WO2014012403A1

WO2014012403A1 - Piezoelectric-triboelectric hybrid-film nanogenerator

Info

Publication number: WO2014012403A1
Application number: PCT/CN2013/077245
Authority: WO
Inventors: 范凤茹
Original assignee: 纳米新能源（唐山）有限责任公司
Priority date: 2012-07-20
Filing date: 2013-06-14
Publication date: 2014-01-23
Also published as: CN202679272U

Abstract

A piezoelectric-triboelectric hybrid-film nanogenerator. The nanogenerator comprises: a first high-molecular polymer insulating layer (10); a first electrode (11) arranged on a first side surface (10a) of the first high-molecular polymer insulating layer (10); a second high-molecular polymer insulating layer (12); a second electrode (13) arranged on a first side surface (12a) of the second high-molecular polymer insulating layer (12); an intermediate film (14), the side of the intermediate film (14) having a micro-nano concave-convex structure being in contact with a second side surface (10b) of the first high-molecular polymer insulating layer (10), while the side of the intermediate film (14) not having a micro-nano concave-convex structure is fixed on a second side surface (12b) of the second high-molecular polymer insulating layer (12); a first piezoelectric film (15) coated on the first electrode (11); and a third electrode (16) plated on the first piezoelectric film (15). The total output current of the nanogenerator is increased by a parallel mode through stacking a piezoelectric generator and a triboelectric generator in a single hybrid-film nanogenerator and therefore generation efficiency of the nanogenerator is increased.

Description

Piezoelectric and triboelectric hybrid thin film nanogenerator

Technical field

Field of the Invention This invention relates to the field of nanotechnology and, more particularly, to a piezoelectric and triboelectric hybrid film nanogenerator. Background technique

The piezoelectric effect-based sensor is a self-generating and electromechanical conversion sensor whose sensitive components are made of piezoelectric material. After the piezoelectric material is stressed, the surface generates a charge, which is amplified and converted by the charge amplifier and the measuring circuit to become a power output proportional to the external force received. Polyvinylidene fluoride (hereinafter referred to as: PVDF) piezoelectric film is a PVDF piezoelectric material, which has good piezoelectric properties, flexibility, chemical stability and biocompatibility, and has been widely used. Used in biomedical, acoustic, hydraulic and sensing devices, MEMS and other fields.

For example, Shrinov et al. encapsulated PVDF films on PVDF materials to create pressure sensors, and PVDF pressure sensors manufactured by Gonzales et al. for biomedical applications. Jingang et al. validated PVDF-based deformation and motion sensors.

PVDF can also be made into nanostructured generators of various structures, and the structure can use nanofilm or nanofiber. However, the output power per unit area of such a piezoelectric nano-generator is not high, resulting in low power generation efficiency. Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a piezoelectric and triboelectric hybrid thin film nanogenerator for improving power generation efficiency in view of the deficiencies of the prior art.

The invention provides a piezoelectric and triboelectric hybrid thin film nanogenerator, comprising:

First polymer insulation layer;

a first electrode, located on a first side surface of the first polymer insulating layer; a second polymer insulating layer; a second electrode on the first side surface of the second polymer insulating layer; an intermediate film having a micro-nano-convex structure on one side thereof, the intervening film being provided with one side of the micro-nano concave-convex structure The second side surface of the first polymer polymer insulating layer is in contact with, and the side of the intervening film not provided with the micro/nano convex structure is fixed to the second side surface of the second polymer polymer insulating layer;

a first piezoelectric film coated on the first electrode;

a third electrode, plated on the first piezoelectric film;

The first electrode, the second electrode, and the third electrode are output electrodes of the piezoelectric and triboelectric hybrid thin film nanogenerator.

Further, the piezoelectric and triboelectric hybrid thin film nanogenerator further includes:

a second piezoelectric film coated on the second electrode;

a fourth electrode, plated on the second piezoelectric film;

The first electrode, the second electrode, the third electrode, and the fourth electrode are output electrodes of the piezoelectric and triboelectric hybrid film nanogenerator.

Preferably, the first piezoelectric film is one selected from the group consisting of a polyvinylidene fluoride film, a vinylidene fluoride-trifluoroethylene copolymer film, a nylon 11 film, and a vinylidene cyanide-vinyl acetate alternating copolymer film.

Preferably, the first piezoelectric film and the second piezoelectric film are selected from the group consisting of a polyvinylidene fluoride film, a vinylidene fluoride-trifluoroethylene copolymer film, a nylon 11 film, and an ethylene-based dicyano-vinyl acetate alternating copolymerization. One of the films.

Preferably, the first piezoelectric film or the second piezoelectric film is a non-porous film structure or a porous film structure.

