CN112812475A - Flaky sodium bismuth titanate/polyvinylidene fluoride composite material and preparation method thereof - Google Patents

Flaky sodium bismuth titanate/polyvinylidene fluoride composite material and preparation method thereof Download PDF

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CN112812475A
CN112812475A CN202110202034.9A CN202110202034A CN112812475A CN 112812475 A CN112812475 A CN 112812475A CN 202110202034 A CN202110202034 A CN 202110202034A CN 112812475 A CN112812475 A CN 112812475A
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composite material
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bismuth titanate
drying
polyvinylidene fluoride
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王卓
李妍欣
孔梦蕾
易志辉
吴丹
薛颖
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Shaanxi University of Science and Technology
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Abstract

The invention relates to a sheet sodium bismuth titanate/polyvinylidene fluoride composite material and a preparation method thereof2CO3、Bi2O3、TiO2And NaCl calcination to remove Cl‑Drying and grinding, adding the obtained flaky sodium bismuth titanate powder into an ethanol solution, and drying; adding dopamine hydrochloride and hydrochloric acid containing trihydroxymethyl chloromethane, reacting, and drying the product to obtain dopamine-coated sheet sodium bismuth titanate powder; preparing polyvinylidene fluoride into five parts of solution, respectively adding the powder, preparing a compound on a glass substrate by using the five parts of mixed system in a tape casting method according to the sequence that the concentration of the powder is sequentially increased, drying, performing primary drying at 160-200 ℃, sequentially quenching, and performing secondary drying at 35-55 DEG CAnd (4) secondary drying to obtain the novel dielectric energy storage composite material with high dielectric constant, low dielectric loss, high breakdown field strength and high energy storage density.

Description

Flaky sodium bismuth titanate/polyvinylidene fluoride composite material and preparation method thereof
Technical Field
The invention relates to the technical field of energy storage material preparation, in particular to a flaky sodium bismuth titanate/polyvinylidene fluoride composite material and a preparation method thereof.
Background
With the rapid consumption of fossil fuels, the search for high energy storage materials has accelerated. An electrostatic capacitor is an energy storage device capable of providing a high power density, and is widely used in electronic and electrical equipment.
The ceramic dielectric energy storage material has excellent dielectric property, but the breakdown field strength is lower and the preparation energy consumption is large; polymeric dielectric energy storage materials have good puncture resistance, processability, and flexibility, but poor dielectric properties. The ceramic material and the polymer material are compounded to obtain the ceramic/polymer dielectric energy storage composite material, and the ceramic/polymer dielectric energy storage composite material has the advantages of high dielectric constant, low dielectric loss, breakdown resistance, easiness in processing, low energy consumption and the like, and is widely concerned.
However, the existing ceramic/polymer dielectric energy storage composite material has low dielectric constant and weak breakdown field strength, so that the energy storage density is low, and the ceramic/polymer dielectric energy storage composite material is difficult to be widely applied.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a flaky sodium bismuth titanate/polyvinylidene fluoride composite material and a preparation method thereof, the preparation process is simpler, the production period is short, and a novel dielectric energy storage composite material with high dielectric constant, low dielectric loss, high breakdown field strength and high energy storage density can be obtained.
The invention is realized by the following technical scheme:
a preparation method of a sheet-shaped sodium bismuth titanate/polyvinylidene fluoride composite material comprises the following steps,
step 1, adding Na2CO3、Bi2O3、TiO2Calcining NaCl and the mixture at 800-1000 ℃ to obtain a mixture, wherein Na is2CO3、Bi2O3And TiO2The mass ratio of the total mass of (1) to NaCl is 1 to 1.5, and the amount of Cl in the mixture is determined-Removing, drying and uniformly grinding to obtain flaky sodium bismuth titanate powder;
step 2, adding the flaky sodium bismuth titanate powder into an ethanol solution, drying, adding dopamine hydrochloride and hydrochloric acid containing trihydroxymethyl chloromethane, reacting, and drying the product to obtain dopamine-coated flaky sodium bismuth titanate powder, wherein the proportion of the flaky sodium bismuth titanate powder, the dopamine hydrochloride, the trihydroxymethyl chloromethane and the hydrochloric acid is 0.75 g: (0.02-0.03) g: (0.04-0.06) g: (7-10) mL;
preparing polyvinylidene fluoride into five parts of solution, respectively adding dopamine-coated flaky sodium bismuth titanate powder into the solution, wherein the volume of the powder is 0.5-4.5% of the total volume of the powder and polyvinylidene fluoride, obtaining five parts of mixed systems with sequentially-increased powder concentrations, preparing a compound of the flaky sodium bismuth titanate powder and the polyvinylidene fluoride on a glass substrate by using the five parts of mixed systems by a tape casting method according to the sequentially-increased powder concentrations, and drying the obtained five-layer composite film to obtain a compound A;
and 4, carrying out primary drying on the compound A at 160-200 ℃, then sequentially quenching and carrying out secondary drying at 35-55 ℃ to obtain the flaky sodium bismuth titanate/polyvinylidene fluoride composite material.
Preferably, step 1 is performed with Na2CO3、Bi2O3、TiO2And calcining NaCl at the temperature for 3-8 h.
Preferably, the concentration of the hydrochloric acid in the step 2 is 0.01-0.021 mol/L.
Preferably, in the step 2, the flaky sodium bismuth titanate powder is added into the ethanol solution and stirred for 4-8 hours, and then the obtained sodium bismuth titanate powder is dried.
Preferably, in the step 2, after dopamine hydrochloride and hydrochloric acid containing trihydroxymethyl chloromethane are added, the reaction is carried out for 8-16 hours to obtain a product.
Preferably, step 3 is to add polyvinylidene fluoride into DMF to obtain the solution, wherein the ratio of polyvinylidene fluoride to DMF is 0.1 g: 1 mL.
Preferably, the concentration value of the powder in the mixed system in the step 3 forms an arithmetic progression, wherein the minimum value is 0.5%, and the tolerance is 0.5% -1%.
