Wet-based generator based on iodine triion reversible chemical reaction and preparation method thereof

Abstract

The invention discloses a wet-based generator based on a reversible chemical reaction of triiodide ions and a preparation method thereof, and relates to the technical field of new energy generators, the wet-based generator comprises two carbon electrode plates and gel located between the two carbon electrode plates, the triiodide ions are introduced into the gel, and the triiodide ions are introduced into the gel. One of the two carbon electrode plates is provided with a plurality of pore channels, and the two carbon electrode plates are connected through carbon fiber wires. The device designed by the invention is simple in structure, the preparation process in the preparation method is easy to operate, the wet-based generator based on the gel containing the triiodide ions not only has considerable current output and stable power generation performance, but also can effectively prolong the power generation life by reusing the iodide ions, and in addition, the device has good application prospects. The humidity adaptability of the device designed by the invention is wider, and large relative humidity span is not limited.

Description

Technical Field

[0001] The present invention relates to the technical field of new energy generators, and in particular to a wet-based generator based on the reversible chemical reaction of triiodine ions and a preparation method thereof. Background Art

[0002] The ubiquitous moisture in ambient air provides a natural green energy reservoir, attracting widespread interest in the development of moisture-induced energy harvesting technology. This technology can effectively utilize the adsorption of hygroscopic materials with water molecules in the atmosphere to convert the chemical energy in moisture into electrical energy. However, most traditional wet-based electricity generation devices (MEGs) work in a single water adsorption process. When the water adsorption tends to an equilibrium state, the MEG will stop outputting electrical energy, which reflects the shortcomings of unsustainable and non-repeatable power generation of traditional devices. Due to the serious dependence between high relative humidity and the power generation performance of MEG, it is still a challenge to achieve sustainable power generation of wet-based power generation devices under natural conditions. At the same time, the alternating change of relative humidity (RH) from high to low during a day is a common natural phenomenon in the hydrological cycle. Therefore, it is a wise choice to use the phenomenon of cyclic changes in relative humidity to extend the life of the device.

[0003] In the above context, Qu Liangti's research group reported a moisture absorption-desorption full cycle generator and proposed a moisture absorption-desorption power generation device (MADG) based on porous ion gel assembly, which can spontaneously absorb moisture at high relative humidity and desorb at low relative humidity, thereby generating cyclic power output. However, the power generation process of this generator is the unidirectional movement of sodium ions, so there may be a situation where the ion transport is exhausted after a long period of power generation and the power generation stops. There is also a prior art that discloses a technology that drives the selective migration of ions on a polycationic membrane by humidity cycle to achieve the continuous conversion of chemical energy in moisture into electrical energy under the environment of moisture cycle, which can achieve long-term continuous power generation. The main functional layer of this technology is the polycationic membrane. Specifically, the self-assembled membrane consists of channels composed of polycation clusters sandwiched between two layers of ionic liquid, one of which is isolated from the ambient air, while the other is directly exposed to the environment. When the ionic liquid is in contact with the ambient air, the device shows the ability to spontaneously generate ionic current with a high power density. This phenomenon originates from the difference in water content of the transmembrane ionic liquid layer caused by the ongoing moisture absorption / desorption process. The difference in water content stimulates the selective transmembrane ion flux. Due to the enhanced charge repulsion, the flux of cations passing through the polycation clusters is greatly suppressed. However, the transmission of anions between polycation clusters is amplified, making the daily cyclic humidity change have the potential to be a reliable energy source. It can trigger ionic current and convert it into electronic current. However, this technology still has the following problems: (1) The preparation process of polycationic membrane is complicated and time-consuming; (2) The current reverse humidity of this technology is RH 50%, which has certain weather restrictions. In some rainy seasons or dry seasons, the working life of the wet-based generator based on this technology will be affected. At the same time, since the output of the device is not reversed, it means that the movement of ions is unidirectional. The unidirectional movement of ions will result in a limited life of the device. Therefore, it is urgent to develop a device that is easy to prepare and has a wide range of weather adaptability to utilize the diurnal moisture cycle. Summary of the invention

[0004] The present invention provides a wet-based generator based on the reversible chemical reaction of triiodine ions, which solves the technical problems of the existing wet-based generators having a complicated preparation process and a narrow weather adaptability range.

