CN114773645B - Dielectric flexible film and preparation method thereof - Google Patents
Dielectric flexible film and preparation method thereof Download PDFInfo
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- CN114773645B CN114773645B CN202210491992.7A CN202210491992A CN114773645B CN 114773645 B CN114773645 B CN 114773645B CN 202210491992 A CN202210491992 A CN 202210491992A CN 114773645 B CN114773645 B CN 114773645B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002033 PVDF binder Substances 0.000 claims abstract description 99
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 99
- 239000000084 colloidal system Substances 0.000 claims abstract description 90
- 229910002115 bismuth titanate Inorganic materials 0.000 claims abstract description 65
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 30
- 238000005266 casting Methods 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000010791 quenching Methods 0.000 claims abstract description 14
- 230000000171 quenching effect Effects 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004146 energy storage Methods 0.000 abstract description 30
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 239000010410 layer Substances 0.000 description 29
- 230000005684 electric field Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002356 single layer Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- -1 titanium ions Chemical class 0.000 description 1
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/008—Wide strips, e.g. films, webs
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The application provides a dielectric flexible film and a preparation method thereof. The preparation method of the dielectric flexible film comprises the following steps: s1: preparing two-dimensional nano bismuth titanate by using titanium dioxide and bismuth nitrate as raw materials; s2: adding the two-dimensional nano bismuth titanate into an organic solvent, uniformly mixing, adding PVDF, and stirring to obtain a two-dimensional bismuth titanate/PVDF colloid; s3: preparing a two-dimensional bismuth titanate/PVDF colloid into a composite colloid film by adopting a solution casting method; s4: and drying, heat treating and quenching the composite colloid film to obtain the dielectric flexible film. The dielectric flexible film has excellent performances in breakdown resistance, dielectric constant, energy storage density, energy storage efficiency and the like.
Description
Technical Field
The application relates to the technical field of dielectric films, in particular to a dielectric flexible film and a preparation method thereof.
Background
With the development of technology, energy markets dominant in energy fields such as mobile electronic devices, pulse energy systems, new energy automobiles and the like begin to have higher pursuits on energy storage performance (energy storage density and energy storage efficiency) of dielectric energy storage film materials. At present, polyvinylidene fluoride (PVDF) polymer-based flexible materials are widely applied in the field of energy collection, but weak ferroelectricity severely restricts the improvement of the energy storage performance of the materials. In contrast, the ferroelectric ceramic material with high dielectric constant is used as filler to be compounded with the PVDF substrate, and the prepared composite film has good energy storage performance.
However, the property of the ferroelectric ceramic material has certain influence on the breakdown field intensity, the energy storage density and the like of the composite film, and the breakdown field intensity is reduced due to the agglomeration effect easily generated when the material is introduced, so that the improvement of the energy storage density is restrained, and meanwhile, the breakdown field intensity cannot be greatly improved.
In view of this, the present application has been made.
Disclosure of Invention
The application aims to provide a dielectric flexible film and a preparation method thereof, wherein the dielectric flexible film has excellent performances in the aspects of breakdown resistance, dielectric constant, energy storage density, energy storage efficiency and the like.
The application provides a preparation method of a dielectric flexible film, which comprises the following steps:
s1: preparing two-dimensional nano bismuth titanate (2D-BTO for short) by taking titanium dioxide and bismuth nitrate as raw materials;
s2: adding the two-dimensional nano bismuth titanate into an organic solvent, uniformly mixing, adding PVDF, and stirring to obtain a two-dimensional bismuth titanate/PVDF colloid (called as 2D-BTO/PVDF colloid for short);
s3: preparing a two-dimensional bismuth titanate/PVDF colloid into a composite colloid film by adopting a solution casting method;
s4: and drying, heat treating and quenching the composite colloid film to obtain the dielectric flexible film.
The dielectric flexible film of the application takes a ferroelectric material Bismuth Titanate (BTO) with higher dielectric constant as a filler to be compounded with a PVDF substrate; particularly, the bismuth titanate adopts two-dimensional nano bismuth titanate, and the two-dimensional nano bismuth titanate can form an electron conduction barrier in the substrate while considering the length-diameter ratio and the polarizability, so that the conduction and the extension of an electronic tree are prevented, the breakdown field intensity is effectively improved, and the overall energy storage performance is further improved.
