Carbon dioxide absorption and release devices

Abstract

A carbon dioxide capture and release device comprising: a first composite comprising a first carbon-containing conductive material and a ferrocene derivative chemically bonded to the surface of the first conductive material; and an electrode material having the first composite on the surface thereof.

Description

【Technical Field】 【0001】 The present disclosure relates to a carbon dioxide absorption and release device. 【Background Art】 【0002】 As a technology for reducing carbon dioxide (CO2), a greenhouse gas, carbon dioxide separation and recovery has attracted attention. The carbon dioxide separation and recovery technology is mainly used when separating and recovering carbon dioxide contained in exhaust gas from factories or the atmosphere from other substances. 【0003】 The recovered carbon dioxide is used for "CCU (Carbon dioxide Capture and Utilization)" which produces chemicals, fuels, etc. using carbon dioxide, "CCS (Carbon dioxide Capture and Storage)" which stores carbon dioxide deep underground, etc. Technologies for recovering, utilizing, and storing such carbon dioxide are called "CCUS". 【Prior Art Documents】 【Patent Documents】 【0004】 【Patent Document 1】 Japanese Patent Application Laid-Open No. 2023-033072 【Non-Patent Documents】 【0005】 【Non-Patent Document 1】 S. Voskian, T. A. Hatton, Energy Environ. Sci., 12, 3530 (2019) 【Summary of the Invention】 【0006】 One aspect of the present embodiment is a carbon dioxide absorption and release device as follows. (1) A first composite including a first conductive material containing carbon and a ferrocene derivative chemically bonded to the surface of the first conductive material, An electrode material having the first composite on its surface, A carbon dioxide absorption and release device, including one. (2) The carbon dioxide absorption and release device according to (1), wherein the ferrocene derivative has an amino group. (3) The carbon dioxide absorption and release device according to (1), wherein the ferrocene derivative is chemically bonded to the surface of the first conductive material via a linker. (4) The carbon dioxide absorption and release device according to (3), wherein the ferrocene derivative has a carboxyl group. (5) The carbon dioxide absorption and release device according to (3), wherein the ferrocene derivative has an alkene group. (6) The linker is the carbon dioxide absorption and release device described in (3) above, wherein the linker has an amino group. (7) The linker is the carbon dioxide absorption and release device according to (3) above, wherein the linker has an alkene group. (8) The carbon dioxide absorption and release device according to any one of (1) to (7), wherein the first conductive material comprises one or more selected from the group consisting of graphene oxide, carbon nanotubes, activated carbon, regular mesoporous carbon, and graphene mesosponge. (9) The carbon dioxide absorption and release device according to any one of (1) to (8), wherein the first conductive material has one or more shapes selected from the group consisting of sheet, flake, stick, fiber, tube, and flake. (10) The carbon dioxide absorption and release device according to any one of (1) to (9), further comprising an electrolyte held in the first composite. (11) The electrode material comprises one or more selected from the group consisting of carbon, aluminum, copper, stainless steel, and nickel, and further comprises a current collector having one or more shapes selected from the group consisting of sheet-like, flake-like, stick-like, plate-like, and mesh-like, A carbon dioxide absorption and release device according to any one of (1) to (10), wherein the surface of the current collector has the first composite. (12) A first electrode layer comprising the electrode material, A second electrode layer comprising a porous electrode material having a second composite on its surface, which includes a carbon dioxide adsorbent and a second conductive material containing carbon, An insulating layer located between the first electrode layer and the second electrode layer, A carbon dioxide absorption and release device according to any one of (1) to (11) above, comprising the above. (13) A first electrode layer comprising the electrode material and having a first surface and a second surface located opposite to the first surface, A second electrode layer and a third electrode layer, each comprising a porous electrode material having a second composite on its surface, which includes a carbon dioxide adsorbent and a second conductive material containing carbon, A first insulating layer located between the first surface and the second electrode layer, A second insulating layer located between the second surface and the third electrode layer A carbon dioxide absorption and release device according to any one of (1) to (11) above, comprising the above. [Brief explanation of the drawing] 【0007】 [Figure 1] This is a schematic diagram of a carbon dioxide absorption and release device 10 according to Embodiment 1, which is one aspect of this embodiment. [Figure 2] This is a schematic diagram showing an example of the structure of the composite 11 according to Embodiment 1. [Figure 3] This is a schematic diagram of a carbon dioxide absorption and release device 20 according to Embodiment 2, which is one aspect of this embodiment. [Figure 4] This is a schematic diagram of a carbon dioxide absorption and release device 30 according to Embodiment 3, which is one aspect of this embodiment. [Figure 5] This graph shows the CV measurement results for Test Example 4. [Figure 6] This graph shows the CV measurement results for Test Example 8. [Figure 7] This graph shows the CV measurement results for Test Example 10. [Modes for carrying out the invention] 【0008】 In the carbon dioxide absorption and release devices disclosed in Non-Patent Document 1 and Patent Document 1, redox active molecules capable of electron transfer are physically fixed on the surface of a conductive material such as a carbon nanotube in a carbon dioxide absorbent. In physical fixation, there was room for improvement in terms of binding properties. Therefore, there is an expectation of providing a carbon dioxide absorption and release device with high electron conductivity and high binding properties between the active molecules and the conductive material. Next, embodiments of the present disclosure will be described in detail with reference to the drawings. It should be understood that the present disclosure is not limited to the following embodiments, and design changes, improvements, etc. can be appropriately made based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present disclosure. 