CN113429600B - 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
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 9
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- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K2003/0806—Silver
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
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Abstract
The invention discloses a silver-titanium dioxide filler-polyvinylidene fluoride-doped dielectric composite film and a preparation method thereof, and is characterized in that the composite film is formed by filling a silver-titanium dioxide filler in a polyvinylidene fluoride matrix, wherein the silver-titanium dioxide filler is of a core-shell structure, a core layer is a bark-shaped one-dimensional titanium dioxide nanowire with flaky titanium dioxide coated on the surface, and a shell layer is silver nanoparticles modified on the surface of the flaky titanium dioxide; the advantages are that under lower electric field intensity, the device has extremely high polarization, higher charge and discharge efficiency and extremely high energy density.
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 dielectric 3 The 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 far-reaching importance.
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 ceramic phase ratio of several hundred or even several thousand, dielectric polymerεMuch lower values, low dielectric constants of these polymers: (ε<10 Limit the energy density and thus their applications. Polymer-based nanocomposites incorporating a polymer matrixE b With 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 amount of one-dimensional nano filler (nano wire, nano rod, etc.), and the anisotropy can be used to increase electric field intensity, but the polarization is not increasedOften 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. Although conventional common dielectric polymers such as biaxially oriented polypropylene (BOPP), polyimide (PI), epoxy resin (EP), polystyrene (PS), etc. have ultrahigh 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, and because various fillers are difficult to realize uniform dispersion in a polymer matrix and are easy to agglomerate and intertwine, the loss and 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 which has extremely high polarization, high charge and 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 utility model provides a silver-titanium dioxide filler mixes dielectric composite film of polyvinylidene fluoride, composite film fill in polyvinylidene fluoride base body by silver-titanium dioxide (Ag @ TO) filler and compound and form, silver-titanium dioxide filler be core-shell structure, wherein the nuclear layer be the bark form surface cladding have one-dimensional titanium dioxide nano wire (TO NWs) of slice titanium dioxide (p-TO), the shell is for decorating silver nanoparticle (Ag NPs) on slice titanium dioxide surface.
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 nuclear layer is 225-950 nm, the diameter of the one-dimensional titanium dioxide nanowire is 62-550 nm correspondingly, 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 the 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 h, centrifuging, collecting precipitates, and drying TO obtain bark-shaped one-dimensional titanium dioxide nanowires 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 30min; fully immersing the flask into an oil bath kettle, and when the temperature rises to 140 ℃, adding AgNO 3 Slowly 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), which is not favorable for achieving the expected energy storage performance;
(4) Preparation of dielectric composite film
0.00615-0.02461 g of silver-titanium dioxide filler is dispersed in 3.5 mL organic solvent N-N Dimethylformamide (DMF), then ultrasonic 1 h is carried out, 2 h is stirred, 0.5 g polyvinylidene fluoride (PVDF) is added, 24 h is stirred, and a solution casting method is adopted to prepare the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film with the silver-titanium dioxide filler volume fraction of 0.5-2%.
Preferably, the step (1) is specifically as follows: uniformly dispersing titanium dioxide nanopowder in 10M aqueous solution of sodium hydroxide, performing ultrasonic dispersion for 30min, magnetically stirring 12H, transferring the mixture into a reaction kettle, heating 24H in a forced air drying oven at 200 ℃, taking out, naturally cooling, washing with deionized water to neutrality, soaking in 0.2M aqueous solution of 4H to obtain H 2 Ti 3 O 7 And (3) washing the hydrate with deionized water to be neutral, drying, and then carrying out heat treatment on 3 h at 400 ℃ 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 And (3) 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 titanium dioxide nanowires (TO NWs) in 40 mL isopropanol, magnetically stirring 0.5 h, adding 0.06 mL Diethylenetriamine (DETA) solution, dropwise adding a mixed solution consisting of 4 mL isopropyl Titanate (TIP) solution and 20 mL 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 the bark-shaped one-dimensional titanium dioxide nanowires with the surface coated with the flaky titanium dioxide, wherein the rotational speed of centrifugal collection is 4000 TO 5000 r/min. The effect of the diethylenetriamine solution is to make the titanium dioxide grow along a certain direction, the adding amount is accurately controlled to be 0.06 mL, which can affect the roughness of the shell layer, namely the interface area, and at the same time, 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 under sealed conditions at 150-200 r/min, and the stirring time is controlled at 3 minutes.
