium dioxide nanowires (TO @ TO) coated with platy titanium dioxide, wherein the rotational speed of the centrifugal collection is 4000-5000 r/min; the titration is carried out at a rate of 1 mL/min, if the rate of the titration is too high, large spheres as shown in the figure 1 are generated, and the generation of micron-sized large spherical titanium dioxide has great influence on the later preparation of the film, which is very important. The filler synthesized by the dropping speed used in the experiment has uniform appearance and almost no large ball is formed. For too slow a drop, theoretically, the effect may be better, but this would take longer, not in line with the industrial concept of efficient production. The isopropyl titanate and the isopropanol are uniformly stirred at the speed of 150-200 r/min under the sealing condition, and the stirring time is controlled to be 3 minutes, so that the oxidation is avoided.
3. Preparation of Ag @ TO @ TO
Dissolving 0.1g of bark-like titanium dioxide (TO @ TO) in 40 mL of ethylene glycol, putting the mixture into a flask, carrying out ultrasonic treatment for 2 minutes, adding 0.001 g of polyvinylpyrrolidone (PVP), and stirring and dissolving for 30 min; fully immersing the flask into an oil bath kettle, and when the temperature rises to 140 ℃, adding AgNO3Slowly dripping ethylene glycol solution into the flask, keeping the oil bath at 140 ℃ for 25 min, simultaneously keeping stirring at a low speed, cooling TO room temperature, alternately centrifugally cleaning for 4 times by using deionized water and ethanol, and drying TO obtain the silver-titanium dioxide filler (Ag @ TO), wherein AgNO is3The ethylene glycol solution is prepared by mixing 0.0016 g AgNO3Dissolving in 20 mL of ethylene glycol and uniformly stirring to obtain the product.
4. Preparation of Ag @ TO @ TO/PVDF composite film
First, 0.00615 g of silver-titanium dioxide filler (Ag @ TO @ TO) was dispersed in 3.5 mL of organic solvent N-N Dimethylformamide (DMF), then ultrasonic treatment is carried out for 1 h, stirring is carried out for 2 h, then 0.5 g of polyvinylidene fluoride (PVDF) is added, stirring is carried out for 24 h, removing bubbles from the mixed solution by vacuum treatment, dripping 1-2 ml of the mixed solution onto a conductive surface of conductive glass (FTO, the area of 3 cm x 4 cm), immediately paving the conductive surface by using a scraper, quickly putting the mixed solution into a 60 ℃ oven for vacuum drying for 6 h, continuously heating to 200 ℃ after redundant solvent DMF is completely evaporated, preserving heat for 10 min, quickly putting the taken composite film into ice water for quenching, cleaning and drying, and obtaining the dielectric composite film of the silver-titanium dioxide filler doped polyvinylidene fluoride, wherein the volume fraction of the silver-titanium dioxide filler is 0.5%.
Example 2
The difference from the above example 1 is that: in the step 4, 0.00615 g of Ag @ TO @ TO filler is dispersed in 3.5 mL of organic solvent N-N Dimethylformamide (DMF), then ultrasonic treatment is carried out for 1 h, stirring is carried out for 2 h, then 0.5 g of polyvinylidene fluoride (PVDF) is added, stirring is carried out for 24 h, and the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film with the silver-titanium dioxide filler volume fraction of 1% is prepared by adopting a solution casting method.
Example 3
The difference from the above example 1 is that: in the step 4, 0.01848 g of Ag @ TO @ TO filler is dispersed in 3.5 mL of organic solvent N-N Dimethylformamide (DMF), then ultrasonic treatment is carried out for 1 h, stirring is carried out for 2 h, then 0.5 g of polyvinylidene fluoride (PVDF) is added, stirring is carried out for 24 h, and the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film with the silver-titanium dioxide filler volume fraction of 1.5% is prepared by adopting a solution casting method.
Example 4
The difference from the above example 1 is that: in the step 4, 0.02461g of Ag @ TO @ TO filler is dispersed in 3.5 mL of organic solvent N-N Dimethylformamide (DMF), then ultrasonic treatment is carried out for 1 h, stirring is carried out for 2 h, then 0.5 g of polyvinylidene fluoride (PVDF) is added, stirring is carried out for 24 h, and the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film with the silver-titanium dioxide filler volume fraction of 2% is prepared by adopting a solution casting method.
