CN108251971B - Flexible piezoelectric nanofiber membrane and preparation method and application thereof - Google Patents
Flexible piezoelectric nanofiber membrane and preparation method and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
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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
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/092—Forming composite materials
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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
- H10N30/30—Piezoelectric or electrostrictive devices with mechanical input and electrical output, e.g. functioning as generators or sensors
- H10N30/302—Sensors
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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
Abstract
A flexible piezoelectric nanofiber membrane and a preparation method and application thereof mainly relate to the field of piezoelectricity. According to the preparation method of the flexible piezoelectric nanofiber membrane, the PVDF fibers are modified by doping ZnO nanoparticles in the PVDF fibers by using an electrostatic spinning method, so that the piezoelectric performance of the final flexible piezoelectric nanofiber membrane is improved, and the preparation method is novel, simple, low in manufacturing cost and beneficial to popularization and application. Therefore, the flexible piezoelectric nanofiber membrane and the preparation method thereof have the advantages of simple preparation process, low cost and easy realization of large-area preparation, and the prepared nanofiber membrane has good piezoelectric performance, so that a piezoelectric device (application of the flexible piezoelectric nanofiber membrane) has better electrical performance output, and therefore the flexible piezoelectric nanofiber membrane and the preparation method and application thereof have important popularization and application values and wide application prospects.
Description
Technical Field
The invention relates to the field of piezoelectricity, in particular to a flexible piezoelectric nanofiber membrane and a preparation method and application thereof.
Background
The modern society is increasingly demanding and consuming energy, and the traditional fossil energy petroleum and coal is becoming limited. Therefore, there is a need to develop a new clean energy to overcome this energy demand. Piezoelectric materials are crystalline materials that develop a voltage across their faces when subjected to a compressive force, converting mechanical energy into electrical energy.
Compared with inorganic materials, PVDF has high chemical stability, acid and alkali corrosion resistance, good bending and stretching properties, large piezoelectric constant, large frequency response range, certain flexibility, good biocompatibility and better adhesion to soft tissues such as skin, etc. compared with inorganic materials, PVDF has five different crystal forms α, gamma, delta and epsilon, nonpolar α polymorphic form (TGTG' dihedral conformation) is highly thermodynamically stable, and the melting process is directly formed.
At present, the PVDF material mainly has the problem of poor electrical property output in the aspect of piezoelectric property, and cannot well meet the use requirement of a piezoelectric sensor.
Disclosure of Invention
The invention aims to provide a flexible piezoelectric nanofiber membrane which has good piezoelectric performance.
Another object of the present invention is to provide a method for preparing a flexible piezoelectric nanofiber membrane, which has a simple preparation process and a low manufacturing cost, and can obtain a flexible piezoelectric nanofiber membrane with good piezoelectric properties.
Another object of the present invention is to provide a use of a flexible piezoelectric nanofiber membrane, which has good electrical performance output.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of a flexible piezoelectric nanofiber membrane, which comprises the following steps:
mixing and stirring a dimethyl sulfoxide solution of zinc acetate and an ethanol solution of tetramethylammonium hydroxide in sequence, adding ethyl acetate to precipitate nano particles, adding ethanolamine to stabilize the nano particles, then centrifugally separating out ZnO nano particles, and drying the ZnO nano particles; dissolving PVDF in a mixed solution of acetone and dimethylacetamide to obtain a PVDF solution; dissolving the dried ZnO nanoparticles into a mixed solution of acetone and dimethylacetamide, adding a PVDF solution, heating in a water bath, and stirring to obtain a spinning precursor solution; preparing the spinning precursor solution into an electrostatic spinning film by using electrostatic spinning equipment, drying the electrostatic spinning film, and heating at 140-145 ℃ for 2-2.5 h.
The invention provides a flexible piezoelectric nanofiber membrane, wherein the flexible piezoelectric nanofiber membrane is prepared by the preparation method of the flexible piezoelectric nanofiber membrane.
The invention provides an application of the flexible piezoelectric nanofiber membrane, wherein the flexible piezoelectric nanofiber membrane is applied to the preparation of a piezoelectric device.
