Carbon dioxide capture and release device

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

Carbon dioxide absorption and release device

[0001] The present disclosure relates to a carbon dioxide absorption and release device.

[0002] Carbon dioxide separation and capture has attracted attention as a technology for reducing the greenhouse gas carbon dioxide (CO2). Carbon dioxide separation and capture technology is mainly used to separate and capture carbon dioxide contained in exhaust gases from factories and in the atmosphere from other substances.

[0003] The captured carbon dioxide can be used in "Carbon dioxide Capture and Utilization (CCU)," which uses carbon dioxide to produce chemicals, fuels, etc., and "Carbon dioxide Capture and Storage (CCS)," which stores carbon dioxide deep underground. These technologies for capturing, utilizing, and storing carbon dioxide are called "CCUS."

[0004] Japanese Patent Application Laid-Open No. 2023-033072

[0005] S. Voskian, TA Hatton, Energy Environ. Sci., 12, 3530 (2019)

[0006] One aspect of this embodiment is a carbon dioxide absorption / release device as follows: (1) A carbon dioxide absorption / release device comprising: a first composite including a first conductive material containing carbon and a ferrocene derivative chemically bonded to the surface of the first conductive material; and an electrode material having the first composite on its surface. (2) The carbon dioxide absorption / release device according to (1), in which the ferrocene derivative has an amino group. (3) The carbon dioxide absorption / release device according to (1), in which the ferrocene derivative is chemically bonded to the surface of the first conductive material via a linker. (4) The carbon dioxide absorption / release device according to (3), in which the ferrocene derivative has a carboxy group. (5) The carbon dioxide absorption / release device according to (3), in which the ferrocene derivative has an alkene group. (6) The carbon dioxide absorption / release device according to (3), in which the linker has an amino group. (7) The carbon dioxide absorption / release device according to (3), in which the linker has an alkene group. (8) The carbon dioxide absorption / 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, ordered mesoporous carbon, and graphene mesosponge. (9) The carbon dioxide absorption / 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 a sheet, a thin plate, a stick, a fiber, a tube, and a flake. (10) The carbon dioxide absorption / release device according to any one of (1) to (9), further comprising an electrolyte held in the first composite. (11) The carbon dioxide absorption / release device according to any one of (1) to (10), wherein the electrode material includes one or more selected from the group consisting of carbon, aluminum, copper, stainless steel, and nickel, and further includes a current collector having one or more shapes selected from the group consisting of a sheet, a flake, a stick, a plate, and a mesh, and the first composite is disposed on a surface of the current collector.(12) The carbon dioxide absorption / release device according to any of (1) to (11), comprising: a first electrode layer containing the electrode material, a second electrode layer containing a porous electrode material having on its surface a second composite containing a carbon dioxide adsorbent and a second conductive material containing carbon, and an insulating layer located between the first electrode layer and the second electrode layer. (13) The carbon dioxide absorption / release device according to any of (1) to (11), comprising: a first electrode layer containing 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 containing a porous electrode material having on its surface a second composite containing 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, and a second insulating layer located between the second surface and the third electrode layer.

[0007] FIG. 1 is a schematic diagram of a carbon dioxide absorption and release device 10 according to embodiment 1, which is one aspect of the present embodiment. FIG. 2 is a schematic diagram showing an example of the structure of a composite 11 according to embodiment 1. FIG. 3 is a schematic diagram of a carbon dioxide absorption and release device 20 according to embodiment 2, which is one aspect of the present embodiment. FIG. 4 is a schematic diagram of a carbon dioxide absorption and release device 30 according to embodiment 3, which is one aspect of the present embodiment. FIG. 5 is a graph showing the CV measurement results according to test example 4. FIG. 6 is a graph showing the CV measurement results according to test example 8. FIG. 7 is a graph showing the CV measurement results according to test example 10.

[0008] In the carbon dioxide absorption / release devices disclosed in Non-Patent Document 1 and Patent Document 1, redox-active molecules capable of donating and receiving electrons to a carbon dioxide absorbent are physically fixed to the surface of a conductive material such as carbon nanotubes. Physical fixation leaves room for improvement in terms of binding strength. Therefore, it is desirable to provide a carbon dioxide absorption / release device with high electronic conductivity and high binding strength 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 that appropriate design changes, improvements, and the like may be made based on the ordinary knowledge of those skilled in the art within the scope of the present disclosure.