【0009】 [Embodiment 1] (Configuration of Carbon Dioxide Absorption and Release Device) FIG. 1 shows a schematic diagram of a carbon dioxide absorption and release device 10 according to Embodiment 1 of the present disclosure. The configuration shown in FIG. 1 is an example and is not limited thereto. The carbon dioxide absorption and release device 10 has a composite body 11 on the surface of an electrode material 12. When the electrode material 12 is plate-shaped as shown in FIG. 1, the composite body 11 may be located on both surfaces or only on one surface. The composite body 11 may be located on a part of the surface of the electrode material 12 or on the entire surface of the electrode material 12. 【0010】 <First Composite>[ The complex 11, which is the first complex of the carbon dioxide absorption and release device 10, includes a first conductive material containing carbon and a ferrocene derivative chemically bonded to its surface. The ferrocene derivative may contain an amino group (NH2-) or an alkene group (CH2=CH-), and may be chemically bonded to the surface of the first conductive material containing carbon via a linker. FIG. 2 shows an embodiment of the structure of the complex 11. In the form shown in FIG. 2, the complex 11 contains polyvinylferrocene, which is a ferrocene derivative chemically bonded to the surface of graphene oxide, which is a first conductive material 13 containing carbon, via a linker 15 (diazonium salt of p-phenylenediamine). Hereinafter, the first conductive material containing carbon is simply referred to as the first conductive material. 【0011】 <First Conductive Material> The first conductive material contained in the complex 11 may include a carbon material having good conductivity. The carbon material can be one or more selected from the group consisting of graphene oxide, carbon nanotubes, activated carbon, regular mesoporous carbon, and graphene mesosponge. Also, the shape of the first conductive material is not particularly limited, and a shape suitable for a desired device configuration can be used. The first conductive material may have one or more shapes selected from the group consisting of, for example, sheet-like, flake-like, stick-like, fiber-like, tube-like, and flake-like. The first conductive material may be non-porous or porous. 【0012】 Graphene oxide is a sheet-like or flake-like structure with a thickness of about 1 nm. Graphene oxide has a number of oxygen-containing functional groups such as hydroxy groups, carboxy groups, carbonyl groups, and epoxy groups on the surface of single-layer graphene. 【0013】 [[ID=·13]] Graphene oxide is a sheet-like or flake-like structure and is rich in flexibility. Therefore, the complex 11 using graphene oxide as the first conductive material has high flexibility. 【0014】 As mentioned above, graphene oxide is not particularly limited as long as it is a sheet-like or flake-like structure with a thickness of approximately 1 nm and has a large number of oxygen-containing functional groups on the surface of the single layer of graphene. For example, reduced graphene oxide, modified graphene oxide, etc., can be used as graphene oxide. Reduced graphene oxide is graphene oxide having functional groups in which some or all of the large number of oxygen-containing functional groups have been reduced. Modified graphene oxide is graphene oxide having functional groups in which some or all of the large number of oxygen-containing functional groups have been modified with a desired functional group. 【0015】 Carbon nanotubes are materials made of carbon and possess properties such as high electrical conductivity, light weight, high strength, large specific surface area, and flexibility. Carbon nanotubes are carbon-based materials that have a cylindrical shape formed by winding a graphene sheet. Carbon nanotubes include single-walled carbon nanotubes and multi-walled carbon nanotubes, depending on the number of components in their peripheral wall. A composite 11 using single-walled carbon nanotubes has high flexibility. On the other hand, a composite 11 using multi-walled carbon nanotubes has high strength. Carbon nanotubes may have structures such as chiral (helical), zigzag, or armchair types. 【0016】 Activated carbon is a substance whose main component is carbon that has undergone chemical or physical treatment (activation / revitalization). The surface of activated carbon is highly porous, and the interior of its fine pores is intricately structured. Due to this structure, activated carbon can adsorb many substances, mainly organic matter. The activated carbon contained in composite 11 can be molded into sheets, flakes, sticks, tubes, etc., through processing and used. 【0017】 Regular mesoporous carbon is a porous carbon having regular pores with a diameter of 2 to 50 nm. The surface of regular mesoporous carbon is highly porous, and this structure allows it to adsorb many substances, mainly organic matter. Furthermore, regular mesoporous carbon has uniform pores and exhibits superior diffusion performance and molecular selectivity compared to activated carbon with non-uniform pore sizes, thus improving the function of the carbon dioxide absorption and release device 10. The regular mesoporous carbon contained in the composite 11 can be molded into sheets, flakes, sticks, tubes, etc., through processing and used. 【0018】 Graphene mesosponge is a new carbon material developed by Tohoku University, featuring a bubbly pore structure with 3-8 nm pores and pore walls composed of a single layer of defect-free graphene sheets. Thanks to its meticulously designed nanostructure, graphene mesosponge achieves both superior porosity and oxidation resistance—that is, chemical durability—significantly exceeding that of conventional carbon materials. Furthermore, because graphene mesosponge is flexible, it can be reversibly compressed and restored. This allows it to follow the movement of active materials that undergo rapid structural changes during charging and discharging, resulting in excellent mechanical durability. 