Carbon dioxide adsorption battery and charging / discharging device

Abstract

One aspect of the present invention is a carbon dioxide adsorption battery comprising: a positive electrode; a negative electrode; a separator that is disposed between the positive electrode and the negative electrode; and electrolyte layers that are respectively disposed between the positive electrode and the separator and between the negative electrode and the separator. The positive electrode is gas permeable. The electrolyte layers each include an electrolytic solution in which carbon dioxide can be dissolved and a redox compound which has an N-oxy radical group in the molecule thereof. The separator suppresses permeation of the redox compound but is permeable to the electrolytic solution.

Description

[Technical Field]

[0001] The present invention relates to a carbon dioxide adsorption battery and a charge / discharge device. [Background technology]

[0002] Carbon dioxide is a substance widely distributed on Earth, accounting for approximately 0.04% of the atmosphere, and is also widely used in industry. Examples of uses of carbon dioxide include foaming gas for carbonated beverages, bath additives, and fire extinguishing agents, dry ice used for cooling, and emergency air refills for bicycle tires. Carbon dioxide can also be used as an extraction solvent for extracting caffeine and other substances by bringing it to a supercritical state. Carbon dioxide is also used in lasers used in industrial processing and carbon dioxide lasers used in medical laser scalpels. Furthermore, carbon dioxide is sometimes used as a compressor refrigerant instead of fluorocarbon-based refrigerants. Carbon dioxide is also used in agriculture, for example, for forcing strawberries and for carbon dioxide fertilization to accelerate the growth of plants such as aquatic plants in ornamental aquariums. Carbon dioxide is also used in controlled atmosphere (CA) storage of fresh agricultural produce.

[0003] As described above, carbon dioxide is used in various fields, and therefore, there is a demand for a method of obtaining carbon dioxide by, for example, separating carbon dioxide from a gas containing carbon dioxide, such as air. Carbon dioxide is also said to be a causative substance of global warming. For this reason, there is a demand for separating carbon dioxide from a gas containing carbon dioxide and utilizing the carbon dioxide. In order to utilize carbon dioxide, there is a demand for the development of, for example, a method of separating carbon dioxide from a gas containing carbon dioxide, an apparatus for adsorbing and separating carbon dioxide, and an apparatus for utilizing carbon dioxide.

[0004] Various methods have been proposed for separating carbon dioxide from a mixed gas containing oxygen and carbon dioxide, such as air. Examples of such separation methods include a method in which a carbon dioxide adsorbent is used to adsorb carbon dioxide in the air, and then the carbon dioxide adsorbed by the adsorbent is desorbed, thereby separating carbon dioxide from the air. Examples of adsorbents that adsorb carbon dioxide include activated carbon, amine solvents, and aqueous potassium carbonate solutions. More specifically, examples of carbon dioxide separation methods using an adsorbent include pressure swing adsorption (PSA), in which carbon dioxide is adsorbed onto the adsorbent under high pressure, and then the pressure is reduced to desorb the carbon dioxide from the adsorbent. Examples of adsorbents used in separating carbon dioxide using this PSA method include the adsorbents described in Patent Document 1.

[0005] Patent Document 1 describes a carbon dioxide adsorbent comprising a composition in which 2 to 80 equivalent percent of the sodium ions in a sodium-containing aluminosilicate have been ion-exchanged with barium ions. Patent Document 1 discloses that it is possible to provide an adsorbent that has a high selectivity for carbon dioxide and a large absorption capacity even under conditions of high moisture content. Patent Document 1 also discloses that this adsorbent can be suitably used for separating and concentrating carbon dioxide by a PSA method.

[0006] Examples of devices for adsorbing and separating carbon dioxide include the acidic gas adsorption / desorption device described in Patent Document 2 and the carbon dioxide separation device described in Patent Document 3.

[0007] Patent Document 2 describes an acidic gas adsorption / desorption device having an acidic gas adsorption / desorption layer including a compound and a substrate that can adsorb and desorb acidic gases such as carbon dioxide by oxidation and reduction, and a pair of electrodes that sandwich the acidic gas adsorption / desorption layer.

[0008] Patent Document 3 describes a carbon dioxide separation device comprising an electrolyte layer, a pair of electrodes disposed on the electrolyte layer with the electrolyte layer sandwiched therebetween, and a voltage application unit that applies a voltage between the pair of electrodes, wherein each of the pair of electrodes is gas-permeable, and the electrolyte layer contains an electrolytic solution capable of dissolving carbon dioxide and a redox compound having an N-oxy radical group in its molecule.

[0009] Furthermore, examples of devices that utilize carbon dioxide include the batteries described in Non-Patent Documents 1 and 2.

[0010] Non-Patent Document 1 proposes a method for utilizing carbon dioxide, in which a battery is charged while absorbing carbon dioxide.

[0011] Non-Patent Document 2 proposes a carbon dioxide rechargeable battery incorporating a redox system. Specifically, the proposed carbon dioxide rechargeable battery uses poly-1,4-anthraquinone and polyvinylferrocene in the negative and positive electrodes, respectively. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] Japanese Patent Application Publication No. 7-39752 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-36128 [Patent Document 3] Japanese Patent Application Publication No. 2018-1131 [Non-patent literature]

[0013] [Non-Patent Document 1] Aliza Khurram et al.,“Tailoring the Discharge Reaction in Li-CO2 Batteries through Incorporation of CO2 Capture Chemistry”,Joule 2,2649-2666,December 19,2018 [Non-patent document 2] Sahag Voskian et al., “Faradaic electro-swing reactive adsorption for CO2 Capture”, Energy & Environmental Science, 2019, 12, 3530-3547 Summary of the Invention

[0014] An object of the present invention is to provide a carbon dioxide adsorption battery that can be charged while easily adsorbing carbon dioxide from a gas containing carbon dioxide, and to provide a charge / discharge device that includes the carbon dioxide adsorption battery.

[0015] One aspect of the present invention is a method for producing a medicament for use in a pharmaceutical composition comprising: negative electrode and, positive electrode and the above negative electrode and the above positive electrode a separator disposed between the negative electrode and the separator and positive electrode and an electrolyte layer disposed between the separator and the negative electrode is a gas-permeable electrode, the electrolyte layer contains an electrolyte solution capable of dissolving carbon dioxide and a redox compound having an N-oxy radical group in the molecule, and the separator inhibits permeation of the redox compound and is permeable to the electrolyte solution. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a carbon dioxide adsorption battery according to an embodiment of the present invention during charging. [Figure 2]FIG. 2 is a schematic cross-sectional view showing an example of the configuration of a carbon dioxide adsorption battery according to an embodiment of the present invention during discharge. [Figure 3] FIG. 3 is a schematic cross-sectional view showing another example of the configuration of the carbon dioxide adsorption battery according to an embodiment of the present invention during charging. [Figure 4] FIG. 4 is a schematic cross-sectional view showing another example of the configuration of the carbon dioxide adsorption battery according to an embodiment of the present invention during charging. [Figure 5] FIG. 5 is a schematic cross-sectional view showing another example of the configuration of a carbon dioxide adsorption battery during discharge according to an embodiment of the present invention. [Figure 6] FIG. 6 is a schematic diagram showing an example of the configuration of a charge / discharge device according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0017] As described above, methods for separating carbon dioxide by the PSA method, such as the method using an adsorbent described in Patent Document 1, require pressurization and depressurization. Furthermore, even if the method is not a PSA method, a method for separating carbon dioxide using an adsorbent requires not only an operation for adsorbing carbon dioxide onto the adsorbent but also an operation for desorbing the carbon dioxide adsorbed on the adsorbent, such as a heat treatment. For this reason, carbon dioxide separation methods using an adsorbent have required a relatively large amount of energy and / or a relatively large device.

[0018] There is a demand for a method for separating carbon dioxide that is simple and does not require a large amount of energy or a relatively large apparatus for separating carbon dioxide.

[0019] Patent Document 2 discloses that acidic gases can be adsorbed and desorbed in a solid state. Specifically, the method described in Patent Document 2 first applies a voltage between electrodes to adsorb the acidic gas into an acidic gas adsorption / desorption layer. The voltage applied between the electrodes is then reversed so that the current flowing through the acidic gas adsorption / desorption layer disposed between the electrodes is in the opposite direction to that during adsorption, thereby desorbing the acidic gas from the acidic gas adsorption / desorption layer. Thus, in the method described in Patent Document 2, the voltage applied between the electrodes is reversed when adsorbing the acidic gas into the acidic gas adsorption / desorption layer and when desorbing the adsorbed acidic gas from the acidic gas adsorption / desorption layer. Focusing on carbon dioxide as an acidic gas, even when attempting to separate carbon dioxide using the device described in Patent Document 2, the voltage applied between the electrodes must be reversed, as described above. For this reason, the method described in Patent Document 2, like the case where the adsorbent described in Patent Document 1 is used, may require a relatively large amount of energy or a relatively large device.

[0020] Patent Document 3 discloses that it is possible to provide a carbon dioxide separation device that can easily separate carbon dioxide from a gas that contains carbon dioxide. Patent Document 3 discloses that this carbon dioxide separation device can separate carbon dioxide without reversing the voltage applied between a pair of electrodes between when carbon dioxide is adsorbed and when it is released. Specifically, it discloses that by applying a voltage between a pair of electrodes provided in the carbon dioxide separation device, carbon dioxide that has permeated one electrode binds to a compound having an N-oxy radical group in its molecule, and the compound to which this carbon dioxide is bound flows to the other electrode side, where carbon dioxide is released from the compound.

[0021] According to the investigations of the present inventors, it was not possible to store electricity in the carbon dioxide separation device described in Patent Document 3. Specifically, as described above, the carbon dioxide separation device described in Patent Document 3 applies a voltage between the pair of electrodes, causing a continuous flow of carbon dioxide, and therefore, when carbon dioxide is being separated, current always flows in one direction, and therefore it is thought that electricity cannot be stored.

[0022] Non-Patent Document 1 discloses a storage battery that adsorbs carbon dioxide during charging, but the inventors have found that the storage battery described in Non-Patent Document 1 has poor durability, such as a short battery cycle life, making it difficult to put into practical use.

