CN117161378A - Piezoelectric nano generator, preparation method thereof and wireless sensing system - Google Patents
Piezoelectric nano generator, preparation method thereof and wireless sensing system Download PDFInfo
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 67
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Abstract
The application provides a piezoelectric nano generator based on coaxial heterostructure composite piezoelectric fibers, a preparation method thereof and a wireless sensing system. According to the preparation method, a layer of Ag nano particles is coated on the surface of BT, a coaxial needle is used for carrying out a spinning preparation process, and finally PENG is prepared. The application can improve the effective polarization voltage of the piezoelectric particles in the polarization process and enhance the stress transmission of the piezoelectric particles. The application has higher piezoelectric output performance, realizes the application of PENG in a wireless sensing system, and can realize large-scale industrialized application.
Description
Technical Field
The application relates to the technical field of electronic devices, in particular to a piezoelectric nano-generator, a preparation method thereof and a wireless sensing system based on the piezoelectric nano-generator.
Background
With the popularity of the internet of things in everyday life, new demands are being made on the energy supply of sensors, portable and embedded electronic devices involved therein. The aim sought is for the power supply device to be portable, to operate continuously and to operate maintenance-free. However, the above-described devices are still today based on conventional battery powered. The problems of replacement, waste treatment and the like caused by battery power supply not only cause a plurality of inconveniences for device use and maintenance, but also are unfavorable for environmental protection, which is contrary to the ideal design of people. Therefore, development of nano self-driven devices that are small in size, light in weight, and capable of taking energy from the surrounding environment and converting it into electric energy is one of the best options for solving the energy supply problem.
A flexible piezoelectric nano generator (PENG) based on an organic/inorganic composite material is a device that realizes mechanical energy-electric energy conversion by piezoelectric effect; inorganic piezoelectric materials such as BaTiO 3 、PbZrTiO 3 And ZnSnO 3 Has excellent piezoelectric performance, while organic materials such as polyvinylidene fluoride (PVDF) and Polydimethylsiloxane (PDMS) have low density, good flexibility and easy processing, and the combination of the two is a simple and effective method for preparing flexible PENG. It can respond to complex conditions such as bending, torsion, stretching and the like, and can meet the requirements of wearable/embedded devices with different shapesA demand; low frequency mechanical energy such as that produced by human walking, muscle stretching, mechanical vibration, air flow, etc. can be collected.
In the prior art, PENG based on organic/inorganic composite materials is prepared by adopting an electrostatic spinning technology, wherein a polarization process and a stress transmission process have important influence on the piezoelectric output of PENG. In the technology, the inorganic piezoelectric particles are wrapped in the organic polymer material, and the organic material is usually an insulating polymer, and the inorganic piezoelectric material is usually a semiconductor, so that most of polarization voltage is consumed by the organic material in the polarization process, and the polarization voltage really applied to the inorganic piezoelectric particles is very small. In addition, in the stress transmission process, when external force is applied to the PENG, most of the external force is consumed by the flexible polymer material, and the stress really transmitted to the piezoelectric particles is not large. Therefore, the output performance of the PENG is low due to the above drawbacks of the polarization process and the stress transfer process in the related art.
Disclosure of Invention
Aiming at the defect of lower PENG output performance caused by lower effective polarization electric field and low stress transfer efficiency of piezoelectric particles in the prior art, the application provides a preparation method of a piezoelectric nano generator based on coaxial heterostructure composite piezoelectric fibers.
