Energy conversion device, preparation method and use thereof

Abstract

The present application relates to an energy conversion device, which comprises: an upper conductive layer; a lower conductive layer; which is arranged below the upper conductive layer; at least one piezoelectric micro / nano unit and a fluid arranged between the upper conductive layer and the lower conductive layer; wherein the piezoelectric micro / nano unit has piezoelectric properties and is immersed in the fluid. The present application also relates to a preparation method and use of the energy conversion device.

Description

Technical Field

[0001] The present application relates to the field of energy. Specifically, the present application relates to an energy conversion device, a preparation method thereof and uses thereof. Background Art

[0002] The world's main forms of energy are fossil energy, nuclear energy and solar energy, but the limited nature of fossil energy, the safety of nuclear energy use and the difficulty of nuclear waste disposal have made the search for sustainable, green and pollution-free energy more urgent.

[0003] As a green renewable energy source, molecular thermal motion contains huge energy. Taking ideal gas as an example, at room temperature (27°C), the average translational kinetic energy of thermal motion of each mole of gas molecules is 3.7 kJ / mol. Because there are a huge number of liquids and gases on the earth, even if part of the energy can be converted into electrical energy, it will have a profound impact on the energy structure. In addition, molecular thermal motion is a special kind of material motion, which is essentially different from ordinary mechanical motion. It follows the laws of thermodynamics, which means that thermal motion is a never-ending random motion and does not cause destructive effects on the environment / ecology. In addition, molecular thermal motion does not have many usage problems as mentioned above like some other energy sources. Summary of the invention

[0004] In one aspect, the present application provides an energy conversion device, comprising:

[0005] an upper conductive layer;

[0006] A lower conductive layer disposed below the upper conductive layer;

[0007] at least one piezoelectric micro / nano unit and a fluid disposed between the upper conductive layer and the lower conductive layer;

[0008] The piezoelectric micro / nano unit has piezoelectric properties and is immersed in the fluid.

[0009] In some embodiments of the energy conversion device, one end of the piezoelectric micro / nano unit is fixed on the surface of the lower conductive layer facing the upper conductive layer, and the other end is in contact with the upper conductive layer. In some embodiments, the upper conductive layer covers the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed. In some embodiments, the piezoelectric micro / nano unit comprises a piezoelectric micro / nano material selected from hexagonal stilbene type piezoelectric material, perovskite type piezoelectric material, polymer piezoelectric material and a combination thereof or consists of the piezoelectric micro / nano material.

[0010] In some other embodiments of the energy conversion device, the energy conversion device further comprises at least one additional micro / nano unit, one end of the piezoelectric micro / nano unit is fixed on the surface of the lower conductive layer facing the upper conductive layer, one end of the additional micro / nano unit is fixed on the surface of the upper conductive layer facing the lower conductive layer, and the other end of the piezoelectric micro / nano unit is a free end, so that the piezoelectric micro / nano unit can contact the additional micro / nano unit when randomly vibrating; wherein the other end of the additional micro / nano unit is optionally a free end;

[0011] The additional micro / nano unit satisfies at least one of the following (i) and (ii):

[0012] (i) the additional micro / nano unit comprises a material capable of forming a Schottky junction or a heterojunction with the piezoelectric micro / nano unit or is composed of a material capable of forming a Schottky junction or a heterojunction with the piezoelectric micro / nano unit;

[0013] (ii) The surface of the additional micro / nano unit is coated with a shell material; the shell material is a material that can form a Schottky junction or a heterojunction with the piezoelectric micro / nano unit.

[0014] In some embodiments, the piezoelectric micro / nano units on the surface of the lower conductive layer and the additional micro / nano units on the surface of the upper conductive layer form a fork.

[0015] In some embodiments, the micro / nano material in the additional micro / nano unit is the same as or different from the piezoelectric micro / nano material in the piezoelectric micro / nano unit.

[0016] In some embodiments, when the micro / nano material in the additional micro / nano unit is the same as the piezoelectric micro / nano material in the piezoelectric micro / nano unit, the surface of the additional micro / nano unit is coated with the shell material.

[0017] In some embodiments, the additional micro / nano unit is a non-piezoelectric micro / nano unit.

[0018] In some embodiments, the piezoelectric micro / nano unit comprises or consists of a piezoelectric semiconductor micro / nano material.

[0019] In some other embodiments of the energy conversion device, the at least one piezoelectric micro / nano unit is more than two piezoelectric micro / nano units, one end of the piezoelectric micro / nano unit is fixed on two surfaces of the upper conductive layer and the lower conductive layer facing each other, and the other end of each piezoelectric micro / nano unit on at least one of the upper conductive layer and the lower conductive layer is a free end, so that the piezoelectric micro / nano unit with a free end on the at least one conductive layer can contact the piezoelectric micro / nano unit on the other conductive layer when randomly vibrating;

[0020] Wherein, the surface of the piezoelectric micro / nano unit on the surface of the upper conductive layer or the surface of the piezoelectric micro / nano unit on the surface of the lower conductive layer is wrapped with a shell material; the shell material is a material that can form a Schottky junction or a heterojunction with the piezoelectric micro / nano unit.

[0021] In some embodiments, the piezoelectric micro / nano units on the surface of the upper conductive layer and the piezoelectric micro / nano units on the surface of the lower conductive layer form a fork.

[0022] In some embodiments, the piezoelectric micro / nano unit comprises or consists of a piezoelectric semiconductor micro / nano material.

[0023] In another aspect, the present application provides a method for manufacturing an energy conversion device, comprising:

[0024] providing an upper conductive layer;

[0025] Providing a lower conductive layer and disposing it below the upper conductive layer;

[0026] Disposing at least one piezoelectric micro / nano unit and a fluid between the upper conductive layer and the lower conductive layer;

[0027] The piezoelectric micro / nano unit is immersed in the fluid.

[0028] In some embodiments of the method, the method further comprises:

[0029] Fixing step: fixing one end of the piezoelectric micro / nano unit on the surface of the lower conductive layer; in some embodiments, the fixing step includes growing the piezoelectric micro / nano unit on the surface of the lower conductive layer; in some embodiments, the growth is oriented vertically to the surface of the conductive layer;

[0030] Assembling step: contacting the other end of the fixed piezoelectric micro / nano unit with the upper conductive layer; in some embodiments, the assembling step includes covering the upper conductive layer on the surface of the lower conductive layer on which the piezoelectric micro / nano unit is grown;

[0031] Fluid introduction step: optionally introducing the fluid before, after or during the assembly step; in some embodiments, the fluid introduction step includes introducing the fluid to the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed before the assembly step; in some embodiments, the fluid introduction step includes introducing the fluid between the upper conductive layer and the lower conductive layer after the assembly step; in some embodiments, the fluid introduction step includes performing the assembly step in an atmosphere of the fluid as a gas to introduce the fluid during the assembly process; in some embodiments, the fluid introduction step includes introducing a liquid between the upper conductive layer and the lower conductive layer after the assembly step;

[0032] In some embodiments, the method further comprises a device packaging step; in some embodiments, the device packaging step comprises physical packaging or chemical packaging, and in some embodiments, the packaging is mechanical packaging, or packaging using adhesives or tapes.

[0033] In some embodiments, the piezoelectric micro / nano unit comprises or consists of a piezoelectric micro / nano material selected from a hexagonal spar-type piezoelectric material, a perovskite-type piezoelectric material, a polymer piezoelectric material, and a combination thereof;

[0034] In some embodiments, when the piezoelectric micro / nano unit comprises a piezoelectric micro / nano material selected from a perovskite-type piezoelectric material, a polymer piezoelectric material, and a combination thereof, the device is polarized before the fluid introduction step; in some embodiments, the polarization step comprises applying an electric field between the upper conductive layer and the lower conductive layer, so that the spontaneous polarization is preferentially oriented along the direction of the electric field under the action of the electric field.