[0005] The technical solution adopted by the present invention is as follows:

[0006] A wet-based generator based on the reversible chemical reaction of triiodine ions, the wet-based generator comprising two carbon electrode plates and a gel located between the two carbon electrode plates, triiodine ions are introduced into the gel, one of the two carbon electrode plates is provided with a plurality of pores, and the two carbon electrode plates are connected by carbon fiber wires.

[0007] The design key points of this application are mainly to use reversible reactions as the driving force for ion movement to improve the utilization rate of ions, thereby achieving long-term and efficient power generation of the power generation device, which is specifically embodied as a reversible reaction device of triiodine ions.

[0008] Preferably, the preparation process of introducing triiodine ions into the gel comprises the following steps:

[0009] (1) Introducing acid into sodium iodide solution;

[0010] (2) The formed gel is immersed in an acidified sodium iodide solution for 1 to 48 hours to obtain a gel containing triiodine ions.

[0011] Preferably, the preparation process of introducing triiodine ions into the gel is as follows: soaking the shaped hydrogel containing acidic groups in a sodium iodide solution for 1 to 48 hours to obtain the gel containing triiodine ions.

[0012] The method for preparing the wet-based generator based on the reversible chemical reaction of triiodine ions comprises the following steps:

[0013] (1) Making a carbon electrode plate and a porous carbon electrode plate: coating a commercial carbon slurry on a PET film and waiting for it to dry naturally to obtain a carbon electrode plate, and punching holes in the carbon electrode plate to obtain a porous carbon electrode plate;

[0014] (2) placing a gel containing triiodine ions on a carbon electrode plate, and then covering the porous carbon electrode plate on the gel containing triiodine ions to form a sandwich structure;

[0015] (3) A wet-based generator is obtained by connecting the carbon electrode plate and the porous carbon electrode plate using a carbon fiber wire and sealing the carbon fiber wire.

[0016] Furthermore, the pores of the porous carbon electrode plate are punched by a laser cutting machine, the diameter of the pores is 1.7 mm, and the spacing between the pores is 0.8 mm.

[0017] Furthermore, the following steps are taken to control the moisture content of the gel containing triiodine ions before preparing a wet-based generator: the soaked gel containing triiodine ions is placed in a drying oven at 75° C. for 2.5 to 3.5 hours to make the moisture content of the gel moderate, and then placed in an atmospheric environment or a fixed humidity environment for 10 to 20 hours to wait for its moisture absorption and dehumidification equilibrium.

[0018] Furthermore, the carbon fiber wire is fixed to the carbon electrode plate and the porous carbon electrode plate by using a conductive carbon tape.

[0019] Furthermore, the carbon fiber wire is sealed with a transparent tape.

[0020] In summary, compared with the prior art, the present invention has the following advantages and beneficial effects:

[0021] 1. The present invention introduces iodine triions into the hydrogel to obtain a gel containing iodine triions that can respond to changes in external humidity, wherein the reversible redox reaction of the dissociation and synthesis of iodine triions is regulated by humidity, so that it can continue to work in a changing humidity environment, such as Figure 1 As shown. Based on the wet-based generator prepared in this way, one side of the gel containing triiodine ions is exposed to the air, and the other side is isolated from the air. In a high humidity environment, the triiodine ions near the surface of the gel containing triiodine ions that are in contact with the air tend to dissociate. The concentration difference of iodine ions produced after dissociation prompts iodine ions to move downward with water molecules to generate ion current; conversely, in a low humidity environment, triiodine ions tend to be synthesized, and iodine ions move from bottom to top to generate reverse current. Compared with traditional wet-based power generation devices, this device not only has considerable current output and stable power generation performance, but also allows iodine ions to be reused and effectively improve the power generation life.

[0022] 2. The device of the present invention has excellent ability to respond to changes in ambient humidity due to the moderate hygroscopic properties of sodium iodide. As long as the ambient humidity is higher or lower than the ambient humidity of the current gel absorption and dehumidification equilibrium, the device will absorb or dehumidify, thereby generating a corresponding electrical signal. In other words, the humidity adaptability of the device is wider and is not limited to large relative humidity spans (such as from RH93% to 15%).