The application provides a preparation method of a piezoelectric nano generator based on coaxial heterostructure composite piezoelectric fibers, which is characterized by comprising the following steps of:
s1: adding Barium Titanate (BT) nanoparticles to a composition comprising SnCl 2 In a mixed solution with HCl, stirring for 1 hour, wherein SnCl 2 The concentration is 0.08mol/L, and the concentration of HCl is 0.01mol/L;
s2: cleaning Barium Titanate (BT) particles in the step S1 with purified water, adding the cleaned Barium titanate particles into silver ammonia solution, and stirring for 1-2 hours to enable Ag nano-rudiments to be deposited on the surfaces of the Barium Titanate (BT) nano-particles, wherein the concentration of the silver ammonia solution is 0.3-0.5mol/L;
s3: placing Barium Titanate (BT) particles with Ag rudiments coated on the surfaces in a mixed solution consisting of 1.5mL of formaldehyde solution, 4-8mL of silver ammonia solution and 8.5-12.5mL of alcohol, stirring for at least 12 hours for full reaction, and thus obtaining Barium Titanate (BT) piezoelectric particles with Ag nanospheres coated on the surfaces, wherein the formaldehyde solution has the concentration of 0.03-0.06mol/L, the silver ammonia solution has the concentration of 0.3-0.5mol/L and the alcohol concentration of 99.7%;
s4: preparing 3ml of N, N-dimethylformamide and 7ml of acetone solution into a solvent, taking 1g of polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) and 0.25g of Barium Titanate (BT) with Ag nanospheres coated on the surface, mixing with the solvent, and stirring for at least 12 hours to prepare a solution a;
s5: preparing 3ml of N, N dimethylformamide and 7ml of acetone solution into a solvent, taking 1g of polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) and 0.25g of Barium Titanate (BT), mixing with the solvent, and stirring for at least 12 hours to prepare a solution b;
s6: placing the prepared solution a and the prepared solution b into a syringe a and a syringe b respectively, and performing a spinning preparation process by using a coaxial needle, wherein the solution a is a coaxial inner layer, and the solution b is a coaxial outer layer;
s7: and (3) adding the electrode to the prepared spinning fiber membrane, packaging the spinning fiber membrane in polyimide plastic, and leaving upper and lower electrode wires out to obtain the piezoelectric nano generator (PENG).
Preferably, the specification of the Barium Titanate (BT) is nanopowder, <100nm particle size (BET),. Gtoreq. 99%trace metals basis.
Preferably, the specification of the polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) is average Mw-275,000by GPC,average Mn-107,000, and is in the form of billets.
Preferably, the spinning voltage is 18kV, the rotation speed of the collecting rod is 200rpm, the distance between the coaxial needle and the collecting rod is 15cm, and the pushing speed of the injector is 20 mu l/min.
Preferably, ag coated on the surface of Barium Titanate (BT) is 6nm and uniformly distributed.
Preferably, in the coaxial heterostructure composite piezoelectric fiber, four main elements Ba, ti, O, ag are uniformly distributed.
The second aspect of the application provides a piezoelectric nano-generator obtained by the preparation method.
The application provides a self-driven soil humidity wireless sensing system adopting the piezoelectric nano generator, which is characterized by supplying power to the sensing system by collecting wind energy, and comprising a chip, a Bluetooth module and a four-wire system soil humidity sensor.
Preferably, the chip is an STM32F103C8T6 chip, the Bluetooth module is an HC-05 Bluetooth module, and the four-wire system soil humidity sensor is an ELECFANS four-wire system soil humidity sensor.
Preferably, the piezoelectric nano generator is connected with the STM32F103C8T6 chip through a rectifying circuit, the Vcc, RXD, TXD pin of the HC-05 Bluetooth module is respectively connected with the Vdd1, the PA9 and the PA10 pin of the STM32F103C8T6 chip, and the pins Vcc and A0 of the ELECFANS four-wire soil humidity sensor are respectively connected with the Vdd2 and the PA1 pin of the STM32F103C8T6 chip.
