Potential difference power generation device, preparation method thereof and integrated power generation module

Abstract

The invention discloses a potential difference power generation device, a preparation method thereof and an integrated power generation module. The potential difference power generation device comprises a first electrolytic tank containing an acidic electrolyte and a second electrolytic tank containing an alkaline electrolyte, a first inert electrode and a second inert electrode, one end of the first inert electrode is immersed in the acidic electrolyte, one end of the second inert electrode is immersed in the alkaline electrolyte, the other end of the first inert electrode is connected with the electric load through a wire, and the other end of the second inert electrode is connected with the electric load through a wire; the bipolar membrane is arranged between the acidic electrolyte and the alkaline electrolyte; and the switch is arranged on the wire between the first inert electrode and the electric load or the wire between the second inert electrode and the electric load. The potential difference power generation device only relates to conversion between surrounding environment energy and electric energy, and the electric energy is generated and output through on / off of the external circuit switch. The whole electricity generation process is not limited by specific stimulation environments such as illumination, humidity and temperature.

Description

Technical Field

[0001] The present application belongs to the technical field of potential difference power generation devices, and specifically relates to a potential difference power generation device, a preparation method thereof, and an integrated power generation module. Background Art

[0002] Modern industrial production and research have an increasing demand for electricity. As the supply of fossil fuels gradually decreases, researchers are focusing on building a safe, eco-friendly, efficient and sustainable energy production system. It is well known that the environment is rich in clean energy, and the collection and conversion of these energies can effectively alleviate the problems of energy shortage and environmental pollution. Among them, various advanced energy generation technologies including photovoltaics, thermoelectricity and hydroelectricity have been developed one after another, but they are still limited by specific environmental conditions such as light, temperature difference, humidity, etc., which makes it difficult to achieve stable and continuous power output. In order to promote the practical application value of the power generation system, it is urgent to develop a device that can generate electricity by itself and is not restricted by the environment and region, and through the coupling analysis of device structure design and power generation mechanism, the surrounding environmental energy can be efficiently converted into usable electrical energy. Summary of the invention

[0003] The present application aims to solve one of the technical problems in the related art at least to a certain extent. To this end, the purpose of the present application is to propose a potential difference power generation device and a preparation method thereof and an integrated power generation module.

[0004] In one aspect of the present application, the present application proposes a potential difference power generation device. According to an embodiment of the present application, the potential difference power generation device includes:

[0005] A first electrolytic cell and a second electrolytic cell, wherein the first electrolytic cell contains an acidic electrolyte and the second electrolytic cell contains an alkaline electrolyte;

[0006] A first inert electrode and a second inert electrode, wherein one end of the first inert electrode is immersed in the acidic electrolyte, one end of the second inert electrode is immersed in the alkaline electrolyte, the other end of the first inert electrode is connected to an electric load via a wire, and the other end of the second inert electrode is connected to the electric load via a wire;

[0007] a bipolar membrane, the bipolar membrane being disposed between the acidic electrolyte and the alkaline electrolyte;

[0008] A switch is provided on a wire between the first inertial electrode and the electric load or on a wire between the second inertial electrode and the electric load.

[0009] According to the potential difference power generation device of the embodiment of the present application, the power generation behavior of the present application is realized by combining the asymmetric double electric layer capacitance and potential difference spontaneously induced by the asymmetric electrolyte-electrode interface. Thanks to the strong specific surface area and conductivity of the electrode itself, it can achieve a current output of tens of milliamperes, which has practical application value. At the same time, the potential difference power generation device induced by the asymmetric electrolyte of the present application only involves the conversion between ambient energy and electrical energy, and realizes the generation and output of electrical energy by opening / closing the external circuit switch. The entire power generation process is not limited by specific stimulus environments such as light, humidity, and temperature. This is unmatched by traditional photovoltaic, thermoelectric, wet electric and other power generation devices, and has a wider application space and value.

[0010] In addition, the potential difference power generation device according to the above embodiment of the present application may also have the following additional technical features:

[0011] In some embodiments of the present application, the first inert electrode includes a first current collector and a first composite conductive hydrogel, the first composite conductive hydrogel is arranged on both sides of one end of the first current collector, and the other end of the first current collector is connected to the electrical load through a wire; and / or, the second inert electrode includes a second current collector and a second composite conductive hydrogel, the second composite conductive hydrogel is arranged on both sides of one end of the second current collector, and the other end of the second current collector is connected to the electrical load through a wire.

[0012] In some embodiments of the present application, the first current collector and the second current collector respectively include at least one of gold wire, platinum wire and carbon wire; and / or, the first composite conductive hydrogel includes reduced graphene oxide and carbon nanotubes, and the mass ratio of the reduced graphene oxide to the carbon nanotubes is 1:(0.1~0.3); and / or, the second composite conductive hydrogel includes reduced graphene oxide and carbon nanotubes, and the mass ratio of the reduced graphene oxide to the carbon nanotubes is 1:(0.1~0.3).

[0013] In some embodiments of the present application, the thickness of the first inert electrode and the second inert electrode are respectively 50 μm to 100 μm.