Preferably, in the step 3, after the casting of one layer of film is finished, drying is carried out for 15-30 min at the temperature of 100-120 ℃, and then the casting of the next layer of film is carried out.
Preferably, in the step 4, the compound A is dried in vacuum at the temperature for 5-15 min and then quenched.
A flaky sodium bismuth titanate/polyvinylidene fluoride composite material prepared by the preparation method of the flaky sodium bismuth titanate/polyvinylidene fluoride composite material.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of a flaky sodium bismuth titanate/polyvinylidene fluoride composite material, which comprises the steps of firstly forming two-dimensional flaky sodium bismuth titanate at a proper raw material ratio and corresponding temperature, then using the flaky sodium bismuth titanate as a ceramic filler, dopamine hydrochloride and hydrochloric acid containing trihydroxymethyl chloromethane are added to form appropriate pH of dopamine-coated two-dimensional flaky bismuth sodium titanate to obtain dopamine-coated flaky bismuth sodium titanate powder, simultaneously, PVDF is used as a polymer matrix, a mixed system with five parts of sodium bismuth titanate powder with sequentially increased concentration is used for preparing a composite material on a glass substrate by a tape casting method, hydroxylation treatment and dopamine coating enable the two-dimensional flaky sodium bismuth titanate with a compact structure and the PVDF to have good compatibility, micro-capacitance is formed by utilizing two-dimensional flaky ceramic fillers, the dielectric constants of the ceramic filler and the polymer matrix are greatly different, so that interface polarization is generated, and the dielectric constant of the composite material is improved; meanwhile, the two-dimensional flaky sodium bismuth titanate with compact structure is arranged in parallel in the composite material and serves as a barrier layer to exert space barrier effect, so that the growth of an electric tree is hindered, a breakdown path is prolonged, the composite material is not easy to break down, the breakdown strength of the composite material is improved, the two-dimensional flaky sodium bismuth titanate with compact structure is in the composite material under the action of an electric field, free charges in the composite material are distributed on the sodium bismuth titanate more uniformly, the accumulation of charges is avoided, the breakdown strength of the composite material is also improved, a gradient electric field exists among layers in the composite material, the gradient electric field regulates and controls the distribution of the internal electric field of the composite material under the action of an external electric field, the buffer effect is achieved, the growth of the electric tree can be weakened, the breakdown strength is improved, and finally the dielectric constant and the breakdown field strength of the sodium bismuth titanate/PVDF composite material are improved, the energy storage density of the dielectric energy storage composite material is improved. The flaky sodium bismuth titanate prepared by the method is lead-free ceramic and meets the requirement of environmental protection.
Drawings
FIG. 1 is an X-ray diffraction chart of the flaky sodium bismuth titanate powder obtained in example 1 of the present invention.
FIG. 2 is a scanned graph of the flaky sodium bismuth titanate powder obtained in example 1 of the present invention.
FIG. 3 is an X-ray diffraction chart of the composite materials obtained in comparative example 1 and examples 1 to 5 of the present invention.
FIG. 4 is a scan of a composite material obtained in example 5 of the present invention having a filler content of 0.5 vol% in the initial layer and a filler gradient of 1 vol% in NBT4 in the adjacent layers.
FIG. 5 is a dielectric constant diagram of a five-layer gradient composite material obtained in comparative example 1 and examples 1 to 5 of the present invention.
FIG. 6 is a dielectric loss chart of the five-layer gradient composite material obtained in comparative example 1 and examples 1 to 5 of the present invention.
FIG. 7 is a hysteresis chart of a composite material obtained in example 1 of the present invention, in which the filler content in the initial layer is 0.5 vol%, and the filler content in NBT4 in the adjacent two layers is 0.5 vol%.
FIG. 8 is a hysteresis chart of a composite material obtained in example 2 of the present invention, in which the filler content in the initial layer is 0.5 vol%, and the filler content in NBT4 in the adjacent two layers is 0.625 vol%.
FIG. 9 is a hysteresis chart of a composite material obtained in example 3 of the present invention, in which the filler content in the initial layer is 0.5 vol%, and the filler content in NBT4 in the adjacent two layers is 0.75 vol%.
FIG. 10 is an electrical hysteresis chart of a composite material obtained in example 4 of the present invention, in which the filler content in the initial layer is 0.5 vol%, and the filler gradient of NBT4 in the adjacent two layers is 0.875 vol%.
FIG. 11 is a hysteresis chart of a composite material obtained in example 5 of the present invention, in which the filler content in the initial layer is 0.5 vol% and the filler content in NBT4 in the adjacent two layers is 1 vol%.
FIG. 12 is a Weibull distribution diagram of breakdown strength of five-layer gradient composite materials obtained in comparative example 1 and examples 1 to 5 of the present invention.
FIG. 13 is a graph of energy storage density of the five-layer gradient composite material obtained in comparative example 1 and examples 1 to 5.
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.
When the two-dimensional ceramic filler is compounded with the polymer matrix, the dielectric constant of the composite material can be improved, the space blocking effect is achieved, the electric tree can be effectively blocked, the conductive path in the composite material is prolonged, and the effect of improving the breakdown field intensity is achieved. Meanwhile, the construction of the gradient electric field in the composite material generates interface polarization, plays a buffering role in electric field breakdown, and improves the breakdown field strength to increase the energy storage density. Sodium bismuth titanate of the formula Na0.5Bi4.5Ti4O15The high-dielectric ceramic (NBT 4 for short) is a high-dielectric ceramic, and is used as a two-dimensional ceramic filler to form a two-dimensional filler multilayer gradient composite material with a polymer matrix polyvinylidene fluoride (PVDF for short), so that the high-dielectric ceramic can generate large energy storage density.
