CN113155328B - Flexible passive pressure sensor, preparation method and wearable touch sensor - Google Patents
Flexible passive pressure sensor, preparation method and wearable touch sensor Download PDFInfo
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Classifications
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- 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
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Abstract
The invention belongs to the technical field of novel flexible sensors, and discloses a flexible passive pressure sensor, a preparation method and a wearable touch sensor, wherein PVDF powder is added into a beaker containing dimethylformamide solutionStirring to form pasty slurry; baTiO of core-shell structure 3 Adding the @ ZnO material into a beaker containing dimethylformamide solution, and performing ultrasonic dispersion; adding the white solution into the PVDF transparent pasty slurry, continuously stirring to form uniform white pasty slurry, and placing the slurry into a vacuum drying oven for maintenance; pouring the slurry into a manufactured mold, uniformly dispersing the slurry in the mold by using a scraper, placing the mold in a vacuum drying oven for holding, drying the slurry to form a piezoelectric film, and drying; the aluminum foil electrodes are attached to the upper surface and the lower surface of the piezoelectric film, the golden finger PI packaging device is used, the direct-current high-voltage power supply is connected with the upper electrode and the lower electrode, and the flexible piezoelectric force sensor is obtained through polarization. The invention has higher electrical performance output and sensitivity.
Description
Technical Field
The invention belongs to the technical field of novel flexible sensors, and particularly relates to a flexible passive pressure sensor, a preparation method and a wearable touch sensor.
Background
In recent years, due to the changes of living habits and dietary structures, various chronic health diseases are gradually developed in the middle-aged and young people, the incidence rate is continuously rising, and the medical equipment is occupied in a large amount and simultaneously a great deal of inconvenience and trouble are brought to the daily life of people when the medical equipment is used for health detection in hospitals. The flexible wearable electronic equipment is favored by people due to the advantages of small size, light weight, portability, comfortable wearing, real-time monitoring, health, environmental protection and the like, and represents an unparalleled charm in the field of next-generation medical health monitoring. The presence of the battery increases the size and weight of the portable device and the timed replacement and maintenance of the battery also causes a number of inconveniences. Therefore, it is of great importance to develop a flexible wearable sensor that is capable of self-powering. Among the pressure sensors of various types, the flexible piezoelectric pressure sensor developed according to the piezoelectric effect is one of the most widely studied passive flexible pressure sensors at present due to the advantages of simple structure, low cost, high sensitivity and the like.
Polyvinylidene fluoride (PVDF) is a polymer made up of a plurality of repeating units [ CH ] 2 -CF 2 ]The thermoplastic semi-crystalline polymer has ultrahigh flexibility, sufficient mechanical strength, stable chemical resistance and excellent piezoelectricity, and is widely applied to the fields of wearable electronic equipment and energy acquisition devices. PVDF has five distinct crystalline phases, α, β, δ, γ, epsilon, wherein the crystalline β phase has a high piezoelectric coefficient. Although PVDF polymers have good flexibility and durability, they are far lower than the dielectric constant and piezoelectric coefficient d of inorganic piezoelectric materials 33 Which is a serious drawback in its application. To solve this problem, researchers have developed two approaches: adding a functional nanomaterial into the PVDF matrix to destroy the symmetrical structure of polyvinylidene fluoride and promote the formation of polar crystal form beta phase; a base nanomaterial of high piezoelectric properties is added to the PVDF matrix to improve the overall piezoelectric response. Among them, zinc oxide is a wurtzite piezoelectric material and a functional material that promotes the formation of PVDF piezoelectric phase, and lead-free BTO is considered as the most environmentally friendly perovskite material and provides high piezoelectric performance and high dielectric constant.
Currently, znO or BaTiO based 3 There have been many reports on developed pressure sensors, but based on BaTiO 3 Flexible self-powered voltage sensors prepared from @ ZnO have been reported. BaTiO 3 ZnO on the surface of the piezoelectric material with the @ ZnO structure strengthens the connection between nano particles and polymers, improves the content of beta phase of piezoelectric phase in PVDF, and is BaTiO in performance 3 And ZnO can provide higher piezoelectric coefficient and dielectric constant, improve voltage output performance, and uniformly disperse nano particles to improve the sensitivity of the device. Thus, for BaTiO 3 The flexible passive pressure sensor prepared by the @ ZnO has profound research significance.