[0023] 3. The device designed by the present invention has a simple structure, and the preparation process in the preparation method is easy to operate. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a working principle diagram of the device of the present invention;

[0025] Figure 2 It is a schematic diagram of the device structure of the present invention;

[0026] Figure 3 The top (upper) and front (lower) optical microscope images of the device of the present invention;

[0027] Figure 4 This is a scanning electron micrograph of the gel after being soaked in sodium iodide;

[0028] Figure 5 This is a current performance diagram of the device of Example 1 at high humidity and low humidity;

[0029] Figure 6 This is a current performance diagram of the device of Example 1 under small humidity changes;

[0030] Figure 7This is a current performance diagram of the device of Example 2 at high humidity and low humidity;

[0031] Figure 8 This is a current performance diagram of different salt ion devices under high humidity and low humidity in Example 3;

[0032] Fig. 9 This is a current performance diagram of the trisodium iodide ion gel device of Example 3 after multiple cycles under high humidity (current is positive) and low humidity (current is negative). DETAILED DESCRIPTION

[0033] The present invention will be described in detail below in conjunction with specific implementations and examples, and the advantages and various effects of the present invention will be more clearly presented. It should be understood by those skilled in the art that these specific implementations and examples are used to illustrate the present invention, rather than to limit the present invention.

[0034] Throughout the specification, unless otherwise specifically stated, the terms used herein should be understood as meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. In the event of a conflict, the present specification takes precedence.

[0035] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0036] like Figure 2 As shown, the wet-based generator prepared by the present invention includes two carbon electrode plates and a gel containing triiodine ions located between the two carbon electrode plates, one of the two carbon electrode plates is provided with a plurality of pores, and the two carbon electrode plates are connected by carbon fiber wires.

[0037] The present application will be described in detail below with reference to embodiments and experimental data.

[0038] Example 1

[0039] The wet-based generator prepared in this embodiment uses a gel containing triiodine ions that adopts a gel solution containing acidic groups. The preparation process of the gel containing triiodine ions and the wet-based generator is as follows:

[0040] S1. Preparation of sodium iodide solution: prepare 30 mL of 1 M sodium iodide solution.

[0041] S2. Preparation of hydrogel precursor solution and gel forming: First weigh the required materials acrylamide (AM) 6g, 2-acrylamide-2-methylpropanesulfonic acid (AMPS) 2.1g, crosslinker: N,N'-methylenebisacrylamide (MBA) 15mg and photoinitiator 2959: 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone 15mg. After the materials are prepared, put them in a beaker, add 30mL of deionized water, and stir with a magnetic stirrer at room temperature for 20min until all the reagents are dissolved. Then seal it with a sealing film and place it in a light-proof environment. Add the monomer solution dropwise to a 1.5*.15*0.3cm mold and irradiate it with a 30W ultraviolet lamp for 20min to successfully prepare the hydrogel.

[0042] S3, introduction of sodium iodide: the prepared hydrogel is placed in a sodium iodide solution and soaked for 48 hours to prepare a gel containing triiodine ions;

[0043] S4. Control of the moisture content of the gel: The soaked gel is placed in a drying oven at 75°C for about 3 hours to make the moisture content of the gel moderate, and then placed in the atmosphere or a specified humidity environment for 12 hours to wait for its moisture absorption and dehumidification equilibrium.

[0044] S5. Preparation and connection of electrodes: The carbon electrode is prepared by coating a commercial carbon paste on a PET film and waiting for it to dry naturally before use. The porous electrode is prepared by using a laser cutting machine to punch holes with a diameter of 1.7 mm and a spacing of 0.8 mm, for a total of 5*6 holes. Two carbon electrodes are placed on both sides of the hydrogel, one carbon electrode is a porous carbon electrode, and the other is a normal carbon electrode. Use conductive carbon tape to connect the carbon fiber wire and the carbon electrode, and use transparent tape to seal the carbon fiber wire to prevent liquid from entering the carbon fiber wire. The device can then work in different humidity environments. The optical microscope image of the prepared device is shown below. Figure 3 As shown, the morphology of the gel after sodium iodide treatment was also characterized, such as Figure 4 The current data under high humidity and low humidity are shown in Figure 5 As shown, the current response curve was tested in an environment with small humidity changes. First, the ambient humidity (RH55%) was transferred to an environment with RH43%, then to an environment with RH60% for a period of time, and then to an environment with RH43%. Finally, the corresponding performance changes were shown in Figure 6 shown.