The method comprises the steps of firstly coating a layer of Ag nano particles on the surface of BT by adopting a chemical inoculation reduction method, then mixing and stirring BT and BT coated with Ag in PVDF macromolecules to prepare a solution a and a solution b, respectively placing the solution a and the solution b in two syringes, and carrying out spinning preparation by using a coaxial needle, wherein the solution a is a coaxial inner layer, the solution b is a coaxial outer layer, and packaging the prepared spinning fiber membrane with an electrode in polyimide plastic, and leaving upper and lower electrode wires to prepare PENG. The application has the beneficial effects that: because Ag is a conductive material, the Ag with an outer layer is attached to the surface of the BT, the local polarization electric field can be enhanced, and therefore the effective polarization voltage of the piezoelectric particles in the polarization process is improved; and the core-shell structure of cladding a layer of Ag nano particles on the surface of the BT can enhance the stress transmission of the piezoelectric particles.
Drawings
Fig. 1 is a process for preparing a piezoelectric nano-generator based on a coaxial heterostructure composite piezoelectric fiber according to the present application.
Fig. 2 is a TEM image of the piezoelectric particles.
Fig. 3 is an X-ray diffraction pattern of atomic compositions and piezoelectric particles.
FIG. 4 is a comparison of the polarization and efficiency differences in stress transfer processes simulated using COMOSL software.
Fig. 5 is a self-driven soil moisture wireless sensing system implemented using the PENG of the present application.
Detailed Description
The application is further illustrated below with reference to examples.
Example 1:
as shown in fig. 1, the preparation process of the piezoelectric nano-generator based on the coaxial heterostructure composite piezoelectric fiber is as follows:
s1: adding Barium Titanate (BT) nanoparticles to a composition comprising SnCl 2 And HCl, wherein SnCl2 concentration is 0.08mol/L and HCl concentration is 0.01mol/L, the specification of the Barium Titanate (BT) is nanopowder,<100nm particle size(BET),≥99％trace metals basis。
s2: cleaning Barium Titanate (BT) particles in the step S1 with purified water, adding the cleaned Barium titanate particles into silver ammonia solution, and stirring for 1 hour to enable Ag nano-rudiments to be deposited on the surfaces of the Barium Titanate (BT) nano-particles, wherein the concentration of the silver ammonia solution is 0.3mol/L; fig. 1 (b) shows BT coated with Ag nanocrystal by chemical seeding method.
S3: placing Barium Titanate (BT) particles with Ag rudiments coated on the surfaces in a mixed solution composed of 1.5mL of formaldehyde solution, 4mL of silver ammonia solution and 8.5mL of alcohol, stirring for 12 hours for complete reaction, and thus obtaining Barium Titanate (BT) piezoelectric particles with Ag nanospheres coated on the surfaces, wherein the formaldehyde solution has a concentration of 0.04mol/L, the silver ammonia solution has a concentration of 0.3mol/L and the alcohol has a concentration of 99.7%; fig. 1 (c) is a schematic diagram of Ag nanosphere-coated BT piezoelectric particles obtained after Ag crystal growth.
Fig. 2 (a) and 2 (b) are Transmission Electron Microscope (TEM) images of BT particles and BT particles coated with Ag, respectively, in which Ag coated on the BT surface has about 6nm and is uniformly distributed. Fig. 2 (c) is a high definition TEM image of Ag with lattice spacings of 0.203nm and 0.231nm corresponding to the (200) and (100) oriented structures of Ag, respectively.
FIG. 3 (a) shows the atomic composition ratio of four elements, wherein Ag accounts for about 8.76%, and the four elements are uniformly distributed; fig. 3 (b) shows the X-ray diffraction pattern of BT particles and Ag-coated, wherein 2θ is 21.9 °,31.7 °,38.1 °,45.0 °,55.9 °,65.5 ° correspond to the (100), (110), (111), (200), (211), (220) characteristic peaks of BT, and 38.5 °,44.2 ° corresponds to the (111), (200), (220), (311) characteristic peaks of face-centered cubic structure Ag, respectively.
S4: preparing 3ml of N, N dimethylformamide and 7ml of acetone solution into a solvent, taking 1g of polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) and 0.25g of Barium Titanate (BT) with Ag nanospheres coated on the surface, mixing with the solvent, and stirring for 12 hours to prepare a solution a; the specification of the polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) is average Mw-275,000by GPC,average Mn-107,000, and is billets.