Preferably, the step (3) is specifically: dissolving 0.1g of bark-shaped titanium dioxide in 40 mL ethylene glycol, placing in a flask, carrying out ultrasonic treatment for 2 minutes, adding 0.001 g polyvinylpyrrolidone (PVP), and stirring for dissolving for 30min; fully immersing the flask into an oil bath pan, and when the temperature rises to 140 ℃, adding AgNO 3 Slowly dripping ethylene glycol solution into the flask, keeping the oil bath at 140 ℃ for 25 min while keeping low-speed stirring, cooling to room temperature, alternately centrifugally cleaning for 4 times by deionized water and ethanol, and drying to obtain silver-titanium dioxide filler, wherein AgNO 3 The ethylene glycol solution is prepared by mixing 0.0016 g AgNO 3 Dissolving in 20 mL ethylene glycol, and stirring.
Preferably, the step (4) is specifically to disperse 0.00615-0.02461 g of silver-titanium dioxide filler (Ag @ TO filler) in 3.5 mL organic solvent N-N Dimethylformamide (DMF), then ultrasonically process 1 h, stir 2 h, add 0.5 g polyvinylidene fluoride (PVDF) and stir 24 h, firstly carry out vacuum treatment on the mixed solution to remove air bubbles, take 1-2 ml of the mixed solution to drip on the conductive surface of conductive glass and immediately pave the conductive surface by a scraper, quickly put the mixed solution into a 60 ℃ oven for vacuum drying 6 h, continuously raise the temperature to 200 ℃ after completely evaporating excess solvent DMF, keep the temperature for 10 min, quickly put the taken composite film into ice water for quenching, clean and dry, and obtain the silver-titanium dioxide filler doped dielectric composite film with 0.5-2% of silver-titanium dioxide filler volume fraction.
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 is used as a filler, so that the field intensity and 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 interface area and polarization of the interface. 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 preparation method thereof have the advantages that the composite film has higher breakdown field strength, extremely high polarization strength and high charge and discharge efficiency, and utilizes the dielectric anisotropy of the one-dimensional nanowires, the coulomb blocking effect of the metal particles, the bark-shaped TiO 2 The large interface area of the filler and the interface polarization brought by the metal silver nanoparticles with smaller sizes are adopted, so that the dielectric property and the energy storage property of the dielectric composite material are improved, the excellent energy storage property is realized, and the filling amount of the filler is onlyWith 1.5 vol.%, a low loading is beneficial for maintaining the flexibility of the composite film. The research result shows that when the electric field intensity is 376 MV/m, 1.5 vol.% Ag @ TO/PVDF nano composite material has the highest intensityU d The value of 16.5J/cm 3 ，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 spectrum of (a) Ag @ TO, (b) SEM images of TO @ TO and (c) Ag @ TO, and an energy spectrum analysis chart of (d-f) Ag @ TO (EDS);
FIG. 3 is a statistical representation of the core layer size distribution of silver-titanium dioxide filler, 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/PVDF composite film, whereinxRepresenting the volume fraction of Ag particles in Ag @ TO @;
FIG. 5 is a graph of the dielectric constant of Ag @ TO/PVDF composite films prepared from fillers with different volume fractions along with the change of frequency;
FIG. 6 is a graph of the loss of Ag @ TO/PVDF composite films prepared from fillers with different volume fractions along with the change of frequency;
FIG. 7 is a breakdown field intensity diagram of Ag @ TO/PVDF composite films prepared from fillers with different volume fractions;
FIG. 8 is a graph of discharge energy density and charge-discharge efficiency of Ag @ 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.
