WO2013181952A1

WO2013181952A1 - A hybrid piezoelectric and triboelectric nanogenerator

Info

Publication number: WO2013181952A1
Application number: PCT/CN2013/072142
Authority: WO
Inventors: 范凤茹; 王中林; 刘军锋
Original assignee: 纳米新能源（唐山）有限责任公司
Priority date: 2012-06-06
Filing date: 2013-03-04
Publication date: 2013-12-12
Also published as: CN103475262B; CN103475262A

Abstract

A hybrid piezoelectric and triboelectric nanogenerator includes: a first superpolymer insulating layer (10); a first electrode (11), located on the surface of the first superpolymer insulating layer (10); a second superpolymer insulating layer (12); a second electrode (13), located on the surface of the second superpolymer insulating layer (12); an intermediate thin film (14), located between the first and the second superpolymer insulating layers; a first piezoelectric nanowire array (15), grown vertically on the first electrode (11); a third superpolymer insulating layer (16), covering the first piezoelectric nanowire array (15); a third electrode (17), located on the surface of the third superpolymer insulating layer (16), a second piezoelectric nanowire array (18), grown vertically on the second electrode (13); a fourth superpolymer insulating layer (19), covering the second piezoelectric nanowire array (18); and a fourth electrode (20), located on the surface of the fourth superpolymer insulating layer (19). The above nanogenerator can greatly improve the generating efficiency.

Description

Piezoelectric and triboelectric hybrid nanogenerators

Technical field

The present invention relates to the field of nanotechnology, and more particularly to a piezoelectric and triboelectric hybrid nanogen generator.

Background technique

Nanotechnology, also known as nanotechnology, is a technique for studying the properties and applications of materials ranging in size from 0.1 to 100 nanometers. The concept of nanoscience was put forward in the early 1980s. Nowadays, nanotechnology has been widely used in materials, machinery, electronics, biology, medicine and many other fields. Among them, nano-generator is a new application of nanotechnology. It utilizes the semiconductor and piezoelectric properties of the oxidized nanorod array to convert mechanical energy into electrical energy in the nanometer scale, thereby outputting alternating current. The mechanical energy that nanogenerators can use includes mechanical vibration, wind kinetic energy, the kinetic energy of water flow, and the energy of muscle stretching. The invention of nanogenerators can integrate nanodevices to achieve truly meaningful nanosystems.

However, the existing nano-generators have many shortcomings, mainly because their output current or output power per unit area is not 4 艮 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 nanogenerator for improving power generation efficiency in view of the deficiencies of the prior art.

The present invention provides a piezoelectric and triboelectric hybrid 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, located on a first side surface of the second polymer insulating layer; an intermediate film having a micro-nano-convex structure on one surface thereof, wherein the intervening film is provided with the micro-nano One side of the uneven structure is in contact with a second side surface of the first polymer insulating layer, and the intermediate film is not provided with one side of the micro/nano uneven structure and the second polymer insulating layer The second side surface is fixed;

a first piezoelectric nanowire array vertically grown on the first electrode;

a third polymer insulating layer covering the first piezoelectric nanowire array; a third electrode located on a surface of the third polymer insulating layer;

a second piezoelectric nanowire array vertically grown on the second electrode;

a fourth polymer insulating layer covering the second piezoelectric nanowire array; a fourth electrode located on a surface of the fourth polymer insulating layer;

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

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, the second polymer insulating layer, the third polymer insulating layer, the fourth polymer insulating layer, and the intermediate layer The materials of the films vary.

Preferably, the materials of the first polymer insulating layer, the second polymer insulating layer, the third polymer insulating layer and the fourth polymer insulating layer are the same. However, it is different from the material of the intermediate film.

