CN112457611B - Polyvinylidene fluoride-based barium strontium titanate nanocomposite and preparation method thereof - Google Patents
Polyvinylidene fluoride-based barium strontium titanate nanocomposite and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyvinylidene fluoride barium strontium titanate nanocomposite and a preparation method thereof, wherein the method comprises the steps of 1, uniformly mixing oxalic acid dihydrate, deionized water, ethanol and tetrabutyl titanate, and then adjusting the pH value to 4.5-5.5; step 2, adding a mixed solution of barium nitrate and strontium nitrate for hydrothermal treatment, aging, filtering the precipitate, washing and drying to obtain a barium strontium titanate precursor; step 3, calcining at 800-900 ℃, cooling to room temperature to obtain barium strontium titanate nano powder, and adding the barium strontium titanate nano powder into the polyvinylidene fluoride solution to be uniformly mixed; and 4, performing normal-pressure drying after the composite is cast on the substrate by adopting a casting method, then performing vacuum drying to obtain a composite, performing quenching treatment on the composite in ice water, and then drying, wherein the polyvinylidene fluoride barium strontium titanate nano composite material formed on the substrate has high energy storage density when being applied to relatively low breakdown field intensity.
Description
Technical Field
The invention relates to the technical field of ferroelectric composite ceramic material preparation, in particular to a polyvinylidene fluoride based barium strontium titanate nano composite material and a preparation method thereof.
Background
Dielectric materials are widely used for energy storage of electrostatic capacitors, commercial dielectric capacitors are mainly ceramic materials at present, and the biggest problem of the ceramic materials is that small-size design cannot be achieved, and then good matching of flexible equipment cannot be achieved. The polymer-based nanocomposite material has the advantages of high pressure resistance, low energy loss and high reliability, can realize small-size production, and can well match flexible equipment, thereby promoting the production of small-sized equipment and the industrial production of flexible electronic equipment.
At present, the realization of high energy storage density of polymer-based nanocomposite materials is mainly realized by utilizing higher breakdown field strength of the polymer-based nanocomposite materials, which means that a very high breakdown electric field must be applied to the dielectric materials to realize high energy storage density, which is very difficult to realize for civil use, the consumption of electric energy is increased while the electric field strength is improved, the service life of the polymer-based nanocomposite materials is further shortened, and therefore, the problem of how to improve the energy storage density of the polymer-based nanocomposite materials under a low breakdown electric field is urgently needed to be solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a polyvinylidene fluoride based barium strontium titanate nanocomposite and a preparation method thereof, the cost is lower, the process is simple, the composite is environment-friendly, and the obtained composite has high energy storage density when being applied to relatively lower breakdown field intensity.
The invention is realized by the following technical scheme:
a preparation method of polyvinylidene fluoride based barium strontium titanate nanocomposite comprises the following steps:
step 1, firstly, according to (20-25) g:100ml: (75-125) ml:3.4032g, uniformly mixing oxalic acid dihydrate, deionized water, ethanol and tetrabutyl titanate to obtain a mixed system A, and then adjusting the pH value of the mixed system A to 4.5-5.5 to obtain a mixed system B;
and 2, adding a mixed solution of barium nitrate and strontium nitrate into the mixed system B to obtain a mixed system C, wherein the molar ratio of barium nitrate to strontium nitrate is 4:6, carrying out hydrothermal treatment on the mixed system C, aging, filtering the precipitate, washing and drying to obtain a barium strontium titanate precursor;
and 4, casting the mixed system D on a substrate by adopting a casting method, drying at normal pressure, then drying in vacuum to obtain a compound, quenching the compound in ice water at 0-5 ℃, and drying to form the polyvinylidene fluoride barium strontium titanate nano composite material on the substrate.
Preferably, in step 1, the ratio of (20-25) g:100ml: (50-100) ml, uniformly mixing oxalic acid dihydrate, deionized water and ethanol to obtain a solution A, and mixing the solution A according to the weight ratio of 3.4032g: and dissolving tetrabutyl titanate in ethanol at a ratio of 25ml to obtain a solution B, and finally uniformly mixing the solution A and the solution B to obtain a mixed system A.
Preferably, ammonia is used in step 1 to adjust the pH of mixed system a.
