CN113394335A - Piezoelectric film, preparation method thereof, piezoelectric film sensor and wearable device - Google Patents
Piezoelectric film, preparation method thereof, piezoelectric film sensor and wearable device Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 20
- 239000011737 fluorine Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002033 PVDF binder Substances 0.000 claims abstract description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 11
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 10
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- 239000011787 zinc oxide Substances 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 77
- 239000002245 particle Substances 0.000 claims description 26
- 239000010409 thin film Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229920002313 fluoropolymer Polymers 0.000 claims description 8
- 239000004811 fluoropolymer Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- 230000010287 polarization Effects 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 3
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002121 nanofiber Substances 0.000 claims description 3
- 239000002073 nanorod Substances 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- -1 glycol ether ester Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 60
- 230000008025 crystallization Effects 0.000 abstract description 60
- 239000013078 crystal Substances 0.000 abstract description 22
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 238000010899 nucleation Methods 0.000 abstract description 6
- 230000006911 nucleation Effects 0.000 abstract description 6
- 229920006254 polymer film Polymers 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004904 shortening Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/16—Measuring force or stress, in general using properties of piezoelectric devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/092—Forming composite materials
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a piezoelectric film and a preparation method thereof, a piezoelectric film sensor and wearing equipment, wherein the piezoelectric film comprises a fluorine-containing polymer film and a nano filler, the nano filler is doped in the fluorine-containing polymer film, and the fluorine-containing polymer matrix comprises at least one of vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, polyvinylidene fluoride, P (VDF-TrFE-CTFE) and P (VDF-TrFE-CFE); the nano filler comprises at least one of copper, titanium dioxide, barium titanate, zinc oxide, indium tin oxide and silicon dioxide. The piezoelectric film is used as a crystal nucleus for heterogeneous nucleation growth in crystal growth by doping the nano filler, so that the crystal growth process of the fluorine-containing polymer can be accelerated, the crystallization time can be greatly shortened, the crystallization rate of the organic piezoelectric film is improved, and the alpha phase without piezoelectric performance can be prevented from being generated in the crystallization process. The doped nano-particle beta phase is easier to form, can promote crystallization and improve the crystallization rate.
Description
Technical Field
The invention relates to the technical field of biosensors, in particular to a piezoelectric film and a preparation method thereof, a piezoelectric film sensor and wearable equipment.
Background
The piezoelectric material is a crystal material with voltage appearing at two ends under the action of external force, and can realize mutual conversion between mechanical energy and electric energy. The characteristics of the piezoelectric material are utilized to manufacture various sensor elements and micro-nano energy devices.
The piezoelectric film made of the piezoelectric material can be applied to wearing products such as shoes and intelligent bracelets to measure mechanical data of sporters, or applied to products containing touch control components such as mobile phones and household appliances. Electrodes are respectively present on both sides of the piezoelectric film, and when the product is viewed in plan, the electrodes on both sides have an overlapping region. When the flexible sensor is under the exogenic action, the piezoelectric film in the sensor produces polarization, can produce induced charge on the electrode of the both sides opposite face of piezoelectric film simultaneously, and through the detection to the electric charge that the flexible sensor produced, can obtain the stress and the strain that the flexible sensor received, finally realize the detection to heart rate, breathing etc.. The piezoelectric performance of the present piezoelectric film needs to be further improved to meet the market demand.
Disclosure of Invention
Accordingly, there is a need for a piezoelectric thin film that can greatly shorten the crystallization time and improve the crystallization rate of the organic piezoelectric thin film.
A piezoelectric thin film, comprising:
a fluoropolymer film;
a nanofiller doped into a fluoropolymer matrix.
The nano particles are mixed in the fluorine-containing polymer film to serve as crystal nuclei for heterogeneous nucleation growth in crystal growth, so that the crystal growth process of the fluorine-containing polymer can be accelerated, the crystallization time can be greatly shortened, and the crystallization rate of the organic piezoelectric film is improved. And the beta phase doped with the nano particles is easier to form, so that the crystallization can be promoted and the crystallization rate can be improved.