[0045] Example 2

[0046] The wet-based generator prepared in this embodiment uses an external acid solution for the gel containing triiodine ions. The preparation process of the gel containing triiodine ions and the wet-based generator is as follows:

[0047] S1. Preparation of sodium iodide solution: prepare 30 mL of 1 M sodium iodide solution.

[0048] S2. Preparation of hydrogel precursor solution and gel forming: First weigh the required materials acrylamide (AM) 6g, crosslinker: N,N'-methylenebisacrylamide (MBA) 15mg and photoinitiator 2959: 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone 15mg. After the materials are prepared, put them in a beaker, add 30mL of deionized water, and stir with a magnetic stirrer at room temperature for 20 minutes until all the reagents are dissolved. Then seal it with a sealing film and place it in a light-proof environment. Add the monomer solution dropwise into a 1.5*.15*0.3cm mold and irradiate it with a 30W ultraviolet lamp for 20 minutes to successfully prepare the hydrogel.

[0049] S3. Introduction of sodium iodide: add 10 mL of 1 M hydrochloric acid into 20 mL of sodium iodide, and then soak the prepared hydrogel in the solution for 48 hours.

[0050] S4. Control of the moisture content of the gel: The soaked gel is placed in a drying oven at 75°C for about 3 hours to make the moisture content of the gel moderate, and then placed in an atmospheric environment or a fixed humidity environment for 12 hours to wait for its moisture absorption and dehumidification equilibrium.

[0051] S5. Preparation and connection of electrodes: The carbon electrode is prepared by coating commercial carbon slurry on a PET film and waiting for it to dry naturally before use. The porous electrode is prepared by punching holes using a laser cutter. The diameter of the hole is 1.7mm and the spacing is 0.8mm, with a total of 5*6 holes. Two carbon electrodes are placed on both sides of the hydrogel, one carbon electrode is a porous carbon electrode, and the other side is a normal carbon electrode. Use conductive carbon tape to connect the carbon fiber wire and the carbon electrode, and use transparent tape to seal the carbon fiber wire to prevent liquid from entering the carbon fiber wire. The device can then work in different humidity environments. The specific data is as follows. Figure 7 shown.

[0052] Example 3

[0053] The wet-based generator prepared in this example is mainly used to demonstrate the beneficial effects of triiodine ions. The gel containing triiodine ions used is a gel solution containing acidic groups, and other salt solutions are prepared for reference. The preparation process of wet-based generators with different salt solutions is as follows:

[0054] S1. Preparation of saline solution: prepare 30 mL of 1M sodium iodide solution, 30 mL of 1M magnesium chloride solution and 30 mL of 1M lithium chloride solution.

[0055] S2. Preparation of hydrogel precursor solution and gel forming: First weigh the required materials acrylamide (AM) 6g, 2-acrylamide-2-methylpropanesulfonic acid (AMPS) 2.1g, crosslinker: N,N'-methylenebisacrylamide (MBA) 15mg and photoinitiator 2959: 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone 15mg. After the materials are prepared, put them in a beaker, add 30mL of deionized water, and stir with a magnetic stirrer at room temperature for 20min until all the reagents are dissolved. Then seal it with a sealing film and place it in a light-proof environment. Add the monomer solution dropwise to a 1.5*.15*0.3cm mold and irradiate it with a 30W ultraviolet lamp for 20min to successfully prepare the hydrogel.

[0056] S3, introduction of salt solution: the prepared hydrogel is placed in different solutions and soaked for 48 hours to prepare gels containing different salt ions;

[0057] S4. Control of the moisture content of the gel: The soaked gel is placed in a drying oven at 75°C for about 3 hours to make the moisture content of the gel moderate, and then placed in the atmosphere or a specified humidity environment for 12 hours to wait for its moisture absorption and dehumidification equilibrium.