In the present application, step S1 includes:
s11: adding titanium dioxide and concentrated hydrochloric acid into deionized water, and uniformly mixing to obtain suspension A;
s12: adding sodium hydroxide solution into the suspension A, and uniformly mixing to obtain a suspension B;
s13: uniformly mixing bismuth nitrate, concentrated nitric acid and deionized water to obtain a mixed solution C;
s14: slowly adding the mixed solution C into the suspension B under stirring, and continuing stirring to obtain a precursor suspension D;
s15: transferring the precursor suspension D into a reaction kettle for hydrothermal reaction to obtain a suspension E;
s16: and (3) centrifuging, ultrasonically stirring and drying the suspension E to obtain the two-dimensional nano bismuth titanate.
Specifically, in step S11, the molar ratio of titanium dioxide to the solute of hydrochloric acid is 1: (3-5) wherein the hydrochloric acid solute refers to a hydrochloric acid component in concentrated hydrochloric acid; the mass volume ratio of the concentrated hydrochloric acid to the deionized water is (1.1-1.2) g: (18-22) mL.
In the step S12, the concentration of the sodium hydroxide solution is 0.002-0.004mol/mL; more specifically, the method for preparing a sodium hydroxide solution may include: thoroughly stirring the sodium hydroxide solid in deionized water until the sodium hydroxide solid is completely dissolved, wherein the mass volume ratio of the sodium hydroxide solid to the deionized water can be (4.7-4.9) g: (38-42) mL.
In step S13, bismuth nitrate may be bismuth nitrate pentahydrate; the concentration of bismuth nitrate in the mixed solution C is 0.00015-0.00025mol/mL; more specifically, the mass to volume ratio between bismuth nitrate pentahydrate, concentrated nitric acid and deionized water may be (1.9-2.0) g: (1.9-2.1) mL: (17-20) mL; in addition, the molar ratio of titanium ions to bismuth ions in the mixed solution may be 3: about 4.
In the step S15, the temperature of the hydrothermal reaction is 180-220 ℃, and the time of the hydrothermal reaction is 45-50h.
In the step S16, the centrifugal rotating speed is 4000-5000r/min, the drying temperature is 60-80 ℃ and the drying time is 8-12h.
Researches show that the structure, the size and the morphology of the two-dimensional nano bismuth titanate prepared by the method have favorable effects on the aspects of dispersibility, slurry viscosity, slurry bubble rate and the like of the 2D-BTO/PVDF colloid filler, and further have favorable effects on the aspects of thickness, density and the like of the dielectric flexible film, so that the breakdown resistance, dielectric constant, energy storage density and energy storage efficiency of the dielectric flexible film are obviously improved.
In the step S2 of the application, the mass ratio of the two-dimensional nano bismuth titanate to PVDF is 1: (14-16) the organic solvent is N-N dimethylformamide; the mass volume ratio of the two-dimensional nano bismuth titanate to the N-N dimethylformamide can be 0.1g: (6-8) mL. In addition, the mixing can be magnetically stirred for 3-5 hours under the sealing condition, and the stirring after PVDF is added can be magnetically stirred for 8-12 hours under the sealing condition.
Further, the preparation method of the application further comprises the following steps: adding PVDF into an organic solvent, and uniformly stirring to obtain PVDF colloid; wherein the mass volume ratio of PVDF to organic solvent is (1.4-1.6) g: (6-8) mL, the organic solvent is N-N dimethylformamide; stirring can be carried out under sealed conditions for 3-5h.
The structure of the dielectric flexible film is not strictly limited in the application, and in an embodiment, the dielectric flexible film can be a single-layer film; at this time, step S3 includes: casting the two-dimensional bismuth titanate/PVDF colloid on ITO conductive glass, flattening the colloid by using a scraper, and heating on a heating table to obtain the composite colloid film.
In another embodiment, the dielectric flexible film of the application can also be a film with a three-layer sandwich structure; at this time, step S3 includes:
s31: casting the first colloid on ITO conductive glass, flattening the colloid by using a scraper, and heating on a heating table to obtain a first colloid film;
s32: casting the second colloid on the first colloid film, flattening the colloid by using a scraper, and heating on a heating table to obtain the second colloid film;
s33: casting the first colloid on the second colloid film, flattening the colloid by using a scraper, and heating on a heating table to obtain a composite colloid film;
the first colloid is one of PVDF colloid and two-dimensional bismuth titanate/PVDF colloid, and the second colloid is the other of PVDF colloid and two-dimensional bismuth titanate/PVDF colloid.