[0023] Non-Patent Document 2 discloses a storage battery that adsorbs carbon dioxide during charging, similar to the technology described in Non-Patent Document 1. However, a quinone compound such as poly-1,4-anthraquinone is used as a primary electron acceptor for carbon dioxide adsorption, and such quinone compounds are known to have low heat resistance. Furthermore, a ferrocene-type compound with iron as the central metal is used in the positive electrode, which is the counter electrode to the negative electrode using the quinone compound. Such a compound is an exotic and expensive compound such as polyvinylferrocene, which is economically undesirable.

[0024] For these reasons, in order to make effective use of carbon dioxide, there is a demand for the development of secondary batteries that can adsorb carbon dioxide during charging by using materials other than these materials.

[0025] As a result of various investigations, the present inventors have found that the above-mentioned object of providing a carbon dioxide adsorption battery that can easily adsorb carbon dioxide from a gas containing carbon dioxide while being rechargeable can be achieved by the present invention described below.

[0026] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these.

[0027] [Carbon dioxide adsorption battery] As shown in FIGS. 1 and 2, a carbon dioxide adsorption battery 10 according to an embodiment of the present invention includes: negative electrode 11 and positive electrode 12 and the above negative electrode 11 and the above positive electrode a separator 16 disposed between the negative electrode 11 and the separator 16 and positive electrode The carbon dioxide adsorption battery 10 includes a separator 16, electrolyte layers 13 provided on both sides of the separator 16, and two electrodes provided on the electrolyte layer 13 with the electrolyte layer 13 sandwiched therebetween. negative electrode 11 and positive electrode The electrode pair 11 and 12 are provided. negative electrode 11 is a gas-permeable electrode. The electrolyte layer 13 contains an electrolyte solution capable of dissolving carbon dioxide and a compound having an N-oxy radical group in the molecule. The separator 16 suppresses the permeation of the redox compound and allows the electrolyte solution to pass through. That is, the separator 16 is less permeable to the redox compound than to the electrolyte solution. The separator 16 is preferably permeable to the electrolyte solution but not to the redox compound. The carbon dioxide adsorption battery 10 has a structure in which gas is permeated through the separator 16. negative electrode The gas supplying device may include a flow path 15 that flows while being in contact with the gas supplying device 11. The flow path 15 is not particularly limited as long as it is a flow path that allows gas to flow.

[0028] 1 and 2 are schematic cross-sectional views showing an example of the configuration of a carbon dioxide adsorption battery according to an embodiment of the present invention (the carbon dioxide adsorption battery 10), with FIG. 1 showing the carbon dioxide adsorption battery 10 during charging and FIG. 2 showing the carbon dioxide adsorption battery 10 during discharging.

[0029] During charging, the carbon dioxide adsorption battery 10 negative electrode The potential of 11 is positive electrode The potential of the negative electrode 11 and the above positive electrode Between 12 and negative electrode11 and the above positive electrode A voltage is applied between the pair of electrodes 12. There is no particular limitation on the charging method of the carbon dioxide adsorption battery 10 as long as the voltage can be applied as described above. For example, as shown in FIG. 1, the carbon dioxide adsorption battery 10 can be charged by negative electrode The potential of 11 is positive electrode The potential of the negative electrode 11 and the above positive electrode 2, the carbon dioxide adsorption battery 10 includes a pair of electrodes 12, and a voltage application unit 14 for applying a voltage between the pair of electrodes 12. negative electrode 11 and the above positive electrode A resistor 17 or the like is provided between a pair of electrodes 12 to discharge the current. negative electrode 11 is , Mitsuru During electricity generation, the carbon dioxide is absorbed from the gas containing carbon dioxide. Cathode When discharging, the carbon dioxide absorbed during charging is released. anode It becomes an electrode. positive electrode 12 is When charging, Anode electrode and becomes the cathode electrode during discharge. .

[0030] The carbon dioxide adsorption battery 10 according to this embodiment can easily separate and adsorb carbon dioxide from a gas containing carbon dioxide. Specifically, as shown in FIG. 1, the carbon dioxide adsorption battery 10 is configured to: negative electrode The potential of 11 is positive electrode When a voltage is applied between these electrodes 11 and 12 so that the potential of the electrode 11 is lower than the potential of the electrode 12, carbon dioxide is separated from the gas containing carbon dioxide as follows. The carbon dioxide adsorption battery 10 is charged by applying a voltage in this manner. Therefore, the carbon dioxide adsorption battery 10 separates carbon dioxide from the gas containing carbon dioxide by circulating a gas containing carbon dioxide, such as air, through the flow path 15. negative electrode When the carbon dioxide adsorption battery 10 is brought into contact with the electrolyte layer 11, carbon dioxide is adsorbed (immobilized) in the electrolyte layer 13, and the battery is simultaneously charged. When the carbon dioxide adsorption battery 10 is discharged as shown in FIG. 2, carbon dioxide is released from the electrolyte layer 13.

[0031] During charging, the carbon dioxide adsorption battery 10 discharges gas with a lower carbon dioxide concentration than the gas such as air supplied from the flow path 15, and during discharging, discharges gas with a higher carbon dioxide concentration than the gas supplied from the flow path 15. Specifically, the gas released from the carbon dioxide adsorption battery during discharging is mainly the gas that was adsorbed by the carbon dioxide adsorption battery during charging, and therefore is gas with a very high carbon dioxide concentration. For these reasons, the carbon dioxide adsorption battery 10 can concentrate carbon dioxide.

[0032] Therefore, the carbon dioxide adsorption battery 10 can adsorb carbon dioxide during charging and release carbon dioxide during discharging. That is, the affinity of carbon dioxide for the electrolyte layer 13 increases during charging, and decreases during discharging. By applying a voltage between the pair of electrodes 11 and 12, the affinity of carbon dioxide for the electrolyte layer 13 can be changed, and carbon dioxide can be adsorbed or released. This adsorption and release can concentrate carbon dioxide. Because the adsorption and release of carbon dioxide are performed by applying a voltage, they can be performed at room temperature and atmospheric pressure.

[0033] The above-described mechanism of action in the carbon dioxide adsorption battery 10 is believed to be as follows.

[0034] The aforementioned negative electrode 11 is the above negative electrode 11 can allow gas present around it to pass through. negative electrode When gas permeates through 11, negative electrode The gas that has permeated through 11 comes into contact with the electrolyte layer 13. negative electrode Carbon dioxide contained in the gas present around 11 is dissolved in the electrolyte solution contained in the electrolyte layer 13 .

[0035] During charging, the carbon dioxide adsorption battery 10 negative electrodeThe potential of 11 is positive electrode 12, i.e., positive electrode The potential of 12 is negative electrode The potential of the negative electrode 11 and the above positive electrode A voltage is applied between a pair of electrodes 11 and 12.

[0036] The redox compound contained in the electrolyte layer 13 is negative electrode On the side closer to 11, negative electrode The potential of 11 is positive electrode Since the potential of the carbon dioxide adsorption battery 10 is higher than that of the battery 12, the N-oxy radical group is reduced to an N-oxy anion group as shown in the following formula (2). Then, as shown in the following formula (3), carbon dioxide dissolved in the electrolyte is bonded to this N-oxy anion group, which promotes the dissolution of carbon dioxide into the electrolyte. Therefore, during charging, the carbon dioxide adsorption battery 10 negative electrode Carbon dioxide is taken in from the side 11 and adsorbed onto the electrolyte layer 13 .

[0037] [ka]

[0038] [ka]

[0039] On the other hand, the redox compound contained in the electrolyte layer 13 is positive electrode On the side closer to 12, positive electrode The potential of 12 is negative electrode Since the potential is lower than that of 11, the N-oxy radical group is oxidized to become an N-oxy cation group, as shown in the following formula (4).

[0040] [ka]

[0041] The separator 16 is permeable to the electrolyte but inhibits the permeation of the redox compound. That is, the redox compound is less likely to permeate the separator 16 than the electrolyte. Therefore, both the redox compound in which the N-oxy radical group is reduced to become an N-oxy anion group and the redox compound to which carbon dioxide is bound permeate the separator, and positive electrode Therefore, even after charging is stopped, if the battery is not discharged, these redox compounds are unlikely to move to the negative electrode The redox compound in which the N-oxy radical group is oxidized to become an N-oxy cation group also permeates the separator 16 and is retained on the side of the separator 16. negative electrode Therefore, even after charging is stopped, if discharging is not performed, the redox compound having the N-oxy cation group in the molecule is unlikely to move to the side of the separator 16 of the electrolyte layer 13. positive electrode As a result, the carbon dioxide adsorption battery 10 can maintain a charged state.

[0042] Next, when the charged carbon dioxide adsorption battery 10 is discharged, the separator 16 of the electrolyte layer 13 releases the positive electrode On the 12 side, the N-oxy cation group returns to the N-oxy radical group. negative electrode On the side 11, carbon dioxide is released from the redox compound as shown in the following formula (6), and the N-oxy anion group returns to the N-oxy radical group as shown in the following formula (7). negative electrode Carbon dioxide can be released from the carbon dioxide adsorption battery 10 through the side 11. The gas released from the carbon dioxide adsorption battery 10 during discharge is mainly the gas that was adsorbed in the carbon dioxide adsorption battery 10 during charging, and therefore has a very high carbon dioxide concentration. This means that the carbon dioxide adsorption battery 10 can concentrate carbon dioxide.

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] As described above, the carbon dioxide adsorption battery 10 can adsorb carbon dioxide during charging and release carbon dioxide during discharging, and is believed to be able to charge while easily adsorbing carbon dioxide from a gas containing carbon dioxide. The carbon dioxide adsorption battery 10 is also believed to be able to concentrate carbon dioxide through the adsorption and release of carbon dioxide as described above. Furthermore, the carbon dioxide adsorption battery 10 uses, instead of the quinone compound, a redox compound having an N-oxy radical group in the molecule, which is more durable than the quinone compound, and therefore has excellent durability.