Through the above analysis, the problems and defects existing in the prior art are as follows: based on BaTiO 3 Flexible self-powered voltage sensors prepared from @ ZnO have been reported. BaTiO 3 Nanoparticles tend to agglomerate, resulting in poor dispersion in the PVDF matrix, and interfacial pore defects and cracks between the two components limit the performance of the flexible pressure sensor. For this reason, many researchers have solved these problems by adding functional materials (e.g., carbon nanotubes, graphene, cellulose, etc.) thereto. Unfortunately, the added functional material does not have piezoelectric properties; functional material and BaTiO 3 The two materials of the nanoparticle are not compounded together, and the problem of dispersibility is not thoroughly solved.
The difficulty of solving the problems and the defects is as follows: the invention is intended to be applied to BaTiO 3 ZnO nano particles coated with wurtzite piezoelectric material on surface can thoroughly solve the problem of BaTiO 3 The dispersion problem is solved, and the overall piezoelectric performance of the sensor is improved. However, baTiO 3 Is a stable perovskite ceramic material, and other materials are difficult to grow and adhere on the smooth surface of the perovskite ceramic material. For this purpose, the invention uses a sol-gel method to produce Zn (OH) by the complexation reaction of the polymer 2 Adhesion to BaTiO 3 Surface, high temperature calcining and synthesizing and attaching to BaTiO 3 ZnO nanoparticles on the surface.
The meaning of solving the problems and the defects is as follows: by this method, the invention solves BaTiO without introducing other non-piezoelectric materials 3 The dispersibility problem in PVDF matrix, the introduction of wurtzite ZnO self-polarized piezoelectric material improves the overall output performance and long-term stability of the device, and provides a new solution for the related research.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a flexible passive pressure sensor, a preparation method and a wearable touch sensor.
The invention is realized in such a way that a preparation method of the flexible passive pressure sensor comprises the following steps:
PVDF powderAdding into beaker containing dimethylformamide solution, stirring in water bath to form uniform transparent paste slurry, and mixing with high-performance piezoelectric material BaTiO 3 The @ ZnO provides a support framework;
BaTiO of core-shell structure 3 Adding the @ ZnO material into a beaker containing dimethylformamide solution, and performing ultrasonic dispersion to enable BaTiO to be 3 Uniformly dispersing @ ZnO in the solution to avoid BaTiO 3 Direct addition of @ ZnO powder to PVDF slurry results in BaTiO 3 The @ ZnO is unevenly dispersed, so that the long-term stability of the device is improved;
adding the obtained white solution into PVDF transparent pasty slurry, continuously stirring to form uniform white pasty slurry, and placing the slurry in a vacuum drying oven for maintaining to extract bubbles existing in the slurry, so as to avoid microscopic holes of the piezoelectric film caused by the existence of the bubbles and subsequent high-voltage polarization failure;
pouring the slurry into a manufactured mold, uniformly dispersing the slurry in the mold by using a scraper, placing the mold in a vacuum drying oven for holding, drying the slurry at low temperature to form a piezoelectric film, and calcining at high temperature to promote PVDF in the piezoelectric film to form more electroactive phases;
the aluminum foil electrodes are attached to the upper surface and the lower surface of the piezoelectric film, and the gold finger PI is used for packaging the device, so that the influence of the environment on the testing performance of the device is avoided; the direct-current high-voltage power supply is connected with the upper electrode and the lower electrode and polarized to lead the BaTiO to be 3 The direction of the electric dipole moment is consistent, so that the piezoelectric output capability is enhanced; obtaining based on BaTiO 3 Flexible piezoelectric pressure sensor made of @ ZnO.
Further, 1 to 2g of PVDF powder purchased from Ala-dine was added to a beaker containing 7 to 10ml of dimethylformamide solution, and the beaker was placed in a water bath at 50 to 70℃and stirred for 1 to 3 hours to promote dissolution of PVDF to form a uniform transparent paste slurry.
