WO2020147443A1 - Moisture power generation method and equipment - Google Patents

Abstract

A moisture power generation method and equipment. The method comprises the following steps: pouring a polymer solution into a culture dish and then placing same in an oven to prepare a polymer power generation film (100) (S101); placing the polymer power generation film (100) on a moisture insulated metal electrode (200), and providing a porous top electrode (300) above the polymer power generation film (100) so as to protect the film form of the polymer power generation film (100) and transmit moisture (S102); applying moisture stimulation to the outside of the metal electrode (200) in a single direction, so as to induce the separation of positive and negative ion pairs inside the polymer power generation film (100) and release free moving carriers (S103); and generating a potential difference and current by means of diffusion of carriers from a high concentration region to a low concentration region, thereby outputting electric power to the outside (S104). In the present method, simple and easily available polymer materials which may be bent, stretched and even self-repaired are employed; at the same time, directional moisture stimulation is employed to be able to implement moisture control without requiring assistance from a laser which is expensive to construct; the present method has the advantage of large-scale integration thanks to the simple testing means and the lack of requirement of other expensive external equipment in the testing process.

Description

Moisture power generation method and device

Cross-reference of related applications

This application claims the priority of the Chinese patent application number "201910051173.9" filed by Tsinghua University on January 18, 2019 with the invention title "Method and Device for Wet Gas Power Generation".

Technical field

The present invention relates to the technical field of functional materials, in particular to a method and device for generating electricity by wet gas.

Background technique

Polymer materials generally have large molecular weight, low density, high mechanical properties, good wear resistance, corrosion resistance and other characteristics, and can be assembled to form flexible, stretchable, and optically transparent films. A functional material is widely used in industrial production and daily life.

Studies have shown that by stimulating a specific material with unidirectional moisture, it can induce the separation of positive and negative ion pairs inside the material, thereby generating electrical energy in the external circuit. This power generation method is green, stable and sustainable, and is expected to become the next generation of green energy collection technology. In related technologies, this power generation method mainly relies on graphene-based materials that are expensive, cumbersome in manufacturing processes, and severely polluted, while related studies based on polymer materials have not been reported.

Summary of the invention

The present invention aims to solve one of the technical problems in the related art at least to a certain extent.

To this end, an object of the present invention is to provide a wet gas power generation method that is simple, efficient, green, sustainable, and recyclable.

Another object of the present invention is to provide a wet gas power generation device.

In order to achieve the above objective, one aspect of the present invention proposes a moisture power generation method, which includes the following steps: pouring the polymer solution into a petri dish and placing it in an oven to prepare a polymer power generation membrane; On a moisture-insulated metal electrode, a porous top electrode is arranged above the polymer power generation membrane to protect the thin film form of the polymer power generation membrane and transmit moisture; by applying unidirectional externally to the metal electrode Moisture stimulation is used to induce the separation of positive and negative ion pairs inside the polymer power generation membrane to release freely moving carriers; and the carriers diffuse from a high concentration area to a low concentration area to generate a potential difference and current, Then output electric energy to the outside.

Compared with the traditional electrochemical moisture polarization method and laser directional reduction method, the moisture power generation method of the embodiment of the present invention can achieve good moisture control by the directional moisture stimulation method without the need for expensive lasers. , The test method is simple, and the test process does not need to resort to other expensive external equipment, which has the advantage of large-scale integration.

In addition, the wet gas power generation method according to the above embodiment of the present invention may also have the following additional technical features:

Further, in an embodiment of the present invention, the step of pouring the polymer solution into a petri dish and placing it in an oven to prepare a polymer film for generating electricity includes: adding the solid content of the polymer solution in the range of 0.1%-30% The polymer solution is poured into a petri dish, and placed in an oven at a preset temperature, so that the polymer power generation membrane is formed after the polymer solution is volatilized.

Optionally, in an embodiment of the present invention, the polymer solution is poly 4-styrene sulfonic acid, poly 4-styrene sulfonate sodium, perfluorosulfonic acid, polyvinyl alcohol, polyacrylic acid, polyacrylic acid Any one or more of sodium, sodium alginate, hydroxyethyl cellulose and dopamine in a complex form.