[0047] ( negative electrode ) The aforementioned negative electrode 11 is not particularly limited as long as it is an electrode that is permeable to gas. negative electrode The electrode 11 may be any conductive material that is permeable to gases such as carbon dioxide and allows current to flow through the electrolyte layer 13 sandwiched between the pair of electrodes 11 and 12. negative electrode It is preferable that 11 is a porous material that has conductivity to the extent that it does not inhibit the movement of electrons, can store electric charges, has excellent breathability, and has a large contact area with gas. negative electrode11 specifically includes an electrode made of a porous conductive material, and more specifically includes a porous body containing carbon as a main component, a porous body made of carbon, and a porous metal layer. Examples of the porous conductive material include porous metal, a porous body containing carbon as a main component, and a porous body made of carbon. As the porous conductive material, these may be used alone or in combination of two or more. That is, negative electrode The electrode 11 may be made of a single conductive material among these porous conductive materials, or may be made of a combination of two or more conductive materials.

[0048] Specific examples of the carbon contained in the porous body include carbonaceous materials such as graphite, carbon nanotubes, activated carbon (e.g., activated carbon fiber), and carbon fiber. The carbon is preferably graphite, carbon nanotubes, activated carbon, or carbon fiber, with activated carbon (e.g., activated carbon fiber) being more preferred in terms of corrosion resistance and specific surface area. The carbon may be any of a variety of carbonaceous materials used alone or in combination of two or more. The carbon-containing porous body is preferably a carbonaceous material in the form of cloth or felt. Therefore, specific examples of the porous electrode include carbon sheets, carbon cloth, and carbon paper. Examples of the porous electrode include carbon-based electrodes using activated carbon or carbon fiber, and highly porosity electrodes using needle-shaped conductive materials. Of the above-mentioned electrodes, the electrode is preferably an electrode made of a conductive material containing at least one material selected from the group consisting of graphite, carbon nanotubes, activated carbon, and carbon fiber. It is believed that such electrodes allow gas to pass through them properly, and that the voltage application unit 14 can apply a voltage between the pair of electrodes 11 and 12 properly. negative electrode By using 11, it is possible to obtain a carbon dioxide adsorption battery that can more effectively adsorb carbon dioxide from a gas containing carbon dioxide during charging and more effectively release carbon dioxide during discharging.

[0049] The porous metal layer is a metal layer having a large number of pores formed therein. The porous metal layer preferably has the pores formed throughout the entire metal layer to provide excellent breathability. The method for obtaining the porous metal layer is not particularly limited, as long as it involves subjecting a metal layer without pores (a metal layer before pore formation) to a process for forming a large number of pores (a method for making the metal layer porous). Examples of such a method include physical methods such as cutting, polishing, and sandblasting, and chemical methods such as electrolytic etching and electroless etching using an acid or base etching solution. The above methods may be used alone or in combination of two or more. The method for making the metal layer porous is preferably a chemical method, since it increases the surface area and makes the pores (pores) denser (more densely packed). The material of the metal layer is not particularly limited, and examples thereof include aluminum, copper, silver, gold, iron, titanium, molybdenum, tungsten, nickel, and alloys thereof. Among these, aluminum is preferred as the material for the metal layer from the viewpoints of cost and processability, and the metal layer before the holes are formed is preferably so-called aluminum foil.

[0050] The aforementioned negative electrode The BET specific surface area of ​​11 is not particularly limited, but for example, 1 m 2 / g or more, and 100m 2 / g or more is more preferable, and 500m 2 / g or more is more preferable. negative electrode The BET specific surface area of ​​11 is preferably large from the viewpoint of gas permeability (breathability). negative electrode 11, 3000m 2 / g or less. negative electrode The BET specific surface area of ​​11 is 1 to 3000 m 2 / g, and 100 to 2500m 2 / g, and more preferably 500 to 2000m2 / g is more preferable. negative electrode If the BET specific surface area of ​​11 is too small, the gas permeability (breathability) decreases, and the permeation of carbon dioxide tends to be inhibited. negative electrode If the BET specific surface area of ​​electrode 11 is too large, the strength of the electrode tends to be insufficient. For these reasons, if the BET specific surface area of ​​electrode 11 is within the above range, it can adsorb and release carbon dioxide over a long period of time, and can be used as a carbon dioxide battery over a long period of time. The BET specific surface area is the specific surface area measured by the BET method and can be measured by a known method. Examples of methods for measuring the BET specific surface area include a method in which a nitrogen adsorption isotherm is measured and the BET specific surface area is calculated from the obtained adsorption isotherm.

[0051] The aforementioned negative electrode 11 may further include a current collector. negative electrode 11 may be made of the porous body, or may include the porous body and the current collector. The current collector is not particularly limited as long as it does not hinder the gas permeation. For example, the current collector may be made of a conductive material and have openings to the extent that the gas permeation is not hindered. More specifically, the current collector may be made of a metal such as mesh metal, punched metal, or expanded metal, or may be a woven or nonwoven fabric made of natural or synthetic fibers plated to have conductivity. Examples of metals that can be used for the current collector include stainless steel, iron, nickel, and copper.

[0052] The porous body and the current collector negative electrodeIn the case of 11, the porous body and the current collector are preferably integrated, and the integration method is not particularly limited. The integrated porous body and current collector may be partially integrated using, for example, ultrasonic welding or plasma welding to ensure electrical conductivity. The integrated porous body and current collector may also be electrically conductive by interposing a conductive material, such as a conductive adhesive, between the porous body and the current collector. The conductive material is not particularly limited, and examples of the conductive material include dispersed metal particles, such as silver, gold, and nickel, carbonaceous conductive materials, and conductive polymers.

[0053] ( positive electrode ) The aforementioned positive electrode The electrode 12 is not particularly limited as long as it is a conductive member that can pass a current through the electrolyte layer 13 sandwiched between the pair of electrodes 11 and 12. positive electrode As the electrode 12, for example, it is preferable that the electrode 12 is provided with a gas permeation blocking portion that blocks gas permeation. positive electrode 12 is preferably configured so as not to come into contact with the outside air. positive electrode However, as described above, when a gas permeation blocking portion that blocks gas permeation is provided and when the battery is configured to not come into contact with the outside air, charging is possible while easily adsorbing carbon dioxide from a gas that contains carbon dioxide, and the charged state can be maintained for a longer period of time. This is thought to be due to the following.

[0054] In the carbon dioxide adsorption battery 10, as described above, the separator 16 suppresses the migration of the redox compound, but the redox compound may permeate the separator 16. For example, in the carbon dioxide adsorption battery 10, the redox compound may permeate the separator 16 of the electrolyte layer 13. negative electrode From the 11th side positive electrodeIt is possible that the redox compound to which carbon dioxide is bound as described above may move to the side 12. When the redox compound to which carbon dioxide is bound moves in this way during charging or while maintaining a charged state, positive electrode Near 12, the redox compound is oxidized, carbon dioxide is released from the redox compound, and the N-oxy anion group returns to the N-oxy radical group. positive electrode When carbon dioxide is released from the 12 side, the migration of the redox compound to which the carbon dioxide is bound can be promoted. positive electrode If 12 is provided with a gas permeation blocking portion that blocks gas permeation and is configured so as not to come into contact with the outside air, it is believed that such promotion of movement can be prevented, and the charged state can be maintained better.

[0055] The aforementioned positive electrode When 12 is an electrode having a gas permeation blocking portion that blocks gas permeation, as shown in FIGS. 1 and 2, positive electrode The electrode may be provided with the main body 21 and the gas permeation blocking portion 22, or the gas permeation blocking portion may be electrically conductive and the electrode may be made of this gas permeation blocking portion.

[0056] The aforementioned positive electrode 12, positive electrode In the case of an electrode including a main body 21 and a gas permeation barrier 22, the gas permeation barrier 22 is positive electrode The gas permeation barrier 22 is provided on the side of the main body 21 opposite to the electrolyte layer 13 side. positive electrode If the electrode 12 is provided on the side opposite to the electrolyte layer 13 side of the main body 21, positive electrode It may also be provided on the electrolyte layer 13 side of the main body 21.

[0057] The aforementioned positive electrode The main body 21 may be any conductive member that can pass a current through the electrolyte layer 13 sandwiched between the pair of electrodes 11 and 12. positive electrode The main body 21 is preferably a conductive material that has conductivity to the extent that it does not hinder the movement of electrons and can store electric charges. positive electrode Since the main body 21 is provided with the gas permeation blocking portion 22, it is preferable that the main body 21 is gas permeable in order to increase the gas contact area. positive electrode The main body 21 is negative electrode The conductive material may be the same as the conductive material exemplified as the electrode used in 11. positive electrode Specific examples of the main body 21 include electrodes made of conductive materials such as carbon materials, metal fibers, metal foils, and conductive polymers, and more specific examples include electrodes made of carbon fibers, activated carbon, and graphite.

[0058] The gas permeation shielding portion 22 is not particularly limited as long as it can block gas permeation. Examples of the gas permeation shielding portion 22 include metal foils such as aluminum foil, copper foil, and nickel foil, and plastic foils coated with conductive pastes such as conductive polymer, graphite, and silver. Examples of the plastic foils include plastic foils containing polyethylene terephthalate (PET), polypropylene (PP), and polyethylene (PE).

[0059] The electrode made of the gas permeation blocking portion is positive electrode The electrode has a configuration that serves both as the main body and the gas permeation shielding portion. Examples of the electrode that is the gas permeation shielding portion include an electrode made of a conductive material that does not allow gases such as carbon dioxide to pass through and that can pass a current through the electrolyte layer 13 sandwiched between the pair of electrodes 11 and 12.

[0060] The aforementioned positive electrode In the case where the heater 12 is configured so as not to come into contact with the outside air, the configuration is as follows: positive electrode There is no particular limitation as long as 12 does not come into contact with the outside air. positive electrode As an example of the case where the air passage 12 is configured not to come into contact with the outside air, for example, as shown in FIG. negative electrode In addition to the battery 11, a carbon dioxide adsorption battery 20 enclosed in a housing 25 can be used. positive electrodeThe carbon dioxide adsorption battery 20 is similar to the carbon dioxide adsorption battery 10 except that the carbon dioxide adsorption battery 12 is enclosed by the casing 25 so as not to come into contact with the outside air. positive electrode 12 does not come into contact with the outside air. There are no particular limitations on the casing 25 as long as it is not permeable to gases, and any casing that can be used as a battery casing may be used. Note that Fig. 3 is a schematic cross-sectional view showing another example of the configuration of a carbon dioxide adsorption battery according to an embodiment of the present invention (the carbon dioxide adsorption battery 20), and shows the carbon dioxide adsorption battery 20 during charging.