Preferably, the material of the first polymer insulating layer and the intermediate film are different, and the material of the second polymer insulating layer and the intermediate film are different.

Preferably, the first polymer insulating layer and the second polymer insulating layer have the same material.

Preferably, the first polymer insulating layer and the second polymer insulating layer are selected from the group consisting of polydecyl acrylate film, polydisiloxane film, polyimide film, aniline eucalyptus Lipid film, polyoxymethylene film, ethyl cellulose film, polyamide film, melamine formaldehyde film, polyethylene glycol succinate film, cellulose film, cellulose acetate film, polyethylene adipate Film, diallyl polyphthalate film, fiber regenerated sponge film, polyurethane elastomer film, styrene propylene copolymer film, styrene butadiene copolymer film, rayon film, polymethyl film, methyl Acrylate film, polyvinyl alcohol film, polyvinyl alcohol film, polyester film, polyisobutylene film, polyurethane flexible sponge film, polyethylene terephthalate film, polyvinyl butyral film, formaldehyde phenol film, a chloroprene film, a butadiene propylene copolymer film, a natural rubber film, a polyacrylonitrile film, an acrylonitrile vinyl chloride film, a polyvinyl propylene glycol film, and a polyvinylidene fluoride film, an intermediate film Choose from another one of them.

Preferably, the first polymer insulating layer, the first electrode, the second polymer insulating layer, the second electrode, the intervening film, the first piezoelectric film and the third electrode are all flexible flat structures.

Preferably, the first polymer insulating layer, the first electrode, the second polymer insulating layer, the second electrode, the intermediate film, the first piezoelectric film, the third electrode, the second piezoelectric film, and The fourth electrodes are all flexible flat structures.

Preferably, the first polymer polymer insulating layer and the second polymer polymer insulating layer have a thickness of 100 μm - 500 μm; the intermediate film has a thickness of 50 μm - ΙΟΟ μηι; The height is less than or equal to 10μηι.

The piezoelectric and triboelectric hybrid thin film nanogenerator provided by the invention comprises a friction electric generator part and a piezoelectric generator part, which is equivalent to realizing parallel connection of a plurality of nano generators in a single mixed thin film nano generator. The output current is enhanced in parallel, greatly increasing the power generation efficiency of the nanogenerator.

BRIEF abstract

Figure la is a cross-sectional view showing a first embodiment of a piezoelectric and triboelectric hybrid thin film nanogenerator provided by the present invention;

1b is a schematic perspective view of a first embodiment of a piezoelectric and triboelectric hybrid thin film nanogenerator provided by the present invention; FIG. 2a is a schematic structural view of a patterned silicon template used for fabricating the intervening film of the present invention; 2b is a schematic view showing the intervening film of the present invention coated on the silicon template of FIG. 2a; FIG. 2c to FIG. 2e are different patterned silicon templates and intervening films having different shapes of micro/nano concavo-convex structures fabricated therefrom Schematic diagram of the decomposition;

3a to 3c are electron micrographs of intervening films having a micro/nano concave-convex structure in a piezoelectric and triboelectric hybrid thin film nanogenerator of the present invention;

4a is a schematic cross-sectional view showing a second embodiment of a piezoelectric and triboelectric hybrid thin film nanogenerator according to the present invention;

Fig. 4b is a perspective view showing the structure of a piezoelectric and triboelectric hybrid thin film nanogenerator according to a second embodiment of the present invention. Fig. 5 is a perspective view showing a three-dimensional structure of the piezoelectric and triboelectric hybrid film nanogenerator shown in Fig. 4b.

Preferred embodiment of the invention

The present invention will be described in detail by the following detailed description of the preferred embodiments of the invention, but the invention is not limited thereto.