Preferably, the mass ratio of barium nitrate to tetrabutyl titanate in step 2 is 1.0454:3.4032.
preferably, the mixed system C in the step 2 is subjected to hydrothermal treatment at 85-95 ℃ for 2-4h.
Preferably, the mixed system C after the hydrothermal treatment in the step 2 is aged for 24-28h; drying at 80-100 deg.C for 24-32h.
Preferably, the barium strontium titanate precursor in step 3 is calcined at the temperature for 1-2h.
Preferably, the solvent of the polyvinylidene fluoride solution in the step 3 is dimethylformamide, and the ratio of polyvinylidene fluoride to dimethylformamide is (0.5-0.6) g: (5-7) ml.
Preferably, the vacuum drying in the step 4 is carried out for 7-10min at the temperature of 200-250 ℃; the composite is quenched in ice water at the temperature for 0.5-2min.
A polyvinylidene fluoride barium strontium titanate nanocomposite obtained by the preparation method of any one of the polyvinylidene fluoride barium strontium titanate nanocomposites.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of a polyvinylidene fluoride based barium-strontium titanate nano composite material, which comprises the steps of using oxalic acid dihydrate as a coprecipitator, using barium nitrate as a barium source, using strontium nitrate as a strontium source and using tetrabutyl titanate as a titanium source, adopting a method of firstly carrying out hydrothermal treatment and then calcining, obtaining barium-strontium titanate nano powder with higher surface energy, small particles and higher pores by optimizing parameters, then compounding the barium-strontium titanate nano powder with polyvinylidene fluoride by a tape casting method, drying at normal pressure and then discharging air in the composite by vacuum drying. In general, PVDF has four structures, α, δ, γ, and β phases, where the α phase is the known conformation with the lowest main chain potential in the PVDF crystal phase, and can be obtained by natural cooling of molten PVDF or by driving off the solvent in the PVDF solution at a temperature higher than 110 ℃, and the β phase is the thermodynamically most stable phase of PVDF, and can be obtained by driving off the solvent at a lower temperature (< 70 ℃) or by high-temperature and high-pressure quenching. In order to promote the crystal form transformation of the nano composite material to form more beta phases, the composite material containing more beta phases can be obtained by quenching the vacuum-dried composite material, so that the finally formed composite material has high energy storage density when being applied to relatively low breakdown field strength. The polyvinylidene fluoride-based barium strontium titanate obtained by the invention belongs to ferroelectric barium strontium titanate ceramic materials, has very excellent dielectric properties, namely high dielectric constant and low dielectric loss, can change the Curie phase transition temperature of the material by adjusting the molar ratio of barium ions to strontium ions during preparation so as to obtain the material with good dielectric properties at room temperature, and can realize regulation and control of energy storage properties at room temperature.
Drawings
Fig. 1 is an XRD pattern of polyvinylidene fluoride barium strontium titanate nanocomposite obtained in example 1 of the present invention.
Fig. 2 is an SEM image of polyvinylidene fluoride barium strontium titanate nanocomposite obtained in example 1 of the present invention.
Fig. 3 is a graph of dielectric constants of polyvinylidene fluoride barium strontium titanate nanocomposites obtained in example 1 of the present invention at different frequencies.
Fig. 4 is a dielectric loss graph of polyvinylidene fluoride barium strontium titanate nanocomposite obtained in example 1 of the present invention at different frequencies.
Fig. 5 is a graph illustrating unipolar hysteresis curves of the polyvinylidene fluoride barium strontium titanate nanocomposite obtained in example 1 of the present invention under different breakdown electric fields.
Fig. 6 is a diagram of energy storage performance of the polyvinylidene fluoride-based barium strontium titanate nanocomposite obtained in example 1 of the present invention under a critical breakdown electric field.
FIG. 7 is a schematic diagram of the method for calculating the energy storage density and energy storage efficiency of the dielectric according to the present invention.
FIG. 8 is a structure diagram of molecular chains of α, γ and β phase PVDF.