1. Detailed description of the preferred embodiments
Example 1
The utility model provides a silver-titanium dioxide filler mixes dielectric composite film of polyvinylidene fluoride, this composite film is formed by silver-titanium dioxide (Ag @ TO) filler is filled in the polyvinylidene fluoride base body complex, silver-titanium dioxide filler nucleocapsid structure, wherein the nuclear layer is the one-dimensional titanium dioxide nano-wire (TO NWs) that the surface cladding has the flaky titanium dioxide (p-TO) that is the bark form, the shell is the silver nanoparticle (Ag NPs) of modification on flaky titanium dioxide surface, its preparation process as follows:
1. synthesizing the titanium dioxide nano powder into a titanium dioxide nano wire (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 aqueous solution of sodium hydroxide, performing ultrasonic dispersion for 30min, magnetically stirring 12H, transferring the mixture into a reaction kettle, heating 24H in a forced air drying oven at 200 ℃, taking out, naturally cooling, washing with deionized water to neutrality, soaking in 0.2M aqueous solution of 4H to obtain H 2 Ti 3 O 7 And (2) washing the hydrate to be neutral by using deionized water, drying, placing the hydrate in an alumina crucible, and carrying out heat treatment on the hydrate 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 titanium dioxide nanowires (TO NWs) in 40 mL isopropanol, magnetically stirring 0.5 h, adding 0.06 mL Diethylenetriamine (DETA) solution, dropwise adding a mixed solution consisting of 4 mL isopropyl Titanate (TIP) solution and 20 mL 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 (TO @ TO) coated with flaky titanium dioxide, wherein the rotational speed of centrifugal collection is 4000 TO 5000 r/min; the titration is carried out at the speed of 1 mL/min, if the dropping speed 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-stage 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 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
Dissolving 0.1g of bark-like titanium dioxide (TO @ TO) in 40 mL ethylene glycol, placing in a flask, ultrasonically treating for 2 min, adding 0.001 g polyvinylpyrrolidone (PVP), and stirring for dissolving for 30min; fully immersing the flask into an oil bath kettle, and when the temperature rises to 140 ℃, adding AgNO 3 Slowly dropping ethylene glycol solution into flask, keeping oil bath at 140 deg.C for 25 min while stirring at low speed, cooling to room temperature, alternately centrifuging with deionized water and ethanol for 4 times, and oven drying to obtain silver-titanium dioxide filler (Ag @ TO), wherein AgNO 3 The ethylene glycol solution is prepared by mixing 0.0016 g AgNO 3 Dissolving in 20 mL ethylene glycol, and stirring.
4. Preparation of Ag @ TO/PVDF composite film
Firstly, 0.00615 g silver-titanium dioxide filler (Ag @ TO) is dispersed in 3.5 mL organic solvent N-N Dimethylformamide (DMF), then 1 h is subjected to ultrasonic sound, 2 h is stirred, then 0.5 g polyvinylidene fluoride (PVDF) is added, 24 h is stirred, bubbles are removed through vacuum treatment of a mixed solution, 1 to 2 ml of the mixed solution is dripped on a conductive surface of conductive glass (FTO, the area is 3 cm x 4 cm), the mixed solution is immediately paved through a scraper, the mixed solution is quickly placed into a 60 ℃ drying oven for vacuum drying 6 h, the temperature is continuously raised to 200 ℃ after the redundant solvent DMF is completely evaporated, the temperature is kept for 10 min, a taken out composite film is quickly placed into ice water for quenching, cleaning and drying are carried out, and the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film with the silver-titanium dioxide filler with the volume fraction of 0.5% is obtained.
Example 2
The difference from the above example 1 is that: in step 4, 0.00615 g of Ag @ TO filler is dispersed in 3.5 mL organic solvent N-N Dimethylformamide (DMF), then ultrasonic 1 h is carried out, 2 h is stirred, 0.5 g polyvinylidene fluoride (PVDF) is added to be stirred for 24 h, and a solution casting method is adopted to prepare the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film with the silver-titanium dioxide filler volume fraction of 1%.
Example 3
The difference from the above example 1 is that: in step 4, 0.01848 g of Ag @ TO filler is dispersed in 3.5 mL organic solvent N-N Dimethylformamide (DMF), then 1 h is subjected to ultrasonic treatment, 2 h is stirred, 0.5 g polyvinylidene fluoride (PVDF) is added and stirred 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 a solution casting method.