In one embodiment, the fluoropolymer comprises at least one of vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, polyvinylidene fluoride, P (VDF-TrFE-CTFE), P (VDF-TrFE-CFE). The adoption of the fluorine-containing polymer can ensure that the crystallization time of the piezoelectric film in the preparation process of the piezoelectric film is short (can be completed in 30 min) and the proportion of beta phase formed by crystallization is high.
In one embodiment thereof, the nanofiller comprises at least one of copper, titanium dioxide, barium titanate, zinc oxide, indium tin oxide, silicon dioxide. The nano filler is more beneficial to shortening the crystallization time and improving the crystallization rate.
In one embodiment, the nano filler is 5 to 30% by mass. The content of the nano filler affects the crystallization time and the crystallization rate, when the content is too low, the crystal growth process cannot be accelerated, and when the content is not high and is too high, the uniformity of film formation is poor, so that the final piezoelectric performance is not uniform.
In one embodiment, the nano-filler is one of a random particle, a nanorod, a nanowire, and a nanofiber.
In one embodiment, the diameter of the nanofiller is between 50nm and 200 nm. The nano-particles with the particle size in the range are more beneficial to shortening the crystallization time and improving the crystallization rate.
In one embodiment, the thickness of the piezoelectric film is 5 μm to 200 μm.
A preparation method of a piezoelectric film comprises the following steps:
dissolving or dispersing the fluorine-containing polymer and the nano filler in an organic solvent to prepare a mixed solution;
coating the mixed solution on a base material, and baking and crystallizing the base material coated with the mixed solution to form a film primary body;
and primarily polarizing the film by adopting a corona polarization mode to form the piezoelectric film with piezoelectric performance.
In one embodiment, the organic solvent may be one or more of MEK, PGMEA, acetone, DMF, tetrahydrofuran, methyl isobutyl ketone, glycol ether, butyl acetate, cyclohexanone, dimethylacetamide, diacetone alcohol, diisobutyl ketone;
the base material is a flexible base material formed by at least one material of PET, PI and PC,
alternatively, the substrate is a rigid substrate.
The invention also provides a piezoelectric film sensor which comprises the piezoelectric film. Compared with the piezoelectric sensor manufactured by the conventional piezoelectric film, the piezoelectric film has better piezoelectric performance.
Furthermore, the invention also provides wearable equipment comprising the piezoelectric film sensor.
The wearing device can be a sleep monitoring belt, an intelligent bracelet and an intelligent watch.
The piezoelectric film is doped with the nano filler and used as a crystal nucleus for heterogeneous nucleation growth in crystal growth, so that the crystal growth process of the fluorine-containing polymer can be accelerated, the crystallization time can be greatly shortened, the crystallization rate of the organic piezoelectric film is improved, and the generation of alpha phase without piezoelectric performance in the crystallization process can be avoided. The doped nano-particle beta phase is easier to form, can promote crystallization and improve the crystallization rate. The crystallization rate of the piezoelectric film is improved from 60% to more than 80%, the crystallization time can be reduced from 4h to 1h, even 30min, and meanwhile, the piezoelectric performance is obviously improved.
Detailed Description
In order that the invention may be more fully understood, it is now described. The following is a description of preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The piezoelectric film of one embodiment can be used for manufacturing a sensor for detecting heartbeat and physiological activity, and particularly comprises a fluorine-containing polymer film and a nano filler, wherein the nano filler is doped in the fluorine-containing polymer film.