FIG. 1 is a schematic cross-sectional view showing a first embodiment of a piezoelectric and triboelectric hybrid thin film nanogenerator according to the present invention, and FIG. 1b is a schematic perspective view of a first embodiment of a piezoelectric and triboelectric hybrid thin film nanogenerator according to the present invention. . As shown in FIGS. 1a and 1b, the piezoelectric and triboelectric hybrid thin film nanogenerator of the present embodiment includes a first piezoelectric generator portion and a triboelectric generator portion. Preferably, the triboelectric generator portion shares one electrode with the first piezoelectric generator portion. As shown in FIGS. 1a and 1b, the triboelectric generator portion is composed of a first electrode 11, a first polymer insulating layer 10, an intermediate film 14, a second polymer insulating layer 12, and a second electrode 13. . Specifically, the first electrode 11 is located on the first side surface 10a of the first polymer insulating layer 10, and the second electrode 13 is located on the first side surface 12a of the second polymer insulating layer 12. The first electrode 11 and the second electrode 13 may be a conductive metal thin film which may be plated on the surface of the corresponding polymer insulating layer by vacuum sputtering or evaporation. The intermediate film 14 is also a high molecular polymer insulating layer between the first polymer insulating layer 10 and the second polymer insulating layer 12. One side surface of the intermediate film 14 has a quadrangular pyramid type micro/nano concave-convex structure. Wherein, the intermediate film 14 One side not provided with the micro-nano uneven structure is fixed on the second side surface 12b of the second polymer insulating layer 12, and the fixing method may be a thin uncured high-molecular polymer insulation. The layer serves as a bonding layer, and after curing, the intermediate film 14 is firmly fixed to the second polymer insulating layer 12. One side of the intermediate film 14 provided with the micro/nano uneven structure is in contact with the second side surface 10b of the first polymer insulating layer 10, and a frictional interface is formed therebetween. Since FIG. 1a is only a schematic view, the gap between the intermediate film 14 and the first polymer polymer insulating layer 10 shown in FIG. 1a does not mean that the two cannot be physically contacted. Thereby, a device similar to a sandwich structure, that is, a triboelectric generator portion of the hybrid thin film nanogenerator of the present invention is finally formed.

1a and 1b show the intermediate film 14 having a quadrangular pyramid type micro/nano concave-convex structure, but the micro/nano concave-convex structure of the intermediate film 14 is not limited thereto, and it may be formed into other shapes, for example, as shown in Fig. 3a. The stripe shape shown is a cubic shape as shown in Fig. 3b, a quadrangular pyramid type as shown in Fig. 3c, or a cylindrical shape or the like. Further, the micro/nano uneven structure of the intermediate film 14 is usually a regular nano- to micro-scale uneven structure.

Regarding the intervening film in the triboelectric generator portion of the hybrid thin film nanogenerator of the present invention, a method of fabricating the intervening film can be carried out by first forming a patterned silicon template and then using the patterned silicon template as a mold. This will be specifically described below in conjunction with Figures 2a-2e and 3a-3c.

2a is a schematic structural view of a patterned silicon template used to fabricate the intervening film of the present invention; FIG. 2b is a schematic view of the interposer film of the present invention coated on the silicon template of FIG. 2a; FIG. 2c to FIG. An exploded schematic view of a silicon template and an intervening film having micro-nano-convex structures having different shapes produced therefrom.

The specific method for fabricating the patterned silicon template as shown in FIG. 2a is as follows: First, a regular pattern is formed on the surface of a 4 inch (100) crystal wafer by photolithography; and then a regular pattern is prepared. The silicon wafer is etched through the corresponding etching process to form an array structure corresponding to the micro/nano convex structure. For example, by anisotropic etching by a wet etching process, a concave quadrangular pyramid array structure can be etched, or an isotropic etching can be performed by a dry etching process, and a concave vertical cleaning can be etched. The wafer is then surface silanized in an atmosphere of trimethyl chlorosilane (e.g., manufactured by Sigma Aldrich) to form the desired patterned silicon template for use in making the intermediate film for use. Next, an explanation will be given of how to form an intermediate film having a surface of a micro-nano uneven structure. Here, an intermediate film made of polydimethylsiloxane (hereinafter referred to as PDMS) is used as an example. First, a PDMS precursor and a curing agent (for example, Sylgard 184, Tow Corning) are mixed at a mass ratio of 10:1 to form a mixture. The mixture is then applied to, for example, the surface of the patterned silicon template as shown in Figure 2a, as shown in Figure 2b, after vacuum degassing, and applied to the surface of the silicon template by spin coating. The excess mixture is applied to form a uniform thin film of PDMS liquid on the surface of the silicon template. Thereafter, the entire silicon template coated with the PDMS liquid film is cured in an environment of 85 ° C for 1 hour, at which time a uniform layer of PDMS film (cured by a PDMS liquid film) having a specific array of micro-nano-convex structures can be used. It is peeled off from the silicon template to form an intervening film of the present invention, that is, a PDMS film having a micro-nano-convex structure array of a specific shape.