Based on the above analysis, the preparation method of the sheet NBT4/PVDF dielectric energy storage composite material comprises the following steps:
1) mixing raw materials sodium carbonate (Na)2CO3) Bismuth oxide (Bi)2O3) Titanium dioxide (TiO)2) And sodium chloride (NaCl) to obtain a mixture block under calcination;
the method comprises the following specific steps:
adding sodium carbonate (Na) into a ball milling tank2CO3) Bismuth oxide (Bi)2O3) Titanium dioxide (TiO)2) Sodium chloride (NaCl), ball stone made of zirconium oxide, anhydrous alcohol and Na2CO3、Bi2O3、TiO2And NaCl to form a powder. Wherein, Na2CO3、Bi2O3And TiO2The mass ratio of the total mass of (A) to NaCl is 1 to 1.5; the powder quality is as follows: the quality of the ball stone is as follows: the mass of the absolute ethyl alcohol is 1:2: 1;
ball milling is carried out for 8-12 h;
thirdly, drying the obtained slurry after the ball milling is finished;
and fourthly, calcining the dried slurry at 800-1000 ℃ for 3-8 h to obtain a mixture block.
2) Washing the mixture block for 3-5 times by using deionized water at 70-100 ℃ to remove Cl in the mixture block-Detecting with silver nitrate solution to ensure the removal, drying and grinding to obtain flake NBT4 powder;
3) adding 40-70% by volume of ethanol solution into the flake NBT4 powder, stirring for 4-8 h, drying, adding dopamine hydrochloride and a coating solution (hydrochloric acid containing trihydroxymethyl chloromethane) into the dried product, stirring, reacting for 8-16 h, and drying the product to obtain dopamine-coated flake NBT4 powder, wherein the mass of the flake NBT4 powder, the mass of the dopamine hydrochloride, and the volume ratio of the trihydroxymethyl chloromethane to the hydrochloric acid is 0.75 g: (0.02-0.03) g: (0.04-0.06) g: (7-10) mL;
generally, only 7-10 mL of hydrochloric acid is needed in laboratory implementation, and 1-1.5 mL of 0.1mol/L hydrochloric acid is taken in preparation, and then the rest is deionized water in dilution.
4) Adding 0.5g of PVDF into 5ml of DMF, stirring for 4-8 hours to prepare a PVDF solution, obtaining five parts by the same method, respectively adding dopamine-coated flaky NBT4 powder into the PVDF solution, stirring for 12-24 hours, wherein the volume of the powder is 0.5% -4.5% of the total volume of the powder and the polyvinylidene fluoride, obtaining five parts of mixed systems with sequentially-increased powder concentration, preparing a flaky NBT4 powder and polyvinylidene fluoride compound on a glass substrate by a tape casting method according to the sequence of sequentially-increased powder concentration, and drying the obtained five-layer composite film.
When the compound is prepared by a casting method, the preparation method is completed by the following steps: firstly, heating a casting machine to 130-160 ℃, and then carrying out casting preparation on the compound on the glass substrate. And after the casting of one layer of film is finished, drying for 15-30 min at 100-120 ℃, and then continuing to perform the casting preparation of the next layer of film until the preparation of the sheet-shaped NBT4 powder and PVDF compound is finished.
And drying the composite of the sheet NBT4 powder and PVDF at 100-120 ℃ for 12-16 h.
5) And drying the composite at 160-200 ℃ in a vacuum state for 5-15 min, quenching with ice water at 5-10 ℃, refrigerating water for 12-15 h by using a refrigerator to obtain enough ice water, and drying at 35-55 ℃ for 15-30 min to obtain the sheet NBT4/PVDF composite material.
The invention adopts a tape casting method to prepare the sheet NBT4/PVDF dielectric energy storage composite material, wherein the sheet NBT4 ceramic powder is prepared by a molten salt growth method. In the composite material, the flaky NBT4 ceramic filler can be arranged in a directional manner, an interface is generated to prevent space charges from moving to two ends of an electrode, the loss of the electrode is reduced, and meanwhile, the flaky NBT4 ceramic filler also serves as a barrier layer to ensure that free charges are uniformly distributed on NBT4 without charge accumulation, and the NBT4 and the barrier layer jointly ensure that the composite material has higher breakdown field intensity; the sheet NBT4 ceramic filler is also arranged in parallel, which can prolong the breakdown path, make the composite material not easy to break down or form conductive path, and improve the breakdown strength. In addition, the gradient electric field among the layers regulates and controls the internal electric field, has a buffering effect on the breakdown of the material, and can weaken the growth of the electric tree so as to improve the breakdown field strength. In addition, the addition of the NBT4 ceramic filler in the form of flakes and the interfacial polarization between the two components of the composite also lead to an increase in the dielectric constant of the gradient composite. Therefore, the sheet NBT4/PVDF gradient dielectric energy storage composite material has higher breakdown field strength and dielectric constant and can obtain larger energy storage density.
Example 1
The invention relates to a preparation method of a sheet NBT4/PVDF composite material (the filler of an initial layer is 0.5 vol%, the concentration gradient of the NBT4 filler of two adjacent layers is 0.5 vol%), which comprises the following steps,
step 1, preparation of flaky Na0.5Bi4.5Ti4O15；
Weighing Na in proportion2CO3、Bi2O3、TiO2And NaCl, in which Na is substituted2CO3、Bi2O3And TiO2The mass ratio of oxides to NaCl of the composition was 1.5: 1; adding the four mixtures, zirconia ball stone and absolute ethyl alcohol into a ball milling tank according to the mass ratio of 1:2:1, carrying out ball milling for 8 hours, and drying; putting the dried mixture into a crucible to calcine at 900 ℃ for 3 hours; grinding the calcined mixture, sieving, placing into a beaker, and washing with 80 deg.C deionized water for 5 times to obtain Cl-Removing, and testing Cl with silver nitrate solution-If the NBT4 powder is completely removed, drying the washed product to obtain sheet NBT4 powder;
step 2, coating the flaky NBT4 powder with dopamine;
weighing 0.75g of NBT4 powder, adding 5mL of deionized water and 5mL of absolute ethyl alcohol, stirring, reacting for 8h, drying, adding 0.03g of dopamine hydrochloride, 0.04g of trihydroxymethyl chloromethane and 10mL of hydrochloric acid, stirring, reacting for 16h, drying, taking 1mL of 0.1mol/L hydrochloric acid when preparing hydrochloric acid, and then diluting the rest part with deionized water to obtain dopamine-coated sheet NBT4 powder;
step 3, taking five small glass bottles with the capacity of 20mL, adding 0.5g of PVDF and 5mL of DMF into each small glass bottle, stirring for 4h, adding dopamine-coated flaky NBT4 powder, stirring and reacting for 18h, wherein the volume of the dopamine-coated flaky NBT4 powder respectively accounts for 0.5%, 1%, 1.5%, 2% and 2.5% of the total volume of the NBT4 powder and the PVDF;
step 4, preparing a pure flaky NBT4 and PVDF gradient composite material by adopting a tape casting method, heating a tape casting machine to 140 ℃, then carrying out tape casting preparation of a multilayer gradient composite material on a glass substrate according to the sequence that the volume fractions of fillers are sequentially increased, after one layer of film is subjected to tape casting, drying at 100 ℃ for 30min, continuing to carry out tape casting preparation of the next layer of film until a five-layer gradient composite film of flaky NBT4 and PVDF is obtained, drying the prepared gradient composite film at 100 ℃ for 12h, and meanwhile, refrigerating water for 12h by using a refrigerator to obtain enough ice water;
and 5, putting the dried sheet-shaped NBT4 and PVDF five-layer gradient composite film into a vacuum drying oven, heating at 200 ℃ for 10min, then quenching with 5 ℃ ice water, and finally drying at 40 ℃ for 20min to obtain the sheet-shaped NBT4/PVDF five-layer gradient composite material with the initial layer filler of 0.5 vol% and the NBT4 filler gradient of 0.5 vol% in two adjacent layers.