[0014] In some embodiments of the present application, the acidic electrolyte includes at least one of hydrochloric acid solution, sulfuric acid solution, nitric acid solution, hydroiodic acid solution, hydrobromic acid solution, perchloric acid solution, copper sulfate solution, ferric chloride solution, ammonium chloride solution, aluminum chloride solution and ferric sulfate solution; and / or the molar concentration of hydrogen ions in the acidic electrolyte is 0.01 mol / L to 1 mol / L.

[0015] In some embodiments of the present application, the alkaline electrolyte includes at least one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution, a sodium bicarbonate solution, a potassium carbonate solution, a potassium bicarbonate solution, a sodium sulfide solution, a potassium sulfide solution, a sodium hydrosulfide solution, a potassium hydrosulfide solution, a sodium acetate solution, a sodium phosphate solution and a sodium hypochlorite solution; and / or the molar concentration of hydroxide ions in the alkaline electrolyte is 0.01 mol / L to 1 mol / L.

[0016] In some embodiments of the present application, the thickness of the bipolar membrane is 80 μm to 100 μm, and the bipolar membrane includes an anion exchange layer, an intermediate catalytic layer and a cation exchange layer stacked in sequence; and / or the switch includes at least one of a mechanical switch, a light-controlled switch, a temperature-controlled switch, a sound-controlled switch, an infrared sensing switch and a moisture switch.

[0017] In a second aspect of the present application, the present application proposes a method for preparing a potential difference power generation device. According to an embodiment of the present application, the method comprises:

[0018] The graphene oxide dispersion, the carbon nanotube dispersion and the hydrazine hydrate reducing agent are mixed and reacted to obtain a composite conductive hydrogel;

[0019] The composite conductive hydrogel is prepared into a first inert electrode and a second inert electrode respectively;

[0020] Adding an acidic electrolyte into a first electrolytic cell and adding an alkaline electrolyte into a second electrolytic cell, wherein the acidic electrolyte and the alkaline electrolyte are separated by a bipolar membrane;

[0021] Immersing one end of a first inert electrode in the acidic electrolyte, immersing one end of a second inert electrode in the alkaline electrolyte, connecting the other end of the first inert electrode to an electric load through a wire, and connecting the other end of the second inert electrode to the electric load through a wire;

[0022] A switch is provided on a conductive line between the first inertial electrode and the electric load or on a conductive line between the second inertial electrode and the electric load.

[0023] According to the method for preparing a potential difference power generation device in the embodiment of the present application, the electrode preparation method of the present application is a wet pressing method, that is, a tablet press is used to directly press the reduced graphene oxide / carbon nanotube composite conductive hydrogel and the current collector into an integrated self-supporting electrode sheet. Under the action of the surface tension of water, the reduced graphene oxide / carbon nanotube electrode structure after pressing is dense and stable and the conductivity is greatly improved, which is conducive to the charge transfer in the process of self-generation of electricity and power output, and improves the energy conversion efficiency. At the same time, the self-supporting electrode prepared by this method does not contain the conductive agent and binder in the traditional electrode slurry, which can effectively avoid the influence of the conductive agent and binder on the inherent potential of the electrode. At the same time, the asymmetric electrolyte induced potential difference power generation device prepared by the method of the present application only involves the conversion between the ambient energy and the electric energy, and realizes the generation and output of electric energy by opening / closing the external circuit switch. The entire power generation process is not limited by specific stimulus environments such as light, humidity, and temperature, which is unmatched by traditional photovoltaic, thermoelectric, wet electricity and other power generation devices, and has a wider application space and value. In addition, the power generation behavior of the potential difference power generation device prepared by the method of the present application is achieved by combining the asymmetric double layer capacitance and potential difference spontaneously induced by the asymmetric electrolyte-electrode interface. Thanks to the strong specific surface area and conductivity of the electrode itself, it can achieve a current output of tens of milliamperes, which has practical application value.

[0024] In addition, the method for preparing a potential difference power generation device according to the above embodiment of the present application may also have the following additional technical features:

[0025] In some embodiments of the present application, in the mixed solution formed by the graphene oxide dispersion, the carbon nanotube dispersion and the hydrazine hydrate reducing agent, the concentration of the graphene oxide is 1 mg / mL to 3 mg / mL, the concentration of the carbon nanotubes is 0.1 mg / mL to 1 mg / mL, and the concentration of the hydrazine hydrate reducing agent is 0.01 mg / mL to 0.06 mg / mL; and / or the reaction temperature is 160°C to 180°C, and the reaction time is 6h to 8h.

[0026] In the third aspect of the present application, the present application proposes an integrated power generation module. According to an embodiment of the present application, the integrated power generation module has a potential difference power generation device as described in the above embodiment or a potential difference power generation device prepared by the method described in the above embodiment. Therefore, the integrated power generation module has all the advantages of the potential difference power generation device, which will not be repeated here.

[0027] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0029] Figure 1 It is a schematic structural diagram of a potential difference power generation device according to an embodiment of the present application.