[0009] [Embodiment 1] (Configuration of Carbon Dioxide Absorption / Release Device) Fig. 1 shows a schematic diagram of a carbon dioxide absorption / release device 10 according to embodiment 1 of the present disclosure. The configuration shown in Fig. 1 is an example, and is not limited to this. The carbon dioxide absorption / release device 10 has a composite 11 on the surface of an electrode material 12. When the electrode material 12 is plate-shaped as shown in Fig. 1, the composite 11 may be located on both surfaces of the electrode material 12, or on only one surface. The composite 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 composite 11, which is the first composite of the carbon dioxide absorption / release device 10, includes a carbon-containing first conductive material and a ferrocene derivative chemically bonded to its surface. The ferrocene derivative may include an amino group (NH-) or an alkene group (CH=CH-), and may be chemically bonded to the surface of the carbon-containing first conductive material via a linker. FIG. 2 shows one embodiment of the structure of the composite 11. In the embodiment shown in FIG. 2, the composite 11 includes polyvinylferrocene, a ferrocene derivative 14, chemically bonded to the surface of graphene oxide, a carbon-containing first conductive material 13, via a linker 15 (diazonium salt of p-phenylenediamine). Hereinafter, the carbon-containing first conductive material will be simply referred to as the first conductive material.

[0011] <First Conductive Material> The first conductive material contained in the composite 11 may contain a carbon material having good conductivity. The carbon material may be one or more selected from the group consisting of graphene oxide, carbon nanotubes, activated carbon, ordered mesoporous carbon, and graphene meso-sponge. The shape of the first conductive material is not particularly limited, and a shape suitable for the desired device configuration may be used. The first conductive material may have one or more shapes selected from the group consisting of, for example, a sheet, a thin film, a stick, a fiber, a tube, and a flake. 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 approximately 1 nm, which has numerous oxygen-containing functional groups, such as hydroxyl groups, carboxyl groups, carbonyl groups, and epoxy groups, on the surface of the single-layer graphene.

[0013] Graphene oxide has a sheet-like or flake-like structure and is highly flexible, so that the composite 11 using graphene oxide as the first conductive material has high flexibility.

[0014] As described above, the graphene oxide is not particularly limited as long as it is a sheet-like or flake-like structure having a thickness of about 1 nm and has a large number of oxygen-containing functional groups on the surface of the single-layer graphene. For example, reduced graphene oxide, modified graphene oxide, etc. can be used as the graphene oxide. Reduced graphene oxide is graphene oxide having functional groups in which some or all of the many oxygen-containing functional groups have been reduced. Modified graphene oxide is graphene oxide having functional groups in which some or all of the many oxygen-containing functional groups have been modified with desired functional groups.

[0015] Carbon nanotubes are substances made of carbon and have properties such as high electrical conductivity, light weight, high strength, large specific surface area, and flexibility. Carbon nanotubes are carbon-based materials having a cylindrical shape formed by rolling up graphene sheets. Carbon nanotubes include single-walled carbon nanotubes and multi-walled carbon nanotubes depending on the number of peripheral walls. Composites 11 using single-walled carbon nanotubes have high flexibility. On the other hand, composites 11 using multi-walled carbon nanotubes have high strength. Carbon nanotubes may have a chiral (spiral) structure, a zigzag structure, an armchair structure, or the like.

[0016] Activated carbon is a substance whose main component is carbon that has been subjected to chemical or physical treatment (activation / activation). The surface of activated carbon is highly porous, and the interior of its tiny holes (pores) is complexly developed. This structure allows activated carbon to adsorb many substances, mainly organic matter. The activated carbon contained in the composite 11 can be processed into shapes such as sheets, flakes, sticks, and tubes for use.

[0017] Regular mesoporous carbon is porous carbon with regular pores having diameters of 2 to 50 nm. The surface of regular mesoporous carbon is highly porous, and this structure allows it to adsorb many substances, primarily organic matter. In addition, regular mesoporous carbon has uniform pores and exhibits superior diffusion and molecular selectivity compared to activated carbon, which has non-uniform pore sizes, thereby further improving the functionality of the carbon dioxide absorption / release device 10. The regular mesoporous carbon contained in the composite 11 can be processed into shapes such as sheets, flakes, sticks, and tubes for use.

[0018] Graphene meso sponge is a new carbon material developed by Tohoku University. It features a bubble-like pore structure of 3 to 8 nm and pore walls composed of a single, defect-free graphene sheet. Graphene meso sponge's precisely designed nanostructure achieves both excellent porosity and oxidation resistance, i.e., chemical durability, far exceeding those of conventional carbon materials. Furthermore, graphene meso sponge's flexibility allows it to be reversibly compressed and restored. This allows it to follow the movements of the active material, which undergoes drastic structural changes during charging and discharging, and it also has excellent mechanical durability.