In each of the above examples, the volume fraction and mass of the silver-titanium dioxide filler (Ag @ TO @ TO) are converted as follows: for silver particles (Ag):
The volume fraction of Ag TO Ag @ TO; energy spectrum analysis is performed by the attached figure 2 of the specification:
to obtain
(ii) a So in the filler Ag @ TO @ TO, when the mass fraction of silver is 13.2 wt.%, the volume fraction equivalent TO silver TO Ag @ TO @ TO is 6 vol.%.
Further by energy spectrum analysis:
（1），
for PVDF:
whereinρ= 1.76 g/cm3Wherein in example 1m = 0.5g；
The volume fraction of PVDF is 99 vol.% when the volume fraction of the filler Ag @ TO @ TO is 1 vol.%.
In this way, it can be seen that,
，
is obtained by the formula:
=0.002869605 cm3 （2），
simultaneous (1) and (2) to obtain:
= 0.000154 cm3，
= 0.002716 cm3(ii) a To obtain
，
， 
Thus, when the filler Ag @ TO @ TO comprises 1 vol.% of the composite film, the filler Ag @ TO @ TO has a mass of 0.01227 g. The calculations are similar for the remaining embodiments.
Second, result analysis
1. FIG. 2 is an XRD plot of (a) Ag @ TO @ TO, (b) SEM images of TO @ TO and (c) Ag @ TO @ TO, and (d-f) energy spectrum analysis plot of Ag @ TO @ TO (EDS). In fig. 2(a), diffraction peaks of Ag NPs can be clearly observed, and can be clearly indexed according to a standard PDF card (No. # 04-0783). Diffraction peaks of TO can also be seen, which can be unambiguously indexed according TO standard PDF cards (No. # 35-0088). Comparing fig. 2(b) and fig. 2(c), it can be seen that Ag NPs are uniformly distributed on the surface of the bark-like TO @ TO having an average diameter of 480 nm, as shown in fig. 3, the silver nanoparticles having an average particle size of 25 nm, and an ultra-small particle size providing conditions for increasing the interfacial area. The interface of the Ag NPs in the Ag @ TO @ TO filler with the polymer matrix, and the interface of the Ag NPs with the bark-like TO @ TO, and the interface of the bark-like TO with the internal titanium dioxide, may contribute TO increasing the interfacial polarization of the Ag @ TO @ TO/PVDF nanocomposite. TO further demonstrate the successful modification of AgNPs TO a bark-like TO @ TO surface, the filler Ag @ TO was characterized by X-ray spectroscopy (EDS), as shown in fig. 3 (d-f), which shows a mass fraction of silver of about 13.2 wt.%, converted TO a volume fraction of 6 vol.% for a uniform representation. The content of silver has a large influence on the energy storage performance of the composite film, and as can be seen from fig. 4, the discharge energy density of each component gradually increases with the increase of the electric field strength. As expected, sinceP m-P rAndE bat the same time, the strength is enhanced,xvol.% Ag @ TO @ TO/PVDF composite film produced 16.3J/cm at 376 MV/m3Highest of (2)U dAnd 7.4 of pure PVDF filmJ/cm3(at 335 MV/m) by a factor of 2.2. Furthermore, withU dOf all nanocompositesηStill at a high level (>75%) of, e.g., 6 vol.% Ag @ TO @ TO/PVDF composite filmηStill remains at the higher 77%. Is kept highηThe main reasons for this are that the TO @ TO of the inner layer is a paraelectric dielectric, and the limited charge transfer and leakage current in Ag @ TO.
2. FIG. 5 is a graph of the dielectric constant of Ag @ TO/PVDF composite films made with different volume fractions of filler as a function of frequency. FIG. 5 shows the frequency dependence of dielectric properties of Ag @ TO @ TO/PVDF composite films made with different volume fractions of filler at room temperature. As shown in FIG. 5, the dielectric constant of the Ag @ TO @ TO/PVDF composite film gradually decreases with the increase of the frequency, because the mobility of the dipole decreases with the increase of the frequency and cannot follow the frequency change of the applied electric field. More importantly, as the volume fraction of Ag @ TO @ TO increases, the dielectric constant of the pure PVDF film and the Ag @ TO @ TO/PVDF composite film increases from 10 TO 21 at 1 KHz, and the dielectric constant of the composite film increases mainly due TO interfacial polarization and space charge polarization. That is, due TO the multi-layer interface in the Ag @ TO filler, under the action of an external electric field, a transmission path of space charge is blocked, and charge is accumulated at the interface, so that the interface polarization effect is enhanced, and further, the dielectric constant is increased.