Further, in an embodiment of the present invention, the method further includes: adjusting the volume of the polymer solution to adjust the thickness of the polymer power generation film to a target thickness.

Further, in an embodiment of the present invention, the temperature for preparing the polymer power generating membrane is 25° C. to 90° C., and the drying time is 2 hours to 12 hours.

Optionally, in an embodiment of the present invention, the materials of the metal electrode and the porous top electrode are gold, silver, copper, aluminum, titanium, chromium, iron, ITO glass, FTO glass, silver paste, Any of carbon cloth, carbon nanotube electrodes, and silver nanowires.

Further, in an embodiment of the present invention, the variation range of the moisture application is 5% to 100%, and the temperature range of the moisture variation is 5°C to 95°C.

In order to achieve the above objective, another aspect of the present invention provides a moisture power generation device, including: a polymer power generation membrane and a metal electrode, the polymer power generation membrane is placed above the metal electrode, and used for opposing the metal electrode Moisture stimulus is applied in a single direction to induce the separation of positive and negative ion pairs inside the polymer power generation membrane, releasing freely moving carriers, which diffuse from the high concentration area to the low concentration area to produce The electric potential difference and current are used to output electric energy to the outside; a porous top electrode, the porous top electrode is placed above the polymer power generation membrane, and is used to protect the film form of the polymer power generation membrane and transmit moisture.

The moisture power generation device of the embodiment of the present invention can output considerable voltage and current, and the output current value is the highest among related reports of moisture power generation materials, and the generated electric energy can be stored in a commercial capacitor as a consumer Power supply, showing excellent electrical characteristics, and the moisture power generation device constructed based on polymer materials has good moisture self-healing characteristics, and can achieve good device performance recovery after damage, showing potential utility Value and application prospects.

In addition, the wet gas power generation device according to the above embodiment of the present invention may also have the following additional technical features:

Further, in an embodiment of the present invention, the preparation process of the polymer power generation membrane is: pour the polymer solution with a solid content ranging from 0.1% to 30% into a petri dish and place it at a preset temperature. In the oven, the polymer power generating membrane is generated after the polymer solution is volatilized.

Optionally, in an embodiment of the present invention, the materials of the metal electrode and the porous top electrode are gold, silver, copper, aluminum, titanium, chromium, iron, ITO glass, FTO glass, silver paste, Any of carbon cloth, carbon nanotube electrodes, and silver nanowires.

The additional aspects and advantages of the present invention will be partially given in the following description, and some will become obvious from the following description, or be understood through the practice of the present invention.

BRIEF DESCRIPTION

The above and/or additional aspects and advantages of the present invention will become apparent and easy to understand from the following description of the embodiments in conjunction with the accompanying drawings, in which:

Fig. 1 is a flowchart of a wet gas power generation method according to an embodiment of the present invention;

Figure 2 is a schematic structural diagram of a wet gas power generation device according to an embodiment of the present invention;

Figure 3 is a photograph of a polymer power generating membrane according to an embodiment of the present invention;

Figure 4 is a scanning electron micrograph of a polymer power generating membrane according to an embodiment of the present invention;

Figure 5 is a diagram of a voltage signal generated by a moisture power generation device of an embodiment of the present invention under stimulation of 80% humidity;

Fig. 6 is a diagram of the current signal generated by the moisture power generation device of an embodiment of the present invention under the stimulation of 80% humidity;

Figure 7 is a self-repairing photo of a wet gas power generation device according to an embodiment of the present invention;

8 is a test performance diagram of a wet gas power generation device before and after self-repair according to an embodiment of the present invention;

Fig. 9 is a test performance diagram of a wet gas power generation device according to an embodiment of the present invention under bending conditions.

detailed description

The embodiments of the present invention are described in detail below. Examples of the embodiments are shown in the accompanying drawings, in which the same or similar reference numerals indicate the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary, and are intended to explain the present invention, but should not be construed as limiting the present invention.

The wet gas power generation method and device proposed according to the embodiments of the present invention will be described below with reference to the drawings. First, the wet gas power generation method proposed according to the embodiments of the present invention will be described with reference to the drawings.