[0035] In other embodiments of the method, the device further comprises an additional micro / nano unit, wherein the additional micro / nano unit satisfies at least one of the following (i) and (ii):

[0036] (i) the additional micro / nano unit comprises a material capable of forming a Schottky junction or a heterojunction with the piezoelectric micro / nano unit or is composed of a material capable of forming a Schottky junction or a heterojunction with the piezoelectric micro / nano unit;

[0037] (ii) a shell material is coated on the surface of the additional micro / nano unit; the shell material is a material that can form a Schottky junction or a heterojunction with the piezoelectric micro / nano unit;

[0038] The method further comprises:

[0039] Fixing step: fixing one end of the piezoelectric micro / nano unit on the surface of the lower conductive layer, and fixing one end of the additional micro / nano unit on the surface of the upper conductive layer, and the other end of the piezoelectric micro / nano unit is a free end, and the other end of the additional micro / nano unit is optionally a free end; in some embodiments, the fixing step includes growing the additional micro / nano unit and the piezoelectric micro / nano unit on the surface of the upper conductive layer and the surface of the lower conductive layer, respectively; in some embodiments, the growth is oriented vertically along the surface of the conductive layer;

[0040] Optional wrapping step: when the additional micro / nano unit does not satisfy the above (i), wrapping the shell material on the surface of the additional micro / nano unit; wherein the shell material is a material capable of forming a Schottky junction or a heterojunction with the piezoelectric micro / nano unit;

[0041] Assembling step: assembling in a manner that the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed and the surface of the upper conductive layer on which the additional micro / nano unit is fixed are opposite to each other, so that the piezoelectric micro / nano unit can contact the additional micro / nano unit when randomly vibrating; wherein, when the additional micro / nano unit does not satisfy the above (i), the upper conductive layer on which the additional micro / nano unit is fixed is the upper conductive layer on which the additional micro / nano unit wrapped by the shell material is fixed;

[0042] In some embodiments, the assembling step includes: placing a gasket on the surface of the lower conductive layer to which the piezoelectric micro / nano unit is fixed, wherein the thickness of the gasket or the thickness of the compressed gasket when the gasket is compressed due to force is not less than the distance from the free end of the piezoelectric micro / nano unit to the surface of the lower conductive layer to which the piezoelectric micro / nano unit is fixed and is less than the sum of the distance from the free end of the piezoelectric micro / nano unit to the surface of the lower conductive layer to which the piezoelectric micro / nano unit is fixed and the distance from the free end of the additional micro / nano unit to the surface of the upper conductive layer to which the additional micro / nano unit is fixed; and placing the upper conductive layer to which the additional micro / nano unit is fixed on the gasket;

[0043] Fluid introduction step: optionally introducing the fluid before or during the assembly step; in some embodiments, the fluid introduction step includes introducing the fluid to the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed and the surface of the upper conductive layer on which the additional micro / nano unit is fixed before the assembly step; in some embodiments, the fluid introduction step includes introducing the fluid as a liquid into the space surrounded by the entire gasket after the gasket is placed, and then placing the upper conductive layer on which the additional micro / nano unit is fixed on the gasket, thereby introducing the fluid during the assembly process; wherein when the additional micro / nano unit does not satisfy the above (i), the surface of the upper conductive layer on which the additional micro / nano unit is fixed is the surface of the upper conductive layer on which the additional micro / nano unit wrapped by the shell material is fixed; in some embodiments, the fluid introduction step includes performing the assembly step in an atmosphere of the fluid as a gas to introduce the fluid during the assembly process.

[0044] In some embodiments, the method further comprises a device packaging step; in some embodiments, the device packaging step comprises physical packaging or chemical packaging, and in some embodiments, the packaging is mechanical packaging, or packaging using adhesives or tapes.

[0045] In some embodiments, the assembling is performed in such a way that the additional micro / nano units on the surface of the upper conductive layer form an interdigitation with the piezoelectric micro / nano units on the surface of the lower conductive layer.

[0046] In some embodiments, the micro / nano material in the additional micro / nano unit is the same as or different from the piezoelectric micro / nano material in the piezoelectric micro / nano unit.

[0047] In some embodiments, when the micro / nano material in the additional micro / nano unit is the same as the piezoelectric micro / nano material in the piezoelectric micro / nano unit, the surface of the additional micro / nano unit is coated with the shell material.

[0048] In some embodiments, the additional micro / nano unit is a non-piezoelectric micro / nano unit.

[0049] In some embodiments, the piezoelectric micro / nano unit comprises or consists of a piezoelectric semiconductor micro / nano material.

[0050] In some embodiments of any of the foregoing aspects, two surfaces of the upper conductive layer and the lower conductive layer that are opposite to each other are substantially parallel.

[0051] In some embodiments of any of the foregoing aspects, the micro / nano unit is a micro / nano array at each occurrence.

[0052] In some embodiments of any of the foregoing aspects, the piezoelectric micro / nano unit and the additional micro / nano unit are each at least partially immersed or completely immersed in the fluid.

[0053] In some embodiments of any of the foregoing aspects, the fluid at least partially or completely fills a space between two surfaces of the upper conductive layer and the lower conductive layer that are opposite to each other.

[0054] In some embodiments of any of the foregoing aspects, the fixing is fixed in an orientation perpendicular to the surface of the conductive layer.

[0055] In some embodiments of any of the foregoing aspects, the energy conversion device further comprises an encapsulation layer; the encapsulation layer is disposed at the periphery of the device. In some embodiments of any of the foregoing aspects, the encapsulation layer comprises an adhesive. In some embodiments of any of the foregoing aspects, the adhesive is selected from epoxy resin, silicone, EVA, and combinations thereof.

[0056] In some embodiments of any of the foregoing aspects, the energy conversion device further includes leads; the leads are led out from the upper conductive layer and the lower conductive layer respectively.

[0057] In some embodiments of any of the foregoing aspects, the fluid is a gas or a liquid.

[0058] In some embodiments of any of the foregoing aspects, the gas is compressed and / or heated.

[0059] In some embodiments of any of the foregoing aspects, the gas is a heavy molecule gas. In some embodiments of any of the foregoing aspects, the gas is a compressed and / or heated heavy molecule gas.

[0060] In some embodiments of any of the foregoing aspects, the gas is air, compressed air, xenon, oxygen, nitrogen, hydrogen, and combinations thereof.

[0061] In some embodiments of any of the foregoing aspects, the fluid is a liquid at an elevated temperature.

[0062] In some embodiments of any of the foregoing aspects, the dielectric constant of the liquid is less than 80, less than 40, less than 10, less than 4.0, less than 3.0, less than 2.5, or less than 2.0.

[0063] In some embodiments of any of the foregoing aspects, the viscosity of the liquid is less than 80,000 mPa·s, less than 8,000 mPa·s, less than 800 mPa·s, less than 800 mPa·s, less than 80 mPa·s, less than 8 mPa·s, or less than 0.8 mPa·s.

[0064] In some embodiments of any of the foregoing aspects, the liquid is a non-polar or weakly polar liquid.

[0065] In some embodiments of any of the foregoing aspects, the liquid is a low viscosity liquid.

[0066] In some embodiments of any of the foregoing aspects, the liquid is a non-polar or weakly polar liquid with low viscosity.

[0067] In some embodiments of any of the foregoing aspects, the liquid is selected from dimethyl carbonate, diethyl carbonate, tetrachloroethylene, cyclopentene, n-octane, n-hexane, ethanol, ethylene dichloride, and combinations thereof.

[0068] In some embodiments of any of the foregoing aspects, the upper conductive layer and the lower conductive layer include a conductive or non-conductive substrate; in some embodiments, the upper conductive layer and the lower conductive layer each independently include a material selected from the following: metals, carbon materials, semiconductor materials and combinations thereof; in some embodiments, the upper conductive layer and the lower conductive layer each independently include a material selected from the following: Au, Pt, Ag, Cu, Zn, ITO, FTO, C and combinations thereof.

[0069] In some embodiments of any of the foregoing aspects, the structures of the upper conductive layer and the lower conductive layer are independently sheets or nanostructures covered with a conductive film layer. In some embodiments of any of the foregoing aspects, the nanostructure is a nanogroove, a nanoarray, or a combination thereof.

[0070] In some embodiments of any of the foregoing aspects, a minimum radial dimension of at least a portion of a cross section of each of the nanounits along its extension direction is 1 nm to 10 μm, 10 nm to 1 μm, 20 nm to 300 nm, 10 nm to 500 nm, or 10 nm to 100 nm.

[0071] In some embodiments of any of the foregoing aspects, the gaps between nanounits in the nanoarray are 5 nm to 20 μm, 20 nm to 5 μm, 50 nm to 1 μm, 80 nm to 500 nm, or 100 nm to 300 nm.

[0072] In some embodiments of any of the foregoing aspects, the piezoelectric micro / nano unit and the additional micro / nano unit are each independently a nanorod, a nanosheet, a nanowire, a nanobelt, a nanotube, a nanohelix, or a combination thereof.

[0073] In some embodiments of any of the foregoing aspects, the piezoelectric semiconductor micro / nano material is selected from hexagonal sintered mineral-type piezoelectric materials.

[0074] In some embodiments of any of the foregoing aspects, the hexagonal quartz-type piezoelectric material is selected from ZnO, GaN, ZnS, CdS, InN, InGaN, CdTe, CdSe, ZnSnO3, and combinations thereof.

[0075] In some embodiments of any of the foregoing aspects, the general formula of the perovskite piezoelectric material is ABO3; wherein A is a rare earth or alkaline earth metal ion, and B is a transition metal ion.

[0076] In some embodiments of any of the foregoing aspects, the perovskite piezoelectric material is selected from lead zirconate titanate PZT, barium titanate BaTiO3, potassium sodium niobate KNN, and combinations thereof.

[0077] In some embodiments of any of the foregoing aspects, the polymer piezoelectric material is selected from polyvinylidene fluoride PVDF and polydimethylsiloxane PDMS.

[0078] In some embodiments of any of the foregoing aspects, the piezoelectric micro / nano unit is a ZnO nanoarray.

[0079] In some embodiments of any of the foregoing aspects, the shell material is a metal material, and the work function value of the metal material is greater than or less than the work function value of the piezoelectric semiconductor micro / nano material.