When the first colloid is a PVDF colloid and the second colloid is a two-dimensional bismuth titanate/PVDF colloid (2D-BTO/PVDF colloid for short), the uppermost layer and the lowermost layer of the dielectric flexible film are PVDF films, the middle layer is a two-dimensional bismuth titanate/PVDF composite film, and the dielectric flexible film is of a PVDF-BTO-PVDF sandwich structure; the first colloid is a two-dimensional bismuth titanate/PVDF colloid, the second colloid is a PVDF colloid, the uppermost layer and the lowermost layer of the dielectric flexible film are two-dimensional bismuth titanate/PVDF composite films at the moment, the middle layer is a PVDF film, and the dielectric flexible film is of a BTO-PVDF-BTO sandwich structure at the moment.
More specifically, when the film is prepared by solution casting, the thickness of the doctor blade may be 65-75 μm, the heating temperature may be 60-70 ℃, and the heating time may be 4-6min.
In the application, in the step S4, the drying temperature is 60-80 ℃ and the drying time is 8-10h; the heat treatment temperature is 190-210 ℃, and the heat treatment time is 8-12min; the quenching temperature is 190-210 ℃ lower than the heat treatment temperature, and the quenching time is 3-7min. In addition, the quenching can be dried again under the drying condition of 60-80 ℃ for 8-10h.
The application also provides a dielectric flexible film which is prepared according to the preparation method.
The implementation of the application has at least the following advantages:
1. the preparation method solves the problems of lower breakdown field intensity and lower energy storage density of the composite film material in the field of dielectrics, the application of the dielectric material in a bendable novel flexible device and the lightweight design of energy storage equipment, and prepares the dielectric flexible film with higher breakdown field intensity and higher energy storage density;
2. the dielectric flexible film has simple preparation process, low cost and industrialized production, wherein the PVDF polymer has good film forming property, and the prepared dielectric flexible film has strong bending property and certain tensile strength and can be used in flexible devices in a large number; meanwhile, the prepared two-dimensional nano bismuth titanate has the advantages that the length-diameter ratio and the polarization ratio are considered, the two-dimensional nano bismuth titanate can be used as an electron conduction barrier in a film, and meanwhile, the uneven interface between the two-dimensional nano bismuth titanate and PVDF can be increased, so that the breakdown field strength and the polarization strength are effectively improved, the overall energy storage performance of the film is further improved, the problem of low energy density of the dielectric film in the prior commercial application is solved, the volume of the dielectric flexible film can be effectively reduced, and the weight burden of energy storage equipment is lightened;
3. the dielectric flexible film of the application can work under higher electric field intensity, and the energy storage density can reach about 16J/cm when the electric field intensity of 600kV/mm is externally applied 3 The remnant polarization was 1.2. Mu.C/cm 2 In addition, the dielectric constant at any frequency is better than that of a pure polymer, the numerical value is stably improved by 5-12 at different frequencies, and the performance of the polymer is excellent in breakdown resistance, dielectric constant, energy storage density, energy storage efficiency and the like.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD powder diffraction pattern of two-dimensional nano bismuth titanate prepared in example 1;
FIG. 2 is an SEM observation characterization map of two-dimensional nano bismuth titanate prepared in example 1; wherein: (a): low magnification SEM image, (b): high magnification SEM images;
FIG. 3 is a hysteresis loop of the dielectric flexible film prepared in example 1;
FIG. 4 is a schematic structural diagram of the dielectric flexible film of example 2 and example 3; wherein: (a): BTO-PVDF-BTO dielectric flexible film, (b): PVDF-BTO-PVDF dielectric flexible film;
FIG. 5 is a cross-sectional SEM of a BTO-PVDF-BTO dielectric flexible film;
FIG. 6 shows the hysteresis loops of the dielectric flexible films prepared in example 2 and example 3; wherein: (a): BTO-PVDF-BTO dielectric flexible film, (b): PVDF-BTO-PVDF dielectric flexible film, (c): a single-layer PVDF film without two-dimensional nano bismuth titanate;
FIG. 7 is a graph showing the change of dielectric constant with temperature spectrum of the dielectric flexible films prepared in example 2 and example 3; wherein: (a): BTO-PVDF-BTO dielectric flexible film, (b): PVDF-BTO-PVDF dielectric flexible film;
fig. 8 shows the dielectric constant-frequency spectra of the dielectric flexible films prepared in example 2 and example 3.