Example 2
The invention relates to a preparation method of a sheet NBT4/PVDF composite material (the filler of an initial layer is 0.5 vol%, the concentration gradient of the NBT4 filler of two adjacent layers is 0.625 vol%), which comprises the following steps,
step 1, preparation of flaky Na0.5Bi4.5Ti4O15；
Weighing Na in proportion2CO3、Bi2O3、TiO2And NaCl, in which Na is substituted2CO3、Bi2O3And TiO2The mass ratio of oxides to NaCl of the composition was 1.5: 1; adding the four mixtures, zirconia ball stone and absolute ethyl alcohol into a ball milling tank according to the mass ratio of 1:2:1, carrying out ball milling for 8 hours, and drying; putting the dried mixture into a crucible to calcine at 900 ℃ for 3 hours; grinding the calcined mixture, sieving, placing into a beaker, and washing with 80 deg.C deionized water for 5 times to obtain Cl-Removing, and testing Cl with silver nitrate solution-If the NBT4 powder is completely removed, drying the washed product to obtain sheet NBT4 powder;
step 2, coating the flaky NBT4 powder with dopamine;
weighing 0.75g of NBT4 powder, adding 5mL of deionized water and 5mL of absolute ethyl alcohol, stirring, reacting for 8h, drying, adding 0.03g of dopamine hydrochloride, 0.04g of trihydroxymethyl chloromethane and 10mL of hydrochloric acid, stirring, reacting for 16h, drying, taking 1mL of 0.1mol/L hydrochloric acid when preparing hydrochloric acid, and then diluting the rest part with deionized water to obtain dopamine-coated sheet NBT4 powder;
step 3, taking five small glass bottles with the capacity of 20mL, adding 0.5g of PVDF and 5mL of DMF into each small glass bottle, stirring for 4h, adding dopamine-coated flaky NBT4 powder, stirring and reacting for 18h, wherein the volume of the dopamine-coated flaky NBT4 powder respectively accounts for 0.5%, 1.125%, 1.75%, 2.375% and 3% of the total volume of the NBT4 powder and the PVDF;
step 4, preparing a pure flaky NBT4 and PVDF gradient composite material by adopting a tape casting method, heating a tape casting machine to 140 ℃, then carrying out tape casting preparation of a multilayer gradient composite material on a glass substrate according to the sequence that the volume fractions of fillers are sequentially increased, after one layer of film is subjected to tape casting, drying at 100 ℃ for 30min, continuing to carry out tape casting preparation of the next layer of film until a five-layer gradient composite film of flaky NBT4 and PVDF is obtained, drying the prepared gradient composite film at 100 ℃ for 12h, and meanwhile, refrigerating water for 12h by using a refrigerator to obtain enough ice water;
and 5, putting the dried sheet-shaped NBT4 and PVDF five-layer gradient composite film into a vacuum drying oven, heating at 200 ℃ for 10min, then quenching with 5 ℃ ice water, and finally drying at 40 ℃ for 20min to obtain the sheet-shaped NBT4/PVDF five-layer gradient composite material with the initial layer filler of 0.5 vol% and the NBT4 filler gradient of 0.625 vol% in two adjacent layers.