【0019】 <Ferrocene derivatives> The ferrocene derivative is chemically bonded to the surface of the first conductive material. The ferrocene derivative may also be chemically bonded to the surface of the first conductive material via a linker. The ferrocene derivative may be a monomer or a polymer. The ferrocene derivative is not particularly limited as long as it can be chemically bonded to the surface of the first conductive material in this manner. The ferrocene derivative may have the basic structure of polyvinylferrocene as shown in formula (1) below. The carbon atoms of the two five-membered rings of ferrocene may each have substituents independently. A linker can be formed between the ferrocene derivative and the carbon atoms of the first conductive material through these substituents. The substituent may be an amino group (NH2-) or an alkene group (CH2=CH-). Alternatively, the carbon atoms of the five-membered rings of ferrocene may be directly bonded to the carbon atoms of the first conductive material. 【0020】 [ka] 【0021】 Ferrocene derivatives are redox-active molecules. When oxidized, ferrocene derivatives release electrons to become a +1 valent cation, and when reduced, they accept electrons and return to their original neutral state. Therefore, by maintaining a predetermined potential in the carbon dioxide absorption and release device 10, the ferrocene derivative releases electrons. Furthermore, because the ferrocene derivative, being a redox-active molecule, is chemically bonded to the surface of the first conductive material, good adhesion to the surface of the first conductive material is achieved. In this way, by modifying the surface of the first conductive material with a ferrocene derivative through chemical bonding, a carbon dioxide absorption and release device with high electronic conductivity and high adhesion between the active molecule and the conductive material can be provided. 【0022】 The linker is not particularly limited as long as it can chemically bond with the functional group of the five-membered ring of the ferrocene derivative and simultaneously with the carbon atoms of the conductive material, and may also be a linker having an amino group. Examples of linkers having an amino group include carbon linear diamines, phenylenediamines such as p-phenylenediamine, and others. The number of carbon atoms in the diamine is not particularly limited, but carbon linear diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine (hexamethylenediamine) may also be used. Carbon linear diamines have high mobility of the alkyl chain, which makes it easier for the five-membered ring of the ferrocene derivative to come into close proximity with the carbon surface. In particular, ethylenediamine is a carbon linear diamine with a short carbon chain, making it a very suitable linker for efficiently transferring electrons from redox-active molecules to the electrode surface. 【0023】 The linker may be a linker having an alkene group. Alternatively, the linker may have both an amino group and an alkene group. Examples of linkers having both an amino group and an alkene group include aminostyrene (shown in formula (3) below), allylamine (shown in formula (4) below), N-(allyl)ethylenediamine, aminoethyl methacrylate (AEMA), and the like. 【0024】 [ka] 【0025】 The alkene groups of aminostyrene and vinylferrocene readily undergo radical polymerization, making it easier to produce aminostyrene-polyvinylferrocene copolymers and increasing the amount of modification. 【0026】 The complex 11 may further contain an electrolyte. The electrolyte is not particularly limited, but can be an ionic salt, a solid electrolyte, or an ionic conductive polymer. 【0027】 <Electrode material> The electrode material 12 of the carbon dioxide absorption / release device 10 may include a current collector on which the composite 11 is provided on the surface. The current collector can be made of known electrode materials. The current collector may include, for example, one or more selected from the group consisting of carbon, aluminum, copper, stainless steel, and nickel. The current collector may also be formed in one or more shapes selected from the group consisting of sheet, flake, stick, plate, and mesh. The current collector may be porous. 【0028】 The current collector functions as a conductor to transfer charge to the composite 11 and cause the ferrocene derivative to respond electrically. By changing the potential of the current collector, the ferrocene derivative contained in the composite 11 can be oxidized and reduced, causing the ferrocene derivative to release electrons. 【0029】 The electrode material 12 of the carbon dioxide absorption / release device 10 may further contain another conductive material containing carbon, in addition to the first conductive material contained in the composite 11. Including another conductive material can reinforce the electrical connections between the composites 11. Furthermore, if the electrode material 12 includes a current collector, it can reinforce the electrical connections between the composite 11 and the current collector. As such other conductive materials, graphene oxide, carbon nanotubes, activated carbon, regular mesoporous carbon, and graphene mesosponge can be used, as well as the first conductive material contained in the composite 11 described above. 【0030】 (Manufacturing method for carbon dioxide absorption and release devices) Next, as an example of a method for manufacturing the carbon dioxide absorption and release device 10, we will describe a case in which a ferrocene derivative is chemically bonded to the surface of a first conductive material via a linker. First, the ferrocene derivative is mixed with an organic solvent. Next, after heating the mixture, linker raw materials such as ethylenediamine, hexamethylenediamine, p-phenylenediamine, aminostyrene, and allylamine are added and ultrasonically stirred. Next, an organic solvent is added to dissolve the reaction solution, and then the reaction solution is added to a water-ethanol mixture or the like to reprecipitate. Next, the precipitate is separated and washed by centrifugation and filtration, and then dissolved in an organic solvent to produce a solution of the linker-modified ferrocene derivative. Next, prepare an aqueous solution of the first conductive material, discard the supernatant solution by centrifugation, and then add the organic solvent and shake. Next, centrifugation is performed again, and after discarding the supernatant solution, the remaining precipitate of the first conductive material is added to the solution of the linker-modified ferrocene derivative and stirred to obtain a mixed solution. Next, the mixed solution is heated to form a paste. After this, if necessary, the solvent is replaced with another solvent, depending on its affinity with the binder. Next, the resulting paste-like mixture is subjected to centrifugation to discard the supernatant solution, and then an organic solvent is added and stirred to produce a composite 11 containing a ferrocene derivative chemically bonded to the surface of the first conductive material. Next, the obtained composite 11 is applied to the surface of the electrode material and heated and dried to form the composite 11 on the surface of the electrode material 12. In this way, the carbon dioxide absorption and release device 10 can be manufactured. 