Preferably, the first polymer insulating layer, the second polymer insulating layer, the third polymer insulating layer and the fourth polymer insulating layer are respectively selected from poly Methyl methacrylate, polydithiosiloxane, polyimide film, aniline furfural 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, benzene Ethylene propylene copolymer film, styrene butadiene copolymer film, rayon film, polyfluorene film, methacrylate film, polyvinyl alcohol film, polyvinyl alcohol film, polyester film, polyisobutylene film, polyurethane flexibility Sponge film, polyethylene terephthalate film, polyvinyl butyral Membrane, formaldehyde phenol film, neoprene film, butadiene propylene copolymer film, natural rubber film, polyacrylonitrile film, acrylonitrile vinyl chloride film, polyethylene propylene glycol film, polyvinylidene fluoride In either case, the intermediate film is selected from the group consisting of the first polymer polymer insulating layer and the second polymer polymer insulating layer. Preferably, the first polymer insulating layer, the first electrode, the second polymer insulating layer, the second electrode, the intermediate film, the third polymer insulating layer, the third electrode, and the fourth high The molecular polymer insulating layer and the fourth electrode are both flexible flat structures, which cause piezoelectric power generation and triboelectric charging by bending or deformation.

Preferably, the micro/nano concave-convex structure on one side surface of the intermediate film is a concave-convex structure of a nanometer to a micron order.

Preferably, the micro/nano concave-convex structure on one surface of the intermediate film is a regular concave-convex structure, and the concave-convex structure is any one of a stripe shape, a cubic shape, a quadrangular pyramid shape, and a cylindrical shape.

Preferably, the first electrode, the second electrode, the third electrode and the fourth electrode are metal films or metal oxides, and the metal film is selected from the group consisting of gold, silver, platinum, aluminum, nickel, Any of copper, titanium, iron, selenium and alloys thereof.

Preferably, the first polymer polymer insulating layer, the second polymer insulating layer, the third polymer insulating layer and the fourth polymer insulating layer have a thickness of 100 μm The thickness of the intervening film is 50 μm - ΙΟΟμηι; the height of the protrusion of the micro-nano-convex structure is less than or equal to 10 μm.

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

BRIEF abstract

1 is a cross-sectional view showing an embodiment of a piezoelectric and triboelectric hybrid nanogenerator provided by the present invention;

Figure 2a shows a schematic representation of the structure of a patterned silicon template used to fabricate the intervening film of the present invention. Figure

Figure 2b shows a schematic view of the intervening film of the present invention coated on the silicon template of Figure 2a; Figures 2c to 2e show different patterned silicon templates and micro-nano bumps having different shapes produced therefrom Schematic diagram of the decomposition of the intervening film of the structure;

3a to 3c are schematic views showing an intermediate film having a micro/nano concave-convex structure in a piezoelectric and triboelectric hybrid nanogenerator of the present invention;

Figure 4 is a cross-sectional view showing the piezoelectric and triboelectric hybrid nanogenerator shown in Figure 1 when bent;

Fig. 5 is a view showing the connection of the piezoelectric and triboelectric hybrid nanogenerator shown in Fig. 1 to an external circuit.

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.

Figure 1 shows a typical structure of a piezoelectric and triboelectric hybrid nanogenerator of the present invention. As shown in FIG. 1, the piezoelectric and triboelectric hybrid nanogenerator of the present invention includes a first piezoelectric generator portion, a second piezoelectric generator portion, and a first piezoelectric generator portion and a second voltage. A triboelectric generator section between the electrical generator sections. Preferably, the triboelectric generator portion shares one electrode with the first and second piezoelectric generator portions, respectively. As shown in FIG. 1, 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 or a metal oxide which may be plated on the surface of the corresponding high molecular 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. The side of the intermediate film 14 that is not provided with the micro-nano uneven structure is fixed on the second side of the second polymer insulating layer 12. On the surface 12b, the fixing method may be to use a thin uncured polymer polymer insulating layer as a bonding layer, and after curing, the intermediate film 14 is firmly fixed to the second polymer insulating layer 12 on. 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. Thereby, a device similar to the sandwich structure, that is, the friction electric generator portion of the hybrid nanogenerator of the present invention is finally formed.

1 shows an intervening film 14 having a quadrangular pyramid type micro/nano uneven structure, but the micro/nano concavo-convex structure of the intervening film 14 is not limited thereto, and it may be formed into other shapes, for example, as shown in FIG. 3a. Stripe shape, cube shape as shown in Fig. 3b, quadrangular pyramid shape as shown in Fig. 3c, or cylindrical shape, and the like. In addition, the micro/nano concavo-convex structure of the intervening film 14 is generally a regular nano- to micro-scale concavo-convex structure. Regarding the intervening film in the triboelectric generator portion of the hybrid 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.