FIG. 9 is a diagram of the unit cell structure of different crystal forms of PVDF.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to a preparation method of a polyvinylidene fluoride barium strontium titanate nanocomposite, which takes a national chemical reagent barium nitrate as a barium source, strontium nitrate as a strontium source, tetrabutyl titanate as a titanium material, a reagent oxalic acid dihydrate as a coprecipitator, ammonia water, deionized water, absolute ethyl alcohol, polyvinylidene fluoride and Dimethylformamide (DMF) as raw materials, and specifically comprises the following steps:
step 1, weighing 20g to 25g of oxalic acid dihydrate into a beaker by using an electronic balance, measuring 50ml to 100ml of deionized water and 50ml to 100ml of ethanol as solvents, heating the mixture to 60 ℃ to 70 ℃ in a water bath, adding the oxalic acid dihydrate into the beaker filled with the mixed solution of the deionized water and the ethanol, continuously magnetically stirring the mixture at the temperature of 60 ℃ to 70 ℃ until the oxalic acid is completely dissolved, marking the mixed solution as solution A, and keeping the temperature to continuously stir the solution A for later use.
And 2, weighing 3.4032g of tetrabutyl titanate, dissolving the tetrabutyl titanate in 25ml of absolute ethyl alcohol solvent, heating in a water bath at 60-70 ℃, magnetically stirring until the tetrabutyl titanate and the absolute ethyl alcohol are completely and uniformly mixed, marking the mixed solution as solution B, and keeping the temperature to continuously stir the solution B for later use.
And 4, mixing the solution A and the solution B, heating in a water bath at 85-95 ℃, magnetically stirring, slowly dripping ammonia water, adjusting the pH value to 4.5-5.5 to obtain a solution D, and keeping the temperature to continuously stir the solution D for later use.
And 5, pouring the solution C into the solution D, and controlling the temperature of the water bath at 85-95 ℃ to react for 2-4h, wherein the precipitate is continuously generated in the process. And aging the obtained liquid for 24-28h, filtering the precipitate, washing with absolute ethyl alcohol, and drying in an oven at 80-100 ℃ for 24-32h to obtain a white powdery precursor of the barium strontium titanate nano powder.
And 6, calcining the obtained precursor powder in a muffle furnace at 800-900 ℃ for 1-2 hours, cooling the calcined precursor powder to room temperature along with the furnace to obtain barium strontium titanate nano powder, and bagging the barium strontium titanate nano powder for later use.
And 7, dissolving 0.5-0.6g of PVDF powder into 5-7ml of Dimethylformamide (DMF) organic solvent at room temperature, adding 0.15-0.17g of barium strontium titanate nano powder obtained in the step 6 into the mixture after the PVDF powder is completely dissolved, and magnetically stirring at room temperature for 12-18 hours to obtain a uniformly dispersed liquid mixture for later use.
And 9, tearing off the polyvinylidene fluoride barium strontium titanate nano composite material obtained in the step 8 from the glass substrate, cutting into small blocks with different sizes, spraying gold on the upper surface and the lower surface, forming a circular electrode with the diameter of 2 or 3 mm on each of the two surfaces of the sample, forming a small capacitor, and waiting for testing.
Example 1
The invention relates to a preparation method of a polyvinylidene fluoride-based barium strontium titanate nanocomposite, which comprises the following steps:
the invention relates to a preparation method of a polyvinylidene fluoride based barium strontium titanate nanocomposite, which takes a traditional Chinese medicine chemical reagent barium nitrate as a barium source, strontium nitrate as a strontium source, tetrabutyl titanate as a titanium material, a reagent oxalic acid dihydrate as a coprecipitator, ammonia water, deionized water, absolute ethyl alcohol, polyvinylidene fluoride and dimethyl formamide (DMF) as raw materials, and specifically comprises the following steps:
step 1, calculating according to the stoichiometric ratio, weighing 25.0000g of oxalic acid dihydrate into a beaker by using an electronic balance, measuring 50ml of ionized water and 50ml of ethanol as solvents, heating the mixture to 70 ℃ in a water bath, adding the oxalic acid dihydrate into the beaker filled with the mixed solution of the ionized water and the ethanol, continuously magnetically stirring the mixture at 70 ℃ until the oxalic acid is completely dissolved, marking the mixed solution as solution A, and keeping the temperature to continuously stir the solution A for later use.