Reference numerals illustrate:
1: two-dimensional nano bismuth titanate; 2: a PVDF base film; 3: PVDF film.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular forms also include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present application will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The preparation method of the dielectric flexible film of the embodiment comprises the following steps:
1. preparation of two-dimensional nano bismuth titanate
1) Adding 0.24g of titanium dioxide powder and 1.18g of concentrated hydrochloric acid into 20mL of deionized water, and fully stirring at normal temperature to obtain suspension A;
2) Adding 4.8g of sodium hydroxide solid into 40mL of deionized water, fully stirring at normal temperature until the sodium hydroxide solid is fully dissolved, adding the suspension A into the deionized water, and fully stirring to form a suspension B;
3) Mixing 1.94g of bismuth nitrate pentahydrate liquid, 2mL of concentrated nitric acid and 18mL of deionized water, and magnetically stirring until the bismuth nitrate pentahydrate liquid, the concentrated nitric acid and the 18mL of deionized water are completely dissolved to obtain a solution C;
4) Slowly adding the solution C into the slowly stirred suspension B, and continuing magnetic stirring to obtain a pale yellow precursor suspension D;
5) Transferring the precursor suspension D into a reaction kettle, performing heat treatment at 200 ℃ for 48 hours, cooling to room temperature to obtain a white suspension, centrifuging the obtained white suspension at 5000r/min, centrifuging with ethanol for 3 times, and performing ultrasonic stirring after the last centrifugation is finished; and then drying for 10 hours at 70 ℃ to obtain white powdery two-dimensional nano bismuth titanate.
XRD powder diffraction pattern detection is carried out on the prepared two-dimensional nano bismuth titanate, and the result is shown in figure 1; the results in fig. 1 show that: the diffraction peak is matched with the standard data card JCPDS#35-0795, which shows that the prepared material is orthorhombic bismuth titanate crystal.
In addition, SEM observation characterization is carried out on the prepared two-dimensional nano bismuth titanate, and the result is shown in figure 2; the results in fig. 2 show that: the SEM images of (a) low magnification and (b) high magnification of the two-dimensional bismuth titanate filler show that the synthesized bismuth titanate crystal is a bismuth titanate nano material with a two-dimensional structure.
2. Preparation of dielectric Flexible films
1) Adding 0.1g of a two-dimensional bismuth titanate powder sample into 7mL of N-N dimethylformamide, and magnetically stirring in a sealed beaker for 4 hours to obtain a suspension F;
2) Adding 1.5g PVDF into the suspension F, and magnetically stirring for 10 hours in a closed beaker at normal temperature to form a stable 2D-BTO/PVDF colloid;
3) The film is prepared by adopting a solution casting method: casting 2D-BTO/PVDF colloid on cleaned ITO conductive glass, flattening the colloid by a doctor blade with the thickness of 70 microns, and heating at 60 ℃ for 5 minutes on a heating table to obtain a 2D-BTO/PVDF colloid film with a single-layer structure;
4) Transferring the 2D-BTO/PVDF colloid film with the single-layer structure into a drying oven, and drying at 70 ℃ for 10 hours to obtain a 2D-BTO/PVDF film (namely film G);
5) Quenching improves the flexibility of the film: transferring the film G into a drying oven at 200 ℃ for heat treatment for 10min; immediately placing the film G into ice water at 0 ℃ for quenching for 3min; and drying the quenched film to obtain the 2D-BTO/PVDF dielectric flexible film.