Figure 2a shows a schematic view of the structure of a patterned silicon template for making the intervening film of the present invention; Figure 2b shows a schematic view of the intervening film of the present invention coated on the silicon template of Figure 2a; Figure 2c to Figure 2e shows an exploded schematic view of a different patterned silicon template and an intervening film having micro-nano-convex structures having different shapes fabricated 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 isopropyl alcohol can be etched out. After cleaning, the silicon wafer is subjected to surface silanization treatment in an atmosphere of trimethyl chlorosilane (for example, manufactured by Sigma Aldrich Co., Ltd.) to form a desired patterned silicon template for use in making an 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, for example, a polydiphenylsiloxane (hereinafter referred to as PDMS) is used to make an intermediate film. First, PDMS is used. The precursor and the curing agent (for example, Sylgard 184, Tow Corning) are mixed at a mass ratio of 10:1 to form a mixture, and then the mixture is applied to, for example, the surface of the patterned silicon template shown in Fig. 2a, as shown in the figure. As shown in 2b, after the vacuum degassing process, the excess mixture applied to the surface of the silicon template is removed by spin coating to form a uniform thin layer on the surface of the silicon template. PDMS liquid membrane. 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 array unit (i.e., the protrusion in the figure) of each PDMS film is limited in size to about 10 μm. Graphical arrays with smaller scale elements can also be produced with dimensions as small as 5μηι 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 (the ruler in the figure) indicates the length of the object ΙΟΟμηι. In addition, a high-magnification scanning electron microscope (SEM) photograph of the micro/nano-convex structure of the intermediate film taken at an angle of 45° is shown in the upper right of each figure, which is the same size as the black thick line (the ruler in the figure). The length is 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. Thus

The quadrangular pyramid unit has a sharp tip with a complete quadrangular pyramid geometry, which will help it 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 nanogenerator provided by the present invention includes a third electrode 17, a third polymer insulating layer 16, a first piezoelectric nanowire array 15 and a first electrode 11, wherein The first piezoelectric generator portion shares the first electrode 11 with the triboelectric generator portion. Specifically, the first piezoelectric nanowire array 15 is vertically grown on one surface of the first electrode 11, and the other surface of the first electrode 11 is plated with the first polymer insulating layer 10, and the third polymer is polymerized. The material insulating layer 16 is covered on the first piezoelectric nanowire array 15, and the third electrode 17 is located on the surface of the third polymer insulating layer 16. The manufacturing method of the first piezoelectric generator portion is specifically: by RF sputtering on the first electrode 11 plated on the surface of the first polymer insulating layer 10 in the friction electric generator portion as described above Method A piezoelectric material (eg ZnO) seed layer is plated. On the piezoelectric material seed layer, the piezoelectric nanowire array is grown by wet chemical method to form the first piezoelectric nanowire array 15. After the growth of the first piezoelectric nanowire array 15 is completed, it is heat-annealed, and then the polymer dielectric insulating layer is covered on the first piezoelectric nanowire array 15 by spin coating to form a third polymer insulation. Layer 16. Finally, a third electrode 17 is coated on the third polymer insulating layer 16. The third electrode 17 is also obtained by plating a metal or a metal oxide (for example, ITO) on the third polymer insulating layer 16 by a method of radio frequency sputtering.