[0019] <Ferrocene Derivative> The ferrocene derivative is chemically bonded to the surface of the first conductive material. The ferrocene derivative may 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. The ferrocene derivative may have a basic skeleton of polyvinylferrocene, as shown in the following formula (1). The carbon atoms of the two five-membered rings of ferrocene may each independently have a substituent. A linker can be formed between the ferrocene derivative and the carbon atom of the first conductive material through this substituent. The substituent may be an amino group (NH2-) or an alkene group (CH2=CH-). Alternatively, the carbon atom of the five-membered ring of ferrocene may be directly bonded to the carbon atom of the first conductive material.

[0020]

[0021] The ferrocene derivative is a redox-active molecule. When oxidized, the ferrocene derivative releases an electron to become a +1-valent cation, and when reduced, it receives an electron and returns to its original neutral state. Therefore, by maintaining a predetermined potential in the carbon dioxide absorption / release device 10, the ferrocene derivative releases an electron. Furthermore, since the ferrocene derivative, which is a redox-active molecule, is chemically bonded to the surface of the first conductive material, it has good adhesion to the surface of the first conductive material. In this way, by modifying the surface of the first conductive material with the ferrocene derivative through chemical bonding, it is possible to provide a carbon dioxide absorption / release device with high electronic conductivity and high adhesion between the active molecule and the conductive material.

[0022] The linker is not particularly limited as long as it can chemically bond to the functional group of the five-membered ring of the ferrocene derivative and simultaneously to the carbon atom of the conductive material, and may be a linker having an amino group. Examples of linkers having an amino group include linear carbon chain diamines and phenylenediamines such as p-phenylenediamine. Furthermore, while the number of carbon atoms in the diamine is not particularly limited, linear carbon chain diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine (hexamethylenediamine) may be used. Linear carbon chain diamines have high alkyl chain mobility, which facilitates the five-membered ring of the ferrocene derivative to approach the carbon surface. In particular, ethylenediamine is a linear carbon chain diamine with a short carbon chain, making it an extremely 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 an amino group and an alkene group. Examples of linkers having an amino group and an alkene group that can be used include aminostyrene shown in the following formula (3), allylamine shown in the following formula (4), N-(allyl)ethylenediamine, and aminoethyl methacrylate (AEMA).

[0024]

[0025] The alkene group of aminostyrene and the alkene group of vinylferrocene are easily radically polymerized, making it easier to produce an aminostyrene-polyvinylferrocene copolymer, and allowing the amount of modification to be increased.

[0026] The composite 11 may further include an electrolyte. The electrolyte component is not particularly limited, but may be an ion-bonding salt, a solid electrolyte, or an ion-conductive polymer.

[0027] <Electrode Material> The electrode material 12 of the carbon dioxide absorption and release device 10 may include a current collector on the surface of which the composite 11 is provided. A known electrode material can be used for the current collector. The current collector may include, for example, one or more materials selected from the group consisting of carbon, aluminum, copper, stainless steel, and nickel. The current collector may be formed into one or more shapes selected from the group consisting of a sheet, a flake, a stick, a plate, and a mesh. The current collector may be porous.

[0028] The current collector functions as a conductor for transmitting charge to the composite 11 and causing 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 or reduced, causing the ferrocene derivative to release electrons.

[0029] The electrode material 12 of the carbon dioxide absorption and release device 10 may further include another conductive material containing carbon in addition to the first conductive material contained in the composite 11. By further including another conductive material, it is possible to reinforce the electrical connection between the composites 11. Furthermore, when the electrode material 12 includes a current collector, it is possible to reinforce the electrical connection between the composite 11 and the current collector. As such another conductive material, like the first conductive material contained in the composite 11 described above, graphene oxide, carbon nanotubes, activated carbon, ordered mesoporous carbon, graphene mesosponge, etc. may be used.