And 2, weighing 3.4032g of tetrabutyl titanate, dissolving the tetrabutyl titanate in 25ml of absolute ethanol solvent, heating in a water bath at 60 ℃, magnetically stirring until the tetrabutyl titanate is completely and uniformly mixed, marking the mixed solution as solution B, and keeping the temperature to continuously stir the solution B for later use.
And 4, mixing the solution A and the solution B, heating in a water bath at 90 ℃, magnetically stirring, slowly dripping ammonia water, adjusting the pH value to 5 to obtain a solution D, and keeping the temperature to continue stirring the solution D for later use.
And 5, pouring the solution C into the solution D, and reacting for 4 hours at the water bath temperature controlled at 85 ℃, wherein the precipitate is continuously generated in the reaction process. And aging the obtained liquid for 28h, filtering the precipitate, washing with absolute ethyl alcohol, and drying in a drying oven at 100 ℃ for 32h to obtain a white powdery precursor of the barium strontium titanate nano powder.
And 6, calcining the obtained precursor powder in a muffle furnace at 900 ℃ for 2 hours, cooling the calcined precursor powder to room temperature along with the furnace to obtain barium strontium titanate nano powder, and bagging the barium strontium titanate nano powder for later use. XRD test of barium strontium titanate nano powder results in XRD pattern as shown in figure 1, and it is known that the powder has no second phase and barium element and strontium element form solid solution Ba 0.4 Sr 0.6 TiO 3 And the sample powder has a good perovskite structure. The barium strontium titanate nano powder is observed by a scanning electron microscope to obtain powder with smaller particles, an SEM image of the powder is shown as figure 2, and the barium strontium titanate nano powder is agglomerated due to higher surface energy, but pores in the agglomeration can increase the contact surface area of the barium strontium titanate nano powder and the polymer and can promote the dielectric property of the barium strontium titanate nano powder.
And 7, dissolving 0.6g of PVDF powder into 7ml of Dimethylformamide (DMF) organic solvent at room temperature, adding 0.17g of barium strontium titanate nano powder obtained in the step 6 into the mixture after the PVDF powder is completely dissolved, and magnetically stirring the mixture at room temperature for 18 hours to obtain a uniformly dispersed liquid mixture for later use.
And 9, tearing off the polyvinylidene fluoride barium strontium titanate nano composite material obtained in the step 8 from the glass substrate, cutting into small blocks with different sizes, spraying gold on the upper surface and the lower surface, forming circular electrodes with the diameters of 2 mm on the two surfaces of the sample respectively, forming small capacitors, and waiting for testing.
And step 10, testing. The dielectric constant of the composite is shown in FIG. 3, from which it can be seen that the dielectric constant of the nanocomposite at 1000Hz is significantly higher, approaching 10, compared to pure PVDF (dielectric constant 6-7). In addition, the dielectric constant of the composite material is large at low frequency, slowly decreases along with the increase of the frequency, and the composite material has better frequency stability. The dielectric loss of the composite material is shown in fig. 4, and it can be seen from the graph that the composite material has a low dielectric loss in the whole case, the dielectric loss of the material decreases with the increase of the dielectric constant at a low frequency, and the dielectric loss of the material increases with the increase of the frequency at a high frequency.
The composite material was tested in different breakdown electric fields by using unipolar hysteresis loops as shown in fig. 5, wherein the abscissa of the highest point of each unipolar hysteresis loop corresponds to the corresponding breakdown electric field, and it can be seen from the hysteresis loops that the polyvinylidene fluoride barium strontium titanate nanocomposite material has a good energy storage density in each breakdown electric field and exhibits typical relaxor ferroelectric characteristics.
The maximum energy storage performance of the composite material under the breakdown electric field is shown in figure 6, and in addition, figure 7 provides a schematic diagram of the principle of a method for calculating the energy storage density and the energy storage efficiency of the dielectric. By utilizing the relation that the energy storage density U and the electric field E are quadratic functions, for the nonlinear dielectric material, the released energy density is related to the difference value between the maximum polarization intensity and the residual polarization intensity, so that the energy storage density and the energy storage efficiency can be calculated through a D-E curve. It is found by calculation that the saturation polarization intensity is about 12 mu C/cm under the electric field with lower 320 (Kv/mm) 2 The maximum energy storage density of the composite material is calculated to reach 12.9625J/cm 2 The energy storage efficiency of the composite material also reaches 75.25 percent, and the composite material belongs to a polymer-based nano composite material with excellent performance.