3. FIG. 6 is a graph of the loss as a function of frequency for Ag @ TO @ TO/PVDF composite films made with different volume fractions of filler. Below low frequencies, the interface polarization dominates, so the losses are relatively large, with increasing frequency the dipole polarization dominates, the losses decrease, and below higher frequencies, mainly the ion polarization and the electron polarization dominate. Despite the loss tangent (tan) of the composite filmδ) Slightly increased due to the increase in free charge, but all samples were kept at a low tan delta level (less than 0.04 at 1 KHz), representing better overall insulation, which provides the potential for high breakdown strength of the nanocomposite films. In summary, compared with pure PVDF film, the Ag @ TO @ TO/PVDF composite film has obviously improved dielectric constant and dielectric propertyThe loss is slightly increased, which is very advantageous for improving the energy storage performance.
4. FIG. 7 is a graph of breakdown field strength for Ag @ TO @ TO/PVDF composite films made with different volume fractions of filler. Breakdown field strength according to the energy storage mechanism of the capacitor (E b) Is one of the key factors for measuring the energy storage performance of the composite material. Thus, as shown in FIG. 7, the present invention is directed TO a pure PVDF film and a Ag @ TO @ TO/PVDF composite filmE bValues were studied for a Weber distribution in which high values of Weber coefficients: (β) Meaning high reliability. The breakdown field intensity of the pure PVDF film and the Ag @ TO @ TO/PVDF composite film shows a trend of increasing and then decreasing along with the increase of the volume fraction of the filler, and in addition, the whole Weber coefficient of the composite filmβAll kept above 15, which shows that the statistical result of the breakdown field strength of the composite film has higher reliability. In addition to this, the present invention is,xvol.% Ag @ TO @ TO/PVDF composite film (x=0.5-1.5) ofE bThe values are significantly higher than pure PVDF (335 MV/m),E bthis increase is mainly due TO the fact that most of the bark-like TO @ TO fillers are oriented in the polymer matrix perpendicular TO the direction of the external electric field, which orientation is beneficial TO increase the tortuosity of the growth path of the electrical tree during breakdown. Meanwhile, according to the coulomb blocking effect, the silver nanoparticles with smaller size (less than 30 nm) can capture part of free electrons and prevent other electrons from entering, so that the silver nanoparticles are equivalent to scattering centers, the migration of free charges is further inhibited, and the tortuosity of a breakdown path is increased, so that the composite material has higher breakdown strength.
5. FIG. 8 is a graph of the discharge energy density and the charge-discharge efficiency of Ag @ TO @ TO/PVDF composite films made of fillers with different volume fractions. As shown in fig. 8, according toP-ECurve calculation of pure PVDF and Ag @ TO @ TO/PVDF composite filmU dAndη. As predicted, sinceP m-P rAndE bwhile enhancing, the 1.5 vol.% Ag @ TO @ TO/PVDF composite film produced 16.4J/cm at 376 MV/m3Highest of (2)U d. 1.5 vol.% Ag @ TO @ TO/PVDF composite film under 376 MV/m electric fieldU d (16.4 J/cm3) Seems to be better than the previous work. With PVDF film (7.4J/cm)3335 MV/m) and commercial BOPP (3.56J/cm)3600 MV/m) in a sample,U drespectively increased by 222% and 460%. Further, as shown in FIG. 8, as followsU dOf all nanocompositesηStill at a high level (>75%) of a composite film such as 1.5 vol.% Ag @ TO @ TO/PVDFηStill remains at the higher 77%. Is kept highηMainly due TO the limited charge transfer and leakage current in Ag @ TO, which is a paraelectric dielectric. Taken together, with such a small volume fraction of Ag @ TO @ TO (1.5 vol.%), a simultaneous realization was madeP m-P r、E b、U dAndηenhancement of (3). According to the invention, by designing the microstructure of the nano filler and integrating the advantages of different media, the overall performance of the composite film is finally improved, and a new idea is provided for preparing the composite dielectric material with higher energy storage density.