The second piezoelectric generator portion of the hybrid nanogenerator provided by the present invention comprises a fourth electrode 20, a fourth polymer insulating layer 19, a second piezoelectric nanowire array 18 and a second electrode 13, wherein The second piezoelectric generator portion shares the second electrode 13 with the triboelectric generator portion. Specifically, the second piezoelectric nanowire array 18 is vertically grown on one surface of the second electrode 13, and the other surface of the second electrode 13 is plated with the second polymer insulating layer 12, and the fourth polymer is polymerized. The insulating layer 19 covers the second piezoelectric nanowire array 18, and the fourth electrode 20 is located on the surface of the fourth polymer insulating layer 19. The manufacturing method of the second piezoelectric generator portion is specifically: by RF sputtering on the second electrode 13 plated on the surface of the second polymer insulating layer 12 in the friction electric generator portion as described above Method A piezoelectric material (eg ZnO) seed layer is plated. On the piezoelectric material seed layer, the piezoelectric nanowire array is grown by wet chemical method to form a second piezoelectric nanowire array 18. After the growth of the piezoelectric nanowire array is completed, it is thermally annealed, and then the polymer electrolyte insulating layer is covered on the second piezoelectric nanowire array 18 by spin coating to form a fourth high molecular polymer insulating layer 19. Finally, a fourth electrode 20 is coated on the fourth polymer insulating layer 19. The fourth electrode 20 is also obtained by plating a metal or a metal oxide (e.g., ITO) on the fourth polymer insulating layer 19 to form a metal oxide coating by means of radio frequency sputtering.

First and second piezoelectric nanogenerator parts and friction electric generator part manufacturing method For example, the specific structures of the first and second piezoelectric nano-generator portions and the triboelectric generator portion may be formed by other manufacturing methods, which are not limited in the present invention.

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 polymer insulating layer, the second polymer polymer insulating layer, the third polymer polymer insulating layer, the fourth polymer insulating layer, and the intermediate film may also be used. Not the same. As still another preferred embodiment, the materials of the first polymer insulating layer, the second polymer insulating layer, the third polymer insulating layer and the fourth polymer insulating layer may be the same, but both The material of the intermediate film is different.

Specifically, the first polymer polymer insulating layer, the second polymer polymer insulating layer, the third polymer polymer insulating layer, and the fourth polymer insulating layer are respectively selected from the group consisting of polydecyl methacrylate and poly 2 Mercaptosiloxane, polyimide film, aniline furfural resin film, polyacetal film, ethyl cellulose film, polyamide film, melamine furfural film, polyethylene glycol succinate 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, polyparaphenylene Acid glycol film, polyvinyl butyral film, furfural phenol film, neoprene film, butadiene propylene copolymer film, natural rubber film, Any one of a polyacrylonitrile film, a acrylonitrile vinyl chloride film, a polyethylene propylene glycol carbonate film, and a polyvinylidene fluoride. The intermediate film is selected from the other ones different from the first high molecular polymer insulating layer and the second high molecular polymer insulating layer.

The first electrode 11, the second electrode 13, the third electrode 17, and the fourth electrode 20 in the above embodiments are all metal thin films or metal oxides, and the metal thin film may be selected from the group consisting of gold, silver, platinum, aluminum, nickel, copper, Any of titanium, iron, selenium and alloys thereof. Preferably, the first polymer polymer insulating layer, the second polymer polymer insulating layer, the third polymer polymer insulating layer and the fourth polymer insulating layer have a thickness of 100 μm to 500 μm; the thickness of the intermediate film is 50μηι -100μηι; the micro-nano bump structure has a protrusion height of less than or equal to 10μηι. The first polymer polymer insulating layer, the first electrode, the second polymer insulating layer, the second electrode, the intermediate film, the third polymer insulating layer, the third electrode, and the fourth polymer insulating Both the layer and the fourth electrode are flexible flat structures which cause piezoelectric power generation and triboelectric charging by bending or deformation.

The power generation principle of the friction electric generator part and the two piezoelectric generator parts will be respectively described below with reference to Figs. 4 and 5. 4 is a schematic cross-sectional view showing the piezoelectric and triboelectric hybrid nanogenerator shown in FIG. 1 when bent; FIG. 5 is a view showing the piezoelectric and triboelectric hybrid nanogenerator shown in FIG. Schematic diagram.