FIG. 8 shows the molecular chain structure diagram of the α, γ and β phase PVDF, and FIG. 9 shows the unit cell structure diagram of the different crystal forms of PVDF.
Example 2
The invention relates to a preparation method of a polyvinylidene fluoride based barium strontium titanate nanocomposite, which comprises the following steps:
step 1, calculating according to the stoichiometric ratio, weighing 20.0000g of oxalic acid dihydrate into a beaker by using an electronic balance, measuring 100ml of ionized water and 100ml of ethanol as solvents, heating the mixture to 70 ℃ in a water bath, adding the oxalic acid dihydrate into the beaker filled with the mixed solution of the ionized water and the ethanol, continuously magnetically stirring the mixture at 70 ℃ until the oxalic acid is completely dissolved, marking the mixed solution as solution A, and keeping the temperature to continuously stir the solution A for later use.
And 2, weighing 3.4032g of tetrabutyl titanate, dissolving the tetrabutyl titanate in 25ml of absolute ethyl alcohol solvent, heating in a water bath at 60 ℃, magnetically stirring until the tetrabutyl titanate and the absolute ethyl alcohol are completely and uniformly mixed, marking the mixed solution as a solution B, and keeping the temperature to continue stirring the solution B for later use.
And 4, mixing the solution A and the solution B, heating in a water bath at 90 ℃, magnetically stirring, slowly dropping ammonia water, adjusting the pH value to 4.5 to obtain a solution D, and keeping the temperature to continue stirring the solution D for later use.
And 5, pouring the solution C into the solution D, and controlling the temperature of the water bath at 95 ℃ to react for 2 hours, wherein the precipitate is continuously generated. And aging the obtained liquid for 24h, filtering the precipitated product, washing the product by using absolute ethyl alcohol, and drying the product in an oven at the temperature of 80 ℃ for 24h to obtain a white powdery precursor of the barium strontium titanate nano powder.
And 6, calcining the obtained precursor powder in a muffle furnace at 800 ℃ for 1 hour, cooling the calcined precursor powder to room temperature along with the furnace to obtain barium strontium titanate nano powder, and bagging the barium strontium titanate nano powder for later use.
And 7, dissolving 0.5g of PVDF powder into 5ml of Dimethylformamide (DMF) organic solvent at room temperature, adding 0.15g of barium strontium titanate nano powder obtained in the step 6 into the mixture after the PVDF powder is completely dissolved, and magnetically stirring for 12 hours at room temperature to obtain a uniformly dispersed liquid mixture for later use.
And 9, removing the polyvinylidene fluoride barium strontium titanate nanocomposite obtained in the step 8 from the glass substrate to obtain the polyvinylidene fluoride barium strontium titanate nanocomposite.
Example 3
The invention relates to a preparation method of a polyvinylidene fluoride based barium strontium titanate nanocomposite, which comprises the following steps:
step 1, calculating according to the stoichiometric ratio, weighing 22.0000g of oxalic acid dihydrate into a beaker by using an electronic balance, measuring 75ml of ionized water and 80ml of ethanol as solvents, heating the mixture to 70 ℃ in a water bath, adding the oxalic acid dihydrate into the beaker filled with the mixed solution of the ionized water and the ethanol, continuously magnetically stirring the mixture at 70 ℃ until the oxalic acid is completely dissolved, marking the mixed solution as solution A, and keeping the temperature to continuously stir the solution A for later use.
And 2, weighing 3.4032g of tetrabutyl titanate, dissolving the tetrabutyl titanate in 25ml of absolute ethyl alcohol solvent, heating in a water bath at 60 ℃, magnetically stirring until the tetrabutyl titanate and the absolute ethyl alcohol are completely and uniformly mixed, marking the mixed solution as a solution B, and keeping the temperature to continue stirring the solution B for later use.
And 4, mixing the solution A and the solution B, heating in a water bath at 90 ℃, magnetically stirring, slowly dropping ammonia water, adjusting the pH value to 5.5 to obtain a solution D, and keeping the temperature to continue stirring the solution D for later use.