In summary, the above composite film is prepared by hydrothermal method to obtain bark-like TiO2The preparation method comprises the following steps of filling (TO @ TO), coating a trace amount of Ag NPs on the TO @ TO outer layer through an oil bath method TO synthesize the Ag @ TO @ TO filling, then compounding the Ag @ TO @ TO filling on a PVDF substrate, preparing an Ag @ TO/PVDF composite film through a scraper coating method, wherein the micro-morphology of the ceramic filling has great influence on the energy storage performance of the composite material. The microstructure of the one-dimensional filler, such as a core-shell structure, is designed, so that the electric field distribution can be more uniform to a certain degree, the area of a multilayer interface is increased, and the interface polarization is increased, so that the electric field intensity and polarization of the composite film are improved, and in addition, the multilayer interface can also inhibit the movement of space charges, so that the efficiency is improved, and finally, the energy storage density is improved. The metal particles can greatly improve the composite material at low filling amountεAnd trace metal particles are coated outside the well-designed one-dimensional core-shell structure filler, so that the polarization of the dielectric composite material can be further improved. In addition, the nano-scale metal filler can often generate the coulomb blocking effect in the composite dielectric medium, and the leakage current is blocked to further improve the leakage currentThe electric field intensity also contributes to the improvement of the charge-discharge efficiency.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (10)
1. A silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film is characterized in that: the composite film is formed by filling a silver-titanium dioxide filler into a polyvinylidene fluoride matrix and compounding, wherein the silver-titanium dioxide filler is of a core-shell structure, the core layer is a bark-shaped one-dimensional titanium dioxide nanowire with the surface coated with flaky titanium dioxide, and the shell layer is silver nanoparticles modified on the surface of the flaky titanium dioxide.
2. The silver-titanium dioxide filler polyvinylidene fluoride-doped dielectric composite film according to claim 1, wherein: the filling volume of the silver-titanium dioxide filler in the polyvinylidene fluoride matrix is 0.5-2%.
3. The silver-titanium dioxide filler polyvinylidene fluoride-doped dielectric composite film according to claim 2, wherein: the filling volume of the silver-titanium dioxide filler in the polyvinylidene fluoride matrix is 1.5%.
4. The silver-titanium dioxide filler polyvinylidene fluoride-doped dielectric composite film according to claim 1, wherein: the diameter of the core layer is 225-950 nm, the diameter of the one-dimensional titanium dioxide nanowire is 62-550 nm, and the average particle size of the silver nanoparticles is 20-30 nm.
5. A preparation method of a silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film is characterized by comprising the following steps:
(1) synthesizing the titanium dioxide nano powder into a titanium dioxide nanowire by a hydrothermal method, and drying for later use;
(2) preparation of bark-like titanium dioxide
Dissolving titanium dioxide nanowires in isopropanol, magnetically stirring, adding a diethylenetriamine solution, dropwise adding a mixed solution consisting of isopropyl titanate and isopropanol according to a volume ratio of 1:5, uniformly mixing, transferring to a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 24 hours, centrifuging, collecting precipitate, and drying to obtain bark-shaped one-dimensional titanium dioxide nanowires with surfaces coated with flaky titanium dioxide;
(3) preparation of silver-titanium dioxide fillers
Dissolving bark-shaped titanium dioxide in ethylene glycol, placing the mixture into a flask, carrying out ultrasonic treatment for 2 minutes, adding polyvinylpyrrolidone, and stirring and dissolving for 30 min; fully immersing the flask into an oil bath kettle, and when the temperature rises to 140 ℃, adding AgNO3Slowly dripping ethylene glycol solution into the flask, keeping the oil bath at 140 ℃ for 25 min, simultaneously keeping low-speed stirring, cooling to room temperature, alternately centrifugally cleaning for 4 times by using deionized water and ethanol, and drying to obtain the silver-titanium dioxide filler;
(4) preparation of dielectric composite film
Dispersing 0.00615-0.02461 g of silver-titanium dioxide filler in 3.5 mL of organic solvent N-N dimethylformamide, then carrying out ultrasonic treatment for 1 h, stirring for 2 h, adding 0.5 g of polyvinylidene fluoride, stirring for 24 h, and preparing the dielectric composite film with the silver-titanium dioxide filler doped with polyvinylidene fluoride, wherein the volume fraction of the silver-titanium dioxide filler is 0.5-2%.