The fluorine-containing polymer is polyvinylidene fluoride (PVDF) with piezoelectric property and derivatives thereof. Polyvinylidene fluoride is a semi-crystalline polymer, has five different crystal forms, namely alpha phase, beta phase, gamma phase, delta phase and epsilon phase, wherein the piezoelectric property of PVDF is mainly represented by the beta phase and the gamma phase, and the higher the content (crystallization rate and crystalline phase ratio) of the beta phase is, the higher the piezoelectric property of PVDF after polarization is. In order to realize high crystallization rate, conventionally, prolonged crystallization time and proper crystallization temperature are usually adopted, which greatly affects production efficiency.
According to the embodiment, the nano particles are mixed in the fluorine-containing polymer film to serve as crystal nuclei for heterogeneous nucleation growth in crystal growth, so that the crystal growth process of the fluorine-containing polymer can be accelerated, the crystallization time can be greatly shortened, and the crystallization rate of the organic piezoelectric film is improved. And the beta phase doped with the nano particles is easier to form, so that the crystallization can be promoted and the crystallization rate can be improved.
Wherein the fluorine-containing polymer comprises at least one of vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, polyvinylidene fluoride, P (VDF-TrFE-CTFE) and P (VDF-TrFE-CFE). The adoption of the fluorine-containing polymer can ensure that the crystallization time of the piezoelectric film in the preparation process of the piezoelectric film is short (can be completed in 30 min) and the proportion of beta phase formed by crystallization is high.
Specifically, the nano filler comprises at least one of copper, titanium dioxide, barium titanate, zinc oxide, indium tin oxide and silicon dioxide; the nano filler is more beneficial to shortening the crystallization time and improving the crystallization rate. In a preferred embodiment, low cost copper, silica, titania are used.
In one embodiment, the mass percentage of the nano filler is 5% to 30%. In particular examples, the mass percentage of the nanofiller may be 5%, 5.5%, 6%, 6.8%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 15%, 20%, 25%, or 30%. The content of the nano filler affects the crystallization time and the crystallization rate, when the content is too low, the crystal growth process cannot be accelerated, and when the content is not high and is too high, the uniformity of film formation is poor, so that the final piezoelectric performance is not uniform.
Further, the nano filler is one of irregular particles, nano rods, nano wires and nano fibers.
Further, the particle size of the nano-filler is 50nm to 200 nm. In specific examples, the nanoparticles may have a particle size of 50nm to 70nm, 50nm to 100nm, or 100nm to 200 nm. The nano-particles with the particle size in the range are more beneficial to shortening the crystallization time and improving the crystallization rate.
The thickness of the piezoelectric film is 5-200 μm.
The piezoelectric film is doped with the nano filler and used as a crystal nucleus for heterogeneous nucleation growth in crystal growth, so that the crystal growth process of the fluorine-containing polymer can be accelerated, the crystallization time can be greatly shortened, the crystallization rate of the organic piezoelectric film is improved, and the generation of alpha phase without piezoelectric performance in the crystallization process can be avoided. The doped nano-particle beta phase is easier to form, can promote crystallization and improve the crystallization rate. The crystallization rate of the piezoelectric film is improved from 60% to more than 80%, the crystallization time can be reduced from 4h to 1h, even 30min, and meanwhile, the piezoelectric performance is obviously improved.
A method of manufacturing a piezoelectric thin film according to an embodiment includes the steps of:
step S100: dissolving or dispersing the fluorine-containing polymer and the nano filler in an organic solvent to prepare a mixed solution, wherein the solvent can be one or more of MEK, PGMEA, acetone, DMF, tetrahydrofuran, methyl isobutyl ketone, glycol ether ester, butyl acetate, cyclohexanone, dimethylacetamide, diacetone alcohol, diisobutyl ketone and the like;
step S110: coating the mixed solution of the fluorine-containing polymer and the nano filler on a substrate, wherein the substrate can be a flexible substrate or a rigid substrate, the flexible substrate can be PET, PI, PC and the like, and the rigid substrate can be glass or a metal plate;
step S120: baking and crystallizing the base material coated with the mixed solution to form a film primary body;
specifically, step S120 is to put the coated substrate into an oven to volatilize the solvent; and crystallizing at 130-150 ℃ for 5-3 h.