As shown in FIG. 5, 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 ammeter 30, wherein the first electrode is connected via an ammeter 30. The circuits of one electrode 11 and the second electrode 13 are referred to as external circuits of the triboelectric generator portion. As shown in FIG. 4, when the layers of the hybrid nanogenerator of the present invention are bent downward, the intermediate film 14 in the triboelectric generator portion has a surface of the micro/nano concave-convex structure and the surface of the first polymer insulating layer 10. The mutual friction generates an electrostatic charge, and the generation of the electrostatic charge changes the 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 electrode, which is the lower potential side, that is, the first electrode 11, to the second electrode 13 having the higher potential, through the external circuit, thereby being in the external circuit. A current is formed in the middle, that is, a current flows in the ammeter 30. When the layers of the hybrid nanogenerator of the present invention are restored to the original state, the layers in the triboelectric generator portion are restored to their original flat state, which is formed between 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 insulating layer 12 is an insulating structure that prevents free electrons from neutralizing inside the triboelectric generator portion, and a reversed potential difference is again generated between the balanced first electrode 11 and the second electrode 13 at this time. The free electrons return from the second electrode 13 to the original one side 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. As shown in FIG. 5, for the first piezoelectric generator portion, the first electrode 11 and the third electrode 17 are output electrodes of current, and an ammeter 31 is externally connected between the first electrode 11 and the third electrode 17; Piezoelectric generator portion, second electrode 13 and fourth electrode 20 It is an output electrode of its current, and an ammeter 32 is externally connected between the second electrode 13 and the fourth electrode 20. The first and second piezoelectric generator portions generate electricity mainly by the piezoelectric effect generated by the piezoelectric nanomaterial located between the two electrodes during the occurrence of bending and recovery. As shown in FIG. 4, when the layers of the hybrid nanogenerator of the present invention are bent downward, in the first piezoelectric generator portion, the first piezoelectric nanowire array 15 is bent and stretched to be pressed. The electrical material ZnO is taken as an example. Since its growth direction corresponds to the C-axis direction of the ZnO crystal (the direction of the vertical growth of the oxidized word, as shown in Fig. 4), and due to the piezoelectric effect of the ZnO material, it will be at the first pressure. The top end of the electrical nanowire array 15 produces a high potential, producing a low potential at the bottom of the first piezoelectric nanowire array 15. At this time, if the external circuit is in an on state, for example, as shown in FIG. 5, the first electrode 11 and the third electrode 17 are connected by the ammeter 31, the free electrons will flow from the first electrode 11 at the bottom of the lower potential to the potential. The top third electrode 17 is high, thereby forming a current in the external circuit of the first piezoelectric generator portion, that is, a current flows from the ammeter 31. The third polymer insulating layer 16 above the first piezoelectric nanowire array 15 will prevent electrons from neutralizing internally. When the layers of the hybrid nanogenerator of the present invention are restored to the original state, the layers in the first piezoelectric generator portion also return to their original flat state, and the piezoelectric effect of the ZnO material will be at the first pressure. A potential difference is again generated between the top end and the bottom end of the electric nanowire array 15, at which time free electrons will flow back from the third electrode 17 via the external circuit (i.e., the circuit connecting the first electrode 11 and the third electrode 17 via the ammeter). The original one side electrode is the first electrode 11, thereby forming a reverse current in the external circuit. The power generation principle of the second piezoelectric generator portion is similar to that of the first piezoelectric generator portion described above, and when the layers of the hybrid nanogenerator of the present invention are bent downward, the first piezoelectric generator portion The first piezoelectric nanowire array 15 is in a stretched state, and the second piezoelectric nanowire array 18 of the second piezoelectric generator portion is in a compressed state, because the piezoelectric effect of the ZnO material is present at the second pressure The top end of the electrical nanowire array 18 (because the second piezoelectric nanowire array 18 is grown downward, the top end of which corresponds to the lower portion of the second piezoelectric nanowire array 18 in the figure) produces a low potential, at the second voltage The bottom of the electrical nanowire array 18 (corresponding to the upper portion of the second piezoelectric nanowire array 18 in the figure) produces a high potential. At this time, if the external circuit is in an on state, for example, as shown in FIG. 5, the second electrode 13 and the fourth electrode 20 are connected by the ammeter 32, the free electrons will flow from the fourth electrode 20 having a lower potential to a higher potential. The second electrode 13 forms a current in an external circuit of the second piezoelectric generator portion, that is, a current flows from the ammeter 32. The fourth polymer insulating layer 19 at the top of the second piezoelectric nanowire array 18 will prevent electrons from neutralizing internally. When the layers of the hybrid nanogenerator of the present invention are restored to their original state, The layers in the two-piezoelectric generator portion also return to their original flat state, and the potential effect of the piezoelectric effect of the ZnO material will again cause a potential difference between the top end and the bottom end of the first piezoelectric nanowire array 18. The free electrons will flow back from the second electrode 13 via the external circuit (i.e., the circuit connecting the second electrode 13 and the fourth electrode 20 via the ammeter) to the original one side electrode, that is, the fourth electrode 20, thereby forming an inverse in the external circuit. To the current. Since the two sets of piezoelectric generator parts are relatively independent, there is no influence between them. In summary, the hybrid nanogenerator of the present invention consists of three parts, namely two piezoelectric generator sections and a triboelectric generator section located between the two piezoelectric generator sections. When the first electrode 11 and the fourth electrode 20 are connected together as an output branch, and the second electrode 13 and the third electrode 17 are connected together as an output branch, the three portions satisfy the linear superposition of the basic circuit connections. The principle, that is, the total output current can be enhanced in parallel regardless of forward stacking or reverse stacking. Therefore, when using the hybrid nanogenerator provided by the present invention, it is equivalent to parallel connection of three nanogenerators (two piezoelectric nanogenerators and one triboelectric nanogenerator) in a single hybrid nanogenerator. The power generation efficiency of nano-generators has been significantly improved.