6. The preparation method of the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film according to claim 5, wherein the step (1) is specifically as follows: uniformly dispersing titanium dioxide nanopowder in 10M sodium hydroxide water solution, performing ultrasonic dispersion for 30min, magnetically stirring for 12 h, transferring the mixture into a reaction kettle, heating at 200 deg.C for 24 h in a forced air drying oven, taking out, naturally cooling, washing with deionized water to neutrality, and washing with deionized waterSoaking in 0.2M hydrochloric acid solution for 4H to obtain H2Ti3O7And (2) washing the hydrate with deionized water to be neutral, drying, and then carrying out heat treatment at 400 ℃ for 3 h to obtain the titanium dioxide nanowire, wherein the mass volume ratio of the titanium dioxide nanopowder to the sodium hydroxide aqueous solution is 1.15 g: 65 ml.
7. The preparation method of the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film according to claim 5, wherein the step (2) is specifically as follows: dissolving 0.08 g of titanium dioxide nanowires in 40 mL of isopropanol, magnetically stirring for 0.5 h, adding 0.06 mL of diethylenetriamine solution, dropwise adding a mixed solution consisting of 4 mL of isopropyl titanate solution and 20 mL of isopropanol at the speed of 1 mL/min, uniformly mixing, transferring to a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 24 h, centrifuging, collecting precipitate, and drying to obtain bark-shaped one-dimensional titanium dioxide nanowires with the surface coated with platy titanium dioxide, wherein the rotation speed of centrifugal collection is 4000-5000 r/min.
8. The method for preparing the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film as claimed in claim 7, wherein the isopropyl titanate and the isopropyl alcohol are uniformly stirred under a sealing condition at a speed of 150-200 r/min, and the stirring time is controlled within 3 minutes.
9. The preparation method of the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film according to claim 7, wherein the step (3) is specifically as follows: dissolving 0.1g of bark-shaped titanium dioxide in 40 mL of ethylene glycol, putting the mixture into a flask, carrying out ultrasonic treatment for 2 minutes, adding 0.001 g of polyvinylpyrrolidone, and stirring and dissolving for 30 min; fully immersing the flask into an oil bath kettle, and when the temperature rises to 140 ℃, adding AgNO3Slowly dripping ethylene glycol solution into the flask, keeping the oil bath at 140 ℃ for 25 min, simultaneously keeping low-speed stirring, cooling to room temperature, alternately centrifugally cleaning for 4 times by using deionized water and ethanol, and drying to obtain the silver-titanium dioxide fillingMaterial of which AgNO3The ethylene glycol solution is prepared by mixing 0.0016 g AgNO3Dissolving in 20 mL of ethylene glycol and uniformly stirring to obtain the product.