Further, 0.05 to 0.15g of BaTiO with a core-shell structure is added 3 The @ ZnO material is added into a beaker containing 3 to 5ml of dimethylformamide solution, and a small amount of BaTiO is added 3 The @ ZnO maintains the flexibility of the piezoelectric sensor while improving the piezoelectric property, and is dispersed by ultrasonic for 30-60 minAnd (5) uniformity.
Further, adding the obtained white solution into PVDF transparent pasty slurry, continuously stirring for 1-3 h at 50-70 ℃, and obtaining BaTiO 3 The @ ZnO was completely dispersed in the PVDF slurry to form a uniform white paste slurry, which was placed in a vacuum oven for 30-90 minutes to extract the bubbles present in the slurry.
And pouring the slurry into a prepared mould, uniformly dispersing the slurry in the mould by using a scraper, placing the mould in a vacuum drying oven at 60-80 ℃ for 1-3 h, drying the slurry to form a piezoelectric film, and drying at 90-120 ℃ for 1-3 h.
Further, aluminum foil electrodes are attached to the upper and lower surfaces of the piezoelectric film, a golden finger PI packaging device is used, a direct-current high-voltage power supply is connected with the upper and lower electrodes, and polarization is carried out for 1-1.5 h at the temperature of 90-120 ℃ to obtain the BaTiO-based piezoelectric film 3 Flexible piezoelectric pressure sensor made of ZnO.
Further, the piezoelectric film is made of BaTiO having a core-shell structure 3 The @ ZnO material is obtained by mixing a PVDF solution, and specifically comprises the following steps:
(1) Dissolving 5-7 g of NaOH in 20-40 ml of deionized water, stirring at room temperature for 10-20 min to completely dissolve NaOH in deionized water to prepare BaTiO 3 The particles provide an alkaline solution environment; 0.6 to 0.8g of Ba (Ac) 2 、0.2～0.3gTiO 2 Adding into NaOH solution to prepare BaTiO 3 The particles provide Ba source and Ti source, and the solution is dispersed uniformly by continuously stirring for 30-60 min at room temperature, so that the subsequent hydrothermal reaction is ensured to be sufficient, and the size of the synthesized target product is uniform;
(2) Transferring the obtained white mixed solution into an autoclave, and carrying out hydrothermal treatment in an oven at 200 ℃ for 24 hours to generate a target product BaTiO 3 ；
(3) Centrifuging the obtained precipitate, washing the obtained product with deionized water and ethanol respectively, and centrifuging for 5-7 times; drying the product at 60-80 deg.c, roasting the obtained powder at 900-1100 deg.c for 1-3 hr to obtain BaTiO 3 Forming a tetragonal phase structure. Obtaining the BaTiO with the wavelength of 140-160 nm 3 A material;
(4) 1-2 g PEG and 0.3 to the upper0.4gZn(Ac) 2 Dissolving in 30-40 ml deionized water, wherein Zn (Ac) 2 As a Zn source for synthesizing ZnO, PEG will generate Zn (OH) 2 Adhesion to BaTiO 3 A surface; stirring at room temperature for 10-30 min to dissolve completely;
(5) Adding the obtained product into the mixed solution obtained in the step (4), continuously stirring for 30-60 min at room temperature to uniformly disperse the material in the mixed solution, and adding 2-4 ml of NH 3 ·H 2 O is stirred for 1 to 3 hours;
(6) Centrifuging the obtained precipitate, washing the obtained product with deionized water and ethanol, and centrifuging for 5-7 times; drying the product at 60-80 deg.c, roasting the obtained powder at 500-600 deg.c for 1-3 hr, and Zn (OH) 2 Converted into ZnO nano-particles. Thus obtaining BaTiO 3 @ ZnO piezoelectric material.