[0061] The aforementioned positive electrode Another example of a case where the heater 12 is configured not to come into contact with the outside air is, for example, a case where two heaters 12 are configured as shown in FIGS. negative electrode The carbon dioxide adsorption battery 30 includes the following: negative electrode 11 plus this negative electrode Different from 11 negative electrode 31, positive electrode 12 and the above negative electrode The carbon dioxide adsorption battery 30 is similar to the carbon dioxide adsorption battery 10 except that the electrolyte layer 13 and the separator 16 are provided between the pair of electrodes 11 and 12. negative electrode 11 plus this negative electrode Different from 11 negative electrode 31, which constitutes the pair of electrodes 11 and 12. positive electrode 12 and the above negative electrode The carbon dioxide adsorption battery 30 is similar to the carbon dioxide adsorption battery 10 except that the electrolyte layer 13 and the separator 16 are provided between the carbon dioxide adsorption battery 30 and the carbon dioxide adsorption battery 10. negative electrode 31 is not particularly limited as long as it is an electrode that is permeable to gas, and for example, negative electrode The carbon dioxide adsorption battery 30 having such a configuration can be used in the above-mentioned positive electrode 4, the above-mentioned negative electrode11 and the above positive electrode 12 and not just between positive electrode 12 and the above negative electrode 31 by applying a voltage from the voltage application unit 14. negative electrode 11 and the above positive electrode 12 and not just between positive electrode 12 and the above negative electrode 5, the carbon dioxide adsorption battery 30 can be charged between the negative electrode 11 and the above positive electrode 12 while charging positive electrode 12 and the above negative electrode The carbon dioxide adsorption battery 30 can also be discharged between the battery 30 and the positive electrode 12 and the above negative electrode 31 while charging negative electrode 11 and the above positive electrode 4 and 5 are schematic cross-sectional views showing another example of the configuration of a carbon dioxide adsorption battery according to an embodiment of the present invention (the carbon dioxide adsorption battery 30). Fig. 4 shows a case where both electrodes are being charged, and Fig. 5 shows a case where one electrode is being charged and the other electrode is being discharged.

[0062] The aforementioned negative electrode 11 and the above positive electrode As described above, 12 is a conductive member that can pass a current to the electrolyte layer 13 sandwiched between the pair of electrodes 11, 12, and the smaller the surface resistance value, the better, for example, it is preferably 1 kΩ / sq or less, and more preferably 200 Ω / sq or less. Furthermore, the smaller the surface resistance value of each electrode, the better, but in reality, the limit is 1 Ω / sq. Therefore, the surface resistance value of each electrode is preferably 1 Ω / sq to 1 kΩ / sq, and more preferably 10 to 200 Ω / sq. Electrodes with such a surface resistance value can suitably pass a current to the electrolyte layer 13, and the carbon dioxide adsorption battery 10 can suitably adsorb carbon dioxide during charging and can suitably release carbon dioxide during discharging. Note that, negative electrodeThe surface resistance value of 31 is negative electrode 11 and the above positive electrode The surface resistance is the same as that of 12.

[0063] The aforementioned negative electrode 11 and the above positive electrode The thickness of 12 is not particularly limited, but it is preferable that it is a thickness that can suitably store electric charges and suitably prevent leakage of the electrolyte. negative electrode 11 and the above positive electrode The thickness of 12 is, for example, preferably 20 μm or more and 10 mm or less, and more preferably 50 μm or more and 5 mm or less. negative electrode 11 and the above positive electrode If 12 is too thin, the strength of the electrode may be insufficient, and it may be difficult to store electric charges. negative electrode 11 and the above positive electrode If the thickness of the carbon dioxide adsorption battery 10 is too large, the carbon dioxide adsorption battery 10 tends to become too large. negative electrode If the layer 11 is too thick, the gas permeability (breathability) decreases, and the permeation of carbon dioxide tends to be inhibited. negative electrode The thickness of 31 is negative electrode The thickness is the same as 11.

[0064] (electrolyte layer) The electrolyte layer 13 is not particularly limited as long as it contains an electrolyte solution capable of dissolving carbon dioxide and a redox compound having an N-oxy radical group in the molecule. As described above, the electrolyte layer 13 is a carbon dioxide separator that contributes to the separation of carbon dioxide by adsorption and release of carbon dioxide.

[0065] The thickness of the electrolyte layer 13 is not particularly limited, but is preferably 0.1 μm to 2 mm, and more preferably 1 μm to 1 mm. negative electrode 11 side thickness and positive electrodeThe thicknesses of the two sides are not particularly limited, but are preferably 0.1 μm to 2 mm, and more preferably 1 μm to 1 mm. If the electrolyte layer 13 is too thin, not only will the amount of carbon dioxide fixation and the amount of electricity stored decrease, but tiny holes, i.e., pinholes, tend to form in the electrolyte layer 13. The formation of pinholes can lead to other problems, such as insufficient carbon dioxide adsorption or the flow of current that does not contribute to carbon dioxide adsorption. Furthermore, if the electrolyte layer 13 is too thick, the diffusion of carbon dioxide adsorbed in the electrolyte layer 13 within the electrolyte layer 13 slows, resulting in a discrepancy between the amount of carbon dioxide fixation and the amount of electricity stored, making it difficult to determine whether carbon dioxide has been sufficiently adsorbed during charging. This is believed to be due to the following: In the carbon dioxide adsorption battery 10, the contribution of the diffusion of carbon dioxide in the electrolyte layer 13 and the diffusion of the redox compound to which carbon dioxide is bound to carbon dioxide to the adsorption of carbon dioxide is greater than the contribution of the diffusion to the charging. Furthermore, when the electrolyte layer 13 is thick, the influence of the diffusion is greater than when it is thin. For these reasons, the difference in the rate of carbon dioxide adsorption between when the electrolyte layer 13 is thick and when it is thin is greater than that of the rate of carbon dioxide adsorption when the electrolyte layer 13 is thin. Therefore, when the electrolyte layer 13 is thin, it is easy to determine whether carbon dioxide has been sufficiently adsorbed from the amount of stored electricity, whereas when the electrolyte layer 13 is thick, as described above, a discrepancy occurs between the amount of fixed carbon dioxide and the amount of stored electricity, making it difficult to determine whether carbon dioxide has been sufficiently adsorbed from the amount of stored electricity. Therefore, it is thought that the thicker the electrolyte layer 13, the more difficult it is to determine whether carbon dioxide has been sufficiently adsorbed during charging. For the same reason, when the electrolyte layer 13 is too thick, it tends to be difficult to determine whether carbon dioxide has been sufficiently released during discharging.

[0066] The electrolytic solution is not particularly limited as long as it is an electrolytic solution capable of dissolving carbon dioxide, and may be an electrolytic solution containing an electrolyte and a solvent, or an electrolytic solution containing an ionic liquid. Note that the electrolytic solution capable of dissolving carbon dioxide may be any solution other than one in which carbon dioxide is not dissolved, that is, an electrolytic solution in which carbon dioxide dissolves even a small amount, and does not require high solubility. This is believed to be due to the following. As described above, the carbon dioxide adsorption battery according to this embodiment is capable of dissolving carbon dioxide by binding and desorption of carbon dioxide to the redox compound during charging. negative electrode Carbon dioxide is taken into the electrolyte layer 13 on the side 11, and during discharge, negative electrode It is believed that the adsorption and release of carbon dioxide proceeds through a mechanism in which carbon dioxide is released from the electrolyte layer 13 on the side 11. Therefore, it is believed that if even a small amount of carbon dioxide dissolves in the electrolytic solution contained in the electrolyte layer 13, the adsorption and release of carbon dioxide proceeds.

[0067] As described above, the electrolyte solution is not particularly limited as long as it is an electrolyte solution capable of dissolving carbon dioxide, but is preferably non-volatile. As described above, the electrolyte solution may be an electrolyte solution containing an electrolyte and a solvent, or an electrolyte solution containing an ionic liquid, but is preferably non-volatile and usable as an electrolyte solution. Specifically, the electrolyte solution is preferably an ionic liquid.

[0068] The solvent is preferably an electrochemically stable compound with a wide potential window, and may be either an aqueous solvent or an organic solvent. Examples of the solvent include water, carbonate compounds, ester compounds, ether compounds, heterocyclic compounds, nitrile compounds, and aprotic polar compounds. Examples of the carbonate compounds include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, and propylene carbonate. Examples of the ester compounds include methyl acetate, methyl propionate, and γ-butyrolactone. Examples of the ether compounds include diethyl ether, 1,2-dimethoxyethane, 1,3-dioxosilane, tetrahydrofuran, and 2-methyl-tetrahydrofuran. Examples of the heterocyclic compounds include 3-methyl-2-oxazolidinone and 2-methylpyrrolidone. Examples of the nitrile compounds include acetonitrile, methoxyacetonitrile, propionitrile, 3-methoxypropionitrile, and valeric acid nitrile. Examples of the aprotic polar compound include sulfolane, dimethyl sulfoxide, and dimethylformamide. The solvent may be any of the solvents exemplified above, or two or more of them may be used in combination. Among the solvents exemplified above, preferred solvents include carbonate compounds such as ethylene carbonate and propylene carbonate, ester compounds such as γ-butyrolactone, heterocyclic compounds such as 3-methyl-2-oxazolidinone and 2-methylpyrrolidone, and nitrile compounds such as acetonitrile, methoxyacetonitrile, propionitrile, 3-methoxypropionitrile, and valeric acid nitrile. When two or more of the solvents are used in combination, water is preferred from the viewpoint of dissolving carbon dioxide.