10. The preparation method of the silver-titanium dioxide filler-doped polyvinylidene fluoride dielectric composite film according to claim 5, wherein the step (4) is specifically that 0.00615-0.02461 g of the silver-titanium dioxide filler is dispersed in 3.5 mL of organic solvent N-N Dimethylformamide (DMF), then ultrasonic treatment is carried out for 1 h, after stirring for 2 h, 0.5 g of polyvinylidene fluoride is added, after stirring for 24 h, the mixed solution is firstly subjected to vacuum treatment to remove bubbles, 1-2 mL of the mixed solution is dripped on the conductive surface of conductive glass and immediately paved by a scraper, the mixed solution is rapidly placed into a 60 ℃ oven for vacuum drying for 6 h, after the redundant solvent DMF is completely evaporated, the temperature is continuously raised to 200 ℃, the temperature is kept for 10 min, the taken out composite film is rapidly placed into ice water for quenching, and cleaning and drying are carried out, and the silver-titanium dioxide filler-doped polyvinylidene fluoride electric film with the silver-titanium dioxide filler volume fraction of 0.5-2% is obtained And (3) medium composite film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110625568.2A CN113429600B (en) | 2021-06-04 | 2021-06-04 | Silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110625568.2A CN113429600B (en) | 2021-06-04 | 2021-06-04 | Silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113429600A true CN113429600A (en) | 2021-09-24 |
| CN113429600B CN113429600B (en) | 2023-02-14 |
Family
ID=77803718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110625568.2A Active CN113429600B (en) | 2021-06-04 | 2021-06-04 | Silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113429600B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113787795A (en) * | 2021-08-11 | 2021-12-14 | 哈尔滨理工大学 | Polypyrrole/polyvinylidene fluoride composite film with sandwich structure and preparation method thereof |
| CN114512341A (en) * | 2022-03-10 | 2022-05-17 | 常州工学院 | Ultralow filler and high-energy-storage-density dielectric material for energy storage capacitor and preparation method thereof |
| CN115926345A (en) * | 2022-12-14 | 2023-04-07 | 陕西科技大学 | Polyvinylidene fluoride/calcium niobate nanosheet @ aluminum oxide composite material and preparation method and application thereof |
| CN117626533A (en) * | 2024-01-25 | 2024-03-01 | 石家庄铁道大学 | NH 2 Preparation method of MIL-125 filled dielectric film |
| CN117650013A (en) * | 2023-10-24 | 2024-03-05 | 中国长江三峡集团有限公司 | Thin film capacitor with high breakdown strength and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550260A (en) * | 2009-05-15 | 2009-10-07 | 吉林大学 | High-dielectric composite material containing silver nanowires and preparation method thereof |
| CN108748942A (en) * | 2018-06-01 | 2018-11-06 | 芜湖市亿仑电子有限公司 | A kind of preparation method of polymer-based dielectric material |
| US20190136109A1 (en) * | 2017-11-07 | 2019-05-09 | Rogers Corporation | Dielectric layer with improved thermally conductivity |
-
2021
- 2021-06-04 CN CN202110625568.2A patent/CN113429600B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550260A (en) * | 2009-05-15 | 2009-10-07 | 吉林大学 | High-dielectric composite material containing silver nanowires and preparation method thereof |
| US20190136109A1 (en) * | 2017-11-07 | 2019-05-09 | Rogers Corporation | Dielectric layer with improved thermally conductivity |
| CN108748942A (en) * | 2018-06-01 | 2018-11-06 | 芜湖市亿仑电子有限公司 | A kind of preparation method of polymer-based dielectric material |
Non-Patent Citations (3)
| Title |
|---|
| WU ZJ, ET AL: "Novel core–shell-structured ironbark-like TiO2 as fillers for excellent discharged energy density of nanocomposites", 《J MATER SCI: MATER ELECTRON》 * |
| XIAO XR, ET AL: "High performance of P(VDF-HFP)/Ag@TiO2 hybrid films with enhanced dielectric permittivity and low dielectric loss", 《RSC ADV》 * |
| 肖兴荣: "Ag-TiO2/P(VDF-HFP)复合材料的制备及性能研究", 《中国优秀博硕士论文全文数据库（硕士）工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113787795A (en) * | 2021-08-11 | 2021-12-14 | 哈尔滨理工大学 | Polypyrrole/polyvinylidene fluoride composite film with sandwich structure and preparation method thereof |
| CN114512341A (en) * | 2022-03-10 | 2022-05-17 | 常州工学院 | Ultralow filler and high-energy-storage-density dielectric material for energy storage capacitor and preparation method thereof |
| CN115926345A (en) * | 2022-12-14 | 2023-04-07 | 陕西科技大学 | Polyvinylidene fluoride/calcium niobate nanosheet @ aluminum oxide composite material and preparation method and application thereof |
| CN117650013A (en) * | 2023-10-24 | 2024-03-05 | 中国长江三峡集团有限公司 | Thin film capacitor with high breakdown strength and preparation method and application thereof |