[0030] (Method for Manufacturing a Carbon Dioxide Absorption / Release Device) Next, as an example of a method for manufacturing a carbon dioxide absorption / release device 10, a case in which a ferrocene derivative is chemically bonded to the surface of a first conductive material via a linker will be described. First, the ferrocene derivative is mixed with an organic solvent. Next, the mixed solution is heated, and then a linker raw material such as ethylenediamine, hexamethylenediamine, p-phenylenediamine, aminostyrene, or allylamine is added and ultrasonically stirred. Next, an organic solvent is added and dissolved to form a reaction solution, and then the reaction solution is placed in a water-ethanol mixed solution or the like to cause reprecipitation. Next, centrifugation and filtration are performed to separate and wash the precipitate, and then the precipitate is dissolved in an organic solvent to produce a solution of a ferrocene derivative modified with a linker. Next, an aqueous solution of the first conductive material is prepared, and after centrifuging and discarding the supernatant solution, an organic solvent is added and the mixture is shaken and mixed. Next, centrifugation is performed again, and the supernatant solution is discarded. The remaining precipitate of the first conductive material is introduced into the solution of the ferrocene derivative modified with the linker and stirred to obtain a mixed solution. Next, the mixed solution is heated to form a paste-like mixture. Thereafter, the solvent is replaced with another solvent if necessary, for example, from the viewpoint of affinity with the binder. Next, the obtained paste-like mixture is centrifuged to discard the supernatant solution, and 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 an electrode material and heated and dried, thereby forming the composite 11 on the surface of the electrode material 12. In this manner, the carbon dioxide absorption and release device 10 can be produced.

[0031] [Embodiment 2] <Electrode-Type Electrochemical Cell> The carbon dioxide absorption / release device according to this embodiment may be an electrode-type electrochemical cell as shown in FIG. 3. The carbon dioxide absorption / release device 20 shown in FIG. 3 includes 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 containing 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 the surface of the first conductive material. The second electrode layer 25 includes a porous electrode material containing 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 source. Although the first electrode layer 21 and the composite 22 are shown separately in FIG. 3 for ease of understanding, the first electrode layer 21 may include the composite 22 therein. The second electrode layer 25 may contain the composite 24 therein.

[0032] The electrode material including the composite 22 contained in the first electrode layer 21 of the carbon dioxide absorption and release device 20 has a configuration similar to the electrode material 12 having the composite 11 on its surface in the carbon dioxide absorption and release device 10 according to the above-described embodiment 1. The surface of the first electrode layer 21 including the electrode material having the composite 22 faces the insulating layer 23.

[0033] The insulating layer 23 is disposed between the first electrode layer 21 and the second electrode layer 25 to separate the first electrode layer 21 and the second electrode layer 25. The insulating layer 23 reduces the occurrence of physical contact between the first electrode layer 21 and the second electrode layer 25, making it less likely for an electrical short circuit to occur. The insulating layer 23 can be a separator or a gas layer such as air. The separator may be a porous material. Examples of materials for the separator include a cellulose film, a resin, and a composite material of resin and ceramic.

[0034] The surface of the second electrode layer 25 having the composite 24 contained in the porous electrode material faces the insulating layer 23 .

[0035] The carbon-containing second conductive material may 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 may be the materials described in the first embodiment. Furthermore, when the second conductive material is a powder, its particle size may be 100 nm or less. This configuration allows the second conductive material to have a large surface area, which allows for enhanced penetration of carbon dioxide and the electrolyte, thereby providing a better carbon dioxide absorption / release device. When the second conductive material is a powder, the lower limit of the particle size is not particularly limited, but in practice it can be set to 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, and the reduced carbon dioxide adsorbent is returned to its original state by desorption and oxidation of carbon dioxide, and by repeating this process. Examples of carbon dioxide adsorbents with such properties include anthraquinone derivatives. Anthraquinone derivatives are redox-active molecules, and as shown in the following formula (2), when an anthraquinone (skeleton) is reduced in the presence of carbon dioxide (E1), carbon dioxide reacts with one of the oxygen atoms to produce carbonate. When further reduced (E'1), carbon dioxide reacts with the other oxygen atom to produce carbonate. The reverse reaction is also possible, and the reduced anthraquinone (skeleton) is returned to its original anthraquinone (skeleton) state by repeatedly desorption and oxidation of carbon dioxide.

[0037]

[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 may be made of a known material used as an electrode. The material of the current collector may include, for example, one or more materials 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 a sheet, a flake, a stick, a plate, and a mesh.

[0039] The current collector is a conductor that transmits electric charge to the composite 24 to cause the carbon dioxide adsorbent to respond electrically. By changing the potential of the current collector, the carbon dioxide adsorbent contained in the composite 24 is oxidized and reduced, and carbon dioxide can be adsorbed and released by the carbon dioxide adsorbent.