[0030] Figure 2 It is a schematic diagram of the process of preparing a dense self-supporting electrode sheet by the wet pressing method proposed in this application.

[0031] Figure 3 It is a curve diagram of voltage and current output of the power generation device of Example 1 of the present application in a cycle in which the circuit is closed for 1 second and opened for 10 minutes.

[0032] Figure 4 It is a curve diagram of voltage and current output of the power generation device of Example 2 of the present application in a cycle in which the circuit is closed for 1 second and opened for 10 minutes.

[0033] Figure 5 It is a curve diagram of voltage and current output of the power generation device of Example 3 of the present application in a cycle in which the circuit is closed for 1 second and opened for 10 minutes.

[0034] Figure 6 It is a schematic diagram of the structure of the integrated power generation module of an embodiment of the present application.

[0035] Figure 7 This is a relationship diagram between the output voltage and output current of the integrated power generation module of Example 4 of the present application.

[0036] Reference numerals:

[0037] 100-potential difference power generation device, 1-first electrolytic cell, 2-second electrolytic cell, 3-acidic electrolyte, 4-alkaline electrolyte, 5-first inert electrode, 5-1-first current collector, 6-second inert electrode, 6-1-second current collector, 7-bipolar membrane, 8-wire, 9-electric load, 10-switch, 1000-integrated power generation module, 200-current collector. DETAILED DESCRIPTION

[0038] Embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present application, and should not be construed as limiting the present application.

[0039] In one aspect of the present application, the present application provides a potential difference power generation device. According to an embodiment of the present application, referring to the attached Figure 1The potential difference power generation device 100 includes: a first electrolytic cell 1 and a second electrolytic cell 2, wherein the first electrolytic cell 1 contains an acidic electrolyte 3, and the second electrolytic cell 2 contains an alkaline electrolyte 4; a first inert electrode 5 and a second inert electrode 6, wherein one end of the first inert electrode 5 is immersed in the acidic electrolyte 3, and one end of the second inert electrode 6 is immersed in the alkaline electrolyte 4, and the other end of the first inert electrode 5 is connected to an electric load 9 through a wire 8, and the other end of the second inert electrode 6 is connected to the electric load 9 through a wire 8; a bipolar membrane 7, wherein the bipolar membrane 7 is arranged between the acidic electrolyte 3 and the alkaline electrolyte 4; and a switch 10, wherein the switch 10 is arranged on the wire 8 between the first inert electrode 5 and the electric load 9 or on the wire 8 between the second inert electrode 6 and the electric load 9.

[0040] That is, the potential difference power generation device 100 includes: a chemically inert symmetrical electrode pair (i.e., a first inert electrode 5 and a second inert electrode 6), an asymmetric electrolyte, a bipolar membrane 7, and a switch 10. The symmetric electrode pair includes an inert electrode material (i.e., a composite conductive hydrogel) and a current collector, respectively, the asymmetric electrolyte is an acidic electrolyte 3 and an alkaline electrolyte 4, respectively, the asymmetric electrolyte is separated by a bipolar membrane 7, the two symmetric electrodes are placed in the asymmetric electrolyte in a face-to-face manner, and the current collector is connected to the switch 10 and the electric load 9 through an external wire 8. The generation and output of reversible electric energy is achieved by controlling the on / off state of the switch 10.

[0041] Among them, the chemical properties of the electrode pair material are stable, and the electrolyte is asymmetric. By placing an inert electrode in an asymmetric electrolyte, an asymmetric intrinsic potential can be generated and an initial potential difference can be formed. In addition, the electrodes and electrolyte in the power generation device are in a static state, and the power generation and discharge process only needs to control the on / off state of the switch 10 to achieve.

[0042] The asymmetric electrolyte-induced potential difference power generation device proposed in the present application is initially opened by controlling the switch 10 to open the entire circuit. At this time, due to the contact between the symmetrical inert electrode pair and the asymmetric electrolyte to form two asymmetric solid-liquid interfaces, the two electrodes carry opposite electrostatic charges and adsorb counterions in the electrolyte to form two asymmetric double layers, thereby generating an initial (inherent) potential difference. When the circuit is closed by controlling the switch 10, electrons flow from the low-potential electrode to the high-potential electrode through the external circuit under the drive of the potential difference. At the same time, the anions / cations adsorbed on the electrode surface are desorbed into the electrolyte body, and the entire circuit generates current until the two electrodes are equipotential (the potential difference is 0). When the switch 10 continues to be disconnected, under the action of the ambient energy, the charges and ions at the asymmetric electrolyte-electrode interface are rearranged to the initial state again and form an inherent potential difference, realizing self-generation. By controlling the intermittent opening / closing process of the switch 10, the power generation device can perform cyclic self-generation behavior.

[0043] The beneficial effects of the potential difference power generation device proposed in this application are described in detail below:

[0044] (1) The electricity generation behavior of the present application is achieved by combining the asymmetric double-layer capacitance and potential difference spontaneously induced by the asymmetric electrolyte-electrode interface. Thanks to the strong specific surface area and conductivity of the electrode itself, a current output of tens of milliamperes can be achieved, which has practical application value.