Example 3
The invention relates to a preparation method of a sheet NBT4/PVDF composite material (the filler of an initial layer is 0.5 vol%, the concentration gradient of the NBT4 filler of two adjacent layers is 0.75 vol%), which comprises the following steps,
step 1, preparation of flaky Na0.5Bi4.5Ti4O15；
Weighing Na in proportion2CO3、Bi2O3、TiO2And NaCl, in which Na is substituted2CO3、Bi2O3And TiO2The mass ratio of oxides to NaCl of the composition was 1.5: 1; adding the four mixtures, zirconia ball stone and absolute ethyl alcohol into a ball milling tank according to the mass ratio of 1:2:1, carrying out ball milling for 8 hours, and drying; putting the dried mixture into a crucible to calcine at 900 ℃ for 3 hours; grinding the calcined mixture, sieving, placing into a beaker, and heating at 80 deg.CWashing with deionized water for 5 times to obtain Cl-Removing, and testing Cl with silver nitrate solution-If the NBT4 powder is completely removed, drying the washed product to obtain sheet NBT4 powder;
step 2, coating the flaky NBT4 powder with dopamine;
weighing 0.75g of NBT4 powder, adding 5mL of deionized water and 5mL of absolute ethyl alcohol, stirring, reacting for 8h, drying, adding 0.03g of dopamine hydrochloride, 0.04g of trihydroxymethyl chloromethane and 10mL of hydrochloric acid, stirring, reacting for 16h, drying, taking 1mL of 0.1mol/L hydrochloric acid when preparing hydrochloric acid, and then diluting the rest part with deionized water to obtain dopamine-coated sheet NBT4 powder;
step 3, taking five small glass bottles with the capacity of 20mL, adding 0.5g of PVDF and 5mL of DMF into each small glass bottle, stirring for 4h, adding dopamine-coated flaky NBT4 powder, stirring and reacting for 18h, wherein the volume of the dopamine-coated flaky NBT4 powder respectively accounts for 0.5%, 1.25%, 2%, 2.75% and 3.5% of the total volume of the NBT4 powder and the PVDF;
step 4, preparing a pure flaky NBT4 and PVDF gradient composite material by adopting a tape casting method, heating a tape casting machine to 140 ℃, then carrying out tape casting preparation of a multilayer gradient composite material on a glass substrate according to the sequence that the volume fractions of fillers are sequentially increased, after one layer of film is subjected to tape casting, drying at 100 ℃ for 30min, continuing to carry out tape casting preparation of the next layer of film until a five-layer gradient composite film of flaky NBT4 and PVDF is obtained, drying the prepared gradient composite film at 100 ℃ for 12h, and meanwhile, refrigerating water for 12h by using a refrigerator to obtain enough ice water;
and 5, putting the dried sheet-shaped NBT4 and PVDF five-layer gradient composite film into a vacuum drying oven, heating at 200 ℃ for 10min, then quenching with 5 ℃ ice water, and finally drying at 40 ℃ for 20min to obtain the sheet-shaped NBT4/PVDF five-layer gradient composite material with the initial layer filler of 0.5 vol% and the NBT4 filler gradient of 0.75 vol% in two adjacent layers.
Example 4
The invention relates to a preparation method of a sheet NBT4/PVDF composite material (the filler of an initial layer is 0.5 vol%, the concentration gradient of the NBT4 filler of two adjacent layers is 0.875 vol%), which comprises the following steps,
step 1, preparation of flaky Na0.5Bi4.5Ti4O15；
Weighing Na in proportion2CO3、Bi2O3、TiO2And NaCl, in which Na is substituted2CO3、Bi2O3And TiO2The mass ratio of oxides to NaCl of the composition was 1.5: 1; adding the four mixtures, zirconia ball stone and absolute ethyl alcohol into a ball milling tank according to the mass ratio of 1:2:1, carrying out ball milling for 8 hours, and drying; putting the dried mixture into a crucible to calcine at 900 ℃ for 3 hours; grinding the calcined mixture, sieving, placing into a beaker, and washing with 80 deg.C deionized water for 5 times to obtain Cl-Removing, and testing Cl with silver nitrate solution-If the NBT4 powder is completely removed, drying the washed product to obtain sheet NBT4 powder;
step 2, coating the flaky NBT4 powder with dopamine;
weighing 0.75g of NBT4 powder, adding 5mL of deionized water and 5mL of absolute ethyl alcohol, stirring, reacting for 8h, drying, adding 0.03g of dopamine hydrochloride, 0.04g of trihydroxymethyl chloromethane and 10mL of hydrochloric acid, stirring, reacting for 16h, drying, taking 1mL of 0.1mol/L hydrochloric acid when preparing hydrochloric acid, and then diluting the rest part with deionized water to obtain dopamine-coated sheet NBT4 powder;
step 3, taking five small glass bottles with the capacity of 20mL, adding 0.5g of PVDF and 5mL of DMF into each small glass bottle, stirring for 4h, adding dopamine-coated flaky NBT4 powder, stirring and reacting for 18h, wherein the volume of the dopamine-coated flaky NBT4 powder respectively accounts for 0.5%, 1.375%, 2.25%, 3.125% and 4% of the total volume of the NBT4 powder and the PVDF;
step 4, preparing a pure flaky NBT4 and PVDF gradient composite material by adopting a tape casting method, heating a tape casting machine to 140 ℃, then carrying out tape casting preparation of a multilayer gradient composite material on a glass substrate according to the sequence that the volume fractions of fillers are sequentially increased, after one layer of film is subjected to tape casting, drying at 100 ℃ for 30min, continuing to carry out tape casting preparation of the next layer of film until a five-layer gradient composite film of flaky NBT4 and PVDF is obtained, drying the prepared gradient composite film at 100 ℃ for 12h, and meanwhile, refrigerating water for 12h by using a refrigerator to obtain enough ice water;
and 5, putting the dried sheet-shaped NBT4 and PVDF five-layer gradient composite membrane into a vacuum drying oven, heating at 200 ℃ for 10min, then quenching with 5 ℃ ice water, and finally drying at 40 ℃ for 20min to obtain the sheet-shaped NBT4/PVDF five-layer gradient composite material with the initial layer filler content of 0.5 vol% and the NBT4 filler gradient of 0.875 vol% in two adjacent layers.