Example 4
The difference from the above example 1 is that: in step 4, 0.02461g of Ag @ TO filler is dispersed in 3.5 mL organic solvent N-N Dimethylformamide (DMF), then ultrasonic 1 h is carried out, 2 h is stirred, then 0.5 g polyvinylidene fluoride (PVDF) is added and stirred 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 conversion relationship between the volume fraction and the mass of the silver-titanium dioxide filler (ag @ to) is as follows: for silver particles (Ag):
The volume fraction of Ag in Ag @ TO; from the description accompanying fig. 2, the energy spectrum analysis:
to obtain
(ii) a So in the filler Ag @ TO, when the mass fraction of silver is 13.2 wt%, the volume fraction equivalent to Ag in Ag @ TO is 6 vol.%.
Further by energy spectrum analysis:
（1），
for PVDF:
whereinρ= 1.76 g/cm 3 Wherein in example 1m = 0.5g；
The volume fraction of PVDF is 99 vol.% when the volume fraction of the filler Ag @ TO is 1 vol.%.
In this way, it can be seen that,
，
is obtained by the formula:
=0.002869605 cm 3 (2) And the simultaneous (1) and (2) are as follows:
= 0.000154 cm 3 ，
= 0.002716 cm 3 (ii) a To obtain
，
， 
So as to be filled withWhen Ag @ TO account for the volume fraction of composite film is 1 vol.%, the quality of filler Ag @ TO @ is 0.01227 g. The calculations are similar for the remaining embodiments.
2. Analysis of results
1. FIG. 2 is an XRD spectrum of (a) Ag @ TO, (b) TO @ TO and (c) SEM images of Ag @ TO, and (d-f) energy spectrum analysis chart of Ag @ 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 have an average particle size of 25 nm, and an ultra-small particle size provides a condition for increasing the interface area. The interface of Ag NPs and polymer matrix in the Ag @ TO filler TO and the interface in Ag NPs and bark form TO @ TO, the interface of bark form TO and inside titanium dioxide may help TO increase the interface polarization of Ag @ TO/PVDF nanocomposite. To further demonstrate the successful modification of AgNPs to the bark-like to surface, the filler ag @ to was characterized using X-ray energy spectroscopy (EDS), as shown in fig. 2 (d-f), it can be seen that the mass fraction of silver was about 13.2 wt%, converted to a volume fraction of 6 vol.% for a unified 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 r AndE b at the same time, the strength is enhanced,xvol.% Ag @ TO/PVDF composite film produced 16.3J/cm at 376 MV/m 3 Highest of (2)U d And 7.4J/cm for pure PVDF film 3 (at 335 MV/m) by a factor of 2.2. Furthermore, withU d Of all nanocompositesηStill at a high level (>75%), e.g., 6 vol.% Ag @ TO/PVDF composite filmηStill remains at the higher 77%. Is kept highηThe main reasons for (1) are that TO @ TO of the inner layer is a paraelectric dielectric, and that the charge transfer and leakage current in Ag @ TO are limited。
2. FIG. 5 is a graph of the dielectric constant of Ag @ TO/PVDF composite films made of different volume fractions of fillers as a function of frequency. FIG. 5 shows the frequency dependence of the dielectric properties of Ag @ 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/PVDF composite film gradually decreases with increasing frequency, and the decrease is caused by the decrease in the mobility of the dipole with increasing frequency and the inability to follow the frequency change of the applied electric field. More importantly, with the increase of the volume fraction of Ag @ TO, the dielectric constants of the pure PVDF film and the Ag @ TO/PVDF composite film are increased from 10 to 21 at 1 KHz, and the dielectric constant of the composite film is increased mainly due to interface polarization and space charge polarization. That is, due to the multi-layered interface in the ag @ to filler, the transmission path of space charge is blocked under the action of an applied electric field, and charge is accumulated at the interface, thereby enhancing the interface polarization effect and further increasing the dielectric constant.