During the research of the embodiments of the present invention, it was found that when an asymmetric humidity is constructed on both sides of the polymer film material, the oxygen-containing functional groups in the material will be hydrolyzed, thereby releasing freely moving carriers. The uneven humidity causes the difference in carrier concentration. Under the action of diffusion, the carriers will diffuse from the high concentration area to the low concentration area. If an external circuit is connected, electrical energy will be output in the external circuit at this time. This process is called For moisture power generation.

Fig. 1 is a flowchart of a wet gas power generation method according to an embodiment of the present invention.

As shown in Figure 1, the wet gas power generation method includes the following steps:

In step S101, the polymer solution is poured into a petri dish and placed in an oven to prepare a polymer power generation membrane.

Specifically, a polymer solution with a solid content ranging from 0.1% to 30% is poured into a petri dish and placed in an oven at a preset temperature to generate a polymer power generation membrane after the polymer solution is volatilized. At the same time, the prepared polymer power generation film can be transparent, stretchable, and can be used as a wearable energy source.

It should be noted that the polymer solution can be poly 4-styrene sulfonic acid (PSSA), poly 4-styrene sulfonate (PSS), perfluorosulfonic acid (Nafion), polyvinyl alcohol (PVA), polyacrylic acid (PAA), sodium polyacrylate (PAAS), sodium alginate (Alg), hydroxyethyl cellulose (HEMC), and dopamine (DA) in any one or a composite form. To put it simply, the polymer power generation membrane of the embodiment of the present invention has the characteristics of simple preparation method, low price, simple and easy-to-obtain raw materials, and large-scale preparation.

Among them, in the embodiment of the present invention, the volume of the polymer solution can be adjusted to adjust the thickness of the polymer power generation film to a target thickness, which can be adjusted from 1 micron to 1 cm.

Further, in an embodiment of the present invention, the temperature for preparing the polymer power generating membrane is 25° C. to 90° C., and the drying time is 2 hours to 12 hours.

The advantages of the embodiments of the present invention are that the traditional moisture power generation materials based on graphene-based materials have complex preparation methods and have greater environmental pollution. At the same time, the generated electric energy is very small; in addition, graphene materials are in natural environment Its stability is poor, its mechanical strength is not high, it cannot be stretched or bent in a wide range, and its preparation method is complicated, and it cannot be used for large-scale industrial production. In the present invention, simple and easy-to-obtain polymer materials are used, which have good mechanical properties, can be bent, stretched, and even self-repair, etc., and can be integrated with the modern polymer industry for simple mass production preparation.

In step S102, the polymer power generation membrane is disposed on a moisture-insulated metal electrode, and a porous top electrode is disposed above the polymer power generation membrane to protect the thin film form of the polymer power generation membrane and transmit moisture.

Among them, the material of the metal electrode and the porous top electrode can be gold, silver, copper, aluminum, titanium, chromium, iron, ITO glass, FTO glass, silver paste, carbon cloth, carbon nanotube electrode and silver nanowire. Any kind.

In step S103, a moisture stimulus is applied to the metal electrode in a single direction to induce the separation of positive and negative ion pairs inside the polymer power generating membrane, and freely moving carriers are released.

It should be noted that, in the embodiment of the present invention, the variation range of moisture application is 5% to 100%, and the temperature range of moisture variation is 5°C to 95°C.

Specifically, the polymer power generation membrane is placed on a moisture-insulated metal electrode, and another porous top electrode is clamped, and moisture stimulation is applied in a single direction from the outside to induce the separation of positive and negative ion pairs inside the polymer power generation membrane. And because the negative ions have a large structure and cannot move on the polymer skeleton, the small positive ions (that is, hydrogen protons) are mainly moved inside, thereby generating electrical energy in the external circuit.

In step S104, carriers are diffused from the high-concentration region to the low-concentration region to generate a potential difference and a current, thereby outputting electric energy to the outside.

According to the moisture power generation method proposed by the embodiment of the present invention, compared with the traditional electrochemical moisture polarization method and laser directional reduction method, the directional moisture stimulation method can achieve good moisture control without the need for high cost. The laser, the testing method is simple, and the testing process does not need to resort to other expensive external equipment, which has the advantage of large-scale integration.