The flexible piezoelectric nanofiber membrane, the preparation method and the application of the flexible piezoelectric nanofiber membrane have the beneficial effects that: according to the preparation method of the flexible piezoelectric nanofiber membrane provided by the embodiment of the invention, the PVDF fibers are modified by doping ZnO nanoparticles in the PVDF fibers by using an electrostatic spinning method, so that the piezoelectric performance of the final flexible piezoelectric nanofiber membrane is improved, and the preparation method is novel, simple, low in manufacturing cost and beneficial to popularization and application. Therefore, the flexible piezoelectric nanofiber membrane and the preparation method and application thereof (for preparing piezoelectric devices such as sensors) provided by the embodiment of the invention are simple in preparation process and low in cost, and the prepared nanofiber membrane has good piezoelectric performance, so that the piezoelectric devices have better electrical output, and therefore, the flexible piezoelectric nanofiber membrane has important popularization and application values.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic structural diagram of a sensor provided in an embodiment of the present invention;
FIG. 2 is a scanning electron microscope atlas of ZnO nano-microsphere particles prepared by the embodiment of the invention;
FIG. 3 is a scanning electron microscope atlas obtained after the surface morphology of the ZnO/PVDF composite flexible piezoelectric nanofiber membrane provided by the embodiment of the invention is amplified;
FIG. 4 is an open circuit voltage measurement map provided by the present invention during a sensor testing process;
fig. 5 is a short-circuit current measurement result map in the sensor test process provided by the present invention.
Icon: 1-a PET film; 2-PU glue; 3-a first electrode; 4-a fibrous film; 5-a second electrode; 6-PET film.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The flexible piezoelectric nanofiber membrane, the preparation method and the application of the flexible piezoelectric nanofiber membrane according to the embodiment of the invention are specifically described below.
The preparation method of the flexible piezoelectric nanofiber membrane provided by the embodiment of the invention comprises the following steps:
s1, mixing and stirring the dimethyl sulfoxide solution of zinc acetate and the ethanol solution of tetramethyl ammonium hydroxide in sequence, adding ethyl acetate to precipitate nano particles, adding ethanolamine to stabilize the nano particles, then centrifugally separating the ZnO nano particles, and drying the ZnO nano particles.
Further, in the process of preparing ZnO nanoparticles, the ratio of the amounts of zinc acetate and tetramethylammonium hydroxide was 3 mmol: 5.5mmol and the amount of ethyl acetate used was 40 mL. The reason why the ethyl acetate is added and the amount of the ethyl acetate is limited is to ensure that the target expected ZnO nanoparticles can be obtained, so that the final ZnO nanoparticle size can also meet the expected requirements.
Further, in the embodiment of the present invention, the particle size of the ZnO nanoparticles after drying is 28 to 32nm, preferably 30 nm. It should be noted that the expected limitation on the particle size of the ZnO nanoparticles is because the particle size of the ZnO nanoparticles has an important influence on the preparation of the spinning precursor solution at the later stage, and further influences the preparation of the final flexible piezoelectric nanofiber film.
Further, in the process of preparing ZnO nanoparticles according to the embodiment of the present invention, the amounts of dimethyl sulfoxide, ethanol, ethyl acetate, and ethanolamine are 30mL, 10mL, 40mL, and 160 μ L, respectively; in the process of centrifugally separating out ZnO nanoparticles, the centrifugal speed of the centrifuge is 10000-. It should be noted that in other embodiments, the amounts of dimethyl sulfoxide, ethanol, ethyl acetate and ethanolamine may be varied to provide a 0.5mL balance based on their respective amounts. In addition, the usage amounts of dimethyl sulfoxide, ethanol, ethyl acetate and ethanolamine are limited in the embodiment of the present invention, so as to ensure sufficient reaction between the zinc acetate solution and the tetramethylammonium hydroxide solution, and ensure the quality of the ZnO nanoparticles after being finally stabilized, separated and dried.
S2, dissolving the PVDF in a mixed solution of acetone and dimethylacetamide to obtain a PVDF solution.
Further, in the process of preparing the PVDF solution in the example of the present invention, the volume ratio of acetone and dimethylacetamide in the mixed solution of acetone and dimethylacetamide is 5: 7, the mass fraction of the PVDF solution is 22-28%, and preferably, the mass fraction of the PVDF solution is 25%. It should be noted that, in the embodiment of the present invention, the volume ratio of acetone to dimethylacetamide is defined to ensure the quality of the subsequent spun fiber; and the mass fraction of the PVDF solution is correspondingly limited so as to ensure that a target expected product can be obtained in the subsequent spinning precursor solution synthesis process.