3. FIG. 6 is a graph of the loss of Ag @ TO/PVDF composite films made of fillers with different volume fractions along with the change of frequency. At low frequencies the interface polarization dominates, so the losses are relatively large, with increasing frequency the dipole polarization dominates, the losses decrease, and at higher frequencies mainly the ion and electron polarization dominates. Despite the loss tangent (tan) of the composite filmδ) Slightly increased due to the increase of free charge, but all samples maintained tan delta at a low level (less than 0.04 at 1 KHz), indicating good overall insulation, which provides the possibility of high breakdown strength of the nanocomposite film. To sum up, compared with a pure PVDF film, the dielectric constant of the Ag @ TO/PVDF composite film is obviously improved, the dielectric loss is slightly increased, and the energy storage performance is very favorable for improving.
4. FIG. 7 is a graph of breakdown field strength for Ag @ TO/PVDF composite films made with different volume fractions of fillers. 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 composites a pure PVDF film with Ag @ TO @/PVDFOf filmsE b Values 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/PVDF composite film shows the 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/PVDF composite film (II)x= 0.5-1.5) ofE b The value is significantly higher than pure PVDF (335 MV/m),E b the increase of (1) is mainly due to the fact that most bark-shaped TO @ TO fillers are oriented in the polymer matrix to be perpendicular to the direction of an external electric field, and the orientation is beneficial to increasing the tortuosity of a growth path of an electric tree in a breakdown process. 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/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/PVDF composite filmU d Andη. As predicted, due toP m -P r AndE b simultaneously, the 1.5 vol.% Ag @ TO/PVDF composite film generates 16.4J/cm when 376 MV/m 3 Highest of (2)U d . 1.5 vol.% Ag @ TO/PVDF composite film under 376 MV/m electric fieldU d (16.4 J/cm 3 ) Seems to be better than the previous work. With PVDF film (7.4J/cm) 3 335 MV/m) and commercial BOPP (3.56J/cm) 3 600 MV/m),U d the improvement is 222% and 460%, respectively. Further, as shown in FIG. 8, as followsU d Of all nanocompositesηStill at a high level (>75%), e.g., 1.5 vol.% Ag @ TO/PVDF composite filmηStill remains at the higher 77%. Is kept highηMainly due to the limited charge transfer and leakage current in to @ to, a paraelectric dielectric, ag @ to. To sum up, with the volume fraction (1.5 vol.%) of Ag @ TO being so small, it is achieved at the same timeP m -P r 、E b 、U d Andηenhancement 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 a composite dielectric material with higher energy storage density.
In summary, the bark-like TiO is prepared by the hydrothermal method in the composite film 2 Pack (TO @ TO), then through the oil bath method at the outer cladding micro-quantity Ag NPs of TO @ TO, synthesized Ag @ TO and packed, later with Ag @ TO pack in the PVDF base member is compound, utilize scraper coating method to prepare Ag @ TO/PVDF combined film, ceramic packing's micro-morphology has very big influence to combined material's energy storage performance. 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 a coulomb blocking effect in the composite dielectric medium, the electric field intensity is further improved by blocking a path of leakage current, and meanwhile, certain contribution is made to the improvement of the charge and 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 (8)
1. A silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film is characterized in that: the composite film is formed by filling silver-titanium dioxide filler into a polyvinylidene fluoride matrix in a composite mode, the silver-titanium dioxide filler is of a core-shell structure, a core layer is a one-dimensional titanium dioxide nanowire with a bark-shaped surface coated with flaky titanium dioxide, a shell layer is silver nanoparticles modified on the surface of the flaky titanium dioxide, the diameter of the core layer is 225-950 nm, the diameter of the one-dimensional titanium dioxide nanowire is 62-550 nm correspondingly, the average particle size of the silver nanoparticles is 20-30 nm, and the filling volume of the silver-titanium dioxide filler in the polyvinylidene fluoride matrix is 0.5-2%.
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 1.5%.
3. 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 tree-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 in a volume ratio of 1:5, 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 coated with flaky titanium dioxide;
(3) Preparation of silver-titanium dioxide fillers
Dissolving bark-like titanium dioxide in ethylene glycol, placing into a flask, performing ultrasonic treatment for 2 min, adding polyvinylpyrrolidone, and stirringDissolving for 30min; fully immersing the flask into an oil bath kettle, and when the temperature rises to 140 ℃, adding AgNO 3 Slowly 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 deionized water and ethanol, and drying to obtain silver-titanium dioxide filler;
(4) Preparation of dielectric composite film
0.00615-0.02461 g of silver-titanium dioxide filler is dispersed in 3.5 mL organic solvent N-N dimethylformamide, then ultrasonic 1 h is carried out, 2 h is stirred, 0.5 g polyvinylidene fluoride is added and stirred for 24 h, and a solution casting method is adopted to prepare the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film with the silver-titanium dioxide filler volume fraction of 0.5-2%.