[0080] In some embodiments of any of the foregoing aspects, the shell material is other semiconductor material capable of forming a heterojunction with the piezoelectric semiconductor micro / nano material.

[0081] In some embodiments of any of the foregoing aspects, the shell material is a metal material selected from Au, Pt, Ag, Ti, Al, and combinations thereof.

[0082] In some embodiments of any of the foregoing aspects, the shell material is a semiconductor material selected from CuO, silicon wafer, Cu2O, NiO, Co3O4, and combinations thereof.

[0083] In some embodiments of any of the foregoing aspects, the shell material is formed by magnetron sputtering, electron beam evaporation, thermal evaporation, or sol-geling the shell material on the surface of the upper conductive layer to which the nano units are fixed.

[0084] In another aspect, the present application provides an article, device or power supply device comprising the energy conversion device of the present disclosure. In some embodiments, the article or device is powered by the energy conversion device.

[0085] On the other hand, the present application provides the use of the energy conversion device of the present disclosure in energy conversion and collection, such as energy storage, sensors, wearable devices, and mobile devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0086] Figure 1 This is a schematic diagram of the structure of the energy conversion device in Example 1.

[0087] Figure 2 The current-voltage curve of the energy conversion device of Example 1 is shown.

[0088] Figure 3 The voltage and current output of the energy conversion device of Example 1 are shown.

[0089] Figure 4 The current and voltage output curves of the energy conversion device of Example 2 are shown.

[0090] Figure 5 The cyclic voltammetry curve of the energy conversion device of Example 2 is shown.

[0091] Figure 6 The current and voltage output curves of the energy conversion device of Example 3 are shown.

[0092] Figure 7 This is a schematic diagram of the structure of the energy conversion device in Example 4. DETAILED DESCRIPTION

[0093] definition

[0094] The following definitions and methods are provided to better define the present application and guide those of ordinary skill in the art in the practice of the present application. Unless otherwise specified, terms are understood according to conventional usage by those of ordinary skill in the relevant art.

[0095] As used herein, the terms "include" and "comprising" should be interpreted as inclusive and open-ended, rather than exclusive. Specifically, when used in the specification and claims, the terms "include" and "comprising" and their variations mean including the specified features, steps, or components. These terms should not be interpreted to exclude the presence of other features, steps, or components.

[0096] As used herein, the term "optional" or "optionally" means that the subsequently described event or circumstance can, but does not have to, occur, and the description includes instances where said event or circumstance occurs and instances where they do not occur.

[0097] Spatially relative terms, such as "below," "under," "down," "above," "up," "above," etc., may be used herein for descriptive purposes, and are thereby used to describe the relationship of one element to another, as illustrated in the accompanying drawings. In addition to the directions described in the accompanying drawings, spatially relative terms are intended to also include different orientations of the device in use, operation, and / or manufacture. For example, if the device in the accompanying drawings is flipped, an element described as "above" or "above" other elements or features would be positioned "below" the other elements or features. Therefore, the exemplary term "above" may include both the upper and lower directions. In addition, the device may be oriented in other ways (e.g., rotated 90 degrees or in other directions), and as such, the spatially relative descriptive symbols used herein are interpreted accordingly.

[0098] The term "polymer piezoelectric material" used in this article generally refers to some piezoelectric materials composed of high molecular polymers.

[0099] The term "micro / nano unit" as used herein refers to a micron unit, a nano unit or a combination thereof.

[0100] The term “heavy molecule gas” used herein refers to a gas having a relative molecular weight of not less than 25 (eg, not less than 25, not less than 40, not less than 60, not less than 80, not less than 100).

[0101] Where a numerical range is given herein, the range includes its endpoints, and all individual integers and fractions within the range, and also includes each narrower range formed by all possible combinations of those endpoints and internal integers and fractions therein to form subgroups of the larger numerical group within the range to the same extent, as if each of those narrower ranges were explicitly given. For example, the minimum radial dimension of at least a portion of the cross section of each of the nanounits in its extension direction is 1 nm to 10 μm, which means that the minimum radial dimension can be, for example, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 24 nm, 28 nm, 30 nm, 32 nm, 35 nm, 38 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, m, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm or 10μm, etc. and the range formed by them, etc.

[0102] In one aspect, the present application provides an energy conversion device, comprising:

[0103] an upper conductive layer;

[0104] A lower conductive layer disposed below the upper conductive layer;

[0105] at least one piezoelectric micro / nano unit and a fluid disposed between the upper conductive layer and the lower conductive layer;

[0106] The piezoelectric micro / nano unit has piezoelectric properties and is immersed in the fluid.

[0107] The basic principle of the energy conversion device of the present invention is: when a piezoelectric material with piezoelectric effect is placed in a fluid, due to the molecular thermal motion of the fluid, the piezoelectric material performs Brownian motion, random vibration, and deformation, thereby generating an electric potential difference on the surface of the material, which is then led out through the electrode to form a detectable current in the external circuit. The electric potential difference of the piezoelectric material is at least partially derived from the molecular thermal motion. The piezoelectric material can include various piezoelectric materials in the art that can produce a piezoelectric effect, including but not limited to a combination of one or more of hexagonal spar piezoelectric materials, perovskite piezoelectric materials, polymer piezoelectric materials, etc.

[0108] In some embodiments of the energy conversion device, one end of the piezoelectric micro / nano unit is fixed on the surface of the lower conductive layer facing the upper conductive layer, and the other end is in contact with the upper conductive layer. In some embodiments, the upper conductive layer covers the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed. In some embodiments, the piezoelectric micro / nano unit comprises a piezoelectric micro / nano material selected from hexagonal stilbene type piezoelectric material, perovskite type piezoelectric material, polymer piezoelectric material and a combination thereof or consists of the piezoelectric micro / nano material.

[0109] The upper conductive layer (e.g., aluminum foil) covering the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed can be directly used as an upper electrode or combined with other electrode materials as an upper electrode, and the lower conductive layer (e.g., FTO conductive surface) can be directly used as a lower electrode. The upper and lower electrodes are respectively led out by leads (e.g., copper wires) to form a detectable current in the external circuit.

[0110] In some other embodiments of the energy conversion device, the energy conversion device further comprises at least one additional micro / nano unit, one end of the piezoelectric micro / nano unit is fixed on the surface of the lower conductive layer facing the upper conductive layer, one end of the additional micro / nano unit is fixed on the surface of the upper conductive layer facing the lower conductive layer, and the other end of the piezoelectric micro / nano unit is a free end, so that the piezoelectric micro / nano unit can contact the additional micro / nano unit when randomly vibrating; wherein the other end of the additional micro / nano unit is optionally a free end;

[0111] The additional micro / nano unit satisfies at least one of the following (i) and (ii):

[0112] (i) the additional micro / nano unit comprises a material capable of forming a Schottky junction or a heterojunction with the piezoelectric micro / nano unit or is composed of a material capable of forming a Schottky junction or a heterojunction with the piezoelectric micro / nano unit;

[0113] (ii) The surface of the additional micro / nano unit is coated with a shell material; the shell material is a material that can form a Schottky junction or a heterojunction with the piezoelectric micro / nano unit.

[0114] In some embodiments, the piezoelectric micro / nano units on the surface of the lower conductive layer and the additional micro / nano units on the surface of the upper conductive layer form a fork.

[0115] In some embodiments, the micro / nano material in the additional micro / nano unit is the same as or different from the piezoelectric micro / nano material in the piezoelectric micro / nano unit.

[0116] In some embodiments, when the micro / nano material in the additional micro / nano unit is the same as the piezoelectric micro / nano material in the piezoelectric micro / nano unit, the surface of the additional micro / nano unit is coated with the shell material.

[0117] In some embodiments, the additional micro / nano unit is a non-piezoelectric micro / nano unit.

[0118] In some embodiments, the piezoelectric micro / nano unit comprises or consists of a piezoelectric semiconductor micro / nano material.

[0119] The shell material can be directly used as the upper electrode, and the lower conductive layer (for example, a metal substrate, such as a Zn sheet) can be directly used as the lower electrode. The upper and lower electrodes are respectively led out by leads to form a detectable current in an external circuit.

[0120] In some other embodiments of the energy conversion device, the at least one piezoelectric micro / nano unit is more than two piezoelectric micro / nano units, one end of the piezoelectric micro / nano unit is fixed on two surfaces of the upper conductive layer and the lower conductive layer facing each other (i.e., one end of a part of the piezoelectric micro / nano units is fixed on the upper conductive layer, and one end of another part of the piezoelectric micro / nano units is fixed on the surface of the lower conductive layer facing the upper conductive layer), and the other end of each of the piezoelectric micro / nano units on at least one of the upper conductive layer and the lower conductive layer is a free end, so that the piezoelectric micro / nano unit with a free end on the at least one conductive layer can contact the piezoelectric micro / nano unit on the other conductive layer when randomly vibrating;

[0121] Wherein, the surface of the piezoelectric micro / nano unit on the surface of the upper conductive layer or the surface of the piezoelectric micro / nano unit on the surface of the lower conductive layer is wrapped with a shell material; the shell material is a material that can form a Schottky junction (such as a metal shell material) or a heterojunction with the piezoelectric micro / nano unit (such as a shell material such as CuO, silicon wafer, Cu2O, NiO, Co3O4, etc.).