Step S130: and primarily polarizing the film by adopting a corona polarization mode to form the piezoelectric film with piezoelectric performance.
The film-formed thin film precursor is subjected to polarization treatment, and the piezoelectric film may be peeled off from the substrate and then polarized, or may be polarized and then peeled off from the substrate.
A piezoelectric thin film sensor includes the piezoelectric thin film. Compared with the piezoelectric sensor manufactured by the conventional piezoelectric film, the piezoelectric film has better piezoelectric performance.
Further, a wearable device of an embodiment includes a piezoelectric film sensor.
The wearable device is used for detecting heartbeat and physiological activities. Wearing equipment if can be for wearing products, the product that contains the touch-control part such as sleep monitoring area, intelligent bracelet, intelligent wrist-watch.
The following are specific examples.
Example 1
The piezoelectric film of the embodiment includes a P (VDF-TrFE-CTFE) copolymer film and nano titanium dioxide particles, wherein the nano titanium dioxide particles are doped in the P (VDF-TrFE-CTFE) copolymer film.
The particle size of the nano titanium dioxide particles is 50 nm; the mass percent of the nano titanium dioxide particles is 7.5 percent;
the thickness of the piezoelectric film is 5-20 μm;
example 2
The piezoelectric film of the embodiment includes a vinylidene fluoride-tetrafluoroethylene copolymer film and nano-copper particles, wherein the nano-copper particles are doped in the vinylidene fluoride-tetrafluoroethylene copolymer film.
The particle size of the nano copper particles is 70 nm; the mass percent of the nano-copper particles is 5 percent;
the thickness of the piezoelectric film is 20 to 80 μm.
Example 3
The piezoelectric film of the present embodiment includes a P (VDF-TrFE-CFE) copolymer film and nano silica particles, wherein the nano silica particles are doped in the P (VDF-TrFE-CFE) copolymer film.
The particle size of the nano silicon dioxide particles is 100 nm; the mass percent of the nano silicon dioxide particles is 7.5 percent;
the thickness of the piezoelectric film is 80-120 μm.
Example 3
The piezoelectric film of the embodiment includes a polyvinylidene fluoride copolymer film and a nano barium titanate rod, wherein the nano barium titanate rod is doped in the polyvinylidene fluoride copolymer film.
The diameter of the nano barium titanate rod is 150 nm; the mass percent of the nano barium titanate rod is 7.5 percent;
the thickness of the piezoelectric film is 120-150 μm.
Example 4
The piezoelectric film of the present embodiment includes a P (VDF-TrFE-CFE) film and a nano barium titanate rod, wherein the nano barium titanate rod is doped in the P (VDF-TrFE-CFE) film.
The particle size of the nano indium tin oxide particles is 200 nm; the mass percent of the nano indium tin oxide particles is 7.5 percent;
the thickness of the piezoelectric film is 150 to 200 μm.
Examples 5 to 10
Examples 5 to 10 differ from example 1 only in the content of the nano titania particles, specifically, the content of the nano titania particles is as shown in table 1 (the ratio in the table is mass percent):
TABLE 1
Comparative example 1
This comparative example is different from example 1 in that the P (VDF-TrFE-CTFE) copolymer thin film is not doped with nano titanium dioxide particles.