4. The preparation method of the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film according to claim 3, wherein the step (1) is specifically as follows: uniformly dispersing titanium dioxide nanopowder in 10M aqueous solution of sodium hydroxide, performing ultrasonic dispersion for 30min, magnetically stirring 12H, transferring the mixture into a reaction kettle, heating 24H in a forced air drying oven at 200 ℃, taking out, naturally cooling, washing with deionized water to neutrality, soaking in 0.2M aqueous solution of 4H to obtain H 2 Ti 3 O 7 And (3) washing the hydrate with deionized water to be neutral, drying, and then carrying out heat treatment on 3 h at 400 ℃ 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 And (3) ml.
5. The preparation method of the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film according to claim 3, wherein the step (2) is specifically as follows: dissolving 0.08 g titanium dioxide nanowires in 40 mL isopropanol, magnetically stirring 0.5 h, adding 0.06 mL diethylenetriamine solution, dropwise adding a mixed solution composed of 4 mL isopropyl titanate solution and 20 mL 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 surface coated with flaky titanium dioxide, wherein the rotational speed of centrifugal collection is 4000-5000 r/min.
6. The method for preparing the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film according to claim 5, wherein the isopropyl titanate and the isopropanol are uniformly stirred under a sealing condition at 150-200 r/min, and the stirring time is controlled within 3 minutes.
7. The method for preparing the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film according to claim 5, wherein the step (3) is specifically as follows: dissolving 0.1g bark-shaped titanium dioxide in 40 mL glycol, placing in a flask, performing ultrasonic treatment for 2 minutes, adding 0.001 g polyvinylpyrrolidone, stirring and dissolving for 30min; fully immersing the flask into an oil bath kettle, and when the temperature rises to 140 ℃, adding AgNO 3 Slowly 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, wherein the AgNO is 3 The ethylene glycol solution is prepared by mixing 0.0016 g AgNO 3 Dissolving in 20 mL ethylene glycol, and stirring.
8. The preparation method of the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film according to claim 3, characterized in that the step (4) is specifically to disperse 0.00615-0.02461 g silver-titanium dioxide filler in 3.5 mL organic solvent N-N Dimethylformamide (DMF), then ultrasonically treat 1 h, stir 2 h, add 0.5 g polyvinylidene fluoride, stir 24 h, firstly carry out vacuum treatment on the mixed solution and pump out air bubbles, take 1-2 ml of the mixed solution to drip on the conductive surface of conductive glass and immediately spread by a scraper, quickly put the mixed solution into a 60 ℃ oven for vacuum drying 6 h, continuously raise the temperature to 200 ℃ after completely drying the mixed solution, keep the temperature for 10 min, quickly put the taken out composite film into ice water for quenching, cleaning and drying, and obtain the silver-titanium dioxide filler doped polyvinylidene fluoride dielectric composite film with the volume fraction of 0.5-2%.
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Citations (2)
| 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 nanowire and preparing 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 |
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Patent Citations (2)
| 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 nanowire and preparing 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 |
Non-Patent Citations (3)
| Title |
|---|
| Ag-TiO2/P(VDF-HFP)复合材料的制备及性能研究;肖兴荣;《中国优秀博硕士论文全文数据库（硕士）工程科技I辑》;20160715;第21、62-63、68页 * |
| High performance of P(VDF-HFP)/Ag@TiO2 hybrid films with enhanced dielectric permittivity and low dielectric loss;Xiao XR, et al;《RSC Adv》;20150904;第5卷;第79342-79347页 * |
| Novel core–shell-structured ironbark-like TiO2 as fillers for excellent discharged energy density of nanocomposites;Wu ZJ, et al;《J Mater Sci: Mater Electron》;20210225;第32卷;第7848-7857页 * |
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