[0122] In some embodiments, the piezoelectric micro / nano units on the surface of the upper conductive layer and the piezoelectric micro / nano units on the surface of the lower conductive layer form a fork.

[0123] In some embodiments, the piezoelectric micro / nano unit comprises or consists of a piezoelectric semiconductor micro / nano material.

[0124] The shell material can be directly used as the upper electrode, and the lower conductive layer (for example, a metal substrate, such as a Zn sheet) can be directly used as the lower electrode. The upper and lower electrodes are respectively led out by leads. The potential difference generated by the semiconductor piezoelectric material is passed through the upper electrode, and the Schottky junction at the interface between the metal and the semiconductor or the PN junction between the semiconductors has a unidirectional conductive rectification characteristic to achieve unidirectional DC output.

[0125] In another aspect, the present application provides a method for manufacturing an energy conversion device, comprising:

[0126] providing an upper conductive layer;

[0127] Providing a lower conductive layer and disposing it below the upper conductive layer;

[0128] Disposing at least one piezoelectric micro / nano unit and a fluid between the upper conductive layer and the lower conductive layer;

[0129] The piezoelectric micro / nano unit is immersed in the fluid.

[0130] In some embodiments of the method, the method further comprises:

[0131] Fixing step: fixing one end of the piezoelectric micro / nano unit on the surface of the lower conductive layer; in some embodiments, the fixing step includes growing the piezoelectric micro / nano unit on the surface of the lower conductive layer; in some embodiments, the growth is oriented vertically to the surface of the conductive layer;

[0132] Assembling step: contacting the other end of the fixed piezoelectric micro / nano unit with the upper conductive layer; in some embodiments, the assembling step includes covering the upper conductive layer on the surface of the lower conductive layer on which the piezoelectric micro / nano unit is grown;

[0133] Fluid introduction step: the fluid may be introduced optionally before, after or during the assembly step; in some embodiments, the fluid introduction step comprises introducing the fluid to the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed before the assembly step; in some embodiments, the fluid introduction step comprises introducing the fluid between the upper conductive layer and the lower conductive layer after the assembly step; in some embodiments, the fluid introduction step comprises performing the assembly step in an atmosphere of the fluid as a gas so as to introduce the fluid during the assembly process; in some embodiments, the fluid introduction step comprises introducing (e.g., dripping) a liquid between the upper conductive layer and the lower conductive layer after the assembly step;

[0134] In some embodiments, the method may further include a device packaging step; in some embodiments, the device packaging step includes physical packaging or chemical packaging, and in some embodiments, the packaging is mechanical packaging, or packaging using an adhesive or tape.

[0135] In some embodiments, the piezoelectric micro / nano unit may include or consist of a piezoelectric micro / nano material selected from a hexagonal spar-type piezoelectric material, a perovskite-type piezoelectric material, a polymer piezoelectric material, and a combination thereof;

[0136] In some embodiments, when the piezoelectric micro / nano unit comprises a piezoelectric micro / nano material selected from a perovskite-type piezoelectric material, a polymer piezoelectric material, and a combination thereof, the device is polarized before the fluid introduction step; in some embodiments, the polarization step comprises applying an electric field between the upper conductive layer and the lower conductive layer, so that the spontaneous polarization is preferentially oriented along the direction of the electric field under the action of the electric field.

[0137] In other embodiments of the method, the device further comprises an additional micro / nano unit, wherein the additional micro / nano unit satisfies at least one of the following (i) and (ii):

[0138] (i) the additional micro / nano unit comprises a material capable of forming a Schottky junction or a heterojunction with the piezoelectric micro / nano unit or is composed of a material capable of forming a Schottky junction or a heterojunction with the piezoelectric micro / nano unit;

[0139] (ii) a shell material is coated on the surface of the additional micro / nano unit; the shell material is a material that can form a Schottky junction or a heterojunction with the piezoelectric micro / nano unit;

[0140] The method further comprises:

[0141] Fixing step: fixing one end of the piezoelectric micro / nano unit on the surface of the lower conductive layer, and fixing one end of the additional micro / nano unit on the surface of the upper conductive layer, and the other end of the piezoelectric micro / nano unit is a free end, and the other end of the additional micro / nano unit is optionally a free end, for example, the other end of the additional micro / nano unit can be a free end, or it can be a non-free end (for example, in contact with the upper conductive layer); in some embodiments, the fixing step includes growing the additional micro / nano unit and the piezoelectric micro / nano unit on the surface of the upper conductive layer and the surface of the lower conductive layer, respectively; in some embodiments, the growth is oriented along the surface of the conductive layer;

[0142] Optional wrapping step: when the additional micro / nano unit does not satisfy the above (i), wrapping the shell material on the surface of the additional micro / nano unit; wherein the shell material is a material capable of forming a Schottky junction or a heterojunction with the piezoelectric micro / nano unit;

[0143] Assembling step: assembling in a manner that the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed and the surface of the upper conductive layer on which the additional micro / nano unit is fixed are opposite to each other, so that the piezoelectric micro / nano unit can contact the additional micro / nano unit when randomly vibrating; wherein, when the additional micro / nano unit does not satisfy the above (i), the upper conductive layer on which the additional micro / nano unit is fixed is the upper conductive layer on which the additional micro / nano unit wrapped by the shell material is fixed;

[0144] In some embodiments, the assembling step includes: placing a gasket on the surface of the lower conductive layer to which the piezoelectric micro / nano unit is fixed, wherein the thickness of the gasket or the thickness of the compressed gasket when the gasket is compressed due to force is not less than the distance from the free end of the piezoelectric micro / nano unit to the surface of the lower conductive layer to which the piezoelectric micro / nano unit is fixed and is less than the sum of the distance from the free end of the piezoelectric micro / nano unit to the surface of the lower conductive layer to which the piezoelectric micro / nano unit is fixed and the distance from the free end of the additional micro / nano unit to the surface of the upper conductive layer to which the additional micro / nano unit is fixed; and placing the upper conductive layer to which the additional micro / nano unit is fixed on the gasket;

[0145] Fluid introduction step: optionally introducing the fluid before or during the assembly step; in some embodiments, the fluid introduction step includes introducing the fluid to the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed and the surface of the upper conductive layer on which the additional micro / nano unit is fixed before the assembly step; in some embodiments, the fluid introduction step includes introducing the fluid as a liquid into the space surrounded by the entire gasket after the gasket is placed, and then placing the upper conductive layer on which the additional micro / nano unit is fixed on the gasket, thereby introducing the fluid during the assembly process; wherein when the additional micro / nano unit does not satisfy the above (i), the surface of the upper conductive layer on which the additional micro / nano unit is fixed is the surface of the upper conductive layer on which the additional micro / nano unit wrapped by the shell material is fixed; in some embodiments, the fluid introduction step includes performing the assembly step in an atmosphere of the fluid as a gas to introduce the fluid during the assembly process.

[0146] In some embodiments, the method further comprises a device packaging step; in some embodiments, the device packaging step comprises physical packaging or chemical packaging, and in some embodiments, the packaging is mechanical packaging, or packaging using adhesives or tapes.

[0147] In some embodiments, the assembling is performed in such a way that the additional micro / nano units on the surface of the upper conductive layer form an interdigitation with the piezoelectric micro / nano units on the surface of the lower conductive layer.

[0148] In some embodiments, the micro / nano material in the additional micro / nano unit is the same as or different from the piezoelectric micro / nano material in the piezoelectric micro / nano unit.

[0149] In some embodiments, when the micro / nano material in the additional micro / nano unit is the same as the piezoelectric micro / nano material in the piezoelectric micro / nano unit, the surface of the additional micro / nano unit is coated with the shell material.

[0150] In some embodiments, the additional micro / nano unit is a non-piezoelectric micro / nano unit.

[0151] In some embodiments, the piezoelectric micro / nano unit comprises or consists of a piezoelectric semiconductor micro / nano material.

[0152] In some embodiments of any of the foregoing aspects, two surfaces of the upper conductive layer and the lower conductive layer that are opposite to each other are substantially parallel.

[0153] In some embodiments of any of the foregoing aspects, the micro / nano unit is a micro / nano array each time it appears. For example, the piezoelectric micro / nano unit and the additional micro / nano unit are both nano arrays.

[0154] In some embodiments of any of the foregoing aspects, the piezoelectric micro / nano unit and the additional micro / nano unit are each at least partially immersed or completely immersed in the fluid.

[0155] In some embodiments of any of the foregoing aspects, the fluid at least partially or completely fills a space between two surfaces of the upper conductive layer and the lower conductive layer that are opposite to each other.

[0156] In some embodiments of any of the foregoing aspects, the fixing is fixing in a direction perpendicular to the surface of the conductive layer. When one end of the piezoelectric material nanostructure is fixed to the lower conductive layer as the lower electrode of the energy conversion device and the other end is a free end, when the piezoelectric material is placed in a fluid, the strain of the free end will be more sufficient due to the fixing of one end.