And S3, dissolving the dried ZnO nanoparticles into a mixed solution of acetone and dimethylacetamide, adding a PVDF solution, heating in a water bath, and stirring to obtain a spinning precursor solution.
Further, in the process of heating in water bath, the heating temperature is 35-45 ℃, and the heating and stirring time is 6 h. It should be noted that, in this embodiment, the parameters of the water bath heating are defined to ensure high-quality synthesis of the spinning precursor solution, so as to ensure the quality requirement of the spinning precursor solution.
S4, preparing the spinning precursor solution into an electrostatic spinning film by using electrostatic spinning equipment, drying the electrostatic spinning film, and heating at 140-145 ℃ for 2-2.5 h.
Further, in order to ensure the quality stability of the electrostatic spinning membrane, the drying temperature is controlled to be 40 ℃ and the drying time is 11.5-12.5h in the process of drying the electrostatic spinning membrane.
In addition, in the embodiment of the invention, when the electrostatic spinning equipment is used for preparing the spinning precursor solution into the electrostatic spinning film, the loading voltage is 17-18kV, the distance between the needle head and the plate is 10-12cm, the propelling speed is 0.02-0.03mL/min, the temperature is 28-29 ℃, the relative air humidity is 40-45%, and the spinning time is 1-1.5 h.
The embodiment of the invention also provides a flexible piezoelectric nanofiber membrane which is prepared by the preparation method of the flexible piezoelectric nanofiber membrane. It should be noted that the flexible piezoelectric nanofiber film provided by the embodiment of the present invention has good piezoelectric performance.
The embodiment of the invention also provides an application of the flexible piezoelectric nanofiber membrane, and particularly, the flexible piezoelectric nanofiber membrane is applied to the preparation of a piezoelectric device. Such as a piezoelectric sensor. It should be noted that the piezoelectric device provided with the flexible piezoelectric nanofiber membrane provided by the embodiment of the invention has better electrical performance output.
Further, in terms of application to the manufacture of piezoelectric devices, the specific operating method is: aluminum foils are respectively pasted on two surfaces of the flexible piezoelectric nanofiber membrane to serve as electrodes, the flexible piezoelectric nanofiber membrane with the electrodes is polarized by adopting a corona polarization method, wherein the polarization conditions are as follows: the polarization time is 3min, the polarization temperature is 60 ℃, the voltage of a needle point electrode is 15kV, the voltage of a metal grid electrode is 1.5kV, the distance between the needle electrode and the sample is 4cm, and the distance between the grid electrode and the sample is 1 cm.
More specifically, as shown in fig. 1, an embodiment of the present invention provides a piezoelectric sensor of a ZnO/PVDF composite flexible piezoelectric nanofiber membrane, where a PET film 1 and a PET film 6 mainly can ensure that a fiber film 4(ZnO/PVDF fiber membrane) is uniformly stressed; the PU glue 2 mainly fixes the fiber film 4 in the PET film 1 and the PET film 6.
The PET film 1 and the PET film 6 with certain thicknesses can be selected to have certain mechanical strength and thickness; in addition, the first electrode 3 and the second electrode 5 can be made of conductive materials such as aluminum foil, copper foil and the like, and copper wire leading electrodes can be connected to the electrodes.
Further, the specific working principle of the piezoelectric sensor is as follows: in the initial state, the PET film 1 and the PET film 6 are not affected by external force, the fiber film 4 is not affected by external force, the centers of gravity of positive and negative charges in the crystal are superposed, and the total electric distance of the whole crystal is equal to zero. When the PET film 1 is acted by external force, the fiber film 4 is stressed uniformly downwards, the centers of gravity of positive and negative charges are not overlapped due to deformation of crystals and ZnO nanoparticles in the fiber film 4, the electric distance is changed, the synergistic effect of the crystals and the ZnO nanoparticles finally causes the upper surface and the lower surface of the fiber film 4 to generate charges with the same electric quantity and opposite polarities, after the external force is removed, the centers of gravity of the positive and negative charges of the crystals and the ZnO nanoparticles are overlapped, the surface of the crystals has no charges, the pressing and separating processes are repeated, and the PVDF fibers and the ZnO nanoparticles have the synergistic effect, so that the surface of the fiber film 4 generates the same charges, and the detection and sensing functions are realized.