[0040] The carbon dioxide absorption / release device 20 adsorbs and releases carbon dioxide in a carbon dioxide adsorbent by changing the potential applied to the device. That is, the carbon dioxide absorption / release device 20 performs gas adsorption / desorption using an electrochemical swing process in which a specific potential is maintained in the forward direction and a different potential is maintained in the reverse direction, repeatedly. In this process, affinity for a substance to be adsorbed, such as carbon dioxide, can be adjusted by using a redox-active molecule that can be oxidized at a predetermined potential and reduced at a different potential. The carbon dioxide absorption / release device 20 can absorb and release carbon dioxide at room temperature by using a composite 24 that absorbs and releases carbon dioxide using such a redox-active molecule.

[0041] The composite 24 may further contain an electrolyte. The component of the electrolyte is not particularly limited, but may be an ion-bonding salt, a solid electrolyte, an ion-conductive polymer, or the like. By further including an electrolyte in the second composite containing the carbon dioxide adsorbent, the electrical conductivity is improved, and the carbon dioxide absorption and release capacity is increased.

[0042] The carbon dioxide absorption / release device 20 uses a porous second electrode layer 25 including the composite 24 described above as a working electrode. A specific potential is applied to this working electrode to apply a charge to the carbon dioxide adsorbent of the composite 24. Furthermore, by using a first electrode layer 21 including an electrode material having a surface on which a composite 22 containing a ferrocene derivative chemically bonded to the surface of a first conductive material is formed as a counter electrode, the ferrocene derivative releases electrons, effectively supplying a charge to the carbon dioxide adsorbent. The carbon dioxide adsorbent is also a redox-active molecule, and receives electrons from the ferrocene derivative to become reduced and adsorb carbon dioxide. Furthermore, by changing the potential of the carbon dioxide absorption / release device 20 from a specific potential to a different predetermined potential, the carbon dioxide adsorbent becomes oxidized, 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 redox state of the carbon dioxide adsorbent included in the composite 24 can be switched between an oxidized state and a reduced state. Furthermore, since the ferrocene derivative, which is a redox active molecule, is chemically bonded to the surface of the first conductive material, the binding to the surface of the first conductive material is good.

[0043] The carbon dioxide absorption / release device 20 is a device that uses a composite that absorbs and releases carbon dioxide using an electrically responsive carbon dioxide adsorbent, and can absorb and release carbon dioxide at room temperature. Therefore, it can be used in equipment for capturing carbon dioxide contained in factory exhaust gases, the atmosphere, etc. Furthermore, carbon dioxide separation and capture technology has attracted a lot of attention in 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 Fig. 4. The carbon dioxide absorption and release device 30 shown in Fig. 4 has a bipolar structure in which the layered structure of the carbon dioxide absorption and release device 20 according to the second embodiment 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 includes the 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 that is a first composite. The composite 22 includes a first conductive material that is a carbon-containing conductive material, and a ferrocene derivative chemically bonded to the surface of the first conductive material. The second electrode layer 25 and the third electrode layer 26 include a porous electrode material containing 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 is electrically connected to the second electrode layers 25 and the third electrode layers 26 at both ends via a power source. The first insulating layer 23 and the second insulating layer 23 may be made of the same material or different materials. Furthermore, the second electrode layer 25 and the third electrode layer 26 may be made of the same material or different materials.

[0045] Like the carbon dioxide absorption / release device 20 according to the second embodiment, the carbon dioxide absorption / release device 30 is a device that uses a second composite that absorbs and releases carbon dioxide using an electrically responsive carbon dioxide adsorbent, and is capable of absorbing and releasing carbon dioxide at room temperature. Therefore, it can be used in devices for recovering carbon dioxide contained in factory exhaust gases, the atmosphere, and the like. Furthermore, because it has a bipolar structure, the cell stack can be made smaller than a laminated structure of a carbon dioxide absorption / release device, i.e., a device having the second electrode layer 25 on only one side of the first electrode layer 21. Furthermore, the carbon dioxide absorption / release device 30 is particularly advantageous in that it increases the carbon dioxide absorption density.

[0046] (Method of Manufacturing Carbon Dioxide Absorption / Desorption Device) Next, a method of manufacturing the carbon dioxide absorption / desorption device 20 will be described. 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, and the mixture is heated, washed, filtered, and then vacuum-dried to produce a composite 24 containing the 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 the mixture is heated and dried to obtain a second electrode layer 25 having the composite 24 on its surface. Separately, a first electrode layer 21 containing a composite 22 containing a ferrocene derivative chemically bonded to the surface of a first conductive material containing carbon is prepared by the manufacturing method described in embodiment 1. Next, an insulating layer 23 is prepared, and the first electrode layer 21 is laminated on one surface of the insulating layer 23, and the second electrode layer 25 is laminated on the other surface. At this time, the first electrode layer 21 is laminated so that the surface having the composite 22 faces the insulating layer 23, and the second electrode layer 25 is laminated so that the surface having the composite 24 faces the insulating layer 23. Next, the first electrode layer 21 and the second electrode layer 25 are electrically connected via a power source, thereby manufacturing the carbon dioxide absorption and release device 20.