Another object of the present invention is to provide a flexible passive pressure sensor manufactured by the manufacturing method of the flexible passive pressure sensor, which is manufactured by a manufacturing method of a flexible passive pressure sensor comprising BaTiO 3 The flexible piezoelectric film comprises flexible piezoelectric films made of ZnO piezoelectric material and PVDF, aluminum foil electrodes attached to the upper surface and the lower surface of the flexible piezoelectric films, and PI packaging materials attached to the surfaces of the aluminum foil electrodes.
It is another object of the present invention to provide a wearable touch sensor comprising the flexible passive pressure sensor.
It is another object of the present invention to provide a medical health monitoring terminal in wireless communication with the wearable tactile sensor.
By combining all the technical schemes, the invention has the advantages and positive effects that: the invention relates to BaTiO prepared by a sol-gel method 3 The synthesis method of the @ ZnO piezoelectric material is simple and the cost is low; the prepared material has higher piezoelectric property, good crystallinity and uniform particle distribution; the prepared flexible pressure sensor has excellent mechanical strength and flexibility, and can work at different frequencies; the prepared flexible pressure sensor has higher electrical performance output and sensitivity, and has the advantages of wearable flexible self-powered sensorHas wide application prospect.
The invention adopts the sandwich structure to package the combined device, has simple device process and small volume, is suitable for mass production, and utilizes BaTiO 3 On one hand, hydroxyl and metal ions on the surface of ZnO are combined with PVDF to tightly connect inorganic nano particles with organic polymers; on the other hand, the piezoelectric materials ZnO and BaTiO 3 The dielectric constant and the piezoelectric coefficient of the device are increased, the formation of a PVDF piezoelectric phase is promoted, the output performance and the durability of the piezoelectric sensor are greatly improved under the combined action of the two aspects, and the performance and the energy collection of the sensor are improved. Meanwhile, the piezoelectric sensor with the sandwich structure adopted by the invention has simple manufacturing process and good flexibility, is beneficial to industrial mass production, and therefore has important application value.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly explain the drawings needed in the embodiments of the present application, and it is obvious that the drawings described below are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flowchart of a method for manufacturing a flexible passive pressure sensor according to an embodiment of the present invention.
FIG. 2 shows a hydrothermal synthesis of perovskite material BaTiO according to an embodiment of the present invention 3 SEM surface topography of (c).
FIG. 3 shows an embodiment of the present invention of (a) pure PVDF film, (b) BaTiO film 3 SEM surface topography of @ ZnO/PVDF film.
Fig. 4 is a fourier infrared spectrogram of a piezoelectric composite film according to an embodiment of the present invention.
Fig. 5 is a schematic structural diagram of a flexible pressure sensor according to an embodiment of the present invention.
FIG. 6 is a graph of voltage and current output of a flexible pressure sensor made from a pure PVDF film provided by an embodiment of the present invention.
FIG. 7 is a diagram of a BaT embodiment of the inventioniO 3 The voltage and current output graph of the flexible pressure sensor is prepared by the ZnO/PVDF film.
FIG. 8 is a graph showing the comparison of electrical performance outputs of BZ-2 sensors at different pressures in an embodiment of the present invention.
FIG. 9 is a graph showing the comparison of electrical performance outputs of BZ-2 sensors at different frequencies in an embodiment of the present invention.
FIG. 10 is a graph of the output of a BZ-2 flexible pressure sensor at voltage fatigue in an embodiment provided by an embodiment of the invention.
FIG. 11 is a graph of voltage output of a flexible pressure sensor over 2000 pressure cycles in an embodiment provided by an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to solve the problems in the prior art, the invention provides a flexible passive pressure sensor, a preparation method and a wearable touch sensor, and the invention is described in detail below with reference to the accompanying drawings.