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 hybrid nanogenerator on the hybrid nanogenerator of the present invention. For example, a plurality of hybrid nano-generators of the present invention may be stacked together to form a multilayer hybrid nano-generator, or may be separately stacked in addition to the hybrid nano-generator of the present invention having the above three nano-generators as needed. a plurality of piezoelectric generators and/or triboelectric generators, wherein the piezoelectric generator and/or the triboelectric generator stacked outside the hybrid nanogenerator of the present invention is not limited to the hybrid nanogenerator according to the present invention 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 nanogenerator of the present invention will now be described in further detail by way of a specific example.

In this embodiment, regarding the triboelectric generator portion of the piezoelectric and triboelectric hybrid nanogenerator of the present invention, wherein the first electrode 11 is made of an indium tin oxide (ITO) conductive film; the first polymer insulation The layer 10 is made of polyethylene terephthalate (hereinafter referred to as PET); the intermediate film 14 is made of PDMS having a quadrangular pyramid type micro-nano uneven structure; the second polymer insulating layer 12 is made of PET. Wherein the first electrode 11 and the second electrode 13 serve as current output The poles, as shown in Figure 5, are connected together by an ammeter.

The specific manufacturing method of the triboelectric generator part is as follows: the first electrode 11, the first polymer insulating layer 10, the intermediate film 14, the second polymer insulating layer 12 and the second electrode 13 are as above 1 is sequentially laminated to form a structure similar to a "sandwich", specifically, the first electrode 11 is plated on the surface of the first polymer insulating layer 10 by evaporation; and the intervening film 14 has a quadrangular pyramid shape. One side of the micro-nano concave-convex structure is in contact with the first polymer-polymer insulating layer 10, and one side of the micro-nano-convex structure having no quadrangular pyramid shape is closely adhered to the second polymer-polymer insulating layer 12; The second electrode 13 is plated on the surface of the second polymer insulating layer 12 by an evaporation method.

In the present embodiment, regarding the first piezoelectric generator portion of the piezoelectric and triboelectric hybrid nanogenerator of the present invention, wherein the third electrode 17 is made of an ITO conductive film; the third polymer insulating layer 16 is aggregated. The decyl methacrylate (hereinafter referred to as PMMA) was fabricated; the first piezoelectric nanowire array 15 was fabricated from a ZnO nanowire array. The third electrode 17 and the first electrode 11 serve as output electrodes of the current, as shown in Fig. 5, and the two are connected together by an ammeter.