[0045] (2) The asymmetric electrolyte-induced potential difference power generation device of the present application only involves the conversion between ambient energy and electric energy, and realizes the generation and output of electric energy by opening / closing the external circuit switch. The entire power generation process is not limited by specific stimulus environments such as light, humidity, and temperature, which is unmatched by traditional photovoltaic, thermoelectric, wet electric and other power generation devices, and has a wider application space and value.

[0046] According to some specific embodiments of the present application, the first inert electrode 5 includes a first current collector 5-1 and a first composite conductive hydrogel, the first composite conductive hydrogel is arranged on both sides of one end of the first current collector 5-1, and the other end of the first current collector 5-1 is connected to the electrical load 9 through a wire 8; and / or, the second inert electrode 6 includes a second current collector 6-2 and a second composite conductive hydrogel, the second composite conductive hydrogel is arranged on both sides of one end of the second current collector 6-2, and the other end of the second current collector 6-2 is connected to the electrical load 9 through a wire 8.

[0047] According to some further specific embodiments of the present application, the first current collector 5 - 1 and the second current collector 6 - 1 respectively include at least one of gold wire, platinum wire and carbon wire, preferably gold wire with strong chemical stability and high conductivity.

[0048] According to some other specific embodiments of the present application, the first composite conductive hydrogel includes reduced graphene oxide and carbon nanotubes, and the mass ratio of reduced graphene oxide to carbon nanotubes is 1:(0.1-0.3), for example, it can be 1:0.1, 1:0.2, 1:0.3, etc., and the first composite conductive hydrogel formed thereby has the advantages of large specific surface area, strong chemical stability, and high conductivity. And / or, the second composite conductive hydrogel includes reduced graphene oxide and carbon nanotubes, and the mass ratio of reduced graphene oxide to carbon nanotubes is 1:(0.1-0.3), for example, it can be 1:0.1, 1:0.2, 1:0.3, etc., and the second composite conductive hydrogel formed thereby has the advantages of large specific surface area, strong chemical stability, and high conductivity.

[0049] According to some specific embodiments of the present application, the thickness of the first inert electrode 5 and the second inert electrode 6 are respectively 50 μm to 100 μm, for example, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, etc.

[0050] In the embodiments of the present application, the specific type of the above-mentioned acidic electrolyte is not particularly limited, and those skilled in the art can select it according to actual needs. As some specific embodiments, the acidic electrolyte includes at least one of hydrochloric acid solution, sulfuric acid solution, nitric acid solution, hydroiodic acid solution, hydrobromic acid solution, perchloric acid solution, copper sulfate solution, ferric chloride solution, ammonium chloride solution, aluminum chloride solution and ferric sulfate solution. Further, the molar concentration of hydrogen ions in the above-mentioned acidic electrolyte is 0.01mol / L to 1mol / L, for example, it can be 0.01mol / L, 0.05mol / L, 0.1mol / L, 0.5mol / L, 1mol / L, etc.

[0051] In the embodiments of the present application, the specific types of the alkaline electrolyte are not particularly limited, and those skilled in the art can select according to actual needs. As some specific embodiments, the alkaline electrolyte includes at least one of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, potassium carbonate solution, potassium bicarbonate solution, sodium sulfide solution, potassium sulfide solution, sodium hydrosulfide solution, potassium hydrosulfide solution, sodium acetate solution, sodium phosphate solution and sodium hypochlorite solution. Further, the molar concentration of hydroxide ions in the alkaline electrolyte is 0.01 mol / L to 1 mol / L, for example, 0.01 mol / L, 0.05 mol / L, 0.1 mol / L, 0.5 mol / L, 1 mol / L, etc.

[0052] According to some specific embodiments of the present application, the thickness of the bipolar membrane is 80 μm to 100 μm, and the bipolar membrane includes an anion exchange layer, an intermediate catalyst layer and a cation exchange layer stacked in sequence, and has excellent mechanical properties. The bipolar membrane can effectively isolate the acidic / alkaline asymmetric electrolyte and promote the intermediate catalyst layer to decompose water into H under reverse bias. + and OH - , thereby ensuring the stability of the acid / alkaline electrolyte and achieving the effective construction of the asymmetric electrode-electrolyte interface.

[0053] In the embodiments of the present application, the types of switches connected to the above-mentioned external circuit include but are not limited to mechanical switches, light-controlled switches, temperature-controlled switches, voice-controlled switches, infrared sensing switches, moisture switches, etc.; the switch control methods include but are not limited to mechanical movement, sound, light, heat, humidity and other stimuli.

[0054] In a second aspect of the present application, the present application proposes a method for preparing the above-mentioned potential difference power generation device. According to an embodiment of the present application, the method comprises the following steps:

[0055] S100: mixing a graphene oxide dispersion, a carbon nanotube dispersion and a hydrazine hydrate reducing agent, reacting to obtain a composite conductive hydrogel;

[0056] In this step, a graphene oxide dispersion, a carbon nanotube dispersion and a hydrazine hydrate reducing agent are mixed as reaction raw materials, and a solvent thermal method is used to prepare a high-reduction-degree reduced graphene oxide (rGO) / carbon nanotube (CNT) three-dimensional structure composite conductive hydrogel through a high-temperature thermal reduction and π-π stacking cross-linking process.