【0031】 [Embodiment 2] <Electrode-type electrochemical cell> The carbon dioxide absorption and release device according to this embodiment may be an electrode-type electrochemical cell as shown in Figure 3. The carbon dioxide absorption and release device 20 shown in Figure 3 comprises a first electrode layer 21, a second electrode layer 25, and an insulating layer 23 located between the first electrode layer 21 and the second electrode layer 25. The first electrode layer 21 includes an electrode material including a composite 22, which is a first composite. The composite 22 includes a first conductive material, which is a conductive material containing carbon, and a ferrocene derivative chemically bonded to its surface. The second electrode layer 25 includes a porous electrode material including a composite 24, which is a second composite. The second electrode layer 25 may be porous. The composite 24 includes a carbon dioxide adsorbent and a second conductive material, which is a conductive material containing carbon. The first electrode layer 21 and the second electrode layer 25 are electrically connected via a power supply. In Figure 3, the first electrode layer 21 and the composite 22 are shown separately for ease of understanding, but the first electrode layer 21 may contain the composite 22 internally. The second electrode layer 25 may contain the composite 24 internally. 【0032】 The electrode material, including the composite 22, contained in the first electrode layer 21 of the carbon dioxide absorption / release device 20 has a configuration similar to the electrode material 12 having the composite 11 of the carbon dioxide absorption / release device 10 according to Embodiment 1 described above on its surface. The first electrode layer 21 containing this electrode material has the surface having the composite 22 facing the insulating layer 23. 【0033】 The insulating layer 23 is positioned between the first electrode layer 21 and the second electrode layer 25, separating them. The insulating layer 23 reduces the occurrence of physical contact between the first electrode layer 21 and the second electrode layer 25, making electrical short circuits less likely. As the insulating layer 23, a separator or a gaseous layer such as air can be used. The separator may be a porous material. Examples of separator materials include cellulose membranes, resins, and composite materials of resins and ceramics. 【0034】 The second electrode layer 25 has a surface containing a composite 24 made of porous electrode material that faces the insulating layer 23. 【0035】 The second conductive material containing carbon can be one or more selected from the group consisting of activated carbon, regular mesoporous carbon, and graphene mesosponge. The activated carbon, regular mesoporous carbon, and graphene mesosponge can be materials as shown in Embodiment 1 above. Furthermore, if the second conductive material is in powder form, its particle size may be 100 nm or less. With this configuration, the large surface area of ​​the second conductive material allows for better penetration of carbon dioxide and electrolyte, providing a more efficient carbon dioxide absorption and release device. While the lower limit of the particle size is not particularly limited when the second conductive material is in powder form, it can practically be 100 nm or more. 【0036】 Carbon dioxide adsorbents are redox-active molecules that react with carbon dioxide when reduced in the presence of carbon dioxide. They may be further reduced and react with carbon dioxide again. The reverse reaction is also possible; the reduced carbon dioxide adsorbent can be returned to its original state by repeated desorption and oxidation of carbon dioxide. An example of a carbon dioxide adsorbent with these properties is anthraquinone derivative. Anthraquinone derivatives are redox-active molecules, and as shown in formula (2) below, when the anthraquinone (skeleton) is reduced in the presence of carbon dioxide (E1), carbon dioxide reacts with one oxygen atom to produce carbonate. When further reduced (E'1), carbon dioxide reacts with the other oxygen atom to produce carbonate as well. The reverse reaction is also possible; the reduced anthraquinone (skeleton) can be returned to the anthraquinone (skeleton) state by repeated desorption and oxidation of carbon dioxide. 【0037】 [ka] 【0038】 The porous second electrode layer 25 allows external carbon dioxide to permeate into the carbon dioxide absorption and release device 20. The second electrode layer 25 may include a porous current collector having a composite 24 on its surface. The current collector can be made of a known material used as an electrode. The material of the current collector may include, for example, one or more selected from the group consisting of carbon, aluminum, copper, stainless steel, and nickel. The current collector may also have one or more shapes selected from the group consisting of sheet, flake, stick, plate, and mesh. 【0039】 The current collector is a conductor that transfers charge to the composite 24, causing the carbon dioxide adsorbent to respond electrically. By changing the potential of the current collector, the carbon dioxide adsorbent contained in the composite 24 can be oxidized and reduced, causing carbon dioxide to be adsorbed and released by the carbon dioxide adsorbent. 【0040】 The carbon dioxide absorption and release device 20 adsorbs and releases carbon dioxide onto a carbon dioxide adsorbent by changing the potential applied to the device. In other words, the carbon dioxide absorption and release device 20 performs gas adsorption and desorption through an electrochemical swing process that repeatedly maintains a specific potential in the forward direction and a different potential in the reverse direction. In this process, the affinity for the substance to be adsorbed, such as carbon dioxide, can be adjusted by using redox-active molecules that can become oxidized at a predetermined potential and reduced at a different potential. By using a composite 24 that absorbs and releases carbon dioxide with such redox-active molecules, the carbon dioxide absorption and release device 20 can absorb and release carbon dioxide at room temperature. 