[0069] The electrolyte is not particularly limited and may include, for example, quaternary ammonium salts, inorganic salts, and hydroxides. Examples of the quaternary ammonium salts include tetramethylammonium tetrafluoroborate, tetra-n-ethylammonium tetrafluoroborate, tetra-n-propylammonium tetrafluoroborate, tetra-n-butylammonium tetrafluoroborate, n-hexadecyltrimethylammonium tetrafluoroborate, tetra-n-hexadecylammonium tetrafluoroborate, tetra-n-octylammonium tetrafluoroborate, tetra-n-ethylammonium perchlorate, tetra-n-butylammonium perchlorate, and tetraoctadecylammonium perchlorate. Examples of the inorganic salts include lithium perchlorate, sodium perchlorate, potassium perchlorate, sodium acetate, potassium acetate, sodium nitrate, and potassium nitrate. Examples of the hydroxides include sodium hydroxide and potassium hydroxide. Among the above-listed electrolytes, tetramethylammonium tetrafluoroborate, tetra-n-ethylammonium tetrafluoroborate, tetra-n-propylammonium tetrafluoroborate, tetra-n-butylammonium tetrafluoroborate, n-hexadecyltrimethylammonium tetrafluoroborate, tetra-n-hexadecylammonium tetrafluoroborate, tetra-n-octylammonium tetrafluoroborate, tetra-n-ethylammonium perchlorate, tetra-n-butylammonium perchlorate, tetraoctadecylammonium perchlorate, lithium perchlorate, sodium perchlorate, sodium acetate, and potassium acetate are preferred. Furthermore, among these, tetra-n-ethylammonium tetrafluoroborate, tetra-n-propylammonium tetrafluoroborate, tetra-n-butylammonium tetrafluoroborate, lithium perchlorate, and sodium perchlorate are more preferred, and tetra-n-butylammonium tetrafluoroborate and lithium perchlorate are even more preferred.The electrolyte may also have a pH buffering ability by stabilizing carbonate ions or bicarbonate ions as a supporting salt. Specific examples of the electrolyte include sodium bicarbonate, sodium carbonate, acetic acid, and sodium acetate. The electrolytes listed above may be used alone or in combination of two or more.

[0070] As described above, the electrolyte solution may be an electrolyte solution containing an ionic liquid (ionic liquid). When an ionic liquid is used as the electrolyte solution, the ionic liquid can have the functions of both an electrolyte and a solvent, without the need to contain both as described above. Furthermore, the electrolyte solution may contain an ionic liquid, and may be a liquid containing an electrolyte in the ionic liquid, a liquid containing a solvent in the ionic liquid, a liquid containing an electrolyte and a solvent in the ionic liquid, or a liquid consisting of the ionic liquid. Furthermore, using an ionic liquid as the electrolyte solution is preferable because the ionic liquid is less likely to volatilize and has high flame retardancy.

[0071] The ionic liquid is not particularly limited as long as it is a known ionic liquid, and examples thereof include imidazolium-based ionic liquids, pyridine-based ionic liquids, alicyclic amine-based ionic liquids, and azonium amine-based ionic liquids. Examples of the ionic liquid include 1-methyl-3-octylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium tetrafluoroborate, 1,3-dimethoxyimidazolium tetrafluoroborate, 1,3-diethoxyimidazolium tetrafluoroborate, 1-methyl-3-octylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-decyl-3-methylimidazolium hexafluorophosphate, 1,3-dimethoxyimidazolium hexafluorophosphate, and 1,3-diethoxyimidazolium hexafluorophosphate. Furthermore, among the ionic liquids exemplified above, 1-methyl-3-octylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonylimide), 1,3-dimethoxyimidazolium tetrafluoroborate, 1-methyl-3-octylimidazolium hexafluorophosphate, and 1-ethyl-3-methylimidazolium hexafluorophosphate are preferred as the ionic liquid.Furthermore, as the ionic liquid, 1-methyl-3-octylimidazolium tetrafluoroborate, 1,3-dimethoxyimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonylimide), 1-butyl-3-methylimidazolium chloride, and 1-methyl-3-octylimidazolium hexafluorophosphate are more preferred, and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonylimide), 1-butyl-3-methylimidazolium chloride, and 1-methyl-3-octylimidazolium tetrafluoroborate are even more preferred.

[0072] The electrolyte layer 13 may be formed by gelling the electrolyte solution. Specifically, a gelling agent for gelling the electrolyte solution may be added, or a gelled electrolyte or polymer electrolyte may be used. Examples of the gelling agent include polymers, gelling agents using techniques such as polymer crosslinking reactions, polymerizable polyfunctional monomers, and oil gelling agents. The gelled electrolyte and polymer electrolyte are not particularly limited as long as they can be used as a gelled electrolyte or polymer electrolyte. Examples include vinylidene fluoride polymers such as polyvinylidene fluoride, acrylic acid polymers such as polyacrylic acid, acrylonitrile polymers such as polyacrylonitrile, polyether polymers such as polyethylene oxide, and compounds having an amide structure in their structure.

[0073] The redox compound is not particularly limited as long as it has an N-oxy radical group in its molecule. The redox compound is preferably a nonvolatile redox compound that adsorbs and desorbs carbon dioxide through electrolytic reduction and electrolytic oxidation. That is, the redox compound adsorbs carbon dioxide through electrolytic reduction as shown in Formulas (2) and (3), and desorbs the adsorbed carbon dioxide through electrolytic oxidation as shown in Formulas (5) and (6). When the voltage application unit 14 applies a voltage between the pair of electrodes 11 and 12, the N-oxy radical group of the redox compound is reduced to an N-oxy anion group, to which carbon dioxide is bound. Furthermore, when the carbon dioxide adsorption battery 10 is discharged, carbon dioxide is desorbed to form an N-oxy anion group, which is then oxidized back to an N-oxy radical. The redox compound is a compound in which the N-oxy radical group changes through oxidation and reduction.

[0074] Specific examples of the redox compound include a compound represented by the following formula (1) and a compound having a group in which one hydrogen atom has been eliminated from the compound represented by the following formula (1). The compound having a group in which one hydrogen atom has been eliminated from the compound represented by the following formula (1) may be any compound having such a group, and may be a compound bonded to another low molecular weight compound or a high molecular weight compound.

[0075] [ka]

[0076] In formula (1), Z is -CR5R6CR7R8-, -CR9R 10 CR 11 R 12 CR 13 R 14 -, -(CR 15 R 16 )O-, -(CR 17 R 18 )NR 27-, -(CR 19 R 20 )O(CR 21 R 22 )-, or -(CR 23 R 24 )NR 28 (CR 25 R 26 )-, R1~R 28 each independently represents a hydrogen atom or a substituent.

[0077] It is preferable that at least one of R1 to R4 is a substituent, more preferably two or more are substituents, and even more preferably all four are substituents. That is, the compound represented by formula (1) is preferably a compound in which two quaternary carbons are bonded to the N-oxy radical group. Furthermore, it is preferable that the redox compound is a compound in which two quaternary carbons are bonded to the N-oxy radical group, or a compound having a group in which one hydrogen atom has been eliminated from this compound. It is believed that such a compound is more likely to undergo oxidation-reduction by the N-oxy radical group, and more preferably allows the redox compound to adsorb and release carbon dioxide. Therefore, by including such a compound in the electrolyte layer, a carbon dioxide adsorption battery can be obtained that can more preferably adsorb carbon dioxide from a carbon dioxide-containing gas during charging and more preferably release carbon dioxide during discharging.

[0078] Z in the compound represented by the formula (1) is -CR5R6CR7R8-, -CR9R 10 CR 11 R 12 CR 13 R 14 -, -(CR 19 R 20 )O(CR 21 R 22 )-, and -(CR 23 R 24 )NR 28 (CR 25 R 26 )- is preferred.

[0079] The R1 to R28 Examples of the substituent in R1 to R2 include a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 10 carbon atoms, a hydroxyl group, an amino group which may be substituted (an unsubstituted or substituted amino group), a carboxyl group, a thiol group, and a silyl group which may be substituted (an unsubstituted or substituted silyl group). 26 Among these, the substituents in R are preferably a hydrocarbyl group having 1 to 30 carbon atoms, a hydroxy group, and an unsubstituted or substituted amino group. 27 , R 28 The substituent in is preferably a hydrocarbyl group having 1 to 30 carbon atoms.

[0080] Here, "optionally substituted" includes both cases where the hydrogen atoms constituting the compound or group described immediately thereafter are unsubstituted and cases where some or all of the hydrogen atoms are substituted with substituents.

[0081] The hydrocarbyl group is not particularly limited and may be linear, branched, or cyclic. Examples of the hydrocarbyl group include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a norbornyl group, an ammonium ethyl group, a benzyl group, an α,α-dimethylbenzyl group, a 1-phenethyl group, a 2-phenethyl group, a vinyl group, a propenyl group, a butenyl group, an oleyl group, an eicosapentaenyl group, a docosahexaenyl group, a 2,2-diphenylvinyl group, a 1,2,2-tri ... Examples of the alkyl group include a phenylvinyl group, a 2-phenyl-2-propenyl group, a phenyl group, a 2-tolyl group, a 4-tolyl group, a 4-trifluoromethylphenyl group, a 4-methoxyphenyl group, a 4-cyanophenyl group, a 2-biphenylyl group, a 3-biphenylyl group, a 4-biphenylyl group, a terphenylyl group, a 3,5-diphenylphenyl group, a 3,4-diphenylphenyl group, a pentaphenylphenyl group, a 4-(2,2-diphenylvinyl)phenyl group, a 4-(1,2,2-triphenylvinyl)phenyl group, a fluorenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 2-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a chrysenyl group, a naphthacenyl group, and a coronyl group.Among these, examples of the hydrocarbyl group include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a benzyl group, an α,α-dimethylbenzyl group, a 1-phenethyl group, a 2-phenethyl group, a vinyl group, a propenyl group, a butenyl group, an oleyl group, an eicosapentaenyl group, a docosahexaenyl group, a 2,2-diphenylvinyl group, a 1,2,2-triphenylvinyl group, a 2-phenyl-2-prop ... Preferred are phenyl, phenyl, 2-tolyl, 4-tolyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, 4-cyanophenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, terphenylyl, 3,5-diphenylphenyl, 3,4-diphenylphenyl, pentaphenylphenyl, 4-(2,2-diphenylvinyl)phenyl, 4-(1,2,2-triphenylvinyl)phenyl, fluorenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 2-anthryl, and 9-phenanthryl groups. Furthermore, among these, the hydrocarbyl group is more preferably a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a benzyl group, or a phenyl group, and even more preferably a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, or a hexyl group.