As shown in fig. 1, the preparation method of the flexible passive pressure sensor provided by the invention comprises the following steps:
s101: adding 1-2 g PVDF powder purchased from Allatin into a beaker containing 7-10 ml of dimethylformamide solution, and placing the beaker into a water bath kettle at 50-70 ℃ to stir for 1-3 hours to form uniform and transparent pasty slurry;
s102: 0.05 to 0.15g of BaTiO with a core-shell structure 3 Adding the @ ZnO material into a beaker containing 3-5 ml of dimethylformamide solution, and carrying out ultrasonic treatment for 30-60 min to uniformly disperse the @ ZnO material;
s103: adding the obtained white solution into PVDF transparent pasty slurry, continuously stirring for 1-3 hours at 50-70 ℃ to form uniform white pasty slurry, and then placing the slurry in a vacuum drying oven for 30-60 min to extract bubbles in the slurry;
s104: slowly pouring the slurry into a prepared mould, uniformly dispersing the slurry in the mould by using a scraper, placing the mould in a vacuum drying oven at 60-80 ℃ for 1-3 h, drying the slurry to form a piezoelectric film, and drying at 90-120 ℃ for 1-3 h;
s105: aluminum foil electrodes are attached to the upper surface and the lower surface of the piezoelectric film, a golden finger PI packaging device is used, a direct-current high-voltage power supply is connected with the upper electrode and the lower electrode, and polarization is carried out for 1-1.5 h at the temperature of 90-120 ℃ to obtain the BaTiO-based piezoelectric film 3 Flexible piezoelectric pressure sensor made of ZnO.
Other steps may be performed by those skilled in the art to make the flexible passive pressure sensor provided by the present invention, and the method for making the flexible passive pressure sensor provided by the present invention in fig. 1 is only one specific embodiment.
BaTiO-based according to the invention 3 Piezoelectric pressure tactile sensor of @ ZnO material, made of a material containing BaTiO 3 The flexible piezoelectric film is made of a @ ZnO piezoelectric material and PVDF, adhesive aluminum foil electrodes attached to the upper surface and the lower surface of the flexible film, electrode lead-out wires and PI packaging materials for isolating static electricity and air environment influences; the method is characterized in that: the piezoelectric film is made of BaTiO with core-shell structure 3 The @ ZnO material is obtained by mixing a PVDF solution, and the material is prepared by the following steps:
(1) Firstly, 5-7 g of NaOH is dissolved in 20-40 ml of deionized water to prepare a strong alkaline solution environment, and the solution is stirred for 10-20 min at room temperature to completely dissolve the NaOH in the deionized water. Adding 0.6-0.8 g Ba (Ac) into NaOH solution 2 、0.2～0.3gTiO 2 Stirring continuously for 30-60 min at room temperature to disperse the solution uniformly;
(2) Transferring the obtained white mixed solution into an autoclave, and carrying out hydrothermal treatment in an oven at 200 ℃ for 24 hours to generate a target product BaTiO 3 ；
(3) Centrifuging the obtained precipitate, washing the obtained product with deionized water and ethanol respectively, and centrifuging for 5-7 times; drying the product at 60-80 deg.c and roasting the obtained powder at 900-1100 deg.c for 1-3 hr. Thus obtaining 150-200nm BaTiO 3 A material;
(4) 1-2 g PEG, 0.3-0.4 g Zn (Ac) 2 Dissolving in 30-40 ml deionized water, stirring at room temperature for 10-30 min to dissolve completely;
(5) Adding the obtained product into the mixed solution obtained in the step (4), continuously stirring for 30-60 min at room temperature to uniformly disperse the material in the mixed solution, and adding 2-4 ml of NH 3 ·H 2 O is stirred for 1 to 3 hours;
(6) And centrifuging the obtained precipitate, washing the obtained product with deionized water and ethanol, and centrifuging for 5-7 times. Drying the product at 60-80 deg.c and roasting the obtained powder at 500-600 deg.c for 1-3 hr. Thus obtaining BaTiO 3 @ ZnO piezoelectric material.
The technical scheme of the invention is further described below with reference to the accompanying drawings.
As shown in FIG. 2, baTiO can be seen 3 The piezoelectric material has uniform particles, the particle size range is 150-200nm, and the shape is tetragonal.
As shown in FIG. 3, baTiO can be seen 3 The ZnO nano particles are uniformly covered on the surface, and the particles are uniform.
As shown in fig. 4, (a) and (b) in the drawing are respectively a pure PVDF film and a composite film doped with a piezoelectric material, the film surface is uniform, and the piezoelectric material is uniformly dispersed in the composite film.