Next, the wet gas power generation device proposed according to the embodiment of the present invention will be described with reference to the accompanying drawings.

Figure 2 is a schematic structural diagram of a wet gas power generation device according to an embodiment of the present invention.

As shown in FIG. 2, the moisture power generation device 10 includes: a polymer power generation membrane 100, a metal electrode 200 and a porous top electrode 300. The wet gas power generation device of the embodiment of the present invention has high voltage and current output, and good bending characteristics, and can also perform self-healing and healing.

Among them, the polymer power generating membrane 100 is placed above the metal electrode, and is used to apply moisture stimulus to the outside of the metal electrode 200 in a single direction to induce the separation of positive and negative ion pairs inside the polymer power generating membrane and release freely moving carriers. , Carriers diffuse from the high-concentration area to the low-concentration area to generate a potential difference and current, and then output electrical energy. The porous top electrode 300 is placed above the polymer power generation membrane to protect the thin film form of the polymer power generation membrane and transmit moisture.

Specifically, the moisture power generation device of the embodiment of the present invention can generate a voltage as high as 0-0.8 volts and a current value of 0-0.2 mA when the humidity changes, and the output power is also the highest among all moisture power generation materials in the related art , The performance method can be performed through simple series, parallel, etc., and the power generation device can successfully charge commercial capacitors and power calculator screens, LED bulbs, LCD screens and other electrical appliances. In addition, the moisture power generation device also exhibits excellent light transmittance, with a transmittance that can be as high as 60%; it exhibits excellent repair characteristics, and can directly moisture-induced self-healing after damage; in addition, Shows high resistance to bending and stretching.

Further, in an embodiment of the present invention, the preparation process of the polymer power generating membrane is: pour the polymer solution with a solid content of 0.1%-30% into a petri dish and place it in an oven at a preset temperature to After the polymer solution is volatilized, a polymer power generation membrane is formed. Among them, the polymer power generation film can be transparent, can be stretched and bent, and used for weaving in wearable fabrics such as masks, showing great advantages in the field of wearable energy.

Optionally, in an embodiment of the present invention, the material of the metal electrode and the porous top electrode is gold, silver, copper, aluminum, titanium, chromium, iron, ITO glass, FTO glass, silver paste, carbon cloth, carbon Either nanotube electrode or silver nanowire.

In the following, the process of preparing the polymer power generation membrane and the moisture power generation device will be described in detail in conjunction with 5 embodiments.

Example 1

(a) As shown in Figure 3, the 1788 type polyvinyl alcohol (PVA) is mixed into a 10% solid content aqueous solution, and the solid content is 30%, the molecular weight is 75000 poly(4-styrene sulfonic acid) (PSSA) ) Mix according to a volume ratio of 1:1 to obtain a solution with a total volume of 5 ml. Pour it into a plastic petri dish with a diameter of 6 mm, and then place it in an oven, set the oven temperature to 45°C and blast dry for 3 hours to obtain a polymer power generation film, which shows good flexibility, and the resulting power generation membrane.

(b) As shown in Figure 4, the polymer power generation membrane obtained above has a flat surface and a compact internal structure.

(c) Preparation of the top electrode of the wet gas power generation device: Take a metal silver electrode sheet with a thickness of 0.2 mm and a size of 1 × 1 cm, and then use laser to drill holes with a diameter of 20 × 20 microns. The resulting porous electrode Place it under the press and treat it with a pressure of 10 kN for 10 minutes for later testing.

(d) As shown in Figure 2, prepare a moisture power generation device: cut the polymer power generation film into 1×1 cm with a blade, place it on a gold sheet with a thickness of 0.2 mm, and then place the porous silver top electrode on it. The fixture is fixed to obtain a moisture power generation device with a sandwich structure.

In this embodiment, the two ends of the power generating device are connected to the electrical test instrument, and moisture is introduced from the porous top electrode at the upper end of the wet gas power generating device, and the generated electrical signals are recorded in real time. The polymer power generation material has good responsiveness to moisture. When the humidity changes, it can induce freely migrating cations inside the polymer power generation material, and directional migration along the humidity stimulation direction, thereby generating a potential difference and current. Output electrical energy. As shown in Figure 5, under the stimulation of 60% humidity, the polymer power film can generate an open circuit voltage of 0.6V, and the electrical signal shows a good correlation with the intermittent application of moisture. Similarly, as shown in Figure 6, the current output of the device also shows the same characteristics as the voltage, and the short-circuit current that a single device can generate is 2 μA.