[0082] The hydrocarbyloxy group is not particularly limited, and may be linear, branched, or cyclic. Examples of the hydrocarbyloxy group include a methoxy group, an ethoxy group, a 1-propyloxy group, a 2-propyloxy group, a 1-butoxy group, a 2-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a decyloxy group, a dodecyloxy group, a 2-ethylhexyloxy group, a 3,7-dimethyloctyloxy group, a cyclopropanoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a 1-adamantyloxy group, a 2-adamantyloxy group, a norbornyloxy group, an ammoniumethoxy group, a trifluoromethoxy group, a benzyloxy group, an α,α-dimethylbenzyloxy group, a 2-phenethyloxy group, a 1-phenethyloxy group, a phenoxy group, an alkoxyphenoxy group, an alkylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group. Among these, the hydrocarbyloxy group is preferably a methoxy group, an ethoxy group, a 1-propyloxy group, a 2-propyloxy group, a 1-butoxy group, a 2-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a decyloxy group, a dodecyloxy group, a 2-ethylhexyloxy group, or a 3,7-dimethyloctyloxy group.Furthermore, among these, the hydrocarbyloxy group is more preferably a methoxy group, an ethoxy group, a 1-propyloxy group, a 2-propyloxy group, a 1-butoxy group, a 2-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, or a hexyloxy group.

[0083] The amino group is not particularly limited, and may be linear, branched, or cyclic. Examples of the amino group include a methylamino group, an ethylamino group, a 1-propylamino group, a 2-propylamino group, a 1-butylamino group, a 2-butylamino group, an isobutylamino group, a tert-butylamino group, a pentylamino group, a hexylamino group, an octylamino group, a decylamino group, a dodecylamino group, a 2-ethylhexylamino group, a 3,7-dimethyloctylamino group, a cyclopropylamino group, a cyclopentylamino group, a cyclohexylamino group, a 1-adamantylamino group, a 2-adamantylamino group, a norbornylamino group, an ammoniumethylamino group, a trifluoromethylamino group, a benzylamino group, an α,α-dimethylbenzylamino group, a 2-phenethylamino group, a 1-phenethylamino group, a phenylamino group, an alkoxyphenylamino group, an alkylphenylamino group, a 1-naphthylamino group, a 2-naphthylamino group, and a pentafluorophenylamino group. Among these, the amino group is preferably methylamino, ethylamino, 1-propylamino, 2-propylamino, 1-butylamino, 2-butylamino, tert-butylamino, pentylamino, hexylamino, octylamino, decylamino, dodecylamino, 2-ethylhexylamino, or 3,7-dimethyloctylamino. Furthermore, the amino group is more preferably methylamino, ethylamino, 1-propylamino, 2-propylamino, 1-butylamino, 2-butylamino, isobutylamino, tert-butylamino, pentylamino, or hexylamino.

[0084] The silyl group is not particularly limited, and examples of the silyl group include a dimethylsilyl group, a diethylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a t-butyldiphenylsilyl group, and a tristrimethylsilyl group.

[0085] As described above, the compound represented by formula (1) is preferably a compound in which two quaternary carbons are bonded to the N-oxy radical group. It is believed that the bonding of a group with large steric hindrance to the site adjacent to the N-oxy radical group in this way increases the stability of the radical and suppresses radical coupling. Therefore, it is believed that by incorporating such a compound into the electrolyte layer, a carbon dioxide adsorption battery can be obtained that can more effectively adsorb carbon dioxide from a carbon dioxide-containing gas during charging and release carbon dioxide during discharging.

[0086] Examples of the compound represented by formula (1) include 1,4-di(1-oxy-2,2,6,6-tetramethyl-1-piperidin-4-yloxy)xylene, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl, N,N-di-tert-butyl nitroxide radical, N,N-diphenyl nitroxide radical, N,N-dinaphthyl nitroxide radical, N,N-di-2-methylphenyl nitroxide radical, N,N-di-3-methylphenyl nitroxide radical, N,N-di-4-methylphenyl nitroxide radical, N ,N-di-2-ethylphenyl nitroxide radical, N,N-di-2-propylphenyl nitroxide radical, N,N-di-2-butylphenyl nitroxide radical, N,N-di-2-pentylphenyl nitroxide radical, N,N-di-2-hexylphenyl nitroxide radical, N,N-di-2-isopropylphenyl nitroxide radical, N,N-di-2-isobutylphenyl nitroxide radical, N,N-di-2-sec-butylphenyl nitroxide radical, N,N-di-2-tert-butylphenyl nitroxide radical , N,N-di-4-tert-butylphenyl nitroxide radical, N,N-di-(3,5-di-tert-butyl)phenyl nitroxide radical, N,N-di-4-pyridyl nitroxide radical, N,N-di-4-pyridazyl nitroxide radical, poly(ethylene glycol)-bis-2,2,6,6-tetramethylpiperidinyloxy radical, N-phenyl-N-oxy-tert-butylamine, N-naphthyl-N-oxy-tert-butylamine, N-tert-butyl-N-oxy-2-quinoline, 2,2,6,6-tetramethyl piperidinyloxy radical (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy radical, 4-amino-2,2,6,6-tetramethylpiperidinyloxy radical, 4-carboxy-2,2,6,6-tetramethylpiperidinyloxy radical, 4-methoxy-2,2,6,6-tetramethylpiperidinyloxy radical, 4-oxo-2,2,6,6-tetramethylpiperidinyloxy radical, 4-acetamido-2,2,6,6-tetramethylpiperidinyloxy radical, 4-octyloxy-2,2,6,Examples include 6-tetramethylpiperidinyloxy radical, 2,2,5,5-tetramethylpyrrolidine-oxy radical, 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine-oxy radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine-oxy radical, 2,2,6,6-tetramethylmorpholine-N-oxy radical, and 2,2,6,6-tetramethylmorpholinepiperazine-N-oxy radical.

[0087] Furthermore, as described above, the redox compound may be a polymeric compound, such as a compound obtained by polymerizing the compound represented by formula (1). Examples of the polymeric compound include compounds obtained by polymerizing a monomer such as a 4-acryloyloxy-2,2,6,6-tetramethylpiperidinyloxy radical, a 4-methacryloyloxy-2,2,6,6-tetramethylpiperidinyloxy radical, a 3-acryloyloxy-2,2,6,6-tetramethylpyrrolidinyloxy radical, a 3-methacryloyloxy-2,2,6,6-tetramethylpyrrolidinyloxy radical, a 4-vinyloyloxy-2,2,6,6-tetramethylpiperidinyloxy radical, or a 4-vinyloyloxy-2,2,5,5-tetramethylpyrrolidinyloxy radical. Furthermore, the polymeric compound may be a compound obtained by polymerizing a single monomer, or may be a compound obtained by polymerizing two or more of the monomers in combination. The polymer compound may be a compound obtained by polymerizing the compound represented by formula (1), or may be a copolymer obtained by copolymerizing the compound with a copolymerizable monomer such as ethylene, propylene, butadiene, isoprene, styrene, vinyl acetate, etc. The copolymerizable monomer may be used alone or in combination of two or more thereof.

[0088] Among the compounds exemplified above, the redox compound is preferably 1,4-di(1-oxy-2,2,6,6-tetramethyl-1-piperidin-4-yloxy)xylene, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl, or poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidinyloxy radical). The redox compounds may be used alone or in combination of two or more.

[0089] The compound represented by formula (1) may be a compound obtained by synthesis using a predetermined synthesis method, or may be a commercially available product. The synthesis method is not particularly limited as long as it is a synthesis method that can obtain the compound represented by formula (1), and examples thereof include a method of nitroxidizing the amino group of a disubstituted amine compound.

[0090] Here, non-volatile means that the substance does not evaporate or does not evaporate immediately at room temperature and pressure. For example, in this specification, 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) is not non-volatile but volatile. Therefore, an indicator of non-volatility is, for example, a boiling point at normal pressure that is higher than 193°C, the boiling point of TEMPO, preferably 200°C or higher, and more preferably 220°C or higher. Another indicator of non-volatility is, for example, a vapor pressure at 20°C that is lower than 0.4 hPa (i.e., less than 0.4 hPa), the vapor pressure of TEMPO (20°C), preferably lower than 0.2 hPa (i.e., less than 0.2 hPa).

[0091] The electrolyte layer 13 may contain components other than the electrolytic solution and the redox compound. Examples of other components contained in the electrolyte layer 13 include polyethylene glycol, polyacrylate, polymethacrylate, and polyvinyl alcohol acetal.

[0092] The electrolyte layer 13 may include a substrate. Examples of the electrolyte layer 13 include a substrate impregnated with the electrolytic solution containing the redox compound. Examples of the substrate include glass fiber filter paper.

[0093] The method for producing the electrolyte layer 13 is not particularly limited as long as the electrolyte layer 13 can be produced. When the electrolyte layer 13 includes the base material, for example, a method can be used in which the redox compound is dispersed or dissolved in the electrolyte solution and the base material is impregnated with the electrolyte solution containing the redox compound. The impregnation is preferably performed while applying ultrasonic vibrations to the electrolyte solution and the base material. This can prevent the formation of minute holes, i.e., pinholes, in the electrolyte layer 13.

[0094] (separator) The separator 16 is not particularly limited as long as it is a separator that suppresses permeation of the redox compound and is permeable to the electrolyte. That is, the separator 16 is less permeable to the redox compound than to the electrolyte. Furthermore, the separator 16 is preferably permeable to the electrolyte but not to the redox compound. The separator 16 is permeable to the electrolyte but is preferably made of a material that suppresses permeation of the redox compound. negative electrode The electrolyte layer 13 on the side 11 and the positive electrode The electrode 12 is provided so as to separate the electrolyte layer 13 from the electrode 12. negative electrode 11 and the above positive electrode12 is separated by the separator 16. Examples of the separator 16 include separators commonly used in lithium secondary batteries, and in particular, separators that have low resistance to ion migration of the electrolyte and excellent electrolyte humidification ability are preferred. Examples of materials for the separator include glass fiber, polyester, polyethylene, polypropylene, and polytetrafluoroethylene (PTFE). The separator materials may be used alone or in combination of two or more. The separator is made of the separator material and may be in the form of a nonwoven fabric or a woven fabric. The pore size of the separator is not particularly limited and is preferably, for example, 0.01 to 10 μm. The thickness of the separator is not particularly limited and is preferably, for example, 5 to 300 μm.