[0157] In some embodiments of any of the foregoing aspects, the energy conversion device further comprises an encapsulation layer; the encapsulation layer is disposed on the entire periphery of the device. In some embodiments of any of the foregoing aspects, the encapsulation layer comprises an adhesive. In some embodiments of any of the foregoing aspects, the adhesive may be selected from epoxy resin, silicone, EVA, and combinations thereof.

[0158] In some embodiments of any of the foregoing aspects, the energy conversion device further includes leads; the leads are led out from the upper conductive layer and the lower conductive layer respectively.

[0159] In some embodiments of any of the foregoing aspects, the fluid may be a gas or a liquid.

[0160] In some embodiments of any of the foregoing aspects, the gas may be a compressed and / or heated gas.

[0161] In some embodiments of any of the foregoing aspects, the gas may be a heavy molecule gas. In some embodiments of any of the foregoing aspects, the gas may be a compressed and / or heated heavy molecule gas.

[0162] In some embodiments of any of the foregoing aspects, the gas is air, compressed air, xenon, oxygen, nitrogen, hydrogen, and combinations thereof.

[0163] In some embodiments of any of the foregoing aspects, the fluid may be a liquid at an elevated temperature.

[0164] In some embodiments of any of the foregoing aspects, the liquid is a non-polar or weakly polar liquid with low viscosity. When the fluid is a liquid, it is usually a non-polar or weakly polar substance and has a relatively low dielectric constant, for example, less than 80 (e.g., less than 79, less than 78, less than 77, less than 76, less than 75, less than 74, less than 73, less than 72, less than 71, less than 70, less than 69, less than 68, less than 67, less than 66, less than 65, less than 64, less than 63, less than 62, less than 61, less than 60, less than 59, less than 58, less than 57, less than 56, less than 55, less than 54, less than 53, less than 52, less than 51, less than 50, less than 49, less than 48, less than 47, less than 46, less than 45, less than 44, less than 43, less than 42, less than 41, less than 43 0, less than 39, less than 38, less than 37, less than 36, less than 35, less than 34, less than 33, less than 32, less than 31, less than 30, less than 29, less than 28, less than 27, less than 26, less than 25, less than 24, less than 23, less than 22, less than 21, less than 20, less than 19, less than 18, less than 17, less than 16, less than 15, less than 14, less than 13, less than 12, less than 11, less than 10, less than 9, less than 8, less than 7, less than 6, less than 5, less than 4, less than 3.8, less than 3.5, less than 3, less than 2.7, less than 2.5, or less than 2), less than 40, less than 10, less than 4.0, less than 3.0, less than 2.5, or less than 2.0, thereby avoiding the presence of freely moving ions in the solution, and generally having a lower viscosity, for example, less than 80000 mPa·s (e.g., 80000 mPa·s, 70000 mPa·s, 60000 mPa·s, 50000 mPa·s, 40000 mPa·s, 30000 mPa·s, 20000 mPa·s, 10000 mPa·s, 9000 mPa·s, 8000 mPa·s, 7000 mPa·s, 6000 mPa·s, 5000 mPa·s, 4000 mPa·s, 3000 mPa·s, 2000 mPa·s, 10000 mPa·s, 9000 mPa·s, 8000 mPa·s, mPa·s, 700mPa·s, 600mPa·s, 500mPa·s, 400mPa·s, 300mPa·s, 200mPa·s, 100mPa·s, 90mPa·s, 80mPa·s, 70mPa·s, 60mPa·s, 50mPa·s, 40mPa·s, 30mP a·s, 20mPa·s, 10mPa·s, 9mPa·s, 8mPa·s, 7mPa·s, 6mPa·s, 5mPa·s, 4mPa·s, 3mPa·s, 2mPa·s, 1mPa·s, 0.9mPa·s, 0.8mPa·s, 0.7mPa·s, 0.6mPa·s, 0.5mPa·s, 0.4mPa·s or 0.3mPa·s, etc.), less than 8000mPa·s, less than 800mPa·s, less than 80mPa·s, less than 8mPa·s, or less than 0.8mPa·s, so as to facilitate the occurrence of molecular thermal motion.

[0165] In some embodiments of any of the foregoing aspects, the liquid is selected from dimethyl carbonate, diethyl carbonate, tetrachloroethylene, cyclopentene, n-octane, n-hexane, ethanol, ethylene dichloride, and combinations thereof.

[0166] In some embodiments of any of the foregoing aspects, the upper conductive layer and the lower conductive layer include a conductive or non-conductive substrate; in some embodiments, the upper conductive layer and the lower conductive layer each independently include a material selected from the following: metal, carbon material, semiconductor material and combinations thereof; in some embodiments, the upper conductive layer and the lower conductive layer each independently include a material selected from the following: Au, Pt, Ag, Cu, Zn, ITO, FTO, C and combinations thereof. When the substrate is a non-conductive substrate, the conductive layer can be obtained by forming the above-mentioned metal, carbon material, semiconductor material on the substrate.

[0167] In some embodiments of any of the foregoing aspects, the structures of the upper conductive layer and the lower conductive layer are independently sheets or nanostructures covered with a conductive film layer. In some embodiments of any of the foregoing aspects, the nanostructure is a nanogroove, a nanoarray, or a combination thereof.

[0168] In some embodiments of any of the foregoing aspects, the minimum radial dimension of at least a portion of the cross section of each of the nanounits along the extension direction thereof is 1 nm to 10 μm (e.g., 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, 21 nm, 22 nm, 24 nm, 28 nm, 30 nm, 32 nm, 35 nm, 38 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 111 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 211 nm, 220 nm, 240 nm, 250 nm, 251 nm, 252 nm, In some embodiments, the piezoelectric material may be sized to have a cross-sectional shape, a diameter or a length, such as 20 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, etc.), 10 nm-1 μm, 20 nm-300 nm, 10 nm-500 nm or 10 nm-100 nm. However, the cross-sectional shape, diameter or length of the piezoelectric material may vary depending on the piezoelectric material and the manufacturing process. The piezoelectric material may be provided with a suitable length according to its extension direction, so that the piezoelectric material may generate Brownian motion when placed in a fluid.

[0169] In some embodiments of any of the foregoing aspects, the gap between the nanounits in the nanoarray is about 5 nm to about 20 μm (e.g., 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, 380 nm, 390 nm, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, 500 nm, 510 nm, 520 nm, 530 nm, 540 nm, 550 nm, 560 nm, 570 nm, 580 nm, 590 nm, 600 nm, 610 nm, 610 nm, 620 nm, 630 nm, 640 nm, 650 nm, 660 nm 10nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm or 10μm), 20nm-5μm, 50nm-1μm, 80nm-500nm, or 100nm-300nm. The size of the space is sufficient to fill the piezoelectric micro / nano material with fluid and also sufficient to bend it to generate piezoelectric potential.

[0170] In some embodiments of any of the foregoing aspects, the piezoelectric micro / nano unit and the additional micro / nano unit are each independently a nanorod, a nanosheet, a nanowire, a nanobelt, a nanotube, a nanohelix, or a combination thereof.

[0171] In some embodiments of any of the foregoing aspects, the piezoelectric semiconductor micro / nano material is selected from hexagonal sintered mineral-type piezoelectric materials.

[0172] In some embodiments of any of the foregoing aspects, the hexagonal quartz-type piezoelectric material is selected from ZnO, GaN, ZnS, CdS, InN, InGaN, CdTe, CdSe, ZnSnO3, and combinations thereof.

[0173] In some embodiments of any of the foregoing aspects, the general formula of the perovskite piezoelectric material is ABO3; wherein A is a rare earth or alkaline earth metal ion, and B is a transition metal ion.

[0174] In some embodiments of any of the foregoing aspects, the perovskite piezoelectric material is selected from lead zirconate titanate PZT, barium titanate BaTiO3, potassium sodium niobate KNN, and combinations thereof.

[0175] In some embodiments of any of the foregoing aspects, the polymer piezoelectric material is selected from polyvinylidene fluoride PVDF and polydimethylsiloxane PDMS.

[0176] In some embodiments of any of the foregoing aspects, the piezoelectric micro / nano unit is a ZnO nanoarray.

[0177] In some embodiments of any of the foregoing aspects, the shell material is a metal material, and the work function value of the metal material is greater than or less than the work function value of the piezoelectric semiconductor micro / nano material.

[0178] In some embodiments of any of the foregoing aspects, the shell material is other semiconductor material capable of forming a heterojunction with the piezoelectric semiconductor micro / nano material.

[0179] In some embodiments of any of the foregoing aspects, the shell material is a metal material selected from Au, Pt, Ag, Ti, Al, and combinations thereof.

[0180] In some embodiments of any of the foregoing aspects, the shell material is a semiconductor material selected from CuO, silicon wafer, Cu2O, NiO, Co3O4, and combinations thereof.

[0181] In some embodiments of any of the foregoing aspects, the shell material is formed by magnetron sputtering, electron beam evaporation, thermal evaporation, or sol-geling the shell material on the surface of the upper conductive layer to which the nano units are fixed.