[0057] According to some specific embodiments of the present application, in the mixed solution formed by the graphene oxide dispersion, the carbon nanotube dispersion and the hydrazine hydrate reducing agent, the concentration of graphene oxide is 1 mg / mL to 3 mg / mL (for example, it can be 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, etc.), the concentration of carbon nanotubes is 0.1 mg / mL to 1 mg / mL (for example, it can be 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.7 mg / mL, 0.9 mg / mL, 1 mg / mL, etc.), and the concentration of the hydrazine hydrate reducing agent is 0.01 mg / mL to 0.06 mg / mL (for example, it can be 0.01 mg / mL, 0.02 mg / mL, 0.04 mg / mL, 0.06 mg / mL, etc.), thereby further ensuring the formation of a composite conductive hydrogel with a large specific surface area, strong chemical stability and high conductivity.

[0058] According to some further specific embodiments of the present application, the reaction temperature is 160°C to 180°C (for example, it can be 160°C, 165°C, 170°C, 175°C, 180°C, etc.), and the reaction time is 6h to 8h (for example, it can be 6h, 6.5h, 7h, 7.5h, 8h, etc.), thereby further ensuring that a highly reduced reduced graphene oxide (rGO) / carbon nanotube (CNT) three-dimensional structure composite conductive hydrogel is prepared through high-temperature thermal reduction and π-π stacking cross-linking process.

[0059] In an embodiment of the present application, the composite conductive hydrogel formed by the above method includes reduced graphene oxide and carbon nanotubes, and the mass ratio of reduced graphene oxide to carbon nanotubes is 1:(0.1~0.3). The composite conductive hydrogel thus formed has the advantages of large specific surface area, strong chemical stability and high conductivity.

[0060] S200: preparing the composite conductive hydrogel into a first inert electrode and a second inert electrode respectively;

[0061] In this step, the composite conductive hydrogel can be cut into a rectangular shape by using an ultraviolet laser cutting system; two composite conductive hydrogel blocks sandwiching a current collector (such as a gold wire) are pressed into an electrode sheet with a thickness of 50 μm to 100 μm by using a tablet press.

[0062] In an embodiment of the present application, the thickness of the first inert electrode and the second inert electrode can be adjusted according to their interface capacitance in the corresponding electrolyte, that is, the chemical stability of the electrolyte during the power generation process is ensured by matching the electrode interface capacitance. As a specific example, the initial length and width of the composite conductive hydrogel block are 2cm×2cm, the initial thickness is adjusted between 0.5cm and 3cm, and the diameter of the current collector filament is 0.1mm.

[0063] S300: adding an acidic electrolyte into a first electrolytic cell and adding an alkaline electrolyte into a second electrolytic cell, wherein the acidic electrolyte and the alkaline electrolyte are separated by a bipolar membrane;

[0064] In this step, two electrolytes can be added to H-type electrolytic cells respectively, wherein the acidic electrolyte is added to the first electrolytic cell and the alkaline electrolyte is added to the second electrolytic cell, and they are separated by a bipolar membrane.

[0065] S400: immersing one end of the first inert electrode in an acidic electrolyte, immersing one end of the second inert electrode in an alkaline electrolyte, connecting the other end of the first inert electrode to an electrical load through a wire, and connecting the other end of the second inert electrode to an electrical load through a wire;

[0066] In this step, the two prepared symmetrical electrode sheets can be placed in two chambers respectively, that is, one end of the first inert electrode is immersed in an acidic electrolyte, and one end of the second inert electrode is immersed in an alkaline electrolyte. The current collector is led out and the chamber cover is covered to form a power generation device. The two current collectors are connected to the control switch and the electrical load of the external circuit to realize a cyclic power generation process.

[0067] S500: Setting a switch on a conductive line between the first inertial electrode and the electric load or on a conductive line between the second inertial electrode and the electric load.

[0068] In this step, a switch is provided on the wire between the first inert electrode and the electric load or on the wire between the second inert electrode and the electric load, and the two current collectors are connected to the control switch of the external circuit and the electric load to realize a cyclic electricity generation process.

[0069] The method for preparing a potential difference power generation device according to an embodiment of the present application has at least one of the following advantages:

[0070] (1) The electrode preparation method of the present application is a wet pressing method, that is, using a tablet press to directly press the reduced graphene oxide / carbon nanotube composite conductive hydrogel and the current collector into an integrated self-supporting electrode sheet, as shown in the attached Figure 2As shown. Under the action of water surface tension, the reduced graphene oxide / carbon nanotube electrode structure after pressing is dense and stable, and the conductivity is greatly improved, which is conducive to charge transfer in the process of self-generation and power output, and improves energy conversion efficiency. At the same time, the self-supporting electrode prepared by this method does not contain the conductive agent and binder in the traditional electrode slurry, which can effectively avoid the influence of the conductive agent and binder on the inherent potential of the electrode.