The first piezoelectric generator portion is specifically fabricated by: RF sputtering on the first electrode 11 plated on the surface of the first polymer insulating layer 10 as described above in the triboelectric generator portion. The method of spraying is to plate a seed layer of ZnO piezoelectric material; on the seed layer of ZnO piezoelectric material, the ZnO nanowire array is grown by wet chemical method to form the first piezoelectric nanowire array 15; after the growth of the ZnO nanowire array is completed, Annealing and annealing, then coating the PMMA layer on the ZnO nanowire array by spin coating to form a third polymer insulating layer 16; finally coating an ITO conductive film on the third polymer insulating layer 16 The ITO conductive film is used as the third electrode 17.

In the present embodiment, regarding the second piezoelectric generator portion of the piezoelectric and triboelectric hybrid nanogenerator of the present invention, wherein the fourth electrode 20 is made of an ITO conductive film; the fourth polymer insulating layer 19 is made of PMMA Fabrication; The second piezoelectric nanowire array 18 is fabricated from a ZnO nanowire array. The fourth electrode 20 and the second electrode 13 serve as output electrodes of the current, as shown in Fig. 5, and the two are connected together by the electric meter.

The second piezoelectric generator portion is specifically fabricated by: RF sputtering on the second electrode 13 plated on the surface of the second polymer insulating layer 12 as described above in the triboelectric generator portion. The method of spraying is applied to the seed layer of ZnO piezoelectric material; on the seed layer of ZnO piezoelectric material, The ZnO nanowire array is grown by wet chemical method to form a second piezoelectric nanowire array 18; after the growth of the ZnO nanowire array is completed, it is heat-annealed, and then the PMMA layer is covered on the ZnO nanowire array by spin coating to form The fourth polymer insulating layer 19 is finally coated with an ITO conductive film on the fourth polymer insulating layer 19, and the ITO conductive film is used as the fourth electrode 20.

Utilizing the hybrid nanogenerator provided by the above embodiments of the present invention, when its effective size is

4.5cmx 1.2cm, the whole thickness is about 1 mm, the bending and release of the hybrid nanogenerator is controlled by a linear motor at a certain frequency, for example, at a frequency of 0.33 Hz and a stress of 0.13%, then the first electrode The maximum output current between 11 and the second electrode 13 can reach 0.8 μΑ, the maximum output current between the first electrode 11 and the third electrode 17 can reach 0.6 μΑ, and the maximum between the second electrode 13 and the fourth electrode 20 The output current can reach 0.6 μΑ. When the first electrode 11 and the fourth electrode 20 are connected together as an output branch, and the second electrode 13 and the third electrode 17 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 nanogenerator of the present invention, the first electrode is made of an indium tin oxide (ITO) conductive film; the first polymer insulation The layer is made of polyethylene terephthalate (hereinafter referred to as PET); the intermediate film is made of PDMS having a quadrangular pyramid type micro-nano-convex structure; the second polymer insulating layer is made of PET; An electrode and a second electrode serve as output electrodes for the current, which are connected together by an ammeter. 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. Ηι ² .

From the above comparison, it can be found that the hybrid nanogenerator provided by the present invention has a significant increase in maximum output current, current density, and maximum output power density compared to the existing single friction electric generator.

Finally, it should be noted that the above list is only specific embodiments of the present invention, and those skilled in the art can change and modify the present invention, if these modifications and variations belong to the present invention. The scope of the invention and its equivalents are to be considered as the scope of the invention.

INDUSTRIAL APPLICABILITY The piezoelectric and triboelectric hybrid nanogenerators provided by the present invention, including a triboelectric generator portion and two piezoelectric generator portions, are equivalent to achieving parallel connection of three nanogenerators in a single hybrid nanogenerator. The total output current is enhanced in parallel, which greatly increases the power generation efficiency of the nanogenerator. 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 assemble a multilayer hybrid nano-generator on the hybrid nano-generator of the present invention. For example, a plurality of hybrid nano-generators of the present invention may be stacked together to form a multilayer hybrid nano-generator, or may be separately stacked in addition to the hybrid nano-generator of the present invention having the above three nano-generators as needed. a plurality of piezoelectric generators and/or triboelectric generators, for example, a plurality of piezoelectric generators or triboelectric generators may be continuously stacked, or a piezoelectric generator and a triboelectric generator may be cross-stacked to further improve nano power generation Machine power generation efficiency.