[0095] As described above, the carbon dioxide adsorption battery 10 is charged by negative electrode The potential of 11 is positive electrode The potential of the negative electrode 11 and the above positive electrode A voltage is applied between a pair of electrodes 11, 12 consisting of a pair of electrodes 11 and 12. For this purpose, the carbon dioxide adsorption battery 10 may be provided with the voltage application unit 14. As described above, during discharge, the carbon dioxide adsorption battery 10 negative electrode 11 and the above positive electrode A resistor 17 or the like is provided between a pair of electrodes 11, 12, which are made up of a carbon dioxide adsorption battery 10, for discharging. The resistor 17 is not particularly limited as long as it can discharge the carbon dioxide adsorption battery 10.

[0096] The voltage application unit 14 is not particularly limited as long as it can apply a voltage between the pair of electrodes 11 and 12. That is, as described above, the voltage application unit 14 negative electrode The potential of 11 is positive electrode A voltage is applied between the pair of electrodes 11 and 12 so that the potential of the pair of electrodes 11 and 12 is lower than the potential of the pair of electrodes 11 and 12. By doing so, when charging, the voltage is applied by the voltage application unit 14, and the negative electrodeCharging can be performed while carbon dioxide is being taken in on the electrode 11 side. The voltage application unit 14 may be an application unit that cannot reverse the voltage applied between the pair of electrodes 11 and 12, and examples thereof include a secondary battery, an external power source, and a capacitor.

[0097] The carbon dioxide adsorption battery 10 is not particularly limited in its manufacturing method as long as it can be manufactured with the above structure. negative electrode 11. The aforementioned positive electrode 1 and 2, for example, by assembling the fuel cell 10 by a general assembly method using the fuel cell 10, the electrolyte layer 13, and the separator 16, and further using the flow path 15, the voltage application unit 14, and the resistor 17, etc., as needed.

[0098] The carbon dioxide adsorption battery 10 negative electrode 11 and the above positive electrodeThe carbon dioxide adsorption battery 10 is charged by applying a voltage to 12. During charging, as described above, the carbon dioxide adsorption battery 10 adsorbs carbon dioxide by binding to the redox compound contained in the electrolyte layer 13. When the carbon dioxide adsorption battery 10 is discharged after charging, the carbon dioxide adsorption battery 10 releases carbon dioxide by desorbing carbon dioxide from the redox compound contained in the electrolyte layer 13. For this reason, it is preferable to use the carbon dioxide adsorption battery 10 so that it adsorbs carbon dioxide during charging and releases carbon dioxide during discharging. Furthermore, the gas released from the carbon dioxide adsorption battery 10 during discharging is mainly the gas adsorbed by the carbon dioxide adsorption battery 10 during charging, and therefore has a very high carbon dioxide concentration. For this reason, the carbon dioxide adsorption battery 10 can concentrate carbon dioxide. That is, the carbon dioxide adsorption battery 10 can also be used as a device for concentrating carbon dioxide. Furthermore, the carbon dioxide adsorption battery 10 adsorbs carbon dioxide from a gas containing carbon dioxide during charging and releases carbon dioxide during discharging, resulting in the release of a gas with a very high carbon dioxide concentration. For this reason, the carbon dioxide adsorption battery 10 can also be used as a device for separating carbon dioxide from a gas containing carbon dioxide.

[0099] [Charge / discharge device] A charge / discharge device according to another embodiment of the present invention is a charge / discharge device including two or more of the carbon dioxide adsorption batteries. The charge / discharge device is not particularly limited as long as it includes two or more of the carbon dioxide adsorption batteries, and an example of the charge / discharge device is a charge / discharge device 40 as shown in FIG. 6.

[0100] The charging / discharging device 40 includes two carbon dioxide adsorption batteries (a first carbon dioxide adsorption battery 10a and a second carbon dioxide adsorption battery 10b). positive electrode Side 10a2 and negative electrode The charging / discharging device 40 can charge the first carbon dioxide adsorption battery 10a by connecting the first carbon dioxide adsorption battery 10a to the side 10a1 via the voltage application unit 14. positive electrodeThe side 10a2 and the voltage application unit 14 are connected by a wiring 61, and the voltage application unit 14 and the first carbon dioxide adsorption battery 10a negative electrode The first carbon dioxide adsorption battery 10a can be charged by connecting the first carbon dioxide adsorption battery 10a to the side 10a1 with a wiring 62. After the first carbon dioxide adsorption battery 10a is charged, negative electrode side 10a1 and the second carbon dioxide adsorption battery 10b negative electrode side 10b1 of the second carbon dioxide adsorption battery 10b is connected by a wiring 66. positive electrode side 10b2 and the first carbon dioxide adsorption battery 10a positive electrode By connecting the first carbon dioxide adsorption battery 10a and the second carbon dioxide adsorption battery 10b with a wiring 65, the first carbon dioxide adsorption battery 10a can be discharged and the second carbon dioxide adsorption battery 10b can be charged. After the second carbon dioxide adsorption battery 10b is charged (after the first carbon dioxide adsorption battery 10a is discharged), negative electrode side 10b1 and the first carbon dioxide adsorption battery 10a negative electrode side 10a1 is connected to the first carbon dioxide adsorption battery 10a by a wiring 64. positive electrode side 10a2 and the second carbon dioxide adsorption battery 10b positive electrodeBy connecting the first carbon dioxide adsorption battery 10a and the second carbon dioxide adsorption battery 10b2 via wiring 63, the second carbon dioxide adsorption battery 10b can be discharged and the first carbon dioxide adsorption battery 10a can be charged. In this way, by once charging the first carbon dioxide adsorption battery 10a, the charging / discharging device can function as a charging / discharging device that can alternately charge and discharge the second carbon dioxide adsorption battery 10b and the first carbon dioxide adsorption battery 10a. Therefore, by including two or more carbon dioxide adsorption batteries, the charging / discharging device can alternately charge and discharge each of the carbon dioxide adsorption batteries. This makes the charging / discharging device highly energy efficient. The charging / discharging device can also separate carbon dioxide. When charging the first carbon dioxide adsorption battery 10a and the second carbon dioxide adsorption battery 10b, a gas containing carbon dioxide (such as air containing nitrogen and carbon dioxide) is supplied through flow path 15a, and nitrogen (nitrogen and unadsorbed carbon dioxide) is discharged through flow path 15b. In addition, when discharging the first carbon dioxide adsorption battery 10a and the second carbon dioxide adsorption battery 10b, carbon dioxide is discharged through a flow path 15c. Note that Fig. 6 is a schematic diagram showing an example of the configuration of a charge / discharge device 40 according to an embodiment of the present invention.

[0101] As described above, this specification discloses various aspects of the technology, the main technologies of which are summarized below.

[0102] One aspect of the present invention is a method for producing a medicament for use in a pharmaceutical composition comprising: negative electrode and, positive electrode and the above negative electrode and the above positive electrode a separator disposed between the negative electrode and the separator and positive electrode and an electrolyte layer disposed between the separator and the negative electrodeis a gas-permeable electrode, the electrolyte layer contains an electrolyte solution capable of dissolving carbon dioxide and a redox compound having an N-oxy radical group in the molecule, and the separator inhibits permeation of the redox compound and is permeable to the electrolyte solution.

[0103] With this configuration, it is possible to provide a carbon dioxide adsorption battery that can be charged while easily adsorbing carbon dioxide from a gas containing carbon dioxide.

[0104] This is thought to be due to the following:

[0105] The aforementioned negative electrode is the above negative electrode It is possible for gas present in the surroundings to pass through. negative electrode When gas passes through the negative electrode The gas that has permeated the electrolyte layer comes into contact with the electrolyte layer. negative electrode Carbon dioxide contained in the surrounding gas is dissolved in the electrolyte solution contained in the electrolyte layer.

[0106] During charging, the carbon dioxide adsorption battery negative electrode The potential of positive electrode That is, the potential is lower than the potential of positive electrode The potential of negative electrode so that the potential is higher than that of negative electrode and the above positive electrode A voltage is applied between

[0107] The redox compound contained in the electrolyte layer is negative electrode On the side closer to negative electrode The potential of positive electrode Since the potential is higher than that of the carbon dioxide adsorption battery, the N-oxy radical group is reduced to an N-oxy anion group. Carbon dioxide dissolved in the electrolyte is then bonded to this N-oxy anion group, which promotes the dissolution of carbon dioxide into the electrolyte. negative electrodeCarbon dioxide is taken in from the electrolyte side and adsorbed onto the electrolyte layer.

[0108] On the other hand, the redox compound contained in the electrolyte layer is positive electrode On the side closer to positive electrode The potential of negative electrode Since the potential is lower than that of the N-oxy radical group, the N-oxy radical group is oxidized to become an N-oxy cation group.

[0109] The separator allows the electrolyte to pass through but inhibits the redox compound from passing through. That is, the redox compound is less likely to pass through the separator than the electrolyte. Therefore, both the redox compound in which the N-oxy radical group is reduced to become an N-oxy anion group and the redox compound to which carbon dioxide is bound pass through the separator and are released. positive electrode Therefore, even after charging is stopped, if the battery is not discharged, these redox compounds are unlikely to move to the negative electrode The redox compound in which the N-oxy radical group is oxidized to become an N-oxy cation group also permeates the separator and is retained on the side. negative electrode Therefore, even after charging is stopped, if the battery is not discharged, the redox compound having the N-oxy cation group in the molecule moves from the separator of the electrolyte layer to the positive electrode As a result, the carbon dioxide adsorption battery can maintain a charged state.

[0110] As described above, it is believed that the carbon dioxide adsorption battery can be charged while easily adsorbing carbon dioxide from a gas containing carbon dioxide. Furthermore, the carbon dioxide adsorption battery has excellent durability because it uses a redox compound having an N-oxy radical group in the molecule, which is more durable than the quinone compound, instead of the quinone compound.