[0047] (Method for Separating and Capturing Carbon Dioxide Using a Carbon Dioxide Absorption and Release Device) The carbon dioxide absorption and release device 20 can separate and capture carbon dioxide from a gas containing carbon dioxide by adsorbing carbon dioxide to the carbon dioxide adsorbent of the composite 24 contained in the second electrode layer 25. Furthermore, the carbon dioxide absorption and release device 20 can desorb carbon dioxide from the carbon dioxide adsorbent to regenerate the carbon dioxide adsorbent. Carbon dioxide can be adsorbed by the composite 24 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 then contacting the composite 24 with a gas containing carbon dioxide while maintaining the potential of the composite 24 at the reduction potential of the carbon dioxide adsorbent. Carbon dioxide can be desorbed from 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 that has adsorbed carbon dioxide becomes the oxidation potential of the carbon dioxide adsorbent, thereby regenerating the carbon dioxide adsorbent. By setting the carbon dioxide absorption and release device 20 after carbon dioxide has been separated from the composite 24 to the reduction potential again, the carbon dioxide adsorption process can be performed again. In this way, the potential of the complex 24 can be switched between a reduction potential and an oxidation potential, thereby enabling the device to be used repeatedly. In the carbon dioxide absorption / release device 20, the first electrode layer 21 including the complex 22 containing the ferrocene derivative chemically bonded to the surface of the first conductive material is further used as the counter electrode, so that the ferrocene derivative can release electrons and effectively supply charge to the carbon dioxide adsorbent.

[0048] The present disclosure will be described in more 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 260 mL of a mixed solution. Next, 5.76 g of tetrabutylammonium tetrafluoroborate (TBATFB) was added to the mixed solution and dissolved. Next, after heating at 100°C, 1.90 g of p-phenylenediamine (p-PD) was added and stirred with 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 mixed solution (water:ethanol = 1:1) to allow reprecipitation. Next, centrifugation and filtration were performed, and the precipitate was separated and washed. Washing was performed with a water-ethanol mixed solution. Next, the precipitate was weighed, and 0.75 g of the obtained precipitate was redissolved in 260 mL of NMP.

[0050] Test Example 2: (Example) Synthesis of a composite in which PVFc is chemically bonded to the surface of graphene oxide via p-phenylenediamine Specific surface area: 900 m 2Graphene oxide (manufactured by Nishina Materials Co., Ltd., product name: Rap eGO (TQ-11)-10) with a molecular weight of 1 / g and an oxidation degree of 55.0% by mass was prepared. Next, to achieve a mass ratio of the synthesized product to graphene oxide of 1:3 in Test Example 1, 100 g of a 2.2 wt % graphene oxide aqueous solution was weighed out. Next, centrifugation was performed for 20 minutes, and after discarding the supernatant solution, 200 mL of NMP was added and the mixture was shaken. Next, centrifugation was performed for 20 minutes, and after discarding the supernatant solution again, 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 5,000 rpm for 30 minutes in a laboratory mixer. Next, the mixture was heated at 100°C for 30 hours in an oil bath, whereby the state changed to a paste. Next, to replace the NMP solvent with Solmix (registered trademark) A-7 manufactured by Japan Alcohol Sales Co., Ltd., the resulting paste was centrifuged at 12,000 g for 20 minutes. The supernatant solution was discarded, and an appropriate amount of Solmix A-7 was added, followed by thorough shaking. Washing by centrifugation was performed twice. Next, the precipitate was dispersed in 420 mL of Solmix A-7 to a total volume of approximately 440 mL (5 mg / mL based on the amount of GO added), and the mixture was stirred at 6,000 rpm for 30 minutes using a laboratory mixer to obtain a composite. As shown in Figure 2, this composite is a first composite in which a ferrocene derivative 14 (PVFc) is chemically bonded to the surface of graphene oxide, the first conductive material 13, via p-phenylenediamine, the linker 15.