FIG. 3 is a schematic diagram of the hysteresis loop of the 2D-BTO/PVDF dielectric flexible film prepared as described above; the results show that: the 2D-BTO/PVDF dielectric flexible film can work under higher electric field intensity, and the energy storage density reaches about 16J/cm when the electric field intensity of 600kV/mm is externally applied 3 The remnant polarization was 0.3. Mu.C/cm 2 。
Example 2
The preparation method of the dielectric flexible film of the embodiment comprises the following steps:
1. preparation of two-dimensional nano bismuth titanate
1) Adding 0.24g of titanium dioxide powder and 1.1g of concentrated hydrochloric acid into 18mL of deionized water, and fully stirring at normal temperature to obtain suspension A;
2) Adding 4.7g of sodium hydroxide solid into 38mL of deionized water, fully stirring at normal temperature until the sodium hydroxide solid is fully dissolved, adding the suspension A into the deionized water, and fully stirring to form a suspension B;
3) 1.9g of bismuth nitrate pentahydrate liquid, 1.9mL of concentrated nitric acid and 17mL of deionized water are mixed, and magnetically stirred until the bismuth nitrate pentahydrate liquid, the concentrated nitric acid and the 17mL of deionized water are completely dissolved to obtain solution C;
4) Slowly adding the solution C into the slowly stirred suspension B, and continuing magnetic stirring to obtain a pale yellow precursor suspension D;
5) Transferring the precursor suspension D into a reaction kettle, performing heat treatment at 180 ℃ for 50 hours, cooling to room temperature to obtain a white suspension, centrifuging the obtained white suspension at 4000r/min, centrifuging with ethanol for 3 times, and performing ultrasonic stirring after the last centrifugation is finished; and then drying for 12 hours at 60 ℃ to obtain white powdery two-dimensional nano bismuth titanate.
2. Preparation of dielectric Flexible films
1) Adding 0.1g of a two-dimensional bismuth titanate powder sample into 7mL of N-N dimethylformamide, and magnetically stirring in a sealed beaker for 4 hours to obtain a suspension F;
2) Adding 1.5g PVDF into the suspension F, and magnetically stirring for 10 hours in a closed beaker at normal temperature to form a stable 2D-BTO/PVDF colloid;
3) Adding 1.5g PVDF into 7mLN-N dimethylformamide, and magnetically stirring in a sealed beaker for 4 hours to obtain transparent PVDF colloid;
4) The film is prepared by adopting a solution casting method: casting 2D-BTO/PVDF colloid on the cleaned ITO conductive glass, flattening the colloid by a doctor blade with the thickness of 70 microns, and heating at 60 ℃ for 5 minutes on a heating table to obtain a first layer film with a single-layer structure (namely a BTO colloid film);
5) Casting transparent PVDF colloid on the first layer film, repeating the operation in the step 4), and forming a second layer film on the first layer film to obtain a colloid film with a double-layer structure;
6) Casting the two-dimensional bismuth titanate/PVDF colloid on the second layer of film, and repeating the operation in the step 4) to obtain a colloid film with a three-layer structure;
7) Transferring the colloid film with the three-layer structure into a drying oven, and drying at 70 ℃ for 10 hours to obtain a film G with a BTO-PVDF-BTO sandwich structure;
8) Quenching improves the flexibility of the film: transferring the film G into a drying oven at 200 ℃ for heat treatment for 10min; immediately placing the film G into ice water at 0 ℃ for quenching for 3min; and drying the quenched film to obtain the BTO-PVDF-BTO dielectric flexible film.
The schematic structural diagram of the prepared BTO-PVDF-BTO dielectric flexible film is shown in fig. 4 (a), wherein the uppermost layer and the lowermost layer are PVDF base films 2 introduced with two-dimensional nano bismuth titanate 1, and the middle layer is a PVDF film 3.
FIG. 5 is a cross-sectional SEM of the BTO-PVDF-BTO dielectric flexible film prepared as described above; the results in fig. 5 show that: the thickness of the BTO-PVDF-BTO dielectric flexible film prepared above was about 15. Mu.m.
And (3) performing a dielectric property test on the prepared BTO-PVDF-BTO dielectric flexible film.
FIG. 6 (a) is a schematic diagram showing the hysteresis loop of the BTO-PVDF-BTO dielectric flexible film prepared as described above; the results show that: the BTO-PVDF-BTO dielectric flexible film can work under higher electric field intensity, and the energy storage density reaches about 11.2J/cm when the electric field intensity of 475kV/mm is applied 3 The remnant polarization was 1.2. Mu.C/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the In addition, referring to fig. 6 (c), the BTO-PVDF-BTO dielectric flexible film operating field strength and energy storage density were 2.6 and 3.9 times, respectively, of the single layer PVDF film without the two-dimensional bismuth titanate introduced.