Finally, experiments show that when the frequency of the external force action is higher, the more piezoelectric charges are generated, and the stronger the signal of the sensor is, so that the piezoelectric signal can be detected by selecting a proper frequency to obtain a better detection effect.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a flexible piezoelectric nanofiber membrane, which comprises the following steps:
preparation of ZnO nanoparticles: mixing a dimethyl sulfoxide (DMSO 30mL) solution of zinc acetate (3mmol) with an ethanol (10mL) solution of tetramethylammonium hydroxide (TMAH 5.5mmol), stirring for 24h, adding ethyl acetate (40mL) to precipitate ZnO nanoparticles, adding ethanolamine (160 mu L) to stabilize the nanoparticles, separating the ZnO nanoparticles by using a centrifuge (10000 rpm), and drying in an oven at 40 ℃ to obtain 30nm microsphere particles.
Preparation of PVDF solution: dissolving PVDF in a mixed solution of acetone and dimethylacetamide (DMAc), wherein the volume ratio of acetone to DMAc is 5: 7, the mass fraction of PVDF is 25%.
Preparation of ZnO/PVDF mixed solution: and dissolving the prepared ZnO nanoparticles into a solution of acetone and DMAc, adding the prepared PVDF solution into the solution, and stirring the mixture for 6 hours in a water bath kettle at 40 ℃ to prepare a spinning precursor solution.
Preparing a ZnO/PVDF composite flexible piezoelectric nanofiber membrane: and (3) putting the prepared spinning precursor solution into a BD type injector, and preparing a round electrostatic spinning film by using electrostatic spinning equipment. Wherein the spinning parameters are as follows: the injector is connected with a 1.5mm tube, a 20G needle is used, the loading voltage is 17kV, the distance between the needle and the plate is 10cm, the propelling speed is 0.03mL/min, the temperature is 28 ℃, the relative air humidity is 42.5 percent, and the spinning time is 1.25 h. And finally, drying the prepared electrostatic spinning membrane in a 40 ℃ drying oven for 12 hours, and heating at 140 ℃ for 2 hours to obtain the flexible piezoelectric nanofiber membrane.
The embodiment also provides a flexible piezoelectric nanofiber membrane, which is prepared by the preparation method of the flexible piezoelectric nanofiber membrane.
The present embodiment also provides an application of the flexible piezoelectric nanofiber membrane as provided in the present embodiment, in particular, the flexible piezoelectric nanofiber membrane is applied on a piezoelectric device. The preparation process of the piezoelectric device comprises the following steps: aluminum foils are respectively pasted on two surfaces of the flexible piezoelectric nanofiber membrane to serve as electrodes, the flexible piezoelectric nanofiber membrane with the electrodes is polarized by adopting a corona polarization method, wherein the polarization conditions are as follows: the polarization time is 3min, the polarization temperature is 60 ℃, the voltage of a needle point electrode is 15kV, the voltage of a metal grid electrode is 1.5kV, the distance between the needle electrode and the sample is 4cm, and the distance between the grid electrode and the sample is 1 cm.
Example 2
The embodiment provides a preparation method of a flexible piezoelectric nanofiber membrane, which comprises the following steps:
preparation of ZnO nanoparticles: mixing a dimethyl sulfoxide (DMSO 30mL) solution of zinc acetate (3mmol) with an ethanol (10mL) solution of tetramethylammonium hydroxide (TMAH 5.5mmol), stirring for 24h, adding ethyl acetate (40mL) to precipitate ZnO nanoparticles, adding ethanolamine (160 mu L) to stabilize the nanoparticles, separating the ZnO nanoparticles by a centrifuge (10010 rpm), and drying in an oven at 40 ℃ to obtain 32nm microsphere particles.
Preparation of PVDF solution: dissolving PVDF in a mixed solution of acetone and dimethylacetamide (DMAc), wherein the volume ratio of acetone to DMAc is 5: 7, the mass fraction of PVDF is 28%.