【0041】 The composite 24 may further contain an electrolyte. The components of the electrolyte are not particularly limited, but can include ionic salts, solid electrolytes, or ionic conductive polymers. By further adding an electrolyte to the second composite containing the carbon dioxide adsorbent, conductivity is improved and the carbon dioxide absorption and release capacity is enhanced. 【0042】 The carbon dioxide absorption and release device 20 uses a porous second electrode layer 25 equipped with the composite 24 described above as the working electrode, and applies a charge to the carbon dioxide adsorbent of the composite 24 by applying a specific potential to this working electrode. Furthermore, by using a first electrode layer 21, which includes an electrode material having a composite 22 containing a ferrocene derivative chemically bonded to the surface of a first conductive material, as the counter electrode, the ferrocene derivative releases electrons, and a charge can be effectively supplied to the carbon dioxide adsorbent. The carbon dioxide adsorbent is also an oxidation-reduction active molecule, and by receiving electrons from the ferrocene derivative, it enters a reduced state and adsorbs carbon dioxide. In addition, by changing the potential in the carbon dioxide absorption and release device 20 from a certain potential to a different predetermined potential, the carbon dioxide adsorbent enters an oxidized state, and the carbon dioxide adsorbent desorbs carbon dioxide. In this way, by controlling the potential between the first electrode layer 21 and the second electrode layer 25, the oxidation-reduction state of the carbon dioxide adsorbent contained in the composite 24 can be switched between an oxidized state and a reduced state. Furthermore, because the ferrocene derivative, which is an oxidation-reduction active molecule, is chemically bonded to the surface of the first conductive material, it exhibits good adhesion to the surface of the first conductive material. 【0043】 The carbon dioxide absorption and release device 20 is a device that uses a composite material that absorbs and releases carbon dioxide using an electrically responsive carbon dioxide adsorbent, and can absorb and release carbon dioxide at room temperature. For this reason, it can be used in carbon dioxide recovery equipment contained in factory exhaust gas, atmospheric gas, etc. Furthermore, carbon dioxide separation and recovery technology is attracting a lot of attention from society, and the potential for industrial use of this device is very high. 【0044】 [Embodiment 3] <Electrode-type electrochemical cell> The carbon dioxide absorption and release device according to this embodiment may be an electrode-type electrochemical cell as shown in Figure 4. The carbon dioxide absorption and release device 30 shown in Figure 4 has a bipolar structure in which the stacked structure of the carbon dioxide absorption and release device 20 according to Embodiment 2 described above is provided on both sides of the first electrode layer 21, with the first electrode layer 21 at the center. Specifically, the carbon dioxide absorption and release device 30 comprises a first electrode layer 21 having a first surface and a second surface located opposite the first surface, a second electrode layer 25, a third electrode layer 26, a first insulating layer 23 located between the first surface and the second electrode layer 25, and a second insulating layer 23 located between the second surface and the third electrode layer 26. The first electrode layer 21 includes an electrode material including a composite 22 which is a first composite. The composite 22 includes a first conductive material which is a conductive material containing carbon, and a ferrocene derivative chemically bonded to its surface. The second electrode layer 25 and the third electrode layer 26 include a porous electrode material including a composite 24 which is a second composite. The second electrode layer 25 and the third electrode layer 26 may be porous. The composite 24 includes a carbon dioxide adsorbent and a second conductive material which is a conductive material containing carbon. The central first electrode layer 21 and the second electrode layers 25 and third electrode layers 26 at both ends are electrically connected via a power supply. The first insulating layer 23 and the second insulating layer 23 may be made of the same material or different materials. Similarly, the second electrode layer 25 and the third electrode layer 26 may be made of the same material or different materials. 【0045】 The carbon dioxide absorption and release device 30, like the carbon dioxide absorption and release device 20 according to Embodiment 2, is a device that uses a second composite that absorbs and releases carbon dioxide with an electrically responsive carbon dioxide adsorbent, and can absorb and release carbon dioxide at room temperature. For this reason, it can be used in a carbon dioxide recovery device that contains carbon dioxide in factory exhaust gas, the atmosphere, etc. Furthermore, because it has a bipolar structure, it is possible to miniaturize the cell stack compared to the stacked structure of the carbon dioxide absorption and release device, i.e., when the second electrode layer 25 is on only one side of the first electrode layer 21. In addition, the carbon dioxide absorption and release device 30 is particularly advantageous in that it increases the carbon dioxide absorption density. 【0046】 (Manufacturing method for carbon dioxide absorption and release devices) Next, we will describe the manufacturing method of the carbon dioxide absorption and release device 20. First, a carbon dioxide adsorbent is added to a second conductive material containing carbon, and the mixture is ultrasonically stirred in a solvent to obtain a suspension. Next, a base such as triethylamine is added to the obtained suspension, followed by heat treatment, washing, filtration, and vacuum drying to produce a composite 24 containing a carbon dioxide adsorbent chemically bonded to the surface of the second conductive material. Next, the obtained composite 24 is applied to the surface of a second electrode layer 25 containing a porous electrode material, and heated and dried to obtain a second electrode layer 25 having the composite 24 on its surface. In addition, a first electrode layer 21 is prepared separately by the manufacturing method described in Embodiment 1, which includes a composite 22 containing a ferrocene derivative chemically bonded to the surface of a first conductive material containing carbon. Next, an insulating layer 23 is prepared, and a first electrode layer 21 is laminated on one side of the insulating layer 23, and a second electrode layer 25 is laminated on the other side. At this time, the first electrode layer 21 is laminated so that the side having the composite 22 faces the insulating layer 23, and the second electrode layer 25 is laminated so that the side having the composite 24 faces the insulating layer 23. Next, the carbon dioxide absorption and release device 20 is manufactured by electrically connecting the first electrode layer 21 and the second electrode layer 25 via a power supply. 