S5: 3ml of N, N dimethylformamide and 7ml of acetone solution are prepared into a solvent, 1g of polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) and 0.25g of Barium Titanate (BT) are taken, and the solvent is mixed and stirred for 12 hours to prepare a solution b; fig. 1 (d) shows the process of obtaining solution a and solution b; the specification of the polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) is average Mw-275,000by GPC,average Mn-107,000, and is billets.
S6: placing the prepared solution a and the prepared solution b into a syringe a and a syringe b respectively, and performing a spinning preparation process by using a coaxial needle, wherein the solution a is a coaxial inner layer, and the solution b is a coaxial outer layer; FIG. 1 (e) shows a coaxial electrospinning process in which a spinning voltage of 18kV, a collector bar rotation speed of 200rpm, a coaxial needle distance of 15cm from the collector bar, and a syringe pushing speed of 20. Mu.l/min were set.
S7: and (3) packaging the prepared spinning fiber membrane with the electrode in polyimide plastic, and leaving upper and lower electrode wires to obtain the piezoelectric nano generator (PENG), wherein (f) in fig. 1 shows the finally obtained PENG.
Fig. 4 is a graph showing the efficiency differences between the piezoelectric fiber film of the conventional process simulated by using COMOSL software and the piezoelectric fiber film of the present application in the polarization and stress transfer processes. FIG. 4a is a simulation of polarization voltage of a piezoelectric fiber (a-I) prepared based on a conventional process and a piezoelectric fiber (a-II) prepared according to the present application under the same polarization condition. It can be seen that the present application can significantly improve the polarization voltage distribution acting on the piezoelectric filler. Fig. 4b shows the simulation of stress transfer of the above two PENGs under 30N external force, and the result shows that the structure designed by the present application is more favorable for improving the stress transfer efficiency between the piezoelectric fillers. Fig. 4c shows the resulting piezoelectric potential at the surface of two PENGs, again indicating that the design of the present application will produce a greater piezoelectric output.
Embodiment two:
as shown in fig. 5, the self-driven soil humidity wireless sensing system is realized by adopting the PENG based on the first embodiment, and the self-driven soil humidity wireless sensing system supplies power to the sensing system by collecting wind energy and transmits the measured temperature and humidity data to the mobile phone for monitoring. The system comprises a chip, a Bluetooth module and a four-wire system soil humidity sensor, and fig. 5 (a) is a physical photograph of the system.
The chip is an STM32F103C8T6 chip, the Bluetooth module is an HC-05 Bluetooth module, and the four-wire system soil humidity sensor is an ELECFANS four-wire system soil humidity sensor. FIG. 5 (b) shows the STM32F103C8T6 chip, HC-05 Bluetooth module and ELECFANS four-wire soil moisture sensor assembly in the system.