And 5, pouring the solution C into the solution D, and controlling the temperature of the water bath at 90 ℃ to react for 3 hours, wherein the precipitate is continuously generated in the process. And aging the obtained liquid for 26 hours, filtering the precipitate, washing the precipitate by using absolute ethyl alcohol, and drying the precipitate in a drying oven at 90 ℃ for 28 hours to obtain a white powdery precursor of the barium strontium titanate nano powder.
And 6, calcining the obtained precursor powder in a muffle furnace at 850 ℃ for 1.5 hours, cooling the calcined precursor powder to room temperature along with the furnace to obtain barium strontium titanate nano powder, and bagging the barium strontium titanate nano powder for later use.
And 7, dissolving 0.55g of PVDF powder into 6ml of Dimethylformamide (DMF) organic solvent at room temperature, adding 0.16g of barium strontium titanate nano powder obtained in the step 6 into the mixture after the PVDF powder is completely dissolved, and magnetically stirring for 15 hours at room temperature to obtain a uniformly dispersed liquid mixture for later use.
And 9, removing the polyvinylidene fluoride barium strontium titanate nanocomposite obtained in the step 8 from the glass substrate to obtain the polyvinylidene fluoride barium strontium titanate nanocomposite.
Claims (5)
1. A preparation method of polyvinylidene fluoride based barium strontium titanate nanocomposite is characterized by comprising the following steps:
step 1, firstly, according to (20-25) g:100ml: (50-100) ml, uniformly mixing oxalic acid dihydrate, deionized water and ethanol to obtain a solution A, and mixing the solution A according to the weight ratio of 3.4032g: dissolving tetrabutyl titanate in ethanol at a ratio of 25ml to obtain a solution B, finally uniformly mixing the solution A and the solution B to obtain a mixed system A, then adjusting the pH of the mixed system A to 4.5-5.5, wherein the mass ratio of barium nitrate to tetrabutyl titanate is 1.0454:3.4032, obtaining a mixed system B;
and 2, adding a mixed solution of barium nitrate and strontium nitrate into the mixed system B to obtain a mixed system C, wherein the molar ratio of barium nitrate to strontium nitrate is 4:6, carrying out hydrothermal treatment on the mixed system C at 85-95 ℃ for 2-4h, then aging, filtering the precipitate, washing and drying to obtain a barium strontium titanate precursor;
step 3, calcining the barium strontium titanate precursor at 800-900 ℃ for 1-2h, cooling to room temperature to obtain barium strontium titanate nano powder, adding the barium strontium titanate nano powder into a polyvinylidene fluoride solution, uniformly mixing, wherein the solvent of the polyvinylidene fluoride solution is dimethylformamide, and the ratio of polyvinylidene fluoride to dimethylformamide is (0.5-0.6) g: (5-7) ml, wherein the mass ratio of polyvinylidene fluoride to barium strontium titanate nano powder is (0.5-0.6): (0.15-0.17), obtaining a mixed system D;
and 4, carrying out tape casting on the mixed system D on a substrate by adopting a tape casting method, drying at normal pressure, then carrying out vacuum drying at 200-250 ℃ for 7-10min to obtain a compound, carrying out quenching treatment on the compound in ice water at 0-5 ℃, and then drying to form the polyvinylidene fluoride barium strontium titanate nano composite material on the substrate.
2. The method for preparing a polyvinylidene fluoride barium strontium titanate nanocomposite according to claim 1, wherein the pH of the mixed system a is adjusted using ammonia water in step 1.
3. The preparation method of polyvinylidene fluoride barium strontium titanate nanocomposite according to claim 1, wherein the mixed system C after hydrothermal treatment in step 2 is aged for 24-28h; drying at 80-100 deg.C for 24-32h.
4. The method for preparing polyvinylidene fluoride barium strontium titanate nanocomposite according to claim 1, wherein the composite in step 4 is quenched in ice water at the temperature for 0.5-2min.
5. A polyvinylidene fluoride barium strontium titanate nanocomposite obtained by the method for preparing a polyvinylidene fluoride barium strontium titanate nanocomposite according to any one of claims 1 to 4.
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