FIG. 7 (a) is a graph showing the change of dielectric constant of the BTO-PVDF-BTO dielectric flexible film prepared as described above with respect to temperature spectrum line; the results show that: given the appropriate operating frequency, the dielectric constant of the BTO-PVDF-BTO dielectric flexible film can exhibit better stability over a larger temperature range of 18-120 ℃.
FIG. 8 is a dielectric constant-frequency spectrum of the BTO-PVDF-BTO dielectric flexible film prepared as described above; the results show that: the dielectric constant of the BTO-PVDF-BTO dielectric flexible film at any frequency is superior to that of a pure polymer, and the numerical value of the BTO-PVDF-BTO dielectric flexible film at different frequencies is stably improved by 7-12, which shows that the dielectric constant of the BTO-PVDF-BTO dielectric flexible film prepared by the embodiment is obviously improved.
Example 3
The preparation method of the dielectric flexible film of the embodiment comprises the following steps:
1. preparation of two-dimensional nano bismuth titanate
1) Adding 0.24g of titanium dioxide powder and 1.2g of concentrated hydrochloric acid into 22mL of deionized water, and fully stirring at normal temperature to obtain suspension A;
2) Adding 4.9g of sodium hydroxide solid into 42mL of deionized water, fully stirring at normal temperature until the sodium hydroxide solid is fully dissolved, adding the suspension A into the deionized water, and fully stirring to form a suspension B;
3) Mixing 2.0g of bismuth nitrate pentahydrate liquid, 2.1mL of concentrated nitric acid and 20mL of deionized water, and magnetically stirring until the bismuth nitrate pentahydrate liquid, the concentrated nitric acid and the deionized water are completely dissolved to obtain a solution C;
4) Slowly adding the solution C into the slowly stirred suspension B, and continuing magnetic stirring to obtain a pale yellow precursor suspension D;
5) Transferring the precursor suspension D into a reaction kettle, performing heat treatment at 220 ℃ for 45 hours, cooling to room temperature to obtain a white suspension, centrifuging the obtained white suspension 4500r/min, centrifuging with ethanol for 3 times, and performing ultrasonic stirring after the last centrifugation is finished; and then drying for 8 hours at the temperature of 80 ℃ to obtain white powdery two-dimensional nano bismuth titanate. .
2. Preparation of dielectric Flexible films
1) Adding 0.1g of a two-dimensional bismuth titanate powder sample into 7mL of N-N dimethylformamide, and magnetically stirring in a sealed beaker for 4 hours to obtain a suspension F;
2) Adding 1.5g PVDF into the suspension F, and magnetically stirring for 10 hours in a closed beaker at normal temperature to form a stable 2D-BTO/PVDF colloid;
3) Adding 1.5g PVDF into 7mLN-N dimethylformamide, and magnetically stirring in a sealed beaker for 4 hours to obtain transparent PVDF colloid;
4) The film is prepared by adopting a solution casting method: casting PVDF colloid on the cleaned ITO conductive glass, flattening the colloid by a doctor blade with the thickness set to 70 micrometers, and heating at 60 ℃ for 5 minutes on a heating table to obtain a first layer film with a single-layer structure (namely PVDF colloid film);
5) Casting the two-dimensional bismuth titanate/PVDF colloid on the first layer of film, repeating the operation in the step 4), and forming a second layer of film on the first layer of film to obtain a colloid film with a double-layer structure;
6) Casting PVDF colloid on the second layer of film, and repeating the operation in the step 4) to obtain a colloid film with a three-layer structure;
7) Transferring the colloid film with the three-layer structure into a drying oven, and drying at 70 ℃ for 10 hours to obtain a film G with a PVDF-BTO-PVDF sandwich structure;
8) Quenching improves the flexibility of the film: transferring the film G into a drying oven at 200 ℃ for heat treatment for 10min; immediately placing the film G into ice water at 0 ℃ for quenching for 5min; and drying the quenched film to obtain the PVDF-BTO-PVDF dielectric flexible film.