Fig. 5 (c) shows a specific circuit connection scheme. The piezoelectric nano generator is connected with the STM32F103C8T6 chip through a rectifying circuit, the Vcc, RXD, TXD pins of the HC-05 Bluetooth module are respectively connected with the Vdd1, the PA9 and the PA10 pins of the STM32F103C8T6 chip, and the pins Vcc and A0 of the ELECFANS four-wire soil humidity sensor are respectively connected with the Vdd2 and the PA1 pins of the STM32F103C8T6 chip.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the application. Thus, it is intended that the present application also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The preparation method of the piezoelectric nano generator based on the coaxial heterostructure composite piezoelectric fiber is characterized by comprising the following steps of:
s1: adding Barium Titanate (BT) nanoparticles to a composition comprising SnCl 2 In a mixed solution with HCl, stirring for 1 hour, wherein SnCl 2 The concentration is 0.08mol/L, and the concentration of HCl is 0.01mol/L;
s2: cleaning Barium Titanate (BT) particles in the step S1 with purified water, adding the cleaned Barium titanate particles into silver ammonia solution, and stirring for 1-2 hours to enable Ag nano-rudiments to be deposited on the surfaces of the Barium Titanate (BT) nano-particles, wherein the concentration of the silver ammonia solution is 0.3-0.5mol/L;
s3: placing Barium Titanate (BT) particles with Ag rudiments coated on the surfaces in a mixed solution consisting of 1.5mL of formaldehyde solution, 4-8mL of silver ammonia solution and 8.5-12.5mL of alcohol, stirring for at least 12 hours for full reaction, and thus obtaining Barium Titanate (BT) piezoelectric particles with Ag nanospheres coated on the surfaces, wherein the formaldehyde solution has the concentration of 0.03-0.06mol/L, the silver ammonia solution has the concentration of 0.3-0.5mol/L and the alcohol concentration of 99.7%;
s4: preparing 3ml of N, N dimethylformamide and 7ml of acetone solution into a solvent, taking 1g of polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) and 0.25g of Barium Titanate (BT) with Ag nanospheres coated on the surface, mixing with the solvent, and stirring for at least 12 hours to prepare a solution a;
s5: preparing 3ml of N, N dimethylformamide and 7ml of acetone solution into a solvent, taking 1g of polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) and 0.25g of Barium Titanate (BT), mixing with the solvent, and stirring for at least 12 hours to prepare a solution b;
s6: placing the prepared solution a and the prepared solution b into a syringe a and a syringe b respectively, and performing a spinning preparation process by using a coaxial needle, wherein the solution a is a coaxial inner layer, and the solution b is a coaxial outer layer;
s7: and (3) adding the electrode to the prepared spinning fiber membrane, packaging the spinning fiber membrane in polyimide plastic, and leaving upper and lower electrode wires out to obtain the piezoelectric nano generator (PENG).
2. The method of claim 1, wherein the Barium Titanate (BT) has a size of nanopowder, <100nm particle size (BET),. Gtoreq. 99%trace metals basis.
3. The method of claim 2, wherein the polyvinylidene fluoride (Polyvinylidene fluoride, PVDF) has a size of average Mw-275,000by GPC,average Mn-107,000.
4. The method for preparing a piezoelectric nano-generator according to claim 3, wherein the spinning voltage is 18kV, the rotation speed of the collecting rod is 200rpm, the distance between the coaxial needle and the collecting rod is 15cm, and the pushing speed of the injector is 20 μl/min.
5. The method of claim 4, wherein Ag coated on the surface of Barium Titanate (BT) is 6nm and uniformly distributed.
6. The method for preparing a piezoelectric nano-generator according to claim 1, wherein four main elements Ba, ti, O, ag in the coaxial heterostructure composite piezoelectric fiber are uniformly distributed.
7. A piezoelectric nano-generator obtained by the method for preparing the piezoelectric nano-generator based on the coaxial heterostructure composite piezoelectric fiber according to claim 1.
8. A self-driven soil humidity wireless sensing system based on the piezoelectric nano-generator of claim 7, wherein the self-driven soil humidity wireless sensing system supplies power to the sensing system by collecting wind energy, and the system comprises a chip, a Bluetooth module and a four-wire soil humidity sensor.
9. The self-driven soil moisture wireless sensing system of claim 8, wherein the chip is an STM32F103C8T6 chip, the bluetooth module is an HC-05 bluetooth module, and the four-wire soil moisture sensor is an elecans four-wire soil moisture sensor.
10. The self-driven soil humidity wireless sensing system of claim 9, wherein the piezoelectric nano generator is connected with an STM32F103C8T6 chip through a rectifying circuit, a Vcc, RXD, TXD pin of the HC-05 Bluetooth module is respectively connected with Vdd1, PA9 and PA10 pins of the STM32F103C8T6 chip, and pins Vcc and A0 of the ELECFANS four-wire system soil humidity sensor are respectively connected with pins Vdd2 and PA1 of the STM32F103C8T6 chip.
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| CN2023107338253 | 2023-06-20 |
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