【0047】 (Method for separating and recovering carbon dioxide using a carbon dioxide absorption and release device) The carbon dioxide absorption and release device 20 can separate and recover carbon dioxide from a carbon dioxide-containing gas by adsorbing carbon dioxide onto the carbon dioxide adsorbent in the composite 24 contained in the second electrode layer 25. Furthermore, the carbon dioxide absorption and release device 20 can regenerate the carbon dioxide adsorbent by desorbing carbon dioxide from it. By applying a voltage between the first electrode layer 21 and the second electrode layer 25 so that the potential of the composite 24 becomes the reduction potential of the carbon dioxide adsorbent, and bringing the carbon dioxide-containing gas into contact with the composite 24 while maintaining the potential of the composite 24 at the reduction potential of the carbon dioxide adsorbent, carbon dioxide can be adsorbed onto the composite 24. By switching the voltage applied between the first electrode layer 21 and the second electrode layer 25 so that the potential of the composite 24, which has adsorbed carbon dioxide, becomes the oxidation potential of the carbon dioxide adsorbent, carbon dioxide can be desorbed from the composite 24 and the carbon dioxide adsorbent can be regenerated. After carbon dioxide has been separated from the composite 24, the carbon dioxide absorption and release device 20 can be set to the reduction potential again, allowing for the carbon dioxide adsorption process to be performed again. In this way, by switching the potential of the composite 24 between the reduction potential and the oxidation potential, the device can be used repeatedly. In the carbon dioxide absorption and release device 20, a first electrode layer 21 containing a composite 22 containing a ferrocene derivative chemically bonded to the surface of the first conductive material is used as the counter electrode. As a result, the ferrocene derivative releases electrons, and a good charge can be supplied to the carbon dioxide adsorbent. [Examples] 【0048】 The present disclosure will be described in further detail below with reference to examples, but the present disclosure is not limited thereto. 【0049】 <Test Example 1: (Example) Synthesis of p-phenylenediamine-modified polyvinylferrocene> 1.14 g of polyvinylferrocene (PVFc) was added to 1-methyl-2-pyrrolidone (NMP) to prepare a 260 mL mixed solution. Next, 5.76 g of tetrabutylammonium tetrafluoroboric acid (TBATFB) was added to the above mixed solution and dissolved. Next, after heating to 100°C, 1.90 g of p-phenylenediamine (p-PD) was added and the mixture was stirred using an ultra-high-speed stirrer. Next, 1.13 mL of tert-butyl nitrite (tBuONO) was gradually added dropwise to the solution, and the mixture was heated at 100°C for 1 hour. Next, the reaction solution was added to 5 L of a water-ethanol mixture (water:ethanol = 1:1) and reprecipitation was performed. Next, the precipitate was separated and washed by centrifugation and filtration. Washing was performed with a water-ethanol mixture. Next, the precipitate was weighed, and 0.75 g of the resulting precipitate was redissolved in 260 mL of NMP. 【0050】 <Test Example 2: (Example) Synthesis of a complex in which PVFc is chemically bonded to the surface of graphene oxide via p-phenylenediamine> Specific surface area 900m 2 Graphene oxide (manufactured by Nishina Material Co., Ltd., product name: Rap eGO(TQ-11)-10) with an oxidation state of 55.0% by mass was prepared at a concentration of / g. Next, in order to achieve a mass ratio of 1:3 between the synthesized product and graphene oxide in Test Example 1, 100 g of a 2.2 wt% graphene oxide aqueous solution was weighed out. Next, the mixture was centrifuged for 20 minutes, the supernatant was discarded, and then 200 mL of NMP was added and mixed by shaking. Next, the mixture was centrifuged for 20 minutes, the supernatant was discarded again, and the remaining graphene oxide precipitate was added to the solution prepared in Test Example 1 and stirred with a glass rod. Next, the mixture was stirred at 5000 rpm for 30 minutes using a laboratory mixer. Next, heating the mixture in an oil bath at 100°C for 30 hours changed its consistency to a paste. Next, in order to replace the solvent from NMP with Solmix® A-7 manufactured by Nippon Alcohol Sales Co., Ltd., the resulting paste was centrifuged at 12,000 g for 20 minutes. The supernatant solution was discarded, an appropriate amount of Solmix A-7 was added, and the mixture was shaken well. Washing by centrifugation was performed twice. Next, to obtain a complex, the precipitate was dispersed in 420 mL of Solmix A-7 to a total volume of approximately 440 mL (based on the amount of GO added, 5 mg / mL), and stirred at 6000 rpm for 30 minutes using a laboratory mixer. As shown in Figure 2, this complex is a first complex in which a ferrocene derivative 14 (PVFc) is chemically bonded to the surface of graphene oxide, the first conductive material 13, via p-phenylenediamine, which is the linker 15. 【0051】 <Test Example 3: (Example) Preparation of a sample having a complex in which PVFc is chemically bonded to the surface of graphene oxide via p-phenylenediamine> Two mL of the PVFc composite prepared in Test Example 2, in which the PVFc was chemically bonded to the surface of graphene oxide via p-phenylenediamine, and 0.2 mL of a 5% Nafion dispersion solution were placed in a sample tube. After sonication for 30 minutes, 4 μL was taken and dropped onto the surface of a glassy carbon electrode. The sample, which would serve as the first electrode layer for the test device, was dried at 70°C for 30 minutes. 