2c-2e respectively show a silicon template of a PDMS film of three different shapes of micro-nano-convex structure arrays fabricated by the above method, and an exploded view of the corresponding PDMS film produced, wherein FIG. 2c shows A PDMS film of a stripe-shaped micro/nano-convex structure array, FIG. 2d shows a PDMS film having a cubic type micro-nano-convex structure array, and FIG. 2e shows a PDMS film having a quadrangular pyramid-shaped micro-nano-convex structure array. The surface microstructure of the three shapes of the micro/nano relief structure is shown in Figures 3a-3c, and the height of the array unit of each PDMS film (i.e., the protrusion of the micro-nano-convex structure in the figure) is limited to about 10 μm. Graphical arrays with smaller scale elements can also be prepared with dimensions as small as 5 μm and with the same high quality characteristics. Figures 3a-3c show the array elements of the micro/nano-convex structure, the length of the same size as the black thick line (located under ΙΟΟμηι) in the figure, which represents the length of the object ΙΟΟμηι. In addition, the upper right side of each figure also shows a high-magnification SEM photograph of the micro/nano-convex structure of the intermediate film taken at an angle of 45°, which is the same length as the black thick line (under 5μηι). The length of the physical 5μηι. As seen from the high-resolution SEM photograph, the micro/nano bump array structure of the intervening film is very uniform and regular. It can be seen that the plastic micro-nano-concave joints of the large-scale uniform hook can be prepared by the above method of the present invention, and each quadrangular pyramid unit has a sharp tip of a complete quadrangular pyramid geometry, which will be beneficial to Increase the friction area during power generation and increase the power output efficiency of the nanogenerator. In addition, the prepared PDMS film (i.e., the intermediate film) has good stretchability and transparency. The first piezoelectric generator portion of the hybrid thin film nanogenerator provided by the present invention comprises a first electrode 11, a first piezoelectric film 15 and a third electrode 16, wherein the first piezoelectric generator portion and the triboelectric generator The first electrode 11 is partially shared. Specifically, the first piezoelectric film 15 is coated on the first electrode 11, and the third electrode 16 is plated on the first piezoelectric film 15. The manufacturing method of the first piezoelectric generator portion is specifically: above the first electrode 11 plated on the surface of the first polymer insulating layer 10 in the friction electric generator portion, by spin coating and The method of electrostatic spraying applies a piezoelectric material on the first electrode 11 to form a first piezoelectric film 15, and then deposits a metal oxide on the first piezoelectric film 15 by vacuum sputtering or evaporation to form a metal oxide. The third electrode 16. A voltage is applied between the metal electrodes on both sides of the first piezoelectric film 15 (i.e., the first electrode 11 and the third electrode 16) to polarize the piezoelectric material, and the polarized first piezoelectric film 15 has a pressure. Electrical performance.

The power generation principle of the triboelectric generator section and the first piezoelectric generator section will be described below.

For the triboelectric generator portion, the first electrode 11 and the second electrode 13 are output electrodes of a triboelectric generator current, and the two electrodes are connected together by an external circuit. When the layers of the hybrid thin film nanogenerator of the present embodiment are bent downward, the surface of the intervening film 14 in the triboelectric generator portion having the micro/nano concave-convex structure rubs against the surface of the first polymer insulating layer 10 to generate static electricity. The generation of static charge causes a change in capacitance between the first electrode 11 and the second electrode 13, resulting in a potential difference between the first electrode 11 and the second electrode 13. Due to the existence of a potential difference between the first electrode 11 and the second electrode 13, the free electrons will flow from the one side electrode, that is, the lower electrode, which is the lower potential, to the second electrode 13 which is the higher potential side through the external circuit, thereby being in the external circuit. Current is formed in the middle. When the layers of the hybrid thin film nanogenerator of the present embodiment are restored to the original state, the layers in the triboelectric generator portion are restored to their original flat state, and are formed at the first electrode 11 and the second electrode 13 at this time. The internal potential disappears due to the first polymer insulating layer 10 between the first electrode 11 and the intermediate film 14 and the second polymer between the second electrode 13 and the intermediate film 14 in the entire internal portion of the triboelectric generator. The polymer insulating layer 12 is an insulating structure that prevents free electrons from neutralizing inside the triboelectric generator portion, and a balanced potential difference is again generated between the balanced first electrode 11 and the second electrode 13 at this time. Then, the free electrons return from the second electrode 13 to the original one electrode, that is, the first electrode 11, through the external circuit, thereby forming a reverse current in the external circuit. This is the principle of power generation in the friction generator section.

For the first piezoelectric generator portion, the first electrode 11 and the third electrode 16 are outputs of their current An external circuit is externally connected between the first electrode 11 and the third electrode 16; the first piezoelectric generator portion mainly relies on a piezoelectric effect generated by the piezoelectric film located between the two electrodes during bending and recovery And generating electricity. When the layers of the hybrid thin film nanogenerator of the present embodiment are bent downward, in the first piezoelectric generator portion, the first piezoelectric film 15 is in a stretched state, and since the β phase structure has a piezoelectric effect, A high potential is generated at the top of the array (i.e., the side near the third electrode 16), and a low potential is generated at the bottom of the array (i.e., the side close to the first electrode 11), at which time the external circuit is turned on. Then, free electrons will flow from the first electrode 11 having a low potential to the third electrode 16 having a high potential. When the layers of the hybrid thin film nanogenerator of the present embodiment are restored to the original state, the free electrons are then returned to the original one side electrode by the external circuit.