Example 5
The invention relates to a preparation method of a sheet NBT4/PVDF composite material (the initial layer filler is 0.5 vol%, the concentration gradient of the NBT4 filler of two adjacent layers is 1 vol%), which comprises the following steps,
step 1, preparation of flaky Na0.5Bi4.5Ti4O15；
Weighing Na in proportion2CO3、Bi2O3、TiO2And NaCl, in which Na is substituted2CO3、Bi2O3And TiO2The mass ratio of oxides to NaCl of the composition was 1.5: 1; adding the four mixtures, zirconia ball stone and absolute ethyl alcohol into a ball milling tank according to the mass ratio of 1:2:1, carrying out ball milling for 8 hours, and drying; putting the dried mixture into a crucible to calcine at 900 ℃ for 3 hours; grinding the calcined mixture, sieving, placing into a beaker, and washing with 80 deg.C deionized water for 5 times to obtain Cl-Removing, and testing Cl with silver nitrate solution-If the NBT4 powder is completely removed, drying the washed product to obtain sheet NBT4 powder;
step 2, coating the flaky NBT4 powder with dopamine;
weighing 0.75g of NBT4 powder, adding 5mL of deionized water and 5mL of absolute ethyl alcohol, stirring, reacting for 8h, drying, adding 0.03g of dopamine hydrochloride, 0.04g of trihydroxymethyl chloromethane and 10mL of hydrochloric acid, stirring, reacting for 16h, drying, taking 1mL of 0.1mol/L hydrochloric acid when preparing hydrochloric acid, and then diluting the rest part with deionized water to obtain dopamine-coated sheet NBT4 powder;
step 3, taking five small glass bottles with the capacity of 20mL, adding 0.5g of PVDF and 5mL of DMF into each small glass bottle, stirring for 4h, adding dopamine-coated flaky NBT4 powder, stirring and reacting for 18h, wherein the volume of the dopamine-coated flaky NBT4 powder respectively accounts for 0.5%, 1.5%, 2.5%, 3.5% and 4.5% of the total volume of the NBT4 powder and the PVDF;
step 4, preparing a pure flaky NBT4 and PVDF gradient composite material by adopting a tape casting method, heating a tape casting machine to 140 ℃, then carrying out tape casting preparation of a multilayer gradient composite material on a glass substrate according to the sequence that the volume fractions of fillers are sequentially increased, after one layer of film is subjected to tape casting, drying at 100 ℃ for 30min, continuing to carry out tape casting preparation of the next layer of film until a five-layer gradient composite film of flaky NBT4 and PVDF is obtained, drying the prepared gradient composite film at 100 ℃ for 12h, and meanwhile, refrigerating water for 12h by using a refrigerator to obtain enough ice water;
and 5, putting the dried sheet NBT4 and PVDF five-layer gradient composite film into a vacuum drying oven, heating at 200 ℃ for 10min, quenching with 5 ℃ ice water, and finally drying at 40 ℃ for 20min to obtain the sheet NBT4/PVDF five-layer gradient composite material with the initial layer filler of 0.5 vol% and the NBT4 filler gradient of 1 vol% in two adjacent layers.
Example 6
The invention relates to a preparation method of a sheet NBT4/PVDF composite material (the filler of an initial layer is 0.5 vol%, the concentration gradient of the NBT4 filler of two adjacent layers is 0.75 vol%), which comprises the following steps,
step 1, preparation of flaky Na0.5Bi4.5Ti4O15；
Weighing Na in proportion2CO3、Bi2O3、TiO2And NaCl, in which Na is substituted2CO3、Bi2O3And TiO2The mass ratio of oxide to NaCl is 1: 1; adding the four mixtures, zirconia ball stone and absolute ethyl alcohol into a ball milling tank according to the mass ratio of 1:2:1, carrying out ball milling for 8 hours, and drying; the dried mixture is put into a crucible to be calcined,the temperature is 800 ℃, and the time is 5 h; grinding the calcined mixture, sieving, placing into a beaker, and washing with 80 deg.C deionized water for 5 times to obtain Cl-Removing, and testing Cl with silver nitrate solution-If the NBT4 powder is completely removed, drying the washed product to obtain sheet NBT4 powder;
step 2, coating the flaky NBT4 powder with dopamine;
weighing 0.75g of NBT4 powder, adding 5mL of deionized water and 5mL of absolute ethyl alcohol, stirring, reacting for 4h, drying, adding 0.02g of dopamine hydrochloride, 0.06g of trihydroxymethyl chloromethane and 7mL of hydrochloric acid, stirring, reacting for 8h, drying, taking 1.5mL of 0.1mol/L hydrochloric acid when preparing hydrochloric acid, and then diluting the rest part with deionized water to obtain dopamine-coated sheet NBT4 powder;
step 3, taking five small glass bottles with the capacity of 20mL, adding 0.5g of PVDF and 5mL of DMF into each small glass bottle, stirring for 6 hours, adding dopamine-coated flaky NBT4 powder, stirring and reacting for 12 hours, wherein the volume of the dopamine-coated flaky NBT4 powder respectively accounts for 0.5%, 1.25%, 2%, 2.75% and 3.5% of the total volume of the NBT4 powder and the PVDF;
step 4, preparing a pure flaky NBT4 and PVDF gradient composite material by adopting a tape casting method, heating a tape casting machine to 130 ℃, then carrying out tape casting preparation of a multilayer gradient composite material on a glass substrate according to the sequence that the volume fractions of fillers are sequentially increased, drying at 110 ℃ for 20min after the tape casting of one layer of film is finished, continuing to carry out tape casting preparation of the next layer of film until a five-layer gradient composite film of flaky NBT4 and PVDF is obtained, drying the prepared gradient composite film at 110 ℃ for 12h, and meanwhile, refrigerating water for 12h by using a refrigerator to obtain enough ice water;
and 5, putting the dried sheet-shaped NBT4 and PVDF five-layer gradient composite membrane into a vacuum drying oven, heating at 160 ℃ for 15min, then quenching with 5 ℃ ice water, and finally drying at 35 ℃ for 20min to obtain the sheet-shaped NBT4/PVDF five-layer gradient composite material with the initial layer filler of 0.5 vol% and the NBT4 filler gradient of 0.75 vol% in two adjacent layers.