The structural schematic diagram of the PVDF-BTO-PVDF dielectric flexible film prepared above is shown in fig. 4 (b), the uppermost layer and the lowermost layer of the PVDF dielectric flexible film are PVDF films 3, and the middle layer is a PVDF base film 2 which is introduced with two-dimensional nano bismuth titanate 1.
And (3) performing a dielectric property test on the PVDF-BTO-PVDF dielectric flexible film prepared above.
FIG. 6 (b) is the hysteresis loop of the PVDF-BTO-PVDF dielectric flexible film prepared as described above; the results show that: the BTO-PVDF-BTO dielectric flexible film can work under higher electric field intensity, and the energy storage density reaches about 9.7J/cm when the electric field intensity of 450kV/mm is externally applied 3 The remnant polarization was 0.9. Mu.C/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the In addition, referring to fig. 6 (c), the working field strength and the energy storage density of the PVDF-BTO-PVDF dielectric flexible film were 2.7 and 4.5 times, respectively, of the single-layer PVDF film without the two-dimensional bismuth titanate introduced.
FIG. 7 (b) is a graph showing the variation of dielectric constant of the PVDF-BTO-PVDF dielectric flexible film prepared as described above with respect to temperature spectrum line; the results show that: the dielectric constant of the PVDF-BTO-PVDF dielectric flexible film can show better stability in a larger temperature range of 18-120 ℃ when a proper working frequency is given.
FIG. 8 is a dielectric constant-frequency spectrum of the PVDF-BTO-PVDF dielectric flexible film prepared as described above; the results show that: the dielectric constant of the PVDF-BTO-PVDF dielectric flexible film at any frequency is superior to that of a pure polymer, and the numerical value of the PVDF-BTO-PVDF dielectric flexible film at different frequencies is stably improved by 5-10, which shows that the dielectric constant of the PVDF-BTO-PVDF dielectric flexible film prepared by the embodiment is obviously improved.
Comparative example 1
The procedure of example 1 was repeated except that the preparation method of the two-dimensional nano bismuth titanate was changed.
The preparation method of the two-dimensional nano bismuth titanate of the comparative example is as follows:
1) Adding 1.0296g of tetrabutyl titanate into 20mL of deionized water, and fully stirring at normal temperature to obtain suspension A;
2) Adding 4.8g of sodium hydroxide solid into 40mL of deionized water, fully stirring at normal temperature until the sodium hydroxide solid is fully dissolved, adding the suspension A into the deionized water, and fully stirring to form a suspension B;
3) Mixing 1.94g of bismuth nitrate pentahydrate liquid, 2mL of concentrated nitric acid and 18mL of deionized water, and magnetically stirring until the bismuth nitrate pentahydrate liquid, the concentrated nitric acid and the 18mL of deionized water are completely dissolved to obtain a solution C;
4) Slowly adding the solution C into the slowly stirred suspension B, and continuing magnetic stirring to obtain a pale yellow precursor suspension D;
5) Transferring the precursor suspension D into a reaction kettle, performing heat treatment at 200 ℃ for 48 hours, cooling to room temperature to obtain a white suspension, centrifuging the obtained white suspension at 5000r/min, centrifuging with ethanol for 3 times, and performing ultrasonic stirring after the last centrifugation is finished; and then drying for 10 hours at 70 ℃ to obtain white powdery two-dimensional nano bismuth titanate.
The two-dimensional nano bismuth titanate prepared in the above way is used as a raw material, and the step two in the example 1 is adopted to prepare the 2D-BTO/PVDF dielectric flexible film with a single-layer structure.
Dielectric property test is carried out on the 2D-BTO/PVDF dielectric flexible film prepared in the comparative example; the results show that: the energy storage density of the 2D-BTO/PVDF dielectric flexible film of this comparative example was 4.3J/cm when an electric field strength of 220kV/mm was applied 3 The remnant polarization was 0.7. Mu.C/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The 2D-BTO/PVDF dielectric flexible film of this comparative example was broken down upon application of an electric field strength of 475 kV/mm.
Comparative example 2
The two-dimensional nano bismuth titanate of comparative example 1 is used as a raw material, and the step two in example 2 is adopted to prepare the BTO-PVDF-BTO dielectric flexible film with a sandwich structure.