[0051] Test Example 3 (Example) Preparation of a sample having a composite in which PVFc is chemically bonded to the surface of graphene oxide via p-phenylenediamine 2 mL of the composite in which PVFc is chemically bonded to the surface of graphene oxide via p-phenylenediamine, prepared in Test Example 2, and 0.2 mL of a 5% Nafion dispersion solution were placed in a sample tube, and after ultrasonic treatment for 30 minutes, 4 μL was taken and dropped onto the surface of a glassy carbon electrode, and dried at 70° C. for 30 minutes to prepare a sample that was the first electrode layer to be used in a test device.

[0052] Test Example 4: (Example) CV Measurement of a Sample Having a Composite in Which PVFc is Chemically Bonded to the Surface of Graphene Oxide via p-Phenylenediamine A three-electrode electrochemical cell was used as a test device for the sample. The working electrode was the sample, which was the first electrode layer prepared in Test Example 3, a platinum electrode was used as the counter electrode, and a silver-silver chloride electrode (Ag / AgCl) was used as the reference electrode. 1-Butyl, 1-methylpyrrolidinium bis(trifluoromethanesulfonylimide) (BMP-TFSI) was used as the electrolyte. Each electrode was immersed in the electrolyte, and the potential was repeatedly switched between 0 V and 0.8 V relative to the silver-silver chloride reference electrode, and the current flow was measured by scanning at a scan rate of 10 mV / s. In this way, a voltage was applied to the test device sample, and the electrochemical behavior of the composite was evaluated by cyclic voltammetry (CV) measurement. CV measurements were performed using a VersaSTAT3 electrometer manufactured by AMETEK Corporation. The results of the CV measurement are shown in FIG.

[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 poured into 450 mL of hexane to cause precipitation. Next, filtration was performed, and the precipitate was separated and washed. The washing was performed with methanol. Next, the precipitate was weighed, and 0.7 g of the obtained 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: 900 m 2Graphene oxide (manufactured by Nishina Materials Co., Ltd., product name: Rap eGO (TQ-11)-10) with a molecular weight of 1 / g and an oxidation degree of 55.0% by mass was prepared. Next, to achieve a mass ratio of the synthesized product to graphene oxide of 1:3 in Test Example 5, 100 g of a 2.2 wt % graphene oxide aqueous solution was weighed. Next, centrifugation was performed for 20 minutes, and after discarding the supernatant solution, 200 mL of NMP was added and the mixture was shaken. Next, centrifugation was performed for 20 minutes, and after discarding the supernatant solution again, 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 5,000 rpm for 30 minutes in a laboratory mixer. Next, the mixture was heated at 100°C in an oil bath for 30 hours, resulting in a paste-like state. Next, to replace the NMP solvent with Solmix A-7 (manufactured by Japan Alcohol Sales Co., Ltd.), the resulting paste was centrifuged at 12,000 g for 20 minutes. The supernatant solution was discarded, and an appropriate amount of Solmix A-7 was added, followed by thorough shaking. Washing by centrifugation was performed twice. Next, the precipitate was dispersed in 420 mL of Solmix A-7 to make the total volume approximately 440 mL (5 mg / mL based on the amount of GO added), and the mixture was stirred at 6000 rpm for 30 minutes using a laboratory mixer to obtain a composite. As shown in Figure 2, this composite is a first composite in which a ferrocene derivative 14 (PVFc) is chemically bonded to the surface of graphene oxide, the first conductive material 13, via aminostyrene, the linker 15.

[0055] Test Example 7 (Example) Preparation of a sample having a composite in which PVFc is chemically bonded to the surface of graphene oxide via 4-aminostyrene 2 mL of the composite in which PVFc is chemically bonded to the surface of graphene oxide via aminostyrene, prepared in Test Example 6, and 0.2 mL of a 5% Nafion dispersion solution were placed in a sample tube, and after ultrasonic treatment for 30 minutes, 4 μL was taken and dropped onto the surface of a glassy carbon electrode, and dried at 70°C for 30 minutes to prepare a sample that was the first electrode layer to be used in a test device.