Example 7
The invention relates to a preparation method of a sheet NBT4/PVDF composite material (the filler of an initial layer is 0.5 vol%, the concentration gradient of the NBT4 filler of two adjacent layers is 0.875 vol%), which comprises the following steps,
step 1, preparation of flaky Na0.5Bi4.5Ti4O15；
Weighing Na in proportion2CO3、Bi2O3、TiO2And NaCl, in which Na is substituted2CO3、Bi2O3And TiO2The mass ratio of oxides to NaCl of the composition was 1.2: 1; adding the four mixtures, zirconia ball stone and absolute ethyl alcohol into a ball milling tank according to the mass ratio of 1:2:1, carrying out ball milling for 8 hours, and drying; putting the dried mixture into a crucible to calcine at 1000 ℃ for 8 hours; grinding the calcined mixture, sieving, placing into a beaker, and washing with 80 deg.C deionized water for 5 times to obtain Cl-Removing, and testing Cl with silver nitrate solution-If the NBT4 powder is completely removed, drying the washed product to obtain sheet NBT4 powder;
step 2, coating the flaky NBT4 powder with dopamine;
weighing 0.75g of NBT4 powder, adding 5mL of deionized water and 5mL of absolute ethyl alcohol, stirring, reacting for 6h, drying, adding 0.03g of dopamine hydrochloride, 0.05g of trihydroxymethyl chloromethane and 8mL of hydrochloric acid, stirring, reacting for 12h, drying, taking 1.2mL of 0.1mol/L hydrochloric acid when preparing hydrochloric acid, and then diluting the rest part with deionized water to obtain dopamine-coated sheet NBT4 powder;
step 3, taking five small glass bottles with the capacity of 20mL, adding 0.5g of PVDF and 5mL of DMF into each small glass bottle, stirring for 6h, adding dopamine-coated flaky NBT4 powder, stirring and reacting for 24h, wherein the volume of the dopamine-coated flaky NBT4 powder respectively accounts for 0.5%, 1.375%, 2.25%, 3.125% and 4% of the total volume of the NBT4 powder and the PVDF;
step 4, preparing a pure sheet NBT4 and PVDF composite material by adopting a tape casting method, heating a tape casting machine to 160 ℃, then carrying out tape casting preparation of a multilayer gradient composite on a glass substrate according to the sequence that the volume fractions of fillers are sequentially increased, drying at 120 ℃ for 15min after the tape casting of one layer of film is finished, then continuing to carry out tape casting preparation of the next layer of film until a five-layer gradient composite film of the sheet NBT4 and PVDF is obtained, then drying the prepared gradient composite film at 100 ℃ for 12h, and meanwhile, refrigerating water for 12h by a refrigerator to obtain enough ice water;
and 5, putting the dried sheet-shaped NBT4 and PVDF five-layer gradient composite membrane into a vacuum drying oven, heating at 180 ℃ for 5min, then quenching with 5 ℃ ice water, and finally drying at 55 ℃ for 20min to obtain the sheet-shaped NBT4/PVDF five-layer gradient composite material with the initial layer filler content of 0.5 vol% and the NBT4 filler gradient of 0.875 vol% in two adjacent layers.
Comparative example 1
A method for preparing a pure PVDF material, comprising the steps of:
step 1, taking five small glass bottles with the capacity of 20mL, adding 0.5g of PVDF and 5mL of DMF into each small glass bottle, stirring for 4 hours, preparing a pure PVDF gradient material by adopting a tape casting method, heating the tape casting machine to 140 ℃, and sequentially carrying out tape casting preparation on five layers of gradient materials on a glass substrate. After the casting of one layer of film is finished, drying the film at 100 ℃ for 30min, then continuing the casting preparation of the next layer of film until obtaining a pure PVDF five-layer gradient material, drying the prepared gradient material at 100 ℃ for 12h, and meanwhile, refrigerating water for 12h through a refrigerator to obtain enough ice water;
and 2, putting the dried pure PVDF gradient material into a vacuum drying oven, heating at 200 ℃ for 10min, quenching with 5 ℃ ice water, and finally drying at 40 ℃ for 20min to obtain the pure PVDF gradient material.
As can be seen from the graph of fig. 1, the obtained sodium bismuth titanate powder has no impurity phase, good crystallinity, and a characteristic peak in the (00n) direction is distinct, and has a sheet structure parallel to the horizontal direction, indicating that it has good orientation.
As can be seen from FIG. 2, the bismuth sodium titanate powder has a dense structure and good dispersibility, and has a sheet-like structure of about 3 μm, corresponding to FIG. 1.
The spectrum of FIG. 3 detects diffraction peaks of the inorganic filler phase NBT4 and the matrix PVDF. The characteristic peak of NBT4 in the (00n) direction is evident, and it can be demonstrated that the flake-like NBT4 is aligned in the PVDF matrix, and the peak of PVDF is weak, indicating that the NBT4 filler in the composite material has a high degree of orientation.
Fig. 4 shows that the thickness of the composite material is about 20 μm, the gradient delamination is obvious, the interlayer compatibility is good, the defects of cracking, fault and the like do not exist, and the dispersibility of the ceramic filler is good, and the purpose of adding the dotted line is to illustrate that the composite material forms five layers, wherein the black part of the bottommost layer is conductive adhesive, the composite material is hardened by embrittlement treatment by using liquid nitrogen when a cross section required by scanning is obtained, the cross section is irregular when tweezers are operated, and therefore white stains appear in the figure.
As can be seen from FIG. 5, the pure PVDF material has the lowest dielectric constant, and the dielectric constant increases with the increasing content of the ceramic filler, and at 100Hz, the dielectric constant of PVDF is about 9, and the dielectric constant of the composite material is between 14 and 20.
As can be seen from FIG. 6, the dielectric loss of the composite material was low, and the dielectric loss at 100Hz was 0.05 or less. As filler increases, the loss generally increases, indicating that too much filler introduces more defects.
From fig. 7, the hysteresis loop plot of the composite is seen for a first layer of 0.5 vol% filler, followed by a layer-by-layer progression with an interlayer filler gradient of 0.5 vol%. The maximum polarization intensity is increased along with the increase of the electric field, and the maximum polarization value under the 250kV/mm electric field is about 6 mu C/cm2。
From fig. 8, the hysteresis loop of the composite can be seen with a first layer of filler of 0.5 vol% and an interlayer filler gradient of 0.625 vol%. The maximum polarization intensity is increased continuously along with the increase of the electric field, and the maximum polarization value under the electric field of 260kV/mm is about 8 mu C/cm2。
From fig. 9, the hysteresis loop of the composite can be seen with a first layer of filler of 0.5 vol% and an interlayer filler gradient of 0.75 vol%. The maximum polarization intensity is increased continuously with the increase of the electric field, and the maximum polarization value under the 340kV/mm electric field is about 9.5 mu C/cm2。
From FIG. 10The hysteresis loop of the composite was seen with a first layer of 0.5 vol% filler and an interlayer filler gradient of 0.875 vol%. The maximum polarization intensity is increased continuously along with the increase of the electric field, and the maximum polarization value under the 200kV/mm electric field is about 8 mu C/cm2。
From fig. 11, the hysteresis loop plot of the composite is seen for a first layer of 0.5 vol% filler with a 1 vol% interlayer filler gradient. The maximum polarization intensity is increased along with the increase of the electric field, and the maximum polarization value under the electric field of 140kV/mm is about 7 mu C/cm2。
From fig. 12, it can be seen that the breakdown field strength of the composite material is 340kV/mm, the breakdown field strength of the composite material is maximum when the filler of the initial layer is 0.5 vol%, and the filler gradient of NBT4 of the adjacent two layers is 0.75 vol%. Because of the construction of a suitable gradient, it has a strong breakdown strength.