It should be pointed out that thanks to the abundant oxygen functional groups contained in the polymer power generation material, it has good self-healing properties. As shown in Figure 7, after cutting the polymer power film, apply a certain amount of moisture stimulation at the port and keep it for a period of time, the fracture will gradually self-heal and return to the original state. Furthermore, as shown in Fig. 8, the power generation device assembled from the polymer power generation membrane has almost no performance loss before and after healing.

In addition, as shown in Figure 9, the polymer power generation film also has good bending characteristics, and the performance before and after bending remains unchanged. It should be pointed out that the performance of the polymer power generation device can be improved through series and parallel connection, and has the potential for large-scale integration and industrial production. And the generated electric energy can directly drive the LCD display screen to work, showing potential application value.

Example 2

In the embodiment of the present invention, the polymer power generation membrane and the moisture power generation device are prepared according to the method basically the same as that of the embodiment 1. The difference is: (a) Take a poly(4-styrene sulfonic acid) (PSSA) solution with a solid content of 30% and a molecular weight of 75000, and then dry to prepare the membrane; (c) The top electrode is a porous gold electrode, 2×2 cm;

In the embodiment of the present invention, when the relative humidity changes to 90%, the polymer power generating membrane can generate a voltage of up to 0.8V and a current of 200 μA.

Example 3

In this embodiment of the present invention, the polymer power generation membrane and the moisture power generation device are prepared according to the method basically the same as that of the embodiment 1. The difference is: (a) Take 5 mL of solid content to 10%, and dry 1788-type polyvinyl alcohol (PVA) to obtain a film;

In the embodiment of the present invention, when the relative humidity changes by 30%, the polymer power generating membrane can generate a voltage as high as 0.3V and a current of 0.2μA.

Example 4

In this embodiment of the present invention, the polymer power generation membrane and the moisture power generation device are prepared according to the method basically the same as that of the embodiment 1. The difference is: (a) Take 10 mL of perfluorosulfonic acid (Nafion) and dry it at 60°C to obtain a membrane;

In the embodiment of the present invention, when the relative humidity changes to 80%, the polymer power generating membrane can generate a voltage of up to 0.5V and a current of 10μA.

Example 5

In this embodiment of the present invention, the polymer power generation membrane and the moisture power generation device are prepared according to the method basically the same as that of the embodiment 1. The difference is: (a) Take 10 mL of 10000 molecular weight polyacrylate sodium (PAAS) and dry it at 45°C to obtain a film;

In the embodiment of the present invention, when the relative humidity changes to 80%, the polymer power generating membrane can generate a voltage as high as 0.39V and a current of 5μA.

According to the moisture power generation device proposed by the embodiment of the present invention, considerable voltage and current can be output, and the output current value is the highest among the moisture power generation materials reported, and the generated electrical energy can be stored in a commercial capacitor. Powered by electrical appliances, it exhibits excellent electrical characteristics, and the moisture power generation device constructed based on polymer materials has good moisture self-healing characteristics, and can achieve good device performance recovery after damage, showing potential Practical value and application prospects.

In addition, the terms "first" and "second" are used for description purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, the features defined as "first" and "second" may include at least one of the features either explicitly or implicitly. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless specifically defined otherwise.

In the present invention, unless otherwise clearly specified and limited, the terms "installation", "connected", "connected", "fixed" and other terms should be understood in a broad sense, for example, it can be a fixed connection or a detachable connection , Or integrated; may be mechanical connection or electrical connection; may be directly connected, or may be indirectly connected through an intermediary, may be the connection between two elements or the interaction between two elements, unless otherwise specified Limit. Those of ordinary skill in the art can understand the specific meanings of the above terms in the present invention according to specific situations.