[0071] (2) The asymmetric electrolyte-induced potential difference power generation device prepared by the method of the present application only involves the conversion between ambient energy and electric energy, and realizes the generation and output of electric energy by opening / closing the external circuit switch. The entire power generation process is not limited by specific stimulus environments such as light, humidity, and temperature, which is unmatched by traditional photovoltaic, thermoelectric, wet electric and other power generation devices, and has a wider application space and value.

[0072] (3) The power generation behavior of the potential difference power generation device prepared by the method of the present application is achieved by combining the asymmetric double layer capacitance and potential difference spontaneously induced by the asymmetric electrolyte-electrode interface. Thanks to the strong specific surface area and conductivity of the electrode itself, it can achieve a current output of tens of milliamperes, which has practical application value.

[0073] In the third aspect of the present application, the present application proposes an integrated power generation module. According to the embodiments of the present application, referring to the attached Figure 6 The integrated power generation module 1000 has the above potential difference power generation device 100 or the above potential difference power generation device 100 made by the above method. Therefore, the integrated power generation module has all the advantages of the potential difference power generation device, which will not be repeated here.

[0074] Specifically, the integrated power generation module 1000 includes a plurality of potential difference power generation devices 100 connected in series and / or in parallel, and the electrodes between the potential difference power generation devices 100 connected in series and / or in parallel are connected through the current collector 200. The voltage output of the integrated power generation module 1000 increases linearly with the increase in the number of potential difference power generation devices 100 connected in series, and the current output thereof increases with the increase in the number of devices connected in parallel, thereby achieving available voltage and current output.

[0075] The embodiments of the present application are described in detail below. It should be noted that the embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. In addition, unless otherwise explicitly stated, all reagents used in the following embodiments are commercially available or can be synthesized according to this article or known methods, and the reaction conditions not listed are also easily available to those skilled in the art.

[0076] Example 1

[0077] This embodiment provides a potential difference power generation device, and the preparation method thereof is as follows:

[0078] (1) Preparation of graphene oxide and highly conductive self-supporting electrode sheets:

[0079] 1) Preparation of graphene oxide dispersion: GO dispersion was prepared by the improved Hummers method. First, 240 mL of concentrated sulfuric acid was measured, added to a 2 L beaker and cooled using an ice water bath. 9 g of graphene and 9 g of sodium nitrate were weighed and slowly added to the concentrated sulfuric acid, and stirred magnetically for 2 h. After mixing evenly, 27 g of potassium permanganate was weighed and slowly added to the beaker in batches, and stirred in an ice water bath for 1 h. Then the water bath was heated to 35 ° C and stirred for 1.5 h. Then 400 mL of deionized water was slowly added, heated to 80 ° C and kept warm. After stirring for 20 min, 1 L of deionized water was added. When the solution was cooled to room temperature, 60 mL of hydrogen peroxide was added to the beaker and stirred to react to remove the residual potassium permanganate. Gas was released during this process to obtain a brown-yellow mixed solution. Further, the mixed solution obtained in the previous step was allowed to stand overnight, and after the solid in the beaker was naturally settled, it was filtered using a Buchner funnel and filter paper. After the filtration is completed, add a mixture of 200mL of hydrochloric acid and 200mL of deionized water, and use the mixed solution to wash the filter cake. Thereafter, use a mixture of 100mL of hydrochloric acid and 900mL of deionized water to wash the filter cake again. After washing with the mixed solution, add deionized water to soak the filter cake, and then place the filter cake in 700mL of deionized water and mechanically stir for 6h to obtain a GO dispersion. After stirring, centrifuge at 3000r / min for 30min to remove the precipitate to obtain a brown-yellow GO dispersion. Further, the GO dispersion is placed in a dialysis bag for dialyzation until the conductivity of the aqueous solution after dialysis is lower than 10μScm -1 , a pure GO dispersion was obtained.

[0080] 2) Preparation of rGO / CNT hydrogel: Graphene oxide dispersion, carbon nanotube dispersion and hydrazine hydrate were mixed as reaction raw materials, the concentration of graphene oxide in the mixed solution was 3 mg / mL, the concentration of carbon nanotubes in the mixed solution was 0.3 mg / mL, and the concentration of hydrazine hydrate in the mixed solution was 0.03 mg / mL. A highly reduced rGO / CNT composite hydrogel was prepared by a 180°C solvothermal process.

[0081] 3) Preparation of highly conductive self-supporting electrode sheets: The rGO / CNT composite conductive hydrogel was cut into sheet-shaped blocks with an initial length and width of 2 cm×2 cm and an initial thickness of 0.5 cm to 3 cm using a UV laser cutting system, and two composite conductive hydrogel blocks sandwiched with a gold wire with a diameter of 0.1 mm were pressed into electrode sheets with a thickness of 80 μm using a tablet press.