The energy storage density parameter of the composite material can be obtained from FIG. 13, the composite material with the initial layer filler being 0.5 vol% and the NBT4 filler gradient of the two adjacent layers being 0.75 vol% obtains 10.7J/cm under the breakdown field strength of 340kV/mm3Higher than other composite materials.
As can be seen from the above figures, the preparation process of the invention is simple, the energy consumption is low, and the composite material which has the initial layer filler of 0.5 vol% and the adjacent two layers of NBT4 filler with the gradient of 0.75 vol% has excellent dielectric constant, low dielectric loss and high breakdown resistance. According to the invention, through reasonably designing the multilayer gradient structure of the two-dimensional flaky ceramic filler, the dielectric loss of the composite material is reduced, the dielectric constant, the polarization value, the breakdown strength and the energy storage density of the composite material are improved, and meanwhile, good flexibility is kept, so that the preparation method of the high-energy-storage composite material is provided.

Claims (10)

1. A preparation method of a sheet-shaped sodium bismuth titanate/polyvinylidene fluoride composite material is characterized by comprising the following steps,
step 1, adding Na2CO3、Bi2O3、TiO2Calcining NaCl and the mixture at 800-1000 ℃ to obtain a mixture, wherein Na is2CO3、Bi2O3And TiO2The mass ratio of the total mass of (1) to NaCl is 1 to 1.5, and the amount of Cl in the mixture is determined-Removing, drying and uniformly grinding to obtain flaky sodium bismuth titanate powder;
step 2, adding the flaky sodium bismuth titanate powder into an ethanol solution, drying, adding dopamine hydrochloride and hydrochloric acid containing trihydroxymethyl chloromethane, reacting, and drying the product to obtain dopamine-coated flaky sodium bismuth titanate powder, wherein the proportion of the flaky sodium bismuth titanate powder, the dopamine hydrochloride, the trihydroxymethyl chloromethane and the hydrochloric acid is 0.75 g: (0.02-0.03) g: (0.04-0.06) g: (7-10) mL;
preparing polyvinylidene fluoride into five parts of solution, respectively adding dopamine-coated flaky sodium bismuth titanate powder into the solution, wherein the volume of the powder is 0.5-4.5% of the total volume of the powder and polyvinylidene fluoride, obtaining five parts of mixed systems with sequentially-increased powder concentrations, preparing a compound of the flaky sodium bismuth titanate powder and the polyvinylidene fluoride on a glass substrate by using the five parts of mixed systems by a tape casting method according to the sequentially-increased powder concentrations, and drying the obtained five-layer composite film to obtain a compound A;
and 4, carrying out primary drying on the compound A at 160-200 ℃, then sequentially quenching and carrying out secondary drying at 35-55 ℃ to obtain the flaky sodium bismuth titanate/polyvinylidene fluoride composite material.
2. The method for preparing a sodium bismuth titanate/polyvinylidene fluoride sheet composite material according to claim 1, wherein step 1 is carried out by mixing Na2CO3、Bi2O3、TiO2And calcining NaCl at the temperature for 3-8 h.
3. The preparation method of the sodium bismuth titanate/polyvinylidene fluoride sheet composite material according to claim 1, wherein the concentration of the hydrochloric acid in the step 2 is 0.01-0.021 mol/L.
4. The preparation method of the sodium bismuth titanate/polyvinylidene fluoride sheet composite material according to claim 1, wherein in the step 2, the sodium bismuth titanate sheet powder is added into an ethanol solution and then stirred for 4-8 hours, and then the obtained sodium bismuth titanate powder is dried.
5. The preparation method of the sodium bismuth titanate/polyvinylidene fluoride composite material in the sheet shape according to claim 1, wherein the step 2 is to react for 8-16 hours after dopamine hydrochloride and hydrochloric acid containing trihydroxymethyl chloromethane are added to obtain a product.
6. The preparation method of the sodium bismuth titanate/polyvinylidene fluoride composite material in sheet form according to claim 1, wherein step 3 is carried out by adding polyvinylidene fluoride into DMF to obtain the solution, wherein the ratio of polyvinylidene fluoride to DMF is 0.1 g: 1 mL.
7. The method for preparing a sodium bismuth titanate/polyvinylidene fluoride sheet composite material according to claim 1, wherein the concentration value of the powder in the mixing system of step 3 is in an arithmetic progression with a minimum value of 0.5% and a tolerance of 0.5-1%.
8. The preparation method of the flaky sodium bismuth titanate/polyvinylidene fluoride composite material according to claim 1, wherein in the step 3, after one layer of film is cast, the next layer of film is cast after drying for 15-30 min at 100-120 ℃.
9. The preparation method of the sodium bismuth titanate/polyvinylidene fluoride sheet composite material according to claim 1, wherein the compound A is vacuum dried at the temperature for 5-15 min and then quenched in step 4.
10. A flaky sodium bismuth titanate/polyvinylidene fluoride composite material obtained by the method for producing a flaky sodium bismuth titanate/polyvinylidene fluoride composite material according to any one of claims 1 to 9.
CN202110202034.9A 2021-02-23 2021-02-23 Flaky sodium bismuth titanate/polyvinylidene fluoride composite material and preparation method thereof Pending CN112812475A (en)

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