【0052】 <Test Example 4: (Example) CV measurement of a sample having a complex in which PVFc is chemically bonded to the surface of graphene oxide via p-phenylenediamine> A three-electrode electrochemical cell configuration was adopted as the test device for the sample. The working electrode was the first electrode layer prepared in Test Example 3 (the sample), the counter electrode was a platinum electrode, and the reference electrode was a silver-silver chloride electrode (Ag / AgCl). The electrolyte used was 1-butyl,1-methylpyrrolidinium bis(trifluoromethanesulfonylimide) (BMP-TFSI). Each electrode was immersed in the electrolyte solution, and the potential was repeatedly switched within the range of 0V to 0.8V using a silver-silver chloride reference electrode as the reference. The current flowing through the electrodes was measured by scanning at a scanning speed of 10mV / s. In this manner, the electrochemical behavior of the composite was evaluated by cyclic voltammetry (CV) measurement by applying a voltage to the sample of the test device. An AMETEK VersaSTAT3 was used for the CV measurement. The CV measurement results are shown in Figure 5. 【0053】 <Test Example 5: (Example) Synthesis of 4-aminostyrene-modified polyvinylferrocene> 4.5 g of vinylferrocene and 0.4 g of 4-aminostyrene were dissolved in 50 mL of toluene. Next, 0.5 g of azoisobutyronitrile (AIBN) was added to the above mixed solution and dissolved. Next, the mixture was heated at 70°C for 56 hours. Next, the reaction solution was added to 450 mL of hexane and allowed to precipitate. Next, the solution was filtered to separate and wash the precipitate. Washing was performed with methanol. Next, the precipitate was weighed, and 0.7 g of the resulting precipitate was redissolved in 260 mL of NMP. 【0054】 <Test Example 6: (Example) Synthesis of a composite in which PVFc is chemically bonded to the surface of graphene oxide via 4-aminostyrene> Specific surface area 900m 2 Graphene oxide (manufactured by Nishina Material Co., Ltd., product name: Rap eGO(TQ-11)-10) with an oxidation state of 55.0% by mass was prepared at a concentration of / g. Next, in Test Example 5, to achieve a mass ratio of 1:3 between the synthesized product and graphene oxide, 100 g of a 2.2 wt% graphene oxide aqueous solution was weighed out. Next, the mixture was centrifuged for 20 minutes, the supernatant was discarded, and then 200 mL of NMP was added and mixed by shaking. Next, the mixture was centrifuged for 20 minutes, the supernatant was discarded again, and the remaining graphene oxide precipitate was added to the solution prepared in Test Example 5 and stirred with a glass rod. Next, the mixture was stirred at 5000 rpm for 30 minutes using a laboratory mixer. Next, heating the mixture in an oil bath at 100°C for 30 hours changed its consistency to a paste. Next, in order to replace the solvent from NMP with Solmix A-7 manufactured by Nippon Alcohol Sales Co., Ltd., the resulting paste was centrifuged at 12,000 g for 20 minutes. The supernatant solution was discarded, an appropriate amount of Solmix A-7 was added, and the mixture was shaken well. Washing by centrifugation was performed twice. Next, to obtain a complex, the precipitate was dispersed in 420 mL of Solmix A-7 to a total volume of approximately 440 mL (based on the amount of GO added, 5 mg / mL), and stirred at 6000 rpm for 30 minutes using a laboratory mixer. As shown in Figure 2, this complex is a first complex in which a ferrocene derivative 14 (PVFc) is chemically bonded to the surface of graphene oxide, the first conductive material 13, via aminostyrene, which is the linker 15. 【0055】 <Test Example 7: (Example) Preparation of a sample having a complex in which PVFc is chemically bonded to the surface of graphene oxide via 4-aminostyrene> Two mL of the PVFc composite prepared in Test Example 6, in which PVFc is chemically bonded to the surface of graphene oxide via aminostyrene, and 0.2 mL of a 5% Nafion dispersion solution were placed in a sample tube. After sonication for 30 minutes, 4 μL was collected and dropped onto the surface of a glassy carbon electrode. The sample, which would serve as the first electrode layer for the test device, was dried at 70°C for 30 minutes. 【0056】 <Test Example 8: (Example) CV measurement of a sample having a complex in which PVFc is chemically bonded to the surface of graphene oxide via 4-aminostyrene> A three-electrode electrochemical cell configuration was adopted as the test device for the sample. The working electrode was the first electrode layer prepared in Test Example 7, the counter electrode was a platinum electrode, and the reference electrode was a silver-silver chloride electrode (Ag / AgCl). The electrolyte used was 1-butyl,1-methylpyrrolidinium bis(trifluoromethanesulfonylimide) (BMP-TFSI). Each electrode was immersed in the electrolyte solution, and the potential was repeatedly switched within the range of 0V to 0.8V using a silver-silver chloride reference electrode as the reference. The current flowing through the electrodes was measured by scanning at a scanning speed of 10mV / s. In this manner, the electrochemical behavior of the composite was evaluated by cyclic voltammetry (CV) measurement after applying a voltage to the sample of the test device. An AMETEK VersaSTAT3 was used for the CV measurement. The CV measurement results are shown in Figure 6. 【0057】 <Test Example 9: (Comparative Example) Preparation of a sample containing a composite obtained by physically mixing PVFc and graphene oxide> 4.4 mg of PVFc powder, 13.3 mg of graphene oxide, 0.2 mL of 5% Nafion dispersion solution, and 2.0 mL of Solmix A-7 were taken and placed in a sample tube, and sonicated for 30 minutes to physically mix the PVFc and graphene oxide. Next, 4 μL of the solution from the sample tube was taken, dropped onto the surface of a glassy carbon electrode, and dried at 70°C for 30 minutes to prepare a sample for use in the test device. 【0058】 <Test Example 10: (Comparative Example) CV Measurement of a Sample Having a Composite Formed by Physical Mixing of PVFc and Graphene Oxide> A three-electrode electrochemical cell configuration was adopted as the test device for the sample. The sample prepared in Test Example 9 was used as the working electrode, a platinum electrode as the counter electrode, and a silver-silver chloride electrode (Ag / AgCl) as the reference electrode. The electrolyte used was 1-butyl,1-methylpyrrolidinium bis(trifluoromethanesulfonylimide) (BMP-TFSI). Each electrode was immersed in the electrolyte solution, and the potential was repeatedly switched within the range of 0V to 1.0V using a silver-silver chloride reference electrode as the reference. The current flowing through the electrodes was measured by scanning at a scanning speed of 10mV / s. In this manner, the electrochemical behavior of the composite was evaluated by cyclic voltammetry (CV) measurement after applying a voltage to the sample of the test device. An AMETEK VersaSTAT3 was used for the CV measurement. The CV measurement results are shown in Figure 7. 