Preparation of ZnO/PVDF mixed solution: and dissolving the prepared ZnO nanoparticles into a solution of acetone and DMAc, adding the prepared PVDF solution into the solution, and stirring the mixture for 6 hours in a water bath kettle at the temperature of 45 ℃ to prepare a spinning precursor solution.
Preparing a ZnO/PVDF composite flexible piezoelectric nanofiber membrane: and (3) putting the prepared spinning precursor solution into a BD type injector, and preparing a round electrostatic spinning film by using electrostatic spinning equipment. Wherein the spinning parameters are as follows: the injector is connected with a 1.5mm pipe and a 20G needle, the loading voltage is 19kV, the distance between the needle and the plate is 15cm, the propelling speed is 0.04mL/min, the temperature is 31 ℃, the relative air humidity is 50 percent, and the spinning time is 2 h. And finally, drying the prepared electrostatic spinning membrane in a 40 ℃ drying oven for 12 hours, and heating at 142.5 ℃ for 2.25 hours to obtain the flexible piezoelectric nanofiber membrane.
The embodiment also provides a flexible piezoelectric nanofiber membrane, which is prepared by the preparation method of the flexible piezoelectric nanofiber membrane.
The present embodiment also provides an application of the flexible piezoelectric nanofiber membrane as provided in the present embodiment, in particular, the flexible piezoelectric nanofiber membrane is applied on a piezoelectric device. The preparation process of the piezoelectric device comprises the following steps: aluminum foils are respectively pasted on two surfaces of the flexible piezoelectric nanofiber membrane to serve as electrodes, the flexible piezoelectric nanofiber membrane with the electrodes is polarized by adopting a corona polarization method, wherein the polarization conditions are as follows: the polarization time is 3min, the polarization temperature is 60 ℃, the voltage of a needle point electrode is 15kV, the voltage of a metal grid electrode is 1.5kV, the distance between the needle electrode and the sample is 4cm, and the distance between the grid electrode and the sample is 1 cm.
Example 3
The embodiment provides a preparation method of a flexible piezoelectric nanofiber membrane, which comprises the following steps:
preparation of ZnO nanoparticles: mixing a dimethyl sulfoxide (DMSO 30mL) solution of zinc acetate (3mmol) with an ethanol (10mL) solution of tetramethylammonium hydroxide (TMAH 5.5mmol), stirring for 24h, adding ethyl acetate (40mL) to precipitate ZnO nanoparticles, adding ethanolamine (160 mu L) to stabilize the nanoparticles, separating the ZnO nanoparticles by using a centrifuge (10000 rpm), and drying in an oven at 40 ℃ to obtain 28nm microsphere particles.
Preparation of PVDF solution: dissolving PVDF in a mixed solution of acetone and dimethylacetamide (DMAc), wherein the volume ratio of acetone to DMAc is 5: 7, the mass fraction of PVDF is 22%.
Preparation of ZnO/PVDF mixed solution: and dissolving the prepared ZnO nanoparticles into a solution of acetone and DMAc, adding the prepared PVDF solution into the solution, and stirring the mixture for 6 hours in a water bath kettle at the temperature of 35 ℃ to prepare a spinning precursor solution.
Preparing a ZnO/PVDF composite flexible piezoelectric nanofiber membrane: and (3) putting the prepared spinning precursor solution into a BD type injector, and preparing a round electrostatic spinning film by using electrostatic spinning equipment. Wherein the spinning parameters are as follows: the injector is connected with a 1.5mm pipe, a 20G needle is used, the loading voltage is 15kV, the distance between the needle and the plate is 8cm, the propelling speed is 0.01mL/min, the temperature is 26 ℃, the relative air humidity is 35 percent, and the spinning time is 0.5 h. And finally, drying the prepared electrostatic spinning membrane in a 40 ℃ drying oven for 12 hours, and heating at 145 ℃ for 2.5 hours to obtain the flexible piezoelectric nanofiber membrane.
The embodiment also provides a flexible piezoelectric nanofiber membrane, which is prepared by the preparation method of the flexible piezoelectric nanofiber membrane.