In summary, the hybrid thin film nanogenerator of the present embodiment is composed of two parts, namely a first piezoelectric generator portion and a triboelectric generator portion. When the second electrode 13 and the third electrode 16 are connected together as one output branch and the first electrode 11 is used as the other output branch, the two portions satisfy the linear superposition principle of the basic circuit connection, that is, regardless of the forward superposition When stacked in reverse, the total output current can be boosted in parallel. Therefore, when the hybrid thin film nanogenerator provided by the embodiment is used, it is equivalent to parallel connection of two nanogenerators (one piezoelectric nanogenerator and one triboelectric nanogenerator) in a single device, so that nano power generation The power generation efficiency of the machine has been significantly improved.

4a is a schematic cross-sectional view of a second embodiment of a piezoelectric and triboelectric hybrid thin film nanogenerator according to the present invention, and FIG. 4b is a schematic perspective view of a second embodiment of a piezoelectric and triboelectric hybrid thin film nanogenerator according to the present invention. . As shown in Figs. 4a and 4b, the present embodiment further includes a second piezoelectric generator portion based on the first embodiment, and the second piezoelectric generator portion shares one electrode with the triboelectric generator portion.

Specifically, the second piezoelectric generator portion of the hybrid thin film nanogenerator provided in this embodiment includes a second electrode 13, a second piezoelectric film 17, and a fourth electrode 18, wherein the second piezoelectric generator portion and The triboelectric generator portion shares the second electrode 13. Specifically, the second piezoelectric film 17 is coated on the second electrode 13, and the fourth electrode 18 is plated on the second piezoelectric film 17. The manufacturing method of the second piezoelectric generator portion is specifically: above the second electrode 13 plated on the surface of the second polymer insulating layer 12 in the friction electric generator portion, by spin coating and The method of electrostatic spraying applies a piezoelectric material on the second electrode 13, forms a second piezoelectric film 17, and then passes through a vacuum. A second oxide film 17 is plated with a metal oxide by a sputtering method or an evaporation method to form a fourth electrode 18. A voltage is applied between the metal electrodes on both sides of the second piezoelectric film 17 (i.e., the second electrode 13 and the fourth electrode 18) to polarize the piezoelectric material, and the polarized second piezoelectric film 17 has a voltage. Electrical performance.

The power generation principle of the friction electric generator section and the two piezoelectric generator sections will be described below with reference to FIG. Fig. 5 is a perspective view showing the three-dimensional structure of the piezoelectric and triboelectric hybrid film nanogenerator shown in Fig. 4b.

For the friction electric generator part and the first piezoelectric generator part, the power generation principle is the same as that of the first embodiment, and details are not described herein again.

For the second piezoelectric generator portion, the second electrode 13 and the fourth electrode 18 are output electrodes of their currents, and an external circuit is externally connected between the second electrode 13 and the fourth electrode 18. The power generation principle of the second piezoelectric generator portion is similar to that of the first piezoelectric generator portion described above, except that when the layers of the hybrid thin film nanogenerator of the present invention are bent downward, the second pressure The electro-film 17 is in a compressed state, and since its β-phase structure has a piezoelectric effect, a low potential will be generated at the top end of the array (i.e., the side close to the fourth electrode 18) at the bottom of the array (i.e., near the second electrode 13). One side) generates a high potential, and if the external circuit is in an on state at this time, free electrons will flow from the fourth electrode 18 having a low potential to the second electrode 13 having a high potential. When the layers of the hybrid thin film nanogenerator of the present invention are restored to their original state, the free electrons are then returned from the external circuit to the original one side electrode.

In summary, the hybrid thin film nanogenerator of the present embodiment is composed of three parts, i.e., two piezoelectric generator portions and a triboelectric generator portion located between the two piezoelectric generator portions. When the first electrode 11 and the fourth electrode 18 are connected together as one output branch, and the second electrode 13 and the third electrode 16 are connected together as another output branch, the three parts satisfy the linearity of the basic circuit connection. The superposition principle, that is, the total output current can be enhanced in parallel regardless of forward stacking or reverse stacking. Therefore, when the hybrid thin film nanogenerator provided by the embodiment is used, it is equivalent to parallel connection of three nanogenerators (two piezoelectric nanogenerators and one triboelectric nanogenerator) in a single device, so that the nanometer The power generation efficiency of the generator has been significantly improved.

The first and second piezoelectric nano-generator portions and the friction electric generator portion are only one embodiment, and other fabrication methods may be used to form the first and second piezoelectric nano-generator portions and the triboelectric The specific structure of the generator portion is not limited in the present invention. In the above two embodiments, the first piezoelectric film and the second piezoelectric film may be a non-porous film structure or a porous film structure, which is not limited in the present invention.