【0059】 <Test Example 11: (Example) Measurement of cycle maintenance rate of a device having a composite in which PVFc is chemically bonded to the surface of graphene oxide via p-phenylenediamine or 4-aminostyrene> For the test devices fabricated in Test Example 4 and Test Example 8, the cycle maintenance rate was measured after 100 cycles of potential switching. The cycle maintenance rate was defined as the charge amount after 100 cycles relative to the initial charge amount (100%). As a result, the cycle maintenance rate for Test Example 4 was 84.2%, and the cycle maintenance rate for Test Example 8 was 93.5%. 【0060】 <Consideration> As shown in Figures 5 and 6, in the embodiment, when the counter electrode was reduced, the samples prepared in Test Examples 3 and 7, which were the working electrodes, were simultaneously oxidized, resulting in the observation of a single oxidation peak. Similarly, in the reverse reaction, when the counter electrode was oxidized, the samples prepared in Test Examples 3 and 7, which were the working electrodes, were simultaneously reduced, resulting in the observation of a single reduction peak. Furthermore, the samples in the examples showed high reliability, as they did not degrade easily even after repeated cycles of the redox reaction. In addition, as shown in Test Example 11, which is an example, devices with a composite in which PVFc was chemically bonded to the graphene oxide surface via 4-aminostyrene having amino and alkene groups showed a higher cycle retention rate than devices with a composite in which PVFc was chemically bonded to the graphene oxide surface via p-phenylenediamine having a diamino group. On the other hand, in the comparative example, a sample in which PVFc and graphene oxide were physically mixed, i.e., in which PVFc was physically fixed to the graphene oxide surface, the oxidation-reduction characteristics were similar to those in Figure 5 during the initial cycle, as shown in Figure 7, but the amount of charge decreased sharply from the second cycle onward. Thus, the first composite, in which an electron-transferable redox-active molecule is chemically bonded to the surface of a carbon-containing first conductive material, exhibits high electronic conductivity, and the redox-active molecule and the first conductive material are strongly bonded. A carbon dioxide absorption and release device having such a composite has high reliability. [Explanation of symbols] 【0061】 10, 20, 30 Carbon Dioxide Absorption and Release Devices 11, 22, 24 complex 12 Electrode materials 21 1st electrode layer 13. First conductive material 14 Ferrocene derivatives 15 Linker 23 Insulating layer 25 Second electrode layer 26 Third electrode layer

Claims

[Claim 1] A first electrode layer comprising a first conductive material containing one or more carbons selected from the group consisting of graphene oxide, carbon nanotubes, and graphene mesosponge, and a first composite containing a ferrocene derivative covalently bonded to the surface of the first conductive material via a linker, A second electrode layer comprising a porous electrode material having a second composite on its surface, which includes a carbon dioxide adsorbent and a second conductive material containing carbon, An insulating layer located between the first electrode layer and the second electrode layer, A carbon dioxide absorption and release device equipped with the following features. [Claim 2] The carbon dioxide absorption and release device according to claim 1, wherein the ferrocene derivative has an amino group. [Claim 3] The carbon dioxide absorption and release device according to claim 1, wherein the ferrocene derivative has a carboxyl group. [Claim 4] The carbon dioxide absorption and release device according to claim 1, wherein the ferrocene derivative has an alkene group. [Claim 5] The carbon dioxide absorption and release device according to claim 1, wherein the linker has an amino group. [Claim 6] The carbon dioxide absorption and release device according to claim 1, wherein the linker has an alkene group. [Claim 7] The carbon dioxide absorption and release device according to claim 1, wherein the first conductive material has one or more shapes selected from the group consisting of sheet-like, flake-like, stick-like, fiber-like, tubular, and flake-like forms. [Claim 8] The carbon dioxide absorption and release device according to claim 1, further comprising an electrolyte held in the first composite. [Claim 9] The electrode material comprises one or more materials selected from the group consisting of carbon, aluminum, copper, stainless steel, and nickel, and further comprises a current collector having one or more shapes selected from the group consisting of sheet-like, flake-like, stick-like, plate-like, and mesh-like. The carbon dioxide absorption and release device according to claim 1, wherein the surface of the current collector has the first composite. [Claim 10] A first electrode layer comprising a first conductive material containing one or more carbons selected from the group consisting of graphene oxide, carbon nanotubes, and graphene mesosponge, and a first composite comprising a ferrocene derivative covalently bonded to the surface of the first conductive material via a linker, A second electrode layer comprising a porous electrode material having a second composite on its surface, which includes a carbon dioxide adsorbent and a second conductive material containing carbon, An insulating layer located between the first electrode layer and the second electrode layer, Equipped with, The first electrode layer has a first surface and a second surface located on the opposite side of the first surface. A second electrode layer and a third electrode layer, each comprising a porous electrode material having a second composite on its surface, which includes a carbon dioxide adsorbent and a second conductive material containing carbon, A first insulating layer located between the first surface and the second electrode layer, A second insulating layer located between the second surface and the third electrode layer and A carbon dioxide absorption and release device equipped with the following features.

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