[0182] In some embodiments of any of the foregoing aspects, for example, the piezoelectric micro / nano unit is an n-type ZnO nanoarray, and the shell material is a semiconductor material selected from p-type CuO, p-type silicon wafer, p-type Cu2O, p-type NiO, p-type Co3O4 and combinations thereof.

[0183] In another aspect, the present application provides an article, device or power supply device comprising the energy conversion device of the present disclosure. In some embodiments, the article or device is powered by the energy conversion device.

[0184] On the other hand, the present application provides the use of the energy conversion device of the present disclosure in energy conversion and collection, such as energy storage, sensors, wearable devices, and mobile devices.

[0185] The inventions of this application provide one or more of the following advantages:

[0186] (1) The energy conversion device of the present invention can convert molecular thermal motion into electrical energy output.

[0187] (2) The energy source of the energy conversion device of the present invention is the molecular thermal motion, which is rich and extensive and does not have many usage problems like some other energy sources. It can also be integrated with the device to achieve stable external output of electrical energy.

[0188] (3) The energy conversion device of the present invention is environmentally friendly and can be widely used in power supply devices and items and equipment that require it to provide electrical energy, and has a good application prospect.

[0189] Example

[0190] The following examples are for illustration purposes only and are not intended to limit the scope of this application.

[0191] Example 1

[0192] The following combination Figure 1 , describe in detail the device and its manufacturing method of the present invention, Figure 1 The meanings of the reference numerals in the figures are as follows: 1. ZnO semiconductor piezoelectric nanoarray, 2. metal substrate Zn, 3. metal film Au, 4. liquid n-octane, 5. packaging layer, 6. lead.

[0193] Growth of ZnO nanorod arrays by ethylenediamine vapor method:

[0194] Ultrasonicate a 3cm×3cm Zn sheet in ethanol, acetone, and deionized water for 10 minutes, wash it, and blow it dry with nitrogen. Measure a certain amount of ethylenediamine solution and mix it with deionized water, stir it evenly, and form a 3.75mol / L solution. Pour 30mL of the solution into a weighing bottle, stick the Zn sheet to the inside of the weighing bottle cap, mask it, and cover it on the weighing bottle. After placing the weighing bottle at room temperature for 48 hours, take out the Zn sheet, rinse the surface deposits with deionized water, and blow it dry with nitrogen. Prepare ZnO nanorod arrays that grow along the C axis, with a typical length of ~2.5μm and a diameter of ~60nm.

[0195] Upper electrode preparation

[0196] On the surface of the ZnO nanoarray, a layer of Au film is formed as an upper electrode by magnetron sputtering.

[0197] Add Fluid

[0198] Drop n-octane (electronic grade, purity ≥ 99.999%) onto the surface with ZnO nanoarray and Au plating, so that the liquid fills the entire two surfaces. After padding the surface with ZnO array around the surface, the Au plating surface is turned upside down on it, and a certain force is applied on the top to make it in close contact. The thickness of the pad after applying the above force is not less than the distance from the free end of the piezoelectric nanounit (ZnO array) to the surface of the lower conductive layer (Zn sheet) fixing the piezoelectric nanounit and is less than the sum of the distance from the free end of the piezoelectric nanounit to the surface of the lower conductive layer fixing the piezoelectric nanounit and the distance from the free end of the piezoelectric nanounit to the surface of the upper conductive layer (Zn sheet) fixing the piezoelectric nanounit.

[0199] Encapsulation

[0200] Copper wire leads are used and epoxy resin is quickly used to encapsulate the entire device. After the epoxy resin dries for 5 hours, the entire device is completed.

[0201] The current-voltage curve of the energy conversion device formed by the method provided in this embodiment is as follows: Figure 2 As shown, it shows that it has Schottky characteristics, with the Zn sheet as the positive electrode and Au as the negative electrode. Figure 3 are the voltage and current outputs of the energy conversion device, indicating that the energy conversion device has good power generation characteristics and can convert the thermal motion of liquid molecules into electrical energy output.

[0202] Example 2

[0203] Growth of ZnO nanosheet arrays by ethylenediamine vapor method:

[0204] Ultrasonicate a 3cm×3cm Zn sheet in ethanol, acetone, and deionized water for 10 minutes, wash it, and blow it dry with nitrogen. Measure a certain amount of ethylenediamine solution and mix it with deionized water, stir it evenly, and form a 3.75mol / L solution. Pour 30mL of the solution into a beaker, suspend the Zn sheet above the beaker, and seal it. Place the weighing bottle at room temperature for 48 hours, take out the Zn sheet, rinse the surface deposits with deionized water, and blow it dry with nitrogen. Prepare ZnO nanosheet arrays oriented along the C axis, typically 3.5μm high, 40nm wide, and 250nm long.

[0205] Electrical level preparation

[0206] On the surface of the ZnO array, a layer of Au film was deposited as the upper electrode by magnetron sputtering.

[0207] Add Fluid

[0208] Dimethyl carbonate was dripped onto the surface with ZnO array and Au-plated surface, so that the liquid filled the entire two surfaces. After padding the surface with ZnO array around, the Au-plated surface was turned upside down on it, and a certain force was applied from above to make it in close contact.

[0209] Encapsulation

[0210] Copper wire leads are used and epoxy resin is quickly used to encapsulate the entire device. After the epoxy resin dries for 5 hours, the entire device is completed.

[0211] Figure 4 : is the current and voltage output curve of the device of this embodiment. Figure 5 The cyclic voltammetry curve of the device shows that the device has double-layer capacitance behavior, and its output value may be the superposition of capacitance effect and piezoelectric effect.

[0212] Example 3

[0213] Growth of ZnO nanosheet arrays by ethylenediamine vapor method:

[0214] Ultrasonicate a 3cm×3cm Zn sheet in ethanol, acetone, and deionized water for 10 minutes, wash it, and blow it dry with nitrogen. Measure a certain amount of ethylenediamine solution and mix it with deionized water, stir it evenly, and form a 3.75mol / L solution. Pour 30mL of the solution into a beaker, suspend the Zn sheet above the beaker, and seal it. Place the weighing bottle at room temperature for 48 hours, take out the Zn sheet, rinse the surface deposits with deionized water, and blow it dry with nitrogen. Prepare ZnO nanosheet arrays oriented along the C axis, typically 3.5μm high, ~40nm wide, and ~250nm long.

[0215] Electrical level preparation

[0216] On the surface of the ZnO array, a layer of Au film was deposited as the upper electrode by magnetron sputtering.

[0217] Encapsulation

[0218] After padding the surface with ZnO arrays around, the Au-plated surface is turned upside down on it, and a certain force is applied on the top to make it in close contact. Copper foil leads are quickly encapsulated with epoxy resin under vacuum conditions. After the epoxy resin dries for 5 hours, the entire device is completed.

[0219] Figure 6 The current and voltage output curves of the device of this embodiment are shown in Figure 2. The device of embodiment 3 without encapsulated fluid did not detect effective power output.

[0220] Example 4

[0221] The following combination Figure 7 , describe in detail the device and its manufacturing method of the present invention, Figure 7 The meanings of the reference numerals are as follows: 1. BaTiO3 nanorod array, 2. FTO substrate, 3. aluminum foil, 4. liquid n-octane, 5. encapsulation layer, 6. lead.

[0222] The first step is the hydrothermal synthesis of TiO2 nanoarrays

[0223] Place 3cm×3cm×2.2mm FTO in a mixed solution of distilled water, acetone, and isopropanol with a volume ratio of 1:1:1 and ultrasonically treat for 30 minutes, then rinse with methanol and distilled water. Place FTO vertically in a reactor filled with 10mL distilled water, 10mL hydrochloric acid (concentration 37%), and 1mL titanium isopropoxide mixed solution, and seal it. Place the reactor in an oven at 200℃ for 3h. After the reaction is completed, take out the FTO, cool it to room temperature, rinse it with distilled water, and blow it dry with nitrogen.

[0224] The second step is the synthesis of BaTiO3 nanoarrays by hydrothermal method

[0225] The above substrate was placed in a reactor filled with Ba(OH)2·8H2O solution at 170℃ for 8h. After the reaction, the substrate was taken out, cooled to room temperature, rinsed with distilled water, and dried at room temperature. The TiO2 nanoarray grown on FTO was converted into BaTiO3 nanoarray, which was then placed at 600℃ for 30min to reduce defects. The grown BaTiO3 nanorods were ~1μm long and ~90nm in diameter.

[0226] Device polarization

[0227] Aluminum foil was placed on the FTO with BaTiO3 nanorod array as the upper electrode, the FTO conductive surface was used as the lower electrode, and the copper foil was used as the lead. A 120KV / cm DC voltage was applied between the two electrodes and left for 24 hours.

[0228] Device packaging

[0229] n-Octane was dripped between the upper and lower electrodes to fill the entire upper and lower surfaces, and the entire device was encapsulated with epoxy resin.