The dielectric property test is carried out on the BTO-PVDF-BTO dielectric flexible film prepared in the comparative example; the results show that: when an electric field strength of 220kV/mm is applied, the energy storage density of the BTO-PVDF-BTO dielectric flexible film of the comparative example is 3.5J/cm 3 The remnant polarization was 0.3. Mu.C/cm 2 The dielectric constant values at different frequencies are only improved by 2-3; the BTO-PVDF-BTO dielectric flexible film of this comparative example was broken down when an electric field strength of 475kV/mm was applied.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (9)
1. A method for preparing a dielectric flexible film, comprising the steps of:
s1: preparing two-dimensional nano bismuth titanate by using titanium dioxide and bismuth nitrate as raw materials;
s2: adding the two-dimensional nano bismuth titanate into an organic solvent, uniformly mixing, adding PVDF, and stirring to obtain a two-dimensional bismuth titanate/PVDF colloid;
s3: preparing a two-dimensional bismuth titanate/PVDF colloid into a composite colloid film by adopting a solution casting method;
s4: drying, heat treating and quenching the composite colloid film to obtain a dielectric flexible film;
the step S1 comprises the following steps:
s11: adding titanium dioxide and concentrated hydrochloric acid into deionized water, and uniformly mixing to obtain suspension A;
s12: adding sodium hydroxide solution into the suspension A, and uniformly mixing to obtain a suspension B;
s13: uniformly mixing bismuth nitrate, concentrated nitric acid and deionized water to obtain a mixed solution C;
s14: slowly adding the mixed solution C into the suspension B under stirring, and continuing stirring to obtain a precursor suspension D;
s15: transferring the precursor suspension D into a reaction kettle for hydrothermal reaction to obtain a suspension E;
s16: and (3) centrifuging, ultrasonically stirring and drying the suspension E to obtain the two-dimensional nano bismuth titanate.
2. The method according to claim 1, wherein in step S11, the molar ratio of titanium dioxide to the solute of hydrochloric acid is 1: (3-5); in the step S12, the concentration of the sodium hydroxide solution is 0.07-0.08mol/mL; in the step S13, the concentration of bismuth nitrate in the mixed solution C is 0.00015-0.00025mol/mL; in the step S15, the temperature of the hydrothermal reaction is 180-220 ℃, and the time of the hydrothermal reaction is 45-50h; in the step S16, the centrifugal rotating speed is 4000-5000r/min, the drying temperature is 60-80 ℃ and the drying time is 8-12h.
3. The preparation method according to claim 1, wherein in step S2, the mass ratio of the two-dimensional nano bismuth titanate to PVDF is 1: (14-16) the organic solvent is N-N dimethylformamide.
4. The method of manufacturing according to claim 1, further comprising: adding PVDF into an organic solvent, and uniformly stirring to obtain PVDF colloid; wherein the mass volume ratio of PVDF to organic solvent is (1.4-1.6) g: (6-8) mL, the organic solvent is N-N dimethylformamide.
5. The method of claim 1, wherein step S3 comprises: casting the two-dimensional bismuth titanate/PVDF colloid on ITO conductive glass, flattening the colloid by using a scraper, and heating on a heating table to obtain the composite colloid film.
6. The method according to claim 4, wherein step S3 comprises:
s31: casting the first colloid on ITO conductive glass, flattening the colloid by using a scraper, and heating on a heating table to obtain a first colloid film;
s32: casting the second colloid on the first colloid film, flattening the colloid by using a scraper, and heating on a heating table to obtain the second colloid film;
s33: casting the first colloid on the second colloid film, flattening the colloid by using a scraper, and heating on a heating table to obtain a composite colloid film;
the first colloid is one of PVDF colloid and two-dimensional bismuth titanate/PVDF colloid, and the second colloid is the other of PVDF colloid and two-dimensional bismuth titanate/PVDF colloid.
7. The method according to claim 5 or 6, wherein the doctor blade has a thickness of 65 to 75 μm, a heating temperature of 60 to 70 ℃ and a heating time of 4 to 6min.
8. The preparation method according to claim 1, wherein in step S4, the drying temperature is 60-80 ℃ and the drying time is 8-10 hours; the heat treatment temperature is 190-210 ℃, and the heat treatment time is 8-12min; the quenching temperature is 190-210 ℃ lower than the heat treatment temperature, and the quenching time is 3-7min.
9. A dielectric flexible film produced according to the production method of any one of claims 1 to 8.
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