[0082] (2) Device assembly: The customized dual-chamber electrolytic cell and bipolar membrane were assembled and fixed. The dual chambers of the electrolytic cell were separated by a bipolar membrane. Then, 5 mL of a 1 mol / L hydrochloric acid electrolyte and a 1 mol / L sodium hydroxide electrolyte prepared in advance were dripped into the designated chambers of the electrolytic cell using a pipette. The two prepared symmetrical electrode sheets (80 μm thick) were placed in the two chambers, respectively. The gold wire current collectors were led out and the chamber lids were covered to form a power generation device. The two current collectors were connected to the control switch and load of the external circuit to realize a cyclic power generation process.

[0083] (3) Power generation performance test: Under ambient conditions, a Keithley 2612 digital source meter was used to measure the power generation of the device. The current of the voltage output test circuit parameters was set to 0 nA, and the voltage of the current output test circuit parameters was set to 0 V.

[0084] In this embodiment, the asymmetric electrolyte-induced potential difference power generation device is in the open circuit state, and the 80 μm thick symmetric rGO / CNT (m rGO :m CNT =1:0.1) The initial potential difference of the self-supporting electrode in 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide asymmetric solution is about 0.68V. Figure 3 As shown in Figure 2, when the switch is closed for 1 second, the open circuit voltage of the power-generating device drops to about 0V and the peak short-circuit current is 3.2mA / cm 2 When the switch is turned off again, the open circuit voltage of the power-generating device basically recovers to the initial open circuit voltage after about 10 minutes. Therefore, the reversible power generation and recovery process of the power-generating device is controlled by controlling the cyclic operation of closing the switch for 1 second and opening it for 20 minutes, and the power-generating device shows good cycle stability during long-term power generation.

[0085] Example 2

[0086] This embodiment provides a potential difference power generation device, and its preparation method is basically the same as that of embodiment 1, except that:

[0087] (2) Device assembly: The customized dual-chamber electrolytic cell and bipolar membrane were assembled and fixed. The dual chambers of the electrolytic cell were separated by a bipolar membrane. Then, 5 mL of a 1 mol / L hydrochloric acid electrolyte and a 1 mol / L sodium hydroxide electrolyte prepared in advance were dripped into the designated chambers of the electrolytic cell using a pipette. The two prepared symmetrical electrode sheets (50 μm thick) were placed in the two chambers, respectively. The gold wire current collectors were led out and the chamber lids were covered to form a power generation device. The two current collectors were connected to the control switch and load of the external circuit to realize a cyclic power generation process.

[0088] In this embodiment, the asymmetric electrolyte-induced potential difference power generation device is in the open circuit state, and the 50 μm thick symmetric rGO / CNT (m rGO :m CNT =1:0.1) The initial potential difference of the self-supporting electrode in 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide asymmetric solution is about 0.68V. Figure 4 As shown in Figure 2, when the switch is closed for 1 second, the open circuit voltage of the power-generating device drops to about 0V and the peak short-circuit current is 2.5mA / cm 2 When the switch is turned off again, the open circuit voltage of the power-generating device basically recovers to the initial open circuit voltage after about 10 minutes. Therefore, the reversible power generation and recovery process of the power-generating device is controlled by controlling the cyclic operation of closing the switch for 1 second and opening it for 20 minutes, and the power-generating device shows good cycle stability during long-term power generation.

[0089] Example 3

[0090] This embodiment provides a potential difference power generation device, and its preparation method is basically the same as that of embodiment 1, except that:

[0091] 2) Preparation of rGO / CNT hydrogel: Graphene oxide dispersion, carbon nanotube dispersion and hydrazine hydrate were mixed as reaction raw materials, the concentration of graphene oxide in the mixed solution was 1 mg / mL, the concentration of carbon nanotubes in the mixed solution was 0.3 mg / mL, and the concentration of hydrazine hydrate in the mixed solution was 0.03 mg / mL. A highly reduced rGO / CNT composite hydrogel was prepared by a 180°C solvothermal process.

[0092] In this embodiment, the asymmetric electrolyte-induced potential difference power generation device is in the open circuit state, and the 80 μm thick symmetric rGO / CNT (m rGO :m CNT =1:0.3) The initial potential difference of the self-supporting electrode in 1 mol / L hydrochloric acid and 1 mol / L sodium hydroxide asymmetric solution is about 0.68 V. Figure 5 As shown in Figure 2, when the switch is closed for 1 second, the open circuit voltage of the power-generating device drops to about 0V and the peak short-circuit current is 3.5mA / cm 2 When the switch is turned off again, the open circuit voltage of the power-generating device basically recovers to the initial open circuit voltage after about 10 minutes. Therefore, the reversible power generation and recovery process of the power-generating device is controlled by controlling the cyclic operation of closing the switch for 1 second and opening it for 20 minutes, and the power-generating device shows good cycle stability during long-term power generation.

[0093] Example 4

[0094] The asymmetric electrolyte-induced potential difference power generation device prepared in Example 1 is designed to be connected in series as an integrated power generation module, such as Figure 6 As shown. The electrodes between the series devices are connected by gold wire current collectors. The output voltage and current of the integrated power generation module are shown in Figure 7 shown.