[0230] The present invention has been described in detail above with general descriptions and specific embodiments, but it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention and any combination can be made as required. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. An energy conversion device, comprising: an upper conductive layer; a lower conductive layer; It is arranged below the upper conductive layer; at least one piezoelectric micro / nano unit and a fluid disposed between the upper conductive layer and the lower conductive layer; Wherein, the piezoelectric micro / nano unit has piezoelectric properties and is immersed in the fluid; wherein the fluid is a liquid; The energy conversion device further comprises at least one additional micro / nano unit, one end of the piezoelectric micro / nano unit is fixed on the surface of the lower conductive layer facing the upper conductive layer, one end of the additional micro / nano unit is fixed on the surface of the upper conductive layer facing the lower conductive layer, and the other end of the piezoelectric micro / nano unit is a free end, so that the piezoelectric micro / nano unit can contact the additional micro / nano unit when randomly vibrating; The additional micro / nano unit satisfies at least one of the following (i) and (ii): (i) the additional micro / nano unit comprises a material capable of forming a Schottky junction with the piezoelectric micro / nano unit or is composed of a material capable of forming a Schottky junction with the piezoelectric micro / nano unit; (ii) The surface of the additional micro / nano unit is coated with a shell material; the shell material is a material that can form a Schottky junction with the piezoelectric micro / nano unit.

2. The energy conversion device according to claim 1, characterized in that: One end of the piezoelectric micro / nano unit is fixed on the surface of the lower conductive layer facing the upper conductive layer, and the other end is in contact with the upper conductive layer.

3. The energy conversion device according to claim 2, characterized in that: The upper conductive layer covers the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed.

4. The energy conversion device according to claim 1, characterized in that: The other end of the additional micro / nano unit is a free end, and the piezoelectric micro / nano unit on the surface of the lower conductive layer and the additional micro / nano unit on the surface of the upper conductive layer form a fork.

5. The energy conversion device according to claim 1, characterized in that: The micro / nano material in the additional micro / nano unit is the same as or different from the piezoelectric micro / nano material in the piezoelectric micro / nano unit; when the micro / nano material in the additional micro / nano unit is the same as the piezoelectric micro / nano material in the piezoelectric micro / nano unit, the shell material is wrapped on the surface of the additional micro / nano unit.

6. The energy conversion device according to claim 1, characterized in that: The additional micro / nano unit is a non-piezoelectric micro / nano unit.

7. The energy conversion device according to claim 1, characterized in that: The at least one piezoelectric micro / nano unit is more than two piezoelectric micro / nano units, one end of the piezoelectric micro / nano unit is fixed on two surfaces of the upper conductive layer and the lower conductive layer facing each other, and the other end of each piezoelectric micro / nano unit on at least one of the upper conductive layer and the lower conductive layer is a free end, so that the piezoelectric micro / nano unit with a free end on the at least one conductive layer can contact the piezoelectric micro / nano unit on the other conductive layer when randomly vibrating; The surface of the piezoelectric micro / nano unit on the surface of the upper conductive layer or the surface of the piezoelectric micro / nano unit on the surface of the lower conductive layer is wrapped with a shell material; the shell material is a material that can form a Schottky junction with the piezoelectric micro / nano unit.

8. The energy conversion device according to claim 7, characterized in that: The piezoelectric micro / nano units on the surface of the upper conductive layer and the piezoelectric micro / nano units on the surface of the lower conductive layer form a fork.

9. The energy conversion device according to any one of claims 1 to 8, characterized in that: Two surfaces of the upper conductive layer and the lower conductive layer facing each other are substantially parallel.

10. The energy conversion device according to any one of claims 1 to 8, characterized in that: The piezoelectric micro / nano unit and / or the additional micro / nano unit are / is a micro / nano array each time they appear.

11. The energy conversion device according to any one of claims 1 to 8, characterized in that: The piezoelectric micro / nano unit and the additional micro / nano unit are each at least partially immersed or completely immersed in the fluid.

12. The energy conversion device according to any one of claims 1 to 8, characterized in that: The fluid at least partially or completely fills a space between two surfaces of the upper conductive layer and the lower conductive layer facing each other.

13. The energy conversion device according to any one of claims 1 to 8, characterized in that: The fixing is to fix the conductive layer in a direction perpendicular to the surface of the conductive layer.

14. The energy conversion device according to any one of claims 1 to 8, characterized in that: The energy conversion device further comprises a packaging layer, which is arranged on the periphery of the device.

15. The energy conversion device according to claim 14, characterized in that: The encapsulation layer includes an adhesive.

16. The energy conversion device according to claim 15, characterized in that: The adhesive is selected from one or a combination of two or more of epoxy resin, silicone and EVA.

17. The energy conversion device according to any one of claims 1 to 8, characterized in that: The energy conversion device also includes leads; the leads are respectively led out from the upper conductive layer and the lower conductive layer.

18. The energy conversion device according to any one of claims 1 to 8, characterized in that: The fluid is a liquid at an elevated temperature.

19. The energy conversion device of any one of claims 1 to 8, wherein the dielectric constant of the liquid is less than 80.

20. The energy conversion device of any one of claims 1 to 8, wherein the dielectric constant of the liquid is less than 40.

21. An energy conversion device as claimed in any one of claims 1 to 8, wherein the dielectric constant of the liquid is less than 10.

22. The energy conversion device of any one of claims 1 to 8, wherein the dielectric constant of the liquid is less than 4.

0.

23. The energy conversion device of any one of claims 1 to 8, wherein the dielectric constant of the liquid is less than 3.

0.

24. An energy conversion device as claimed in any one of claims 1 to 8, wherein the dielectric constant of the liquid is less than 2.

5.

25. The energy conversion device of any one of claims 1 to 8, wherein the dielectric constant of the liquid is less than 2.

0.

26. The energy conversion device according to any one of claims 1 to 8, wherein the viscosity of the liquid is less than 80000 mPa·s.

27. The energy conversion device according to any one of claims 1 to 8, wherein the viscosity of the liquid is less than 8000 mPa·s.

28. The energy conversion device of any one of claims 1 to 8, wherein the viscosity of the liquid is less than 800 mPa·s.

29. The energy conversion device of any one of claims 1 to 8, wherein the viscosity of the liquid is less than 80 mPa·s.

30. The energy conversion device of any one of claims 1 to 8, wherein the viscosity of the liquid is less than 8 mPa·s.

31. The energy conversion device of any one of claims 1 to 8, wherein the viscosity of the liquid is less than 0.8 mPa·s.

32. The energy conversion device according to any one of claims 1 to 8, characterized in that: The liquid is a non-polar or weakly polar liquid.

33. The energy conversion device according to any one of claims 1 to 8, characterized in that: The liquid is selected from one or a combination of two or more of dimethyl carbonate, diethyl carbonate, tetrachloroethylene, cyclopentene, n-octane, n-hexane, ethanol, and ethylene dichloride.

34. The energy conversion device according to any one of claims 1 to 8, characterized in that: The upper conductive layer and the lower conductive layer each independently include a material selected from the following: one or a combination of two or more of a metal, a carbon material, and a semiconductor material.

35. The energy conversion device according to any one of claims 1 to 8, characterized in that: The upper conductive layer and the lower conductive layer each independently include a material selected from the following: one or a combination of two or more of Au, Pt, Ag, Cu, Zn, ITO, FTO or C.

36. The energy conversion device according to any one of claims 1 to 8, characterized in that: The structures of the upper conductive layer and the lower conductive layer are independently in the form of sheets or nanostructures covered with a conductive film layer.

37. The energy conversion device according to claim 36, characterized in that: The nanostructure is a nanogroove and / or a nanoarray.

38. The energy conversion device according to any one of claims 1 to 8, wherein the minimum radial dimension of at least a portion of the cross section of each of the nano-units along the extension direction thereof is 1 nm to 10 μm.

39. The energy conversion device according to any one of claims 1 to 8, wherein the minimum radial dimension of at least a portion of the cross section of each of the nano-units along the extension direction thereof is 10 nm-1 μm.

40. The energy conversion device according to any one of claims 1 to 8, wherein the minimum radial dimension of at least a portion of the cross section of each of the nano-units along the extension direction thereof is 20 nm-300 nm.

41. The energy conversion device according to any one of claims 1 to 8, wherein the minimum radial dimension of at least a portion of the cross section of each of the nano-units along the extension direction thereof is 10 nm-500 nm.

42. The energy conversion device according to any one of claims 1 to 8, wherein the minimum radial dimension of at least a portion of the cross section of each of the nano-units along the extension direction thereof is 10 nm-100 nm.

43. The energy conversion device according to any one of claims 1 to 8, wherein the piezoelectric micro / nano unit and the additional micro / nano unit are both nano arrays, and the gap between the nano units in the nano array is 5 nm to 20 μm.

44. The energy conversion device according to any one of claims 1 to 8, wherein the piezoelectric micro / nano unit and the additional micro / nano unit are both nano arrays, and the gap between the nano units in the nano array is 20 nm-5 μm.

45. The energy conversion device according to any one of claims 1 to 8, wherein the piezoelectric micro / nano unit and the additional micro / nano unit are both nano arrays, and the gap between the nano units in the nano array is 50 nm-1 μm.

46. ​​The energy conversion device according to any one of claims 1 to 8, wherein the piezoelectric micro / nano unit and the additional micro / nano unit are both nano arrays, and the gap between the nano units in the nano array is 80nm-500nm.