[0111] As described above, when the charged carbon dioxide adsorption battery is discharged, the separator in the electrolyte layer positive electrode On the side of the electrolyte layer, the N-oxy cation group returns to the N-oxy radical group. negative electrode On the other hand, carbon dioxide is released from the redox compound, and the N-oxy anion group returns to the N-oxy radical group. negative electrode The carbon dioxide adsorption battery can release carbon dioxide from the side. The gas released from the carbon dioxide adsorption battery during discharge is mainly the gas that was adsorbed in the carbon dioxide adsorption battery during charge, and therefore has a very high carbon dioxide concentration. This means that the carbon dioxide adsorption battery can concentrate carbon dioxide.

[0112] Therefore, the carbon dioxide adsorption battery can adsorb carbon dioxide during charging and release carbon dioxide during discharging, and this adsorption and release can concentrate carbon dioxide. negative electrode and the above positive electrode Since the heating is performed by applying a voltage between the electrode and the electrode, there is no need for high temperature or high pressure, and the heating can be performed at room temperature and atmospheric pressure.

[0113] In addition, in the carbon dioxide adsorption battery, positive electrode However, it is preferable that the insulating film has a gas permeation blocking portion that blocks gas permeation.

[0114] With this configuration, charging is possible while easily adsorbing carbon dioxide from a gas containing carbon dioxide, and the charged state can be maintained for a longer period of time.

[0115] In addition, in the carbon dioxide adsorption battery, positive electrode However, it is preferable that the heater is configured so as not to come into contact with the outside air.

[0116] With this configuration, charging is possible while easily adsorbing carbon dioxide from a gas containing carbon dioxide, and the charged state can be maintained for a longer period of time.

[0117] The aforementioned positive electrodeHowever, when the battery is provided with a gas permeation blocking section that blocks gas permeation, and when it is configured so as not to come into contact with the outside air, it is possible to charge the battery while easily adsorbing carbon dioxide from a gas containing carbon dioxide, as described above, and the charged state can be maintained for a longer period of time. This is thought to be due to the following reasons.

[0118] In the carbon dioxide adsorption battery, as described above, the separator suppresses the migration of the redox compound, but the redox compound may permeate the separator. negative electrode From the side positive electrode When the redox compound to which carbon dioxide is bound moves during charging or while the charged state is maintained, the redox compound to which carbon dioxide is bound may move to the side of the battery. positive electrode In the vicinity of the redox compound, the redox compound is oxidized, carbon dioxide is released from the redox compound, and the N-oxy anion group returns to the N-oxy radical group. positive electrode When carbon dioxide is released from the side, the migration of the redox compound to which the carbon dioxide is bound can be promoted. positive electrode However, if a gas permeation blocking section that blocks gas permeation is provided and if the battery is configured to not come into contact with the outside air, it is believed that this promotion of movement can be prevented, and the charged state can be maintained better.

[0119] As described above, the carbon dioxide adsorption battery adsorbs carbon dioxide during charging and releases carbon dioxide during discharging. For this reason, it is preferable that the carbon dioxide adsorption battery be used so as to adsorb carbon dioxide during charging and release carbon dioxide during discharging.

[0120] In the carbon dioxide adsorption battery, the redox compound is preferably a compound in which two quaternary carbons are bonded to the N-oxy radical group.

[0121] This configuration allows for more efficient adsorption of carbon dioxide from the carbon dioxide-containing gas, and thus allows for a longer charge state to be maintained, which is believed to be due to more efficient binding and desorption of carbon dioxide to and from the redox compound.

[0122] In the carbon dioxide adsorption battery, the redox compound is preferably a compound represented by the following formula (1) or a compound having a group in which one hydrogen atom has been eliminated from the compound represented by the following formula (1):

[0123] [ka]

[0124] In formula (1), Z is -CR5R6CR7R8-, -CR9R 10 CR 11 R 12 CR 13 R 14 -, -(CR 15 R 16 )O-, -(CR 17 R 18 )NR 27 -, -(CR 19 R 20 )O(CR 21 R 22 )-, or -(CR 23 R 24 )NR 28 (CR 25 R 26 )-, R1~R 28 each independently represents a hydrogen atom or a substituent.

[0125] This configuration allows for more efficient adsorption of carbon dioxide from the carbon dioxide-containing gas, and thus allows for a longer charge state to be maintained, which is believed to be due to more efficient binding and desorption of carbon dioxide to and from the redox compound.

[0126] In addition, in the carbon dioxide adsorption battery, negative electrodeis preferably made of a conductive material containing at least one selected from the group consisting of graphite, carbon nanotubes, activated carbon, and carbon fibers.

[0127] With this configuration, it is possible to adsorb more carbon dioxide from the gas containing carbon dioxide, and it is possible to maintain the charged state for a longer period of time. negative electrode During charging, the carbon dioxide can pass through the negative electrode and the above positive electrode This is thought to be because a voltage can be more suitably applied between the electrodes.

[0128] Another aspect of the present invention is a charge / discharge device including two or more of the carbon dioxide adsorption batteries.

[0129] According to this configuration, as described above, a charging / discharging device including the carbon dioxide adsorption battery can be provided. Furthermore, by including two or more carbon dioxide adsorption batteries, the charging / discharging device can alternately charge and discharge each of the carbon dioxide adsorption batteries. Specifically, first, one of the carbon dioxide adsorption batteries (first battery) is charged. Then, the other carbon dioxide adsorption battery (second battery) connected to the first battery can be charged by discharging the first battery. Then, the first battery can be charged by discharging the second battery. In this way, by charging the first battery once, the charging / discharging device can function as a charging / discharging device that can alternately charge and discharge the second battery and the first battery. This makes the charging / discharging device highly energy efficient. Furthermore, the charging / discharging device can separate carbon dioxide.

[0130] According to the present invention, it is possible to provide a carbon dioxide adsorption battery that can be charged while easily adsorbing carbon dioxide from a gas containing carbon dioxide. Also, according to the present invention, it is possible to provide a charge / discharge device including the carbon dioxide adsorption battery.

[0131] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples. [Example]

[0132] [Example 1] <Fabrication of a carbon dioxide adsorption battery> A carbon dioxide adsorption battery having the structure shown in FIGS. 1 and 2 was fabricated by the following procedure.

[0133] (electrolyte layer) 6.5 g of Poly(vinylidenefluoride-co-hexafluoropropylene) (Sigma-Aldrich) was added to 100.0 g of dimethylformamide (Fujifilm Wako Pure Chemical Industries, Ltd.) and dissolved by stirring at 80° C. for 3 hours. Next, 24.0 g of a compound [poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidinyloxy radical)] (non-volatile) obtained by polymerizing the redox compound, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidinyloxy radical (Tokyo Chemical Industry Co., Ltd.) as a monomer by a conventional anionic polymerization method, was added to the resulting solution, and the mixture was dissolved by stirring at 80° C. for 3 hours. Next, 12.9 g of an ionic liquid [1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (non-volatile) (emimFSI manufactured by Sigma-Aldrich)], an electrolyte capable of dissolving carbon dioxide, was added to the resulting solution, heated to 40°C, and stirred and mixed for 3 hours. Using the liquid thus obtained, a 500 μm-thick liquid film was formed on a glass plate using an applicator and dried under reduced pressure at 60°C for 8 hours. The dried film obtained by the drying was peeled off from the glass plate. This resulted in a dried film with a thickness of 100 μm. This dried film was cut into a size of 20 mm length x 24 mm width and used as an electrolyte layer. When the obtained electrolyte layer was visually inspected, no small holes (pinholes) were observed.

[0134] (electrode: negative electrode and positive electrode ) Carbon paper (GDL35BC manufactured by SGL Carbon Japan Co., Ltd.) was cut into multiple sheets measuring 30 mm long x 30 mm wide x 1 mm thick.

[0135] negative electrode A conductive copper foil tape (used as a tab) was attached to one side of the cut carbon paper.

[0136] positive electrode As for the carbon paper, positive electrode A copper foil (gas permeation shielding part) measuring 30mm long x 30mm wide x 8mm thick is attached to one side of the main body using conductive adhesive (Dotite D-550 manufactured by Fujikura Kasei Co., Ltd.) ( positive electrode Equipped with a main body and a gas permeation barrier positive electrode ) was used.

[0137] (separator) The separator used was a polypropylene separator (Celgard #2400 manufactured by Polypore Corporation) cut into a size of 30 mm length x 30 mm width.

[0138] (flow path) A polytetrafluoroethylene resin plate was cut into a size of 50 mm length x 50 mm width x 5 mm thickness, and two holes were drilled at appropriate locations. A groove with a depth of 1 mm, length of 20 mm, and width of 20 mm was dug in this cut-out resin plate to connect to the holes. This was used as a flow path.

[0139] (carbon dioxide adsorption battery) The electrolyte layer is laminated on both sides of the separator, and the negative electrode On the other hand, positive electrode and then assembling the flow paths on both sides of the stack, positive electrode A carbon dioxide adsorption battery was manufactured so as to have the structure shown in Figures 1 and 2, except that a flow path was also formed on the side. positive electrodeTo ensure there is no gas leakage from the side, positive electrode During charging, the carbon dioxide adsorption battery is negative electrode Conductive copper foil tape and positive electrode A power supply was connected to the copper foil as a voltage application unit. negative electrode Conductive copper foil tape and positive electrode A resistor was connected to the copper foil.

[0140] [evaluation] The carbon dioxide adsorption battery was evaluated by the following evaluation method.

[0141] First, the carbon dioxide adsorption battery was placed in a room temperature (28°C) environment. negative electrode ( Anode during discharge A gas bag filled with carbon dioxide was attached to the hole of the flow path on the side of the electrode. positive electrode ( Cathode during discharge A gas bag filled with nitrogen was attached to the hole of the flow path on the side of the electrode. negative electrode ( Anode during discharge The flow path holes on the side of the electrode positive electrode ( Cathode during discharge A portable carbon dioxide concentration meter (CGP-31 manufactured by DKK-TOA Corporation) was