[0058] S5. Preparation and connection of electrodes: The carbon electrode is prepared by coating a commercial carbon slurry on a PET film and waiting for it to dry naturally before use. The porous electrode is prepared by punching holes using a laser cutter. The diameter of the hole is 1.7 mm and the spacing is 0.8 mm, with a total of 5*6 holes. Two carbon electrodes are placed on both sides of the hydrogel, one carbon electrode is a porous carbon electrode, and the other is a normal carbon electrode. Use conductive carbon tape to connect the carbon fiber wire and the carbon electrode, and use transparent tape to seal the carbon fiber wire to prevent liquid from entering the carbon fiber wire. Except for the different ions introduced, the other conditions of the three devices are exactly the same. The three devices were then placed in high humidity (RH93%) for 1.5 hours, then transferred to low humidity (RH15%) for 1.5 hours, and then transferred to high humidity (RH93%). The measured current performance is as follows Figure 8 As shown, it can be obtained that the initial current of lithium chloride and magnesium chloride gel devices is large, but as time goes by, the performance gradually approaches zero. When the humidity environment is switched, there will be a slight reaction, but the device performance will not reverse. Therefore, the ion utilization rate of traditional devices is low, resulting in a short device life. However, the device with triiodine ions has the ability to change the current performance cyclically with the change of external environmental humidity, reflecting the reuse of ions. At the same time, the performance diagram of multiple cycles using the device is shown in Figure 2. Fig. 9 As shown, it can be found that unlike traditional devices working in a single moisture absorption or dehumidification process, this device can effectively improve the device life.

[0059] Finally, it should be noted that the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article, or device. Although preferred embodiments of the present invention have been described, additional changes and modifications may be made to these embodiments by those skilled in the art once the basic inventive concepts are known. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0060] The above-mentioned embodiments only express the specific implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the protection scope of the present application. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the technical solution concept of the present application, and these all belong to the protection scope of the present application.

Claims

1. A wet-based generator based on the reversible chemical reaction of triiodine ions, characterized in that: The wet-based generator comprises two carbon electrode plates and a gel located between the two carbon electrode plates, wherein the gel contains triiodine ions, one of the two carbon electrode plates is provided with a plurality of pores, and the two carbon electrode plates are connected by carbon fiber wires.

2. The method for preparing a wet-based generator based on the reversible chemical reaction of triiodine ions according to claim 1, characterized in that: The preparation process of introducing triiodine ions into the gel comprises the following steps: (1) Introducing acid into sodium iodide solution; (2) The formed gel is immersed in an acidified sodium iodide solution for 1 to 48 hours to obtain a gel containing triiodine ions.

3. The method for preparing a wet-based generator based on the reversible chemical reaction of triiodine ions according to claim 1, characterized in that: The preparation process of introducing triiodine ions into the gel is as follows: soaking the shaped hydrogel containing acidic groups in a sodium iodide solution for 1 to 48 hours to obtain the gel containing triiodine ions.

4. The method for preparing a wet-based generator based on the reversible chemical reaction of triiodine ions according to any one of claims 1 to 3, characterized in that: The steps include: (1) Making a carbon electrode plate and a porous carbon electrode plate: coating a commercial carbon slurry on a PET film and waiting for it to dry naturally to obtain a carbon electrode plate, and punching holes in the carbon electrode plate to obtain a porous carbon electrode plate; (2) placing a gel containing triiodine ions on a carbon electrode plate, and then covering the porous carbon electrode plate on the gel containing triiodine ions to form a sandwich structure; (3) A wet-based generator is obtained by connecting the carbon electrode plate and the porous carbon electrode plate using a carbon fiber wire and sealing the carbon fiber wire.

5. The method for preparing a wet-based generator based on the reversible chemical reaction of triiodine ions according to claim 4, characterized in that: The pores of the porous carbon electrode plate are punched by a laser cutting machine, the diameter of the pores is 1.7 mm, and the spacing between the pores is 0.8 mm.

6. The method for preparing a wet-based generator based on the reversible chemical reaction of triiodine ions according to claim 4, characterized in that: The following steps are taken to control the moisture content of the gel containing triiodine ions before preparing a wet-based generator: the soaked gel containing triiodine ions is placed in a drying oven at 75° C. for 2.5 to 3.5 hours to make the moisture content of the gel moderate, and then placed in an atmospheric environment or a fixed humidity environment for 10 to 20 hours to wait for its moisture absorption and dehumidification equilibrium.

7. The method for preparing a wet-based generator based on the reversible chemical reaction of triiodine ions according to claim 4, characterized in that: The carbon fiber wire is fixed to the carbon electrode plate and the porous carbon electrode plate by using conductive carbon tape.

8. The method for preparing a wet-based generator based on the reversible chemical reaction of triiodine ions according to claim 4, characterized in that: The carbon fiber conductor is sealed by using a transparent tape.

Images