In the above two embodiments, the first piezoelectric film and the second piezoelectric film may be selected from the group consisting of a polyvinylidene fluoride film, a vinylidene fluoride-trifluoroethylene copolymer film, a nylon 11 film, and an ophthalmic dicyandiamide- One of vinyl acetate alternating copolymer films. That is, the piezoelectric material forming the first piezoelectric film and the second piezoelectric film may be a polyvinylidene fluoride, a vinylidene fluoride-trifluoroethylene copolymer, a nylon 11, or a vinylidene cyanide-vinyl acetate. Things.

As a preferred embodiment, since the first polymer insulating layer and the second polymer insulating layer are in direct contact with the intermediate film, only the first polymer insulating layer and the second polymer are ensured. Both of the insulating layers may be different from the material of the intermediate film. As another preferred embodiment, the materials of the first polymer insulating layer and the second polymer insulating layer may be the same, but are different from the material of the intermediate film.

Specifically, the first polymer insulating layer and the second polymer insulating layer are respectively selected from the group consisting of polydecyl acrylate film, polydisiloxane film, polyimide film, and aniline resin film. , polyacetal film, ethyl cellulose film, polyamide film, melamine furfural film, polyethylene glycol succinate film, cellulose film, cellulose acetate film, polyethylene adipate Film, diallyl phthalate film, fiber regenerated sponge film, polyurethane elastomer film, styrene propylene copolymer film, styrene butadiene copolymer film, rayon film, polyfluorene film, ruthenium Acrylate film, polyvinyl alcohol film, polyvinyl alcohol film, polyester film, polyisobutylene film, polyurethane flexible sponge film, polyethylene terephthalate film, polyvinyl butyral film, furfural Phenol film, neoprene film, butadiene propylene copolymer film, natural rubber film, polyacrylonitrile film, acrylonitrile vinyl chloride film, polyethylene Diphenol carbonate film and polyvinylidene fluoride film of any one of ethylene. The intervening film is selected from the group consisting of a different one of the first high molecular polymer insulating layer and the second high molecular polymer insulating layer.

The first electrode, the second electrode, the third electrode and the fourth electrode in the above two embodiments are all metal thin films, and the metal thin film may be selected from gold, silver, platinum, aluminum, nickel, copper, titanium, iron, selenium or Any of its alloys.

Preferably, the first polymer polymer insulating layer and the second polymer polymer insulating layer have a thickness of 100 μηι-500 μηι; the intermediate film has a thickness of 50 μηι -ΙΟΟμηι; Less than or equal to ΙΟμηΐο

The first polymer insulating layer, the first electrode, the second polymer insulating layer, the second electrode, the intermediate film, the first piezoelectric film, the third electrode, the second piezoelectric film, and the fourth electrode For flexible flat structures, they cause piezoelectric power generation and triboelectric charging by bending or deformation.

Further, in order to more effectively increase the output current or the output power per unit area and improve the power generation efficiency, it is also possible to reassemble the multilayer mixed film nanogenerator on the hybrid thin film nanogenerator of the present invention. For example, a plurality of inventive hybrid thin film nanogenerators may be stacked together to form a multilayer hybrid thin film nanogenerator, or may be in addition to the mixed thin film nanogenerator of the present invention having the above three nanogenerators as needed. A plurality of piezoelectric generators and/or triboelectric generators are respectively stacked, wherein the piezoelectric generator and/or the triboelectric generator stacked outside the hybrid thin film nanogenerator of the present invention are not limited to the hybrid thin film nano according to the present invention. The generator is fabricated. For example, a plurality of piezoelectric generators or triboelectric generators may be continuously stacked, or a piezoelectric generator and a triboelectric generator may be stacked.

The piezoelectric and triboelectric hybrid thin film nanogenerators provided by the present invention can be used as a pressure sensor. The hybrid thin film nanogenerator is composed of a high molecular polymer, and is a flexible flat structure, which can be bent at will, has good stability and mechanical properties, and has a wide range of applications. The hybrid film nanogenerator combines the piezoelectric properties with the triboelectric properties of the polymer polymer insulation layer, which greatly improves the power output capability of the generator and the sensitivity of the self-generating sensor. Due to the production process of the entire device, the cost is low, and mass production can be mass-produced.

The piezoelectric and triboelectric hybrid film nanogenerators of the present invention are described in further detail below by way of a specific example.

In the present embodiment, the piezoelectric and triboelectric hybrid thin film nanogenerator is composed of three parts, namely, a friction electric generator portion and first and second piezoelectric generator portions. Regarding the triboelectric generator portion, wherein the first electrode 11 and the second electrode 13 are made of an indium tin oxide (ITO) conductive film; the first polymer polymer insulating layer 10 is made of polyethylene terephthalate ( The following film is called PET); the intermediate film 14 is made of PDMS having a quadrangular pyramid type micro/nano concave-convex structure; the second polymer insulating layer 12 is made of PET; wherein the first electrode 11 and the second electrode 13 are current Output electrode.