47. The energy conversion device according to any one of claims 1 to 8, wherein the piezoelectric micro / nano unit and the additional micro / nano unit are both nano arrays, and the gap between the nano units in the nano array is 100nm-300nm.

48. The energy conversion device according to any one of claims 1 to 8, characterized in that: The piezoelectric micro / nano unit and / or the additional micro / nano unit are each independently one of nanorods, nanosheets, nanowires, nanobelts, nanotubes or nanohelices, or a combination of two or more thereof.

49. The energy conversion device according to any one of claims 1 to 8, characterized in that: The piezoelectric micro / nano unit contains or consists of a piezoelectric semiconductor micro / nano material.

50. The energy conversion device according to claim 49, characterized in that: The piezoelectric semiconductor micro / nano material is selected from hexagonal quartz-type piezoelectric materials.

51. The energy conversion device according to any one of claims 1 to 8, characterized in that: The piezoelectric micro / nano unit comprises a piezoelectric micro / nano material selected from one or a combination of two or more of hexagonal spar piezoelectric materials, perovskite piezoelectric materials or polymer piezoelectric materials, or is composed of the piezoelectric micro / nano material.

52. The device according to claim 51, characterized in that: The hexagonal fine mineral type piezoelectric material is selected from one or a combination of two or more of ZnO, GaN, ZnS, CdS, InN, InGaN, CdTe, CdSe or ZnSnO3.

53. The energy conversion device according to claim 51, characterized in that: The general formula of the perovskite piezoelectric material is ABO3, wherein A is a rare earth or alkaline earth metal ion, and B is a transition metal ion.

54. The energy conversion device according to claim 51, characterized in that: The perovskite piezoelectric material is selected from one or a combination of two or more of lead zirconate titanate PZT, barium titanate BaTiO3 or potassium sodium niobate KNN.

55. The energy conversion device according to claim 51, characterized in that: The polymer piezoelectric material is selected from polyvinylidene fluoride (PVDF) and / or polydimethylsiloxane (PDMS).

56. The energy conversion device according to any one of claims 1 to 8, characterized in that: The piezoelectric micro / nano unit is a ZnO nano array.

57. The energy conversion device according to claim 49, characterized in that: The shell material is a metal material, and the work function value of the metal material is greater than or less than the work function value of the piezoelectric semiconductor micro / nano material.

58. The energy conversion device according to claim 57, characterized in that: The shell material is a metal or alloy material selected from one or a combination of two or more of Au, Pt, Ag, Ti, Al or C.

59. The energy conversion device according to any one of claims 1 to 8, characterized in that: The shell material is one or a combination of two or more selected from CuO, silicon wafer, Cu2O, NiO or Co3O4.

60. The energy conversion device according to any one of claims 1 to 8, characterized in that: The shell material is formed by magnetron sputtering, electron beam evaporation, thermal evaporation or sol-gel deposition of the shell material on the surface of the upper conductive layer to which the additional micro / nano unit or the piezoelectric micro / nano unit is fixed.

61. A method of manufacturing an energy conversion device as claimed in any one of claims 1 to 60, comprising: providing an upper conductive layer; Providing a lower conductive layer and disposing it below the upper conductive layer; Disposing at least one piezoelectric micro / nano unit and a fluid between the upper conductive layer and the lower conductive layer; immersing the piezoelectric micro / nano unit in the fluid; wherein the fluid is a liquid; The device further comprises an additional micro / nano unit, wherein the additional micro / nano unit satisfies at least one of the following (i) and (ii): (i) the additional micro / nano unit comprises a material capable of forming a Schottky junction with the piezoelectric micro / nano unit or is composed of a material capable of forming a Schottky junction with the piezoelectric micro / nano unit; (ii) the surface of the additional micro / nano unit is coated with a shell material; The shell material is a material capable of forming a Schottky junction with the piezoelectric micro / nano unit; The method further comprises: Fixing step: fixing one end of the piezoelectric micro / nano unit on the surface of the lower conductive layer, and fixing one end of the additional micro / nano unit on the surface of the upper conductive layer, and the other end of the piezoelectric micro / nano unit is a free end.

62. The method of claim 61, wherein: The fixing step includes growing the piezoelectric micro / nano unit on the surface of the lower conductive layer.

63. The method of claim 62, wherein: The other end of the additional micro / nano unit is a free end; the fixing step includes growing the additional micro / nano unit and the piezoelectric micro / nano unit on the surface of the upper conductive layer and the surface of the lower conductive layer, respectively.

64. The method of claim 63, wherein: The growth is oriented vertically to the surface of the conductive layer.

65. The method of claim 61, wherein: The method further comprises: Assembling step: contacting the other end of the fixed piezoelectric micro / nano unit with the upper conductive layer.

66. The method of claim 65, wherein: The fixing step includes growing the piezoelectric micro / nano unit on the surface of the lower conductive layer, and the assembling step includes covering the upper conductive layer on the surface of the lower conductive layer on which the piezoelectric micro / nano unit is grown.

67. The method of claim 65, wherein: The method further comprises: Fluid introducing step: introducing the fluid before, after or during the assembling step.

68. The method of claim 67, wherein: The fluid introducing step includes introducing the fluid to the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed before the assembling step.

69. The method of claim 67, wherein: The fluid introducing step includes introducing the fluid between the upper conductive layer and the lower conductive layer after the assembling step.

70. The method of claim 67, wherein: The fluid introducing step includes performing the assembling step in an atmosphere of the fluid as a gas to introduce the fluid during the assembling process.

71. The method of claim 67, wherein: The piezoelectric micro / nano unit comprises a piezoelectric micro / nano material selected from one or a combination of two or more of hexagonal stilbene piezoelectric materials, perovskite piezoelectric materials, and polymer piezoelectric materials, or is composed of the piezoelectric micro / nano material; when the piezoelectric micro / nano unit comprises a piezoelectric material selected from perovskite piezoelectric materials and / or polymer piezoelectric materials, the device is polarized before the fluid introduction step.

72. The method of claim 71, wherein: The polarization includes applying an electric field between the upper conductive layer and the lower conductive layer, and causing the spontaneous polarization to preferentially orient along the direction of the electric field under the action of the electric field.

73. The method of claim 61, wherein: The method further comprises: Device packaging steps.

74. The method of claim 73, wherein: The device packaging step includes physical packaging or chemical packaging.

75. The method of claim 74, wherein: The packaging is mechanical packaging, or packaging using adhesive or tape.

76. The method of claim 61, wherein: The method further comprises: Wrapping step: when the additional micro / nano unit does not satisfy the above (i), wrapping the shell material on the surface of the additional micro / nano unit; wherein the shell material is a material capable of forming a Schottky junction with the piezoelectric micro / nano unit; Assembling step: assembling in a manner that the surface of the lower conductive layer on which the piezoelectric micro / nano unit is fixed and the surface of the upper conductive layer on which the additional micro / nano unit is fixed face each other, so that the piezoelectric micro / nano unit can contact the additional micro / nano unit when randomly vibrating; wherein, when the additional micro / nano unit does not satisfy the above (i), the upper conductive layer on which the additional micro / nano unit is fixed is the upper conductive layer on which the additional micro / nano unit wrapped by the shell material is fixed; and Fluid introducing step: introducing the fluid before or during the assembling step.

77. The method according to any one of claims 67 to 72 and 76, characterized in that: The assembling step comprises: placing a gasket on the surface of the lower conductive layer to which the piezoelectric micro / nano unit is fixed, wherein the thickness of the gasket or the thickness of the compressed gasket when the gasket is compressed due to force is not less than the distance from the free end of the piezoelectric micro / nano unit to the surface of the lower conductive layer to which the piezoelectric micro / nano unit is fixed and is less than the sum of the distance from the free end of the piezoelectric micro / nano unit to the surface of the lower conductive layer to which the piezoelectric micro / nano unit is fixed and the distance from the free end of the additional micro / nano unit to the surface of the upper conductive layer to which the additional micro / nano unit is fixed; and placing the upper conductive layer to which the additional micro / nano unit is fixed on the gasket, so as to perform the assembling in a manner that the additional micro / nano unit on the surface of the upper conductive layer and the piezoelectric micro / nano unit on the surface of the lower conductive layer form a fork.

78. The method of claim 77, wherein: The fluid introduction step includes introducing the fluid as a liquid into the space surrounded by the entire gasket after the gasket is placed, and then placing the upper conductive layer fixed with the additional micro / nano unit on the gasket, thereby introducing the fluid during the assembly process; wherein when the additional micro / nano unit does not satisfy the above (i), the surface of the upper conductive layer to which the additional micro / nano unit is fixed is the surface of the upper conductive layer to which the additional micro / nano unit wrapped by the shell material is fixed.

79. An article, apparatus or power supply comprising the energy conversion device of any one of claims 1 to 60.

80. The article or apparatus of claim 79, wherein: The article or device is powered by the energy conversion device.

81. Use of the energy conversion device according to any one of claims 1 to 60 in energy conversion and collection.

82. The use according to claim 81, characterized in that: The energy conversion and collection include energy storage, sensors, wearable devices or mobile devices.

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