The present embodiment also provides an application of the flexible piezoelectric nanofiber membrane as provided in the present embodiment, in particular, the flexible piezoelectric nanofiber membrane is applied on a piezoelectric device. The preparation process of the piezoelectric device comprises the following steps: aluminum foils are respectively pasted on two surfaces of the flexible piezoelectric nanofiber membrane to serve as electrodes, the flexible piezoelectric nanofiber membrane with the electrodes is polarized by adopting a corona polarization method, wherein the polarization conditions are as follows: the polarization time is 3min, the polarization temperature is 60 ℃, the voltage of a needle point electrode is 15kV, the voltage of a metal grid electrode is 1.5kV, the distance between the needle electrode and the sample is 4cm, and the distance between the grid electrode and the sample is 1 cm.
Test examples
In order to prove the beneficial effects of the flexible piezoelectric nanofiber membrane and the preparation method thereof, in the test example, the ZnO nanoparticle sample of example 1 and the final ZnO/PVDF composite flexible piezoelectric nanofiber membrane sample are firstly selected and subjected to shape scanning observation, and the results are respectively shown in fig. 2 and fig. 3.
Further, it can be confirmed from fig. 2 that the ZnO nanomicrosphere particles have a good distribution of nanoparticles as expected, each particle is closely adjacent and uniformly dispersed, and the particle sizes are substantially the same. As can be seen from fig. 3, the final ZnO/PVDF composite flexible piezoelectric nanofiber membrane shows a good fiber structure, which also improves a good organization structure foundation for the application of the ZnO/PVDF composite flexible piezoelectric nanofiber membrane in a piezoelectric device.
The piezoelectric testing method is used for carrying out piezoelectric testing on a sensor prepared by applying the piezoelectric device, wherein a voltmeter/ammeter is used for testing the electrical property of the device, and the testing conditions are that the initial position is 50mm, the final position is 110mm, the acceleration is 1m/s × 2, and the maximum speed is 1 m/s.
Further, the following briefly describes the specific working process of the sensor of the present invention in practical use:
the open-circuit voltage and the short-circuit current of the ZnO/PVDF composite flexible piezoelectric nanofiber membrane sensor in the embodiment are measured, and the results are respectively shown in fig. 4 and fig. 5, wherein fig. 4 is the open-circuit voltage measurement result of the ZnO/PVDF composite flexible piezoelectric nanofiber membrane sensor under the action of the linear motor, and fig. 5 is the short-circuit current measurement result of the ZnO/PVDF composite flexible piezoelectric nanofiber membrane sensor under the action of the linear motor.
In addition, in the research process of the invention, the frequency of the applied pressure has a great influence on the actual output power in the actual work of the ZnO/PVDF composite flexible piezoelectric nanofiber membrane-based sensor in each embodiment of the invention. As the pressure frequency increases, the voltage across the membrane increases and the current through the membrane increases.
In summary, according to the preparation method of the flexible piezoelectric nanofiber membrane provided by the embodiment of the invention, the PVDF fiber is modified by doping the ZnO nanoparticles in the PVDF fiber by using an electrostatic spinning method, so that the piezoelectric performance of the final flexible piezoelectric nanofiber membrane is improved, and the preparation method is novel, simple, low in manufacturing cost and beneficial to popularization and application. Therefore, the flexible piezoelectric nanofiber membrane and the preparation method and application thereof (for preparing piezoelectric devices such as sensors) provided by the embodiment of the invention are simple in preparation process, low in cost and easy to realize large-area preparation, and the prepared nanofiber membrane has good piezoelectric performance, so that the piezoelectric devices have better electrical output, and therefore the flexible piezoelectric nanofiber membrane has important popularization and application values and wide application prospects.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (9)
1. A preparation method of a flexible piezoelectric nanofiber membrane is characterized by comprising the following steps:
mixing and stirring a dimethyl sulfoxide solution of zinc acetate and an ethanol solution of tetramethylammonium hydroxide in sequence, adding ethyl acetate to precipitate nano particles, adding ethanolamine to stabilize the nano particles, then centrifugally separating out ZnO nano particles, and drying the ZnO nano particles; the dosage ratio of the zinc acetate to the tetramethylammonium hydroxide is 3 mmol: 5.5 mmol; in addition, the particle size of the dried ZnO nano-particles is 28-32 nm;
dissolving PVDF in a mixed solution of acetone and dimethylacetamide to obtain a PVDF solution;
dissolving the dried ZnO nanoparticles into a mixed solution of acetone and dimethylacetamide, adding a PVDF solution, heating in a water bath, and stirring to obtain a spinning precursor solution;
preparing the spinning precursor solution into an electrostatic spinning film by using electrostatic spinning equipment, drying the electrostatic spinning film, and heating at 140-145 ℃ for 2-2.5 h.