In the present invention, unless otherwise clearly specified and defined, the first feature is "on" or "below" the second feature may be that the first and second features are in direct contact, or the first and second features are indirectly through an intermediary contact. Moreover, the first feature is “above”, “above” and “above” the second feature may be that the first feature is directly above or obliquely above the second feature, or simply means that the first feature is higher in level than the second feature. The first feature is "below", "below" and "below" the second feature may be that the first feature is directly below or obliquely below the second feature, or simply means that the first feature is less horizontal than the second feature.

In the description of this specification, descriptions with reference to the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" etc. mean specific features described in conjunction with the embodiment or example , Structure, materials or features are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. In addition, without contradicting each other, those skilled in the art may combine and combine different embodiments or examples and features of the different embodiments or examples described in this specification.

Although the embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are exemplary and cannot be construed as limitations to the present invention, and those of ordinary skill in the art can understand the above within the scope of the present invention. The embodiments are changed, modified, replaced, and modified.

Claims (10)

1. A wet gas power generation method is characterized in that it comprises the following steps:

   Pour the polymer solution into a petri dish and place it in an oven to prepare a polymer membrane for power generation;

   Disposing the polymer power generation membrane on a moisture-insulated metal electrode, and disposing a porous top electrode above the polymer power generation membrane to protect the thin film form of the polymer power generation membrane and transmit moisture;

   By applying moisture stimulation to the outer unidirectional direction of the metal electrode to induce the separation of positive and negative ion pairs inside the polymer power generation membrane, freely moving carriers are released; and

   The carriers diffuse from the high-concentration area to the low-concentration area to generate a potential difference and current, and then output electric energy to the outside.
2. The wet gas power generation method according to claim 1, wherein the step of pouring the polymer solution into a petri dish and placing it in an oven to prepare a polymer film for power generation comprises:

   The polymer solution with a solid content ranging from 0.1% to 30% is poured into a petri dish, and placed in an oven at a preset temperature, so that the polymer power generation membrane is generated after the polymer solution is volatilized.
3. The moisture power generation method according to claim 2, wherein the polymer solution is poly4-styrene sulfonic acid, poly 4-styrene sulfonate sodium, perfluorosulfonic acid, polyvinyl alcohol, polyacrylic acid , Sodium polyacrylate, sodium alginate, hydroxyethyl cellulose and dopamine in any one or more composite forms.
4. The wet gas power generation method of claim 2, further comprising:

   The volume of the polymer solution is adjusted to adjust the thickness of the polymer power generation film to a target thickness.
5. The wet gas power generation method of claim 2, wherein the temperature for preparing the polymer power generation film is 25°C to 90°C, and the drying time is 2 hours to 12 hours.
6. The wet gas power generation method according to claim 1, wherein the material of the metal electrode and the porous top electrode is gold, silver, copper, aluminum, titanium, chromium, iron, ITO glass, FTO glass, silver Any one of paste, carbon cloth, carbon nanotube electrode and silver nanowire.
7. The wet gas power generation method according to claim 1, wherein the variation range of the moisture application is 5% to 100%, and the temperature range of the moisture change is 5°C to 95°C.
8. A wet gas power generation device, characterized in that it comprises:

   The polymer power generating membrane and the metal electrode, the polymer power generating membrane is placed above the metal electrode, and is used to apply moisture stimulus to the outside of the metal electrode in a single direction to induce positive and negative ions inside the polymer power generating membrane The right separation releases freely moving carriers, which diffuse from the high-concentration area to the low-concentration area to generate a potential difference and current, and then output electric energy to the outside; and

   The porous top electrode, which is placed above the polymer power generating membrane, is used to protect the thin film form of the polymer power generating membrane and transmit moisture.
9. The wet gas power generation device according to claim 8, wherein the preparation process of the polymer power generation membrane is: pour the polymer solution with a solid content ranging from 0.1% to 30% into a petri dish and place it in a petri dish. In an oven at a preset temperature, the polymer power generating membrane is generated after the polymer solution is volatilized.
10. The wet gas power generation device according to claim 8, wherein the material of the metal electrode and the porous top electrode is gold, silver, copper, aluminum, titanium, chromium, iron, ITO glass, FTO glass, silver Any one of paste, carbon cloth, carbon nanotube electrode and silver nanowire.

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