As shown in fig. 5, diffraction peak intensities of piezoelectric phases β, γ and non-piezoelectric phase α in the flexible piezoelectric composite film are shown.
As shown in fig. 6, a sandwich structure of a flexible piezoelectric sensor, a piezoelectric composite film, a surface electrode, a device packaging material is shown in fig. (a), and a flexible BaTiO is shown in fig. (b) 3 A schematic diagram of a ZnO/PVDF piezoelectric sensor device.
As shown in FIG. 7, the pure PVDF film was polarized to output a peak-to-peak voltage of 8V and a maximum short-circuit current of 200 nA.
As shown in FIG. 8, baTiO with different zinc oxide contents was surface-modified 3 Maximum output peak-to-peak voltage in the @ ZnO/PVDF composite film is 26V, and excessive zinc oxide can cause internal current of the composite filmShort circuit causes a decrease in output voltage.
As shown in fig. 9, the flexible sensor gradually increases in output voltage with a gradual increase in pressure.
As shown in fig. 10, the flexible pressure sensor output voltage gradually increases as the frequency of the applied pressure increases.
As shown in fig. 11, the flexible pressure sensor has stable output voltage without significant decrease and stable device performance in 2000 pressure cycles.
The technical scheme of the invention is further described below with reference to specific embodiments.
Comparative example 1:
a flexible pressure sensor is prepared by a piezoelectric composite film made of pure PVDF, and the specific manufacturing process is as follows:
1. 1-2 g of PVDF powder purchased from Allatin is added into a beaker containing 10-15 ml of dimethylformamide solution, and the beaker is placed in a water bath kettle at 50-70 ℃ and stirred for 2-4 hours to form uniform and transparent pasty slurry.
2. The PVDF transparent pasty slurry is placed in a vacuum drying oven for 30-60 min to extract bubbles existing in the slurry.
3. Slowly pouring the slurry into a manufactured mould, uniformly dispersing the slurry in the mould by using a scraper, placing the mould in a vacuum drying oven at 60-80 ℃ for 1-3 h, drying the slurry to form a piezoelectric film, and drying at 90-120 ℃ for 1-3 h.
4. Attaching aluminum foil electrodes to the upper and lower surfaces of the piezoelectric film, using a golden finger PI packaging device, connecting a direct-current high-voltage power supply with the upper and lower electrodes, and polarizing for 1-1.5 h at 90-120 ℃ to obtain the piezoelectric film based on BaTiO 3 Flexible piezoelectric pressure sensor made of ZnO.
Example 1:
1. firstly, 5-7 g of NaOH is dissolved in 20-40 ml of deionized water to prepare a strong alkaline solution environment, and the solution is stirred for 10-20 min at room temperature to completely dissolve the NaOH in the deionized water. Adding 0.6-0.8 g Ba (Ac) into NaOH solution 2 、0.2～0.3gTiO 2 Stirring is continued for 30-60 min at room temperature to disperse the solution uniformly.
2. Transferring the mixed solution into an autoclave, and carrying out hydrothermal treatment in an oven at 200 ℃ for 24 hours to generate a target product BaTiO 3 。
3. Centrifuging the obtained precipitate, washing the obtained product with deionized water and ethanol respectively, and centrifuging for 5-7 times; drying the product at 60-80 deg.c and roasting the obtained powder at 900-1100 deg.c for 1-3 hr. Thus obtaining 150-200nm BaTiO 3 A material.
4. 1-2 g PEG, 0.382g (0.19 g, 0.57g, 0.76 g) Zn (Ac) 2 Dissolving in 30-40 ml deionized water, stirring at room temperature for 10-30 min to dissolve completely.
5. Adding the product obtained in the step 3 into the mixed solution obtained in the step 4, continuously stirring for 30-60 min at room temperature to uniformly disperse the material in the mixed solution, and adding 2-4 ml of NH 3 ·H 2 O is stirred for 1 to 3 hours.