The specific manufacturing method of the triboelectric generator part is: the first electrode 11 and the first high score The sub-polymer insulating layer 10, the intermediate film 14, the second polymer insulating layer 12, and the second electrode 13 are sequentially laminated as shown in FIG. 4a above to form a structure similar to a "sandwich", specifically, the first electrode 11 Plating on the surface of the first polymer insulating layer 10 by vapor deposition; the side of the inter-substrate film 14 having a quadrangular pyramid type micro-nano-convex structure is in contact with the first polymer-polymer insulating layer 10, which does not have One side of the quadrangular pyramid type micro-nano-convex structure is closely adhered to the second polymer-polymer insulating layer 12; the second electrode 13 is plated on the surface of the second polymer-polymer insulating layer 12 by evaporation. Since FIG. 4a is only a schematic view, the presence of a gap between the intermediate film 14 and the first polymer insulating layer 10 illustrated in FIG. 4a does not mean that the two are not in practical contact.

In the present embodiment, regarding the first and second piezoelectric generator portions, wherein the third electrode 16 and the fourth electrode 18 are made of an ITO conductive film; the first piezoelectric film 15 and the second piezoelectric film 17 are made of PVDF. . The third electrode 16 and the first electrode 11 serve as output electrodes of the current of the first piezoelectric generator portion, and the fourth electrode 18 and the second electrode 13 serve as output electrodes of the current of the second piezoelectric generator portion.

The first and second piezoelectric generator parts are specifically prepared by: putting a purchased quantity of PVDF sample into a lOOmL beaker, and measuring a determined volume of diterpene B with a 10 mL pipette The amide (barrel: DMF) dissolved the PVDF sample, sealed the beaker with a plastic wrap, sonicated it for 30 minutes, and dissolved it to obtain a PVDF solution. The PVDF solution is directly coated on the surfaces of the first electrode and the second electrode of the prepared triboelectric generator, and the thickness and uniformity of the coated PVDF film can be controlled by spin coating and electrostatic spraying. The entire device was placed in a vacuum desiccator for drying to obtain a device coated with a PVDF film. A metal electrode is plated on the surface of the prepared PVDF film by a vacuum sputtering method or an evaporation method. Finally, a voltage is applied between the metal electrodes on both sides of each PVDF film to polarize the PVDF film to form a β-phase structure. The applied electric field strength is determined according to the thickness of the PVDF film, and the average is 60ν/μηι. It is 1 hour. The polarized PVDF film has piezoelectric properties, and the metal electrode acts as an output electrode, and the entire device is fabricated.

With the hybrid thin film nanogenerator provided by the above embodiments of the present invention, when the effective size is 4.5 cm x 1.2 cm and the entire thickness is about 1 mm, the bending of the hybrid thin film nanogenerator is controlled by a linear motor at a certain frequency. And release, for example, at a frequency of 0.33 Hz and a stress of 0.13%, at which time the maximum output current between the first electrode 11 and the second electrode 13 can reach 0.8 μΑ. The maximum output current between the first electrode 11 and the third electrode 16 is 0.6 μΑ, and the maximum output current between the second electrode 13 and the fourth electrode 18 is 0.6 μΑ. When the first electrode 11 and the fourth electrode 18 are connected together as an output branch, and the second electrode 13 and the third electrode 16 are connected together as an output branch, the three parts of the hybrid nanogenerator satisfy the basic The linear superposition principle of the circuit connection, so the three parts are superimposed, the maximum output current signal of the whole hybrid nano-generator can be as high as 2 μΑ, and the current density of the whole hybrid nano-generator is about 0.37 A/cm ² .

For the existing single triboelectric generator, which is similar to the triboelectric generator part of the hybrid thin film nanogenerator of the present invention, the first electrode is made of an ITO conductive film; the first polymer polymer insulating layer is made of PET; The intervening film is made of PDMS having a quadrangular pyramid type micro/nano concave-convex structure; the second high molecular polymer insulating layer is made of PET; wherein the first electrode and the second electrode serve as output electrodes of current, and the two are connected by an external circuit together. When the effective size of the triboelectric generator is 4.5 cm x 1.2 cm and the thickness of the entire triboelectric generator is about 460 μm, the bending and release of the triboelectric generator are controlled by a linear motor at a certain frequency, for example, at 0.33 Hz. The frequency of the friction generator makes a maximum output current of 0.7 μΑ, and the current density of the entire triboelectric generator is about 0.13 μΑ/(Μη ² .