[0095] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0096] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. A potential difference power generation device, characterized in that: include: A first electrolytic cell and a second electrolytic cell, wherein the first electrolytic cell contains an acidic electrolyte and the second electrolytic cell contains an alkaline electrolyte; A first inert electrode and a second inert electrode, wherein one end of the first inert electrode is immersed in the acidic electrolyte, one end of the second inert electrode is immersed in the alkaline electrolyte, the other end of the first inert electrode is connected to an electric load via a wire, and the other end of the second inert electrode is connected to the electric load via a wire; a bipolar membrane, the bipolar membrane being disposed between the acidic electrolyte and the alkaline electrolyte; A switch is provided on a wire between the first inertial electrode and the electric load or on a wire between the second inertial electrode and the electric load.

2. The potential difference power generation device according to claim 1, characterized in that: The first inert electrode comprises a first current collector and a first composite conductive hydrogel, wherein the first composite conductive hydrogel is disposed on both sides of one end of the first current collector, and the other end of the first current collector is connected to the electrical load through a wire; And / or, the second inert electrode includes a second current collector and a second composite conductive hydrogel, the second composite conductive hydrogel is arranged on both sides of one end of the second current collector, and the other end of the second current collector is connected to the electrical load through a wire.

3. The potential difference power generation device according to claim 2, characterized in that: The first current collector and the second current collector respectively include at least one of a gold wire, a platinum wire and a carbon wire; And / or, the first composite conductive hydrogel comprises reduced graphene oxide and carbon nanotubes, and the mass ratio of the reduced graphene oxide to the carbon nanotubes is 1:(0.1-0.3); And / or, the second composite conductive hydrogel comprises reduced graphene oxide and carbon nanotubes, and the mass ratio of the reduced graphene oxide to the carbon nanotubes is 1:(0.1-0.3).

4. The potential difference power generation device according to claim 1, characterized in that: The thickness of the first inert electrode and the second inert electrode is 50 μm to 100 μm respectively.

5. The potential difference power generation device according to any one of claims 1 to 4, characterized in that: The acidic electrolyte includes at least one of hydrochloric acid solution, sulfuric acid solution, nitric acid solution, hydroiodic acid solution, hydrobromic acid solution, perchloric acid solution, copper sulfate solution, ferric chloride solution, ammonium chloride solution, aluminum chloride solution and ferric sulfate solution; And / or, the molar concentration of hydrogen ions in the acidic electrolyte is 0.01 mol / L to 1 mol / L.

6. The potential difference power generation device according to any one of claims 1 to 4, characterized in that: The alkaline electrolyte comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution, a sodium bicarbonate solution, a potassium carbonate solution, a potassium bicarbonate solution, a sodium sulfide solution, a potassium sulfide solution, a sodium hydrosulfide solution, a potassium hydrosulfide solution, a sodium acetate solution, a sodium phosphate solution and a sodium hypochlorite solution; And / or, the molar concentration of hydroxide ions in the alkaline electrolyte is 0.01 mol / L to 1 mol / L.

7. The potential difference power generation device according to any one of claims 1 to 4, characterized in that: The bipolar membrane has a thickness of 80 μm to 100 μm, and comprises an anion exchange layer, an intermediate catalyst layer and a cation exchange layer stacked in sequence; And / or, the switch includes at least one of a mechanical switch, a light-controlled switch, a temperature-controlled switch, a voice-controlled switch, an infrared sensor switch and a moisture switch.

8. A method for preparing a potential difference power generation device according to any one of claims 1 to 7, characterized in that: include: The graphene oxide dispersion, the carbon nanotube dispersion and the hydrazine hydrate reducing agent are mixed and reacted to obtain a composite conductive hydrogel; The composite conductive hydrogel is prepared into a first inert electrode and a second inert electrode respectively; Adding an acidic electrolyte into a first electrolytic cell and adding an alkaline electrolyte into a second electrolytic cell, wherein the acidic electrolyte and the alkaline electrolyte are separated by a bipolar membrane; Immersing one end of a first inert electrode in the acidic electrolyte, immersing one end of a second inert electrode in the alkaline electrolyte, connecting the other end of the first inert electrode to an electric load through a wire, and connecting the other end of the second inert electrode to the electric load through a wire; A switch is provided on a conductive line between the first inertial electrode and the electric load or on a conductive line between the second inertial electrode and the electric load.

9. The method for preparing a potential difference power generation device according to claim 8, characterized in that: In the mixed solution formed by the graphene oxide dispersion, the carbon nanotube dispersion and the hydrazine hydrate reducing agent, the concentration of the graphene oxide is 1 mg / mL to 3 mg / mL, the concentration of the carbon nanotube is 0.1 mg / mL to 1 mg / mL, and the concentration of the hydrazine hydrate reducing agent is 0.01 mg / mL to 0.06 mg / mL; And / or, the reaction temperature is 160° C. to 180° C., and the reaction time is 6 h to 8 h.

10. An integrated power generation module, characterized in that: A potential difference power generation device according to any one of claims 1 to 7 or a potential difference power generation device produced by the method according to claim 8 or 9.

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