6. And centrifuging the obtained precipitate, washing the obtained product with deionized water and ethanol, and centrifuging for 5-7 times. Drying the product at 60-80 deg.c and roasting the obtained powder at 500-600 deg.c for 1-3 hr. Obtaining BaTiO 3 The @ ZnO piezoelectric material is denoted as BZ-2 (BZ-1, BZ-3, BZ-4).
7. 1-2 g of PVDF powder purchased from Allatin is added into a beaker containing 7-10 ml of dimethylformamide solution, and the beaker is placed in a water bath kettle at 50-70 ℃ and stirred for 1-3 hours to form uniform and transparent pasty slurry.
8. 0.05 to 0.15g of BaTiO with a core-shell structure 3 The @ ZnO material is added into a beaker containing 3 to 5ml of dimethylformamide solution, and is evenly dispersed by ultrasonic treatment for 30 to 60 minutes.
9. Adding the white solution obtained in the step (2) into PVDF transparent pasty slurry, continuing stirring for 1-3 hours at 50-70 ℃ to form uniform white pasty slurry, and then placing the slurry in a vacuum drying oven for 30-60 min to extract bubbles in the slurry.
10. Slowly pouring the slurry into a manufactured mould, uniformly dispersing the slurry in the mould by using a scraper, placing the mould in a vacuum drying oven at 60-80 ℃ for 1-3 h, drying the slurry to form a piezoelectric film, and drying at 90-120 ℃ for 1-3 h.
11. Attaching aluminum foil electrodes to the upper and lower surfaces of the piezoelectric film, using a golden finger PI packaging device, connecting a direct-current high-voltage power supply with the upper and lower electrodes, and polarizing for 1-1.5 h at 90-120 ℃ to obtain the piezoelectric film based on BaTiO 3 Flexible piezoelectric pressure sensor made of ZnO.
In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more; the positional or positional relationships indicated by the terms "upper", "lower", "left", "right", "inner", "outer", "front", "rear", "head", "tail", etc., are based on the positional or positional relationships shown in the drawings, are merely for convenience in describing the invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the invention. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
It should be noted that the embodiments of the present invention can be realized in hardware, software, or a combination of software and hardware. The hardware portion may be implemented using dedicated logic; the software portions may be stored in a memory and executed by a suitable instruction execution system, such as a microprocessor or special purpose design hardware. Those skilled in the art will appreciate that the above-described apparatus and methods may be implemented using computer-executable instructions and/or embodied in processor control code, such as provided on a carrier medium such as a magnetic disk, CD or DVD-ROM, a programmable memory such as read-only memory (firmware), or a data carrier such as an optical or electronic signal carrier. The device of the present invention and its modules may be implemented by hardware circuitry, such as very large scale integrated circuits or gate arrays, semiconductors such as logic chips, transistors, etc., or programmable hardware devices such as field programmable gate arrays, programmable logic devices, etc., as well as software executed by various types of processors, or by a combination of the above hardware circuitry and software, such as firmware.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (7)
1. The preparation method of the flexible passive pressure sensor is characterized by comprising the following steps of:
adding PVDF powder into a beaker containing dimethylformamide solution, and placing the beaker into a water bath kettle to be stirred to form uniform and transparent pasty slurry;
BaTiO of core-shell structure 3 Adding the @ ZnO material into a beaker containing dimethylformamide solution, and performing ultrasonic dispersion;
adding the obtained white solution into PVDF transparent pasty slurry, continuously stirring to form uniform white pasty slurry, and placing the slurry in a vacuum drying oven for maintaining to extract bubbles in the slurry;
pouring the slurry into a manufactured mold, uniformly dispersing the slurry in the mold by using a scraper, placing the mold in a vacuum drying oven for holding, drying the slurry to form a piezoelectric film, and drying;