And (3) testing:
the crystallization time, the crystallization rate, and the piezoelectric constant (d33) of the piezoelectric films produced in examples 1 to 10 and comparative example 1 were measured, and the test results are shown in table 2 below;
TABLE 2
| Group of | Time of crystallization | Crystallization rate | Piezoelectric constant |
| Example 1 | 5min | 96％ | -28pC/N |
| Example 2 | 5min | 96％ | -27pC/N |
| Example 3 | 5min | 96％ | -28pC/N |
| Example 4 | 5min | 98％ | -35pC/N |
| Example 5 | 10min | 83％ | -25pC/N |
| Example 6 | 9min | 88％ | -25pC/N |
| Example 7 | 5min | 95％ | -27pC/N |
| Example 8 | 5min | 97％ | -28pC/N |
| Example 9 | 4min | 98％ | -23pC/N |
| Example 10 | 3min | 98％ | -23pC/N |
| Comparative example 1 | 4h | 60％ | -20pC/N |
As can be seen from table 2, compared with comparative example 1, the piezoelectric thin films of examples 1 to 10 are doped with the nanofiller to serve as crystal nuclei for heterogeneous nucleation growth during crystal growth, so that the crystal growth process of the fluoropolymer can be accelerated, the crystallization time can be greatly shortened, the crystallization rate of the organic piezoelectric thin film can be improved, and the generation of an alpha phase with no pressure electrical property during the crystallization process can be avoided. The doped nano-particle beta phase is easier to form, can promote crystallization and improve the crystallization rate. The crystallization rate of the piezoelectric film is improved from 60% to more than 80%, the crystallization time can be reduced from 4h to 1h, even 30min, and meanwhile, the piezoelectric performance is obviously improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A piezoelectric film, comprising:
a fluoropolymer film;
a nanofiller doped into the fluoropolymer film.
2. The piezoelectric thin film according to claim 1, wherein the fluoropolymer in the fluoropolymer thin film is at least one of a vinylidene fluoride-tetrafluoroethylene copolymer, a vinylidene fluoride-trifluoroethylene copolymer, polyvinylidene fluoride, P (VDF-TrFE-CTFE), P (VDF-TrFE-CFE).
3. The piezoelectric film of claim 1, wherein the nanofiller comprises at least one of copper, titanium dioxide, barium titanate, zinc oxide, indium tin oxide, silicon dioxide.
4. The piezoelectric film according to claim 1, wherein the nanofiller is present in an amount of 5% to 30% by weight.
5. The piezoelectric thin film according to claim 1, wherein the nano filler is one of a random particle, a nanorod, a nanowire, and a nanofiber.
6. The piezoelectric film according to claim 1, wherein the diameter of the nano filler is 50nm to 200 nm.
7. The piezoelectric film according to claim 1, wherein the thickness of the piezoelectric film is 5 μm to 200 μm.
8. A method for manufacturing a piezoelectric thin film, which is used for manufacturing the piezoelectric thin film according to any one of claims 1 to 7, comprising the steps of:
dissolving or dispersing the fluorine-containing polymer and the nano filler in an organic solvent to prepare a mixed solution;
coating the mixed solution on a base material, and baking and crystallizing the base material coated with the mixed solution to form a film primary body;
and primarily polarizing the film by adopting a corona polarization mode to form the piezoelectric film with piezoelectric performance.
9. The method of manufacturing a piezoelectric film according to claim 8, wherein the organic solvent is one or more of MEK, PGMEA, acetone, DMF, tetrahydrofuran, methyl isobutyl ketone, glycol ether ester, butyl acetate, cyclohexanone, dimethylacetamide, diacetone alcohol, diisobutyl ketone;
the base material is a flexible base material formed by at least one material of PET, PI and PC,
alternatively, the substrate is a rigid substrate.
10. A piezoelectric thin film sensor comprising the piezoelectric thin film according to any one of claims 1 to 7.
11. A wearable device, characterized by comprising the piezoelectric thin film sensor of claim 10.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11932558B1 (en) * | 2020-03-02 | 2024-03-19 | University Of Rhode Island Board Of Trustees | Piezocatalysis using piezoelectric polymers |
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2020
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11932558B1 (en) * | 2020-03-02 | 2024-03-19 | University Of Rhode Island Board Of Trustees | Piezocatalysis using piezoelectric polymers |
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Application publication date: 20210914 |