[0056] Test Example 8: (Example) CV Measurement of a Sample Having a Composite in Which PVFc is Chemically Bonded to the Graphene Oxide Surface via 4-Aminostyrene A three-electrode electrochemical cell was used as a test device for the sample. The working electrode was the sample, which was the first electrode layer prepared in Test Example 7, a platinum electrode was used as the counter electrode, and a silver-silver chloride electrode (Ag / AgCl) was used as the reference electrode. 1-Butyl, 1-methylpyrrolidinium bis(trifluoromethanesulfonylimide) (BMP-TFSI) was used as the electrolyte. Each electrode was immersed in the electrolyte, and the potential was repeatedly switched between 0 V and 0.8 V relative to the silver-silver chloride reference electrode at a scan rate of 10 mV / s to measure the flowing current. By applying a voltage to the test device sample in this way, the electrochemical behavior of the composite was evaluated by cyclic voltammetry (CV) measurement. A VersaSTAT3 (manufactured by AMETEK) 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 Having a Composite Physically Mixed with PVFc and Graphene Oxide 4.4 mg of PVFc powder, 13.3 mg of graphene oxide, 0.2 mL of a 5% Nafion dispersion, and 2.0 mL of Solmix A-7 were placed in a sample tube and ultrasonicated for 30 minutes to physically mix the PVFc and graphene oxide. Next, 4 μL of the solution in the sample tube was dropped onto the surface of a glassy carbon electrode and dried at 70° C. for 30 minutes to prepare a sample for use in a test device.

[0058] Test Example 10: (Comparative Example) CV Measurement of a Sample Having a Composite Physically Mixed with PVFc and Graphene Oxide A three-electrode electrochemical cell was used as a 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. 1-butyl, 1-methylpyrrolidinium bis(trifluoromethanesulfonylimide) (BMP-TFSI) was used as the electrolyte. Each electrode was immersed in the electrolyte, and the potential was repeatedly switched between 0 V and 1.0 V relative to the silver-silver chloride reference electrode, and the current flow was measured by scanning at a scan rate of 10 mV / s. In this way, a voltage was applied to the test device sample, and the electrochemical behavior of the composite was evaluated by cyclic voltammetry (CV) measurement. A VersaSTAT3 manufactured by AMETEK was used for the CV measurement. The CV measurement results are shown in Figure 7.

[0059] Test Example 11: (Example) Measurement of Cycle Retention Rate of 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 prepared in Test Example 4 and Test Example 8, the cycle retention rate after 100 cycles of potential switching was measured. The cycle retention rate was defined as the charge amount after 100 cycles relative to the initial charge amount (100%). As a result, the cycle retention rate of Test Example 4 was 84.2%, and the cycle retention rate of Test Example 8 was 93.5%.

[0060] <Discussion> As shown in Figures 5 and 6, in the Examples, when the counter electrode was reduced, one oxidation peak was observed due to the simultaneous oxidation of the working electrode samples prepared in Test Examples 3 and 7. In the reverse reaction, when the counter electrode was oxidized, one reduction peak was observed due to the simultaneous reduction of the working electrode samples prepared in Test Examples 3 and 7. Furthermore, the samples of the Examples were resistant to degradation and highly reliable even after repeated redox reaction cycles. Additionally, as shown in Test Example 11, a device having a composite in which PVFc was chemically bonded to the graphene oxide surface via 4-aminostyrene having amino and alkene groups exhibited a higher cycle retention rate than a device having a composite in which PVFc was chemically bonded to the graphene oxide surface via p-phenylenediamine having diamino groups. On the other hand, 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, exhibited redox characteristics similar to those in Figure 5 in the initial cycles, as shown in Figure 7, but the charge amount rapidly decreased from the second cycle onwards. In this way, the first complex, in which the redox-active molecule capable of donating and receiving electrons to the carbon dioxide adsorbent is chemically bonded to the surface of the first conductive material containing carbon, has high electronic conductivity and the redox-active molecule and the first conductive material are strongly bound together. A carbon dioxide absorption / release device having such a complex has high reliability.

[0061] 10, 20, 30 Carbon dioxide absorption / release device 11, 22, 24 Composite 12 Electrode material 21 First electrode layer 13 First conductive material 14 Ferrocene derivative 15 Linker 23 Insulating layer 25 Second electrode layer 26 Third electrode layer

Claims

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, activated carbon, and graphene mesosponge, and a first composite comprising a ferrocene derivative chemically bonded to the surface of the first conductive 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 equipped with the following features.

2. The carbon dioxide absorption and release device according to claim 1, wherein the ferrocene derivative has an amino group.

3. The carbon dioxide absorption and release device according to claim 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 claim 3, wherein the ferrocene derivative has a carboxyl group.

5. The carbon dioxide absorption and release device according to claim 3, wherein the ferrocene derivative has an alkene group.

6. The carbon dioxide absorption and release device according to claim 3, wherein the linker has an amino group.

7. The carbon dioxide absorption and release device according to claim 3, wherein the linker has an alkene group.

8. 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.

9. The carbon dioxide absorption and release device according to claim 1, further comprising an electrolyte held in the first composite.

10. 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.

11. 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 according to claim 1, comprising the above.