aluminum foil electrodes are attached to the upper surface and the lower surface of the piezoelectric film, a PI packaging device is used, a direct-current high-voltage power supply is connected with the upper electrode and the lower electrode, and polarization is carried out to obtain a piezoelectric film based on BaTiO 3 Flexible piezoelectric pressure sensor made of @ ZnO;
adding 1-2 g of PVDF powder into a beaker containing 7-10 ml of dimethylformamide solution, and placing the beaker into a water bath kettle at 50-70 ℃ to be stirred for 1-3 hours to form uniform and transparent pasty slurry;
0.05-0.2 g of BaTiO with core-shell structure 3 Adding the @ ZnO material into a beaker containing 3-5 ml of dimethylformamide solution, and carrying out ultrasonic treatment for 30-60 min to uniformly disperse the @ ZnO material;
wherein the piezoelectric film is made of BaTiO with a core-shell structure 3 @ZnOThe PVDF material is obtained by mixing the PVDF material with a PVDF solution, and specifically comprises the following components:
(1) Dissolving 5-7 g of NaOH in 20-40 ml of deionized water to prepare a strong alkaline solution environment, stirring at room temperature for 10-20 min, and completely dissolving the NaOH in the deionized water; adding 0.6 to 0.8g of Ba (Ac) into the NaOH solution 2 、0.2~0.3gTiO 2 Continuously stirring for 30-60 min at room temperature to uniformly disperse the solution;
(2) Transferring the obtained white mixed solution into an autoclave, and carrying out hydrothermal treatment in an oven at 200 ℃ for 24 hours to generate a target product BaTiO 3 ；
(3) Centrifuging the obtained precipitate, washing the obtained product with deionized water and ethanol respectively, and centrifuging for 5-7 times; drying the product at 60-80 ℃, roasting the obtained powder at 900-1100 ℃ for 1-3 hours to obtain 150-200nm BaTiO 3 A material;
(4) 1 to 2g of PEG, 0.3 to 0.4g of Zn (Ac) 2 Dissolving in 30-50 ml deionized water, and stirring at room temperature for 10-30 min to completely dissolve;
(5) Adding the obtained product into the mixed solution obtained in the step (4), continuously stirring for 30min at room temperature to uniformly disperse the material in the mixed solution, and adding 2-4 ml of NH 3 . H 2 O stirring for 1-3 h;
(6) Centrifuging the obtained precipitate, washing the obtained product with deionized water and ethanol, and centrifuging for 5-7 times; drying the product at 60-80 ℃, and roasting the obtained powder at 500-600 ℃ for 1-3 hours to obtain BaTiO 3 @ ZnO piezoelectric material.
2. The method for manufacturing the flexible passive pressure sensor according to claim 1, wherein the obtained white solution is added into PVDF transparent pasty slurry, stirring is continued for 1-3 hours at 50-70 ℃ to form uniform white pasty slurry, and the slurry is placed in a vacuum drying oven for 30-60 min to extract bubbles existing in the slurry.
3. The method for manufacturing the flexible passive pressure sensor according to claim 1, wherein slurry is poured into a manufactured mold, the slurry is uniformly dispersed in the mold by using a scraper, the mold is placed in a vacuum drying oven at 60-80 ℃ for 1-3 hours, the slurry is dried to form a piezoelectric film, and the piezoelectric film is dried at 90-120 ℃ for 1-3 hours.
4. The method for manufacturing a flexible passive pressure sensor according to claim 1, wherein aluminum foil electrodes are attached to upper and lower surfaces of the piezoelectric film, a PI packaging device is used, a direct current high voltage power supply is connected with the upper and lower electrodes, and polarization is performed for 1 to 1.5 hours at 90 to 120 ℃ to obtain a film based on BaTiO 3 Flexible piezoelectric pressure sensor made of ZnO.
5. A flexible passive pressure sensor prepared by the method for preparing a flexible passive pressure sensor according to any one of claims 1 to 4, characterized in that the flexible passive pressure sensor is prepared by a method comprising BaTiO 3 The flexible piezoelectric film is composed of a flexible piezoelectric film made of ZnO piezoelectric material and PVDF, adhesive aluminum foil electrodes attached to the upper surface and the lower surface of the flexible film, and a PI packaging material for isolating static electricity and air environmental influences.
6. A wearable touch sensor comprising the flexible passive pressure sensor of claim 5.
7. A medical health monitoring terminal in wireless communication with the wearable touch sensor of claim 6.
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