2. The method for preparing a flexible piezoelectric nanofiber membrane according to claim 1, wherein in the process of preparing the PVDF solution, the volume ratio of acetone to dimethylacetamide in the mixed solution of acetone and dimethylacetamide is 5: 7; the mass fraction of the PVDF solution is 22-28%.
3. The method for preparing the flexible piezoelectric nanofiber membrane as claimed in claim 1, wherein the heating temperature is 35-45 ℃ and the heating and stirring time is 6 hours in the process of heating in the water bath.
4. The method for preparing the flexible piezoelectric nanofiber membrane according to claim 1, wherein in the process of drying the electrostatic spinning membrane, the drying temperature is 40 ℃ and the drying time is 11.5-12.5 h.
5. The method for preparing the flexible piezoelectric nanofiber membrane according to any one of claims 1 to 4, wherein in the process of preparing the ZnO nanoparticles, the dosage of the dimethyl sulfoxide, the ethanol, the ethyl acetate and the ethanolamine is respectively 30mL, 10mL, 40mL and 160 μ L; in the process of centrifugally separating the ZnO nanoparticles, the centrifugal speed of the centrifugal machine is 10000-10010 r/min.
6. The method for preparing a flexible piezoelectric nanofiber membrane according to claim 5, wherein in the process of preparing the spinning precursor solution into the electrostatic spinning membrane by using the electrostatic spinning equipment, the loading voltage is 17-18kV, the distance between a needle head and a plate is 10-12cm, the propelling speed is 0.02-0.03mL/min, the temperature is 28-29 ℃, the relative air humidity is 40-45%, and the spinning time is 1-1.5 h.
7. A flexible piezoelectric nanofiber membrane, characterized in that the flexible piezoelectric nanofiber membrane is prepared by the preparation method of the flexible piezoelectric nanofiber membrane of any one of claims 1-6.
8. Use of a flexible piezoelectric nanofiber membrane according to claim 7 in the manufacture of a piezoelectric device.
9. The use of the flexible piezoelectric nanofiber membrane according to claim 8, wherein aluminum foils are respectively attached to both sides of the flexible piezoelectric nanofiber membrane as electrodes, and the flexible piezoelectric nanofiber membrane with the electrodes is polarized by adopting a corona polarization method, wherein the polarization conditions are as follows: the polarization time is 3min, the polarization temperature is 60 ℃, the voltage of a needle point electrode is 15kV, the voltage of a metal grid electrode is 1.5kV, the distance between the needle electrode and a sample is 4cm, and the distance between the grid electrode and the sample is 1 cm.
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| CN109576900A (en) * | 2018-11-22 | 2019-04-05 | 四川大学 | A method of promoting composite material piezoelectric property |
| CN110965136B (en) * | 2019-11-08 | 2022-01-28 | 北京科技大学 | Preparation method of flexible piezoelectric nano-generator based on perovskite polymer composite material |
| CN111564549B (en) * | 2020-02-24 | 2021-01-29 | 宁波工程学院 | SiC/ZnO nano heterojunction pressure sensor and preparation method thereof |
| US11932558B1 (en) * | 2020-03-02 | 2024-03-19 | University Of Rhode Island Board Of Trustees | Piezocatalysis using piezoelectric polymers |
| CN113124997A (en) * | 2021-03-11 | 2021-07-16 | 东南大学 | Piezoelectric composite three-dimensional vector hydrophone and preparation method thereof |
| CN113654577A (en) * | 2021-07-14 | 2021-11-16 | 西南交通大学 | ZnO/PVDF nanofiber flexible piezoelectric sensor with multistage core-shell structure and preparation method thereof |
| CN113670487B (en) * | 2021-07-14 | 2022-07-19 | 西南交通大学 | Composite flexible piezoresistive sensor based on bionic multilevel structure and preparation method thereof |
| CN114892282B (en) * | 2022-04-21 | 2023-07-18 | 西南交通大学 | Preparation method and application of piezoelectric fiber with topological structure |
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