From the above comparison, it can be found that the maximum output current, current density and maximum output power density of the hybrid thin film nanogenerator provided by the present invention are significantly improved compared with the existing single triboelectric generator.

It will also be understood that the device structure shown in the figures or embodiments is merely illustrative and represents a logical structure. The modules displayed as separate components may or may not be physically separate, and the components displayed as modules may or may not be physical modules.

The spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of the inventions

Claims

Claim

A piezoelectric and triboelectric hybrid thin film nanogenerator, comprising: a first polymer insulating layer;

a first electrode, located on a first side surface of the first polymer insulating layer; a second polymer insulating layer;

a second electrode on the first side surface of the second polymer insulating layer; an intermediate film having a micro-nano-convex structure on one side thereof, the intervening film being provided with one side of the micro-nano concave-convex structure The second side surface of the first polymer polymer insulating layer is in contact with, and the side of the intervening film not provided with the micro/nano convex structure is fixed to the second side surface of the second polymer polymer insulating layer;

a first piezoelectric film coated on the first electrode;

a third electrode, plated on the first piezoelectric film;

2. The piezoelectric and triboelectric hybrid thin film nanogenerator according to claim 1, further comprising:

a second piezoelectric film coated on the second electrode;

a fourth electrode, plated on the second piezoelectric film;

3. The piezoelectric and triboelectric hybrid thin film nanogenerator according to claim 1, wherein the first piezoelectric film is selected from the group consisting of a polyvinylidene fluoride film, a vinylidene fluoride-trifluoroethylene copolymer film, One of a nylon 11 film, a film of ethylene propylene diacetate-vinyl acetate alternating copolymer.

The piezoelectric and triboelectric hybrid thin film nanogenerator according to claim 2, wherein the first piezoelectric film and the second piezoelectric film are selected from the group consisting of polyvinylidene fluoride film and vinylidene fluoride-three One of a film of a vinyl fluoride copolymer film, a nylon 11 film, and an ethylene-propylene diacetate-vinyl acetate alternating copolymer film.

The piezoelectric and triboelectric hybrid thin film nanogenerator according to claim 2, wherein the first piezoelectric film or the second piezoelectric film is a nonporous film structure or a porous film structure.

The piezoelectric and triboelectric hybrid thin film nanogenerator according to claim 1 or 2, wherein the material of the first polymer insulating layer and the intermediate film are different, and the second high The molecular polymer insulating layer and the intermediate film are made of different materials.

The piezoelectric and triboelectric hybrid thin film nanogenerator according to claim 6, wherein the first polymer insulating layer and the second polymer insulating layer have the same material.

8. The piezoelectric and triboelectric hybrid thin film nanogenerator according to claim 7, wherein the first polymer insulating layer and the second polymer insulating layer are selected from the group consisting of bismuth acrylate. Ester film, polydisiloxane film, polyimide film, aniline resin film, polyacetal film, ethyl cellulose film, polyamide film, melamine furfural film, polyethylene glycol succinic acid Ester film, cellulose film, cellulose acetate film, polyethylene adipate film, poly(phenylene terephthalate film), fiber regenerated sponge film, polyurethane elastomer film, styrene propylene copolymer Film, styrene butadiene copolymer film, rayon film, polyfluorene film, methacrylate film, polyvinyl alcohol film, polyvinyl alcohol film, polyester film, polyisobutylene film, polyurethane flexible sponge film, Polyethylene terephthalate film, polyvinyl butyral film, furfural phenol film, neoprene film, butadiene propylene copolymer film, One of a natural rubber film, a polyacrylonitrile film, an acrylonitrile vinyl chloride film, a polyethylene propylene glycol film, and a polyvinylidene fluoride film, and the intermediate film is selected from the other one.

9. The piezoelectric and triboelectric hybrid thin film nanogenerator according to claim 1, wherein the first polymer insulating layer, the first electrode, the second polymer insulating layer, and the second The electrode, the intervening film, the first piezoelectric film and the third electrode are all flexible flat structures.

The piezoelectric and triboelectric hybrid thin film nanogenerator according to claim 2, wherein the first polymer insulating layer, the first electrode, the second polymer insulating layer, and the second The electrode, the intervening film, the first piezoelectric film, the third electrode, the second piezoelectric film, and the fourth electrode are all flexible flat structures.

The piezoelectric and triboelectric hybrid thin film nanogenerator according to claim 1 or 2, wherein the first polymer insulating layer and the second polymer insulating layer are The thickness is ΙΟΟμηι^ΟΟμηι; the thickness of the intermediate film is 50μηι -ΙΟΟμιη; the height of the protrusion of the micro-nano HJ convex structure is less than or equal to 10μηι.