Claims

Claim

A piezoelectric and triboelectric hybrid nanogenerator comprising: a first 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 surface thereof, the intervening film being provided with one of the micro-nano-concave structures The side is in contact with the second side surface of the first polymer insulating layer, the intermediate film is not provided with one side of the micro/nano uneven structure and the second side of the second polymer insulating layer Fixed surface;

a first piezoelectric nanowire array vertically grown on the first electrode;

a second piezoelectric nanowire array vertically grown on the second electrode;

2. The piezoelectric and triboelectric hybrid nanogenerator according to claim 1, wherein the first polymer insulating layer and the intermediate film are different in material, and the second polymer insulating layer It is different from the material of the intermediate film.

The piezoelectric and triboelectric hybrid nanogenerator according to claim 1, wherein the first polymer insulating layer, the second polymer insulating layer, and the third polymer are polymerized The material insulating layer, the fourth polymer insulating layer, and the intermediate film have different materials.

The piezoelectric and triboelectric hybrid nanogenerator according to claim 1, wherein the first polymer insulating layer, the second polymer insulating layer, and the third polymer The polymer insulating layer and the fourth polymer insulating layer have the same material, but are different from the material of the intermediate film.

The piezoelectric and triboelectric hybrid nanogenerator according to claim 2, wherein the first polymer insulating layer, the second polymer insulating layer, and the third polymer are polymerized The insulating layer and the fourth polymer insulating layer are respectively selected from the group consisting of polydecyl methacrylate, polydithiosiloxane, polyimide film, aniline furfural resin film, polyacetal film, and B. Cellulose film, polyamide film, melamine furfural film, polyethylene glycol succinate film, cellulose film, cellulose acetate film, polyethylene adipate film, polyphthalate Acid diallyl ester film, fiber regenerated sponge film, polyurethane elastomer film, styrene propylene copolymer film, styrene butadiene copolymer film, rayon film, polyfluorene film, methacrylate film, polyethylene Alcohol film, polyvinyl alcohol film, polyester film, polyisobutylene film, polyurethane flexible sponge film, polyethylene terephthalate film, polyvinyl butyral film, Aldehyde phenol film, neoprene film, butadiene propylene copolymer film, natural rubber film, polyacrylonitrile film, acrylonitrile vinyl chloride film, polyethylene propylene glycol film, polyvinylidene fluoride The intervening film is selected from the group consisting of the first polymer polymer insulating layer and the second polymer polymer insulating layer.

The piezoelectric and triboelectric hybrid nanogenerator according to claim 1, wherein the first polymer insulating layer, the first electrode, the second polymer insulating layer, the second electrode, and the intermediate layer The film, the third polymer insulating layer, the third electrode, the fourth polymer insulating layer, and the fourth electrode are all flexible flat structures, which cause piezoelectric power generation and triboelectric charging by bending or deformation.

7. The piezoelectric and triboelectric hybrid nanogenerator according to claim 1, wherein the micro/nano-convex structure is a nano- to micro-scale uneven structure.

8. The piezoelectric and triboelectric hybrid nanogenerator according to claim 7, wherein the micro/nano concave-convex structure is a regular concave-convex structure, and the concave-convex structure is a stripe shape, a cubic shape, a quadrangular pyramid shape, and a cylindrical shape. Any of the shapes.

9. The piezoelectric and triboelectric hybrid nanogenerator according to claim 1, wherein the first electrode, the second electrode, the third electrode, and the fourth electrode are metal thin films or metal oxides The metal film is selected from the group consisting of gold, silver, platinum, aluminum, nickel, copper, titanium, iron, selenium and alloys thereof. Any of them.

The piezoelectric and triboelectric hybrid nanogenerator according to claim 1, wherein the first polymer insulating layer, the second polymer insulating layer, and the third polymer are polymerized The thickness of the insulating layer and the fourth polymer insulating layer is 100 μm to 500 μm; the thickness of the intermediate film is 50 μm to 100 μm; and the height of the protrusion of the micro/nano structure is less than or equal to 10 μm.