| CN117626533A (en) * | 2024-01-25 | 2024-03-01 | 石家庄铁道大学 | NH 2 Preparation method of MIL-125 filled dielectric film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113429600B (en) | 2023-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113429600A (en) | Silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film and preparation method thereof | |
| Wang et al. | Flexible barium titanate@ polydopamine/polyvinylidene fluoride/polymethyl methacrylate nanocomposite films with high performance energy storage | |
| Zhang et al. | Two‐dimensional transition metal carbides and nitrides (MXenes): synthesis, properties, and electrochemical energy storage applications | |
| CN101712784B (en) | A kind of core-shell structure filler/polymer matrix composite material and preparation method thereof | |
| CN1232377C (en) | Preparation method of cubic silver nanocrystalline particles | |
| US20080050573A1 (en) | Silicon Nanosheet , Nanosheet Solution and Process for Producing the Same, Nanosheet -Containing Composite, and Nanosheet Aggregate | |
| CN101024249B (en) | Fine nickel powder and its preparation method | |
| KR20170090449A (en) | Method and Material for Lithium Ion Battery Anodes | |
| Feng et al. | Highly dispersive Ba0. 6 Sr0. 4 TiO3 nanoparticles modified P (VDF‐HFP)/PMMA composite films with improved energy storage density and efficiency | |
| Tao et al. | High dielectric thin films based on barium titanate and cellulose nanofibrils | |
| Niu et al. | Fluorocarboxylic acid-modified barium titanate/poly (vinylidene fluoride) composite with significantly enhanced breakdown strength and high energy density | |
| Adireddy et al. | Polymer-ceramic nanocomposites for high energy density applications | |
| CN107033502A (en) | Sour barium/organic matrix composite membrane of the neodymium-doped titanium of a kind of simple high energy storage density and preparation method thereof | |
| CN110698859A (en) | A silica-coated modified barium titanate/polysulfone dielectric composite material and preparation method thereof | |
| CN113736195B (en) | A kind of high temperature resistant ferroelectric polymer-based dielectric energy storage composite film and its preparation method and application | |
| CN113045845B (en) | TiO (titanium dioxide)2Nano-material-doped double-layer polyvinylidene fluoride composite medium and preparation method thereof | |
| CN106519516B (en) | A kind of dielectric composite material and preparation method thereof based on paraffin cladding barium titanate nano particle | |
| Li et al. | Preparation and studies of MXene@ PDA/PVDF composites with improved dielectric properties | |
| Tsyganov et al. | Thermal behavior of the dielectric response of composites based on poly (vinylidene fluoride) filled with two-dimensional V 2 CT x MXenes | |
| Wang et al. | Structural modification of carbon black for improving the dielectric performance of epoxy based composites | |
| Deng et al. | Achieving a high dielectric constant and low dielectric loss of polymer composites filled with an interface-bonded g-C3N4@ PbS narrow-bandgap semiconductor | |
| Cho et al. | MWCNT-embedded Li4Ti5O12 microspheres interfacially modified with polyaniline as ternary composites for high-performance lithium ion battery anodes | |
| CN113024974B (en) | One-dimensional TiO2 nanowire hybrid structure doped polyvinylidene fluoride composite film and preparation method thereof | |
| CN103755958B (en) | A kind of preparation method of polyimides/CaCu 3 Ti 4 O coated with silver nano particle composite material | |
| Ling et al. | The effects of TiC@ AlOOH core–shell nanoparticles on the dielectric properties of PVDF based nanocomposites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240205 Address after: Room 10, 1st Floor, Comprehensive Building, Food Company, Market Street, Zhongning County, Zhongwei City, Ningxia Hui Autonomous Region, 755100 Patentee after: Ningxia Baolong New Energy Technology Co.,Ltd. Country or region after: China Address before: 315211, Fenghua Road, Jiangbei District, Zhejiang, Ningbo 818 Patentee before: Ningbo University Country or region before: China |
|
| TR01 | Transfer of patent right | ||
| CP03 | Change of name, title or address |
Address after: 755100 Ningxia Hui Autonomous Region Zhongwei City Zhongning County Chengshi Street Food Company Comprehensive Building 1st Floor Room 10 Patentee after: Baolong New Energy Engineering (Ningxia) Co.,Ltd. Country or region after: China Address before: Room 10, 1st Floor, Comprehensive Building, Food Company, Market Street, Zhongning County, Zhongwei City, Ningxia Hui Autonomous Region, 755100 Patentee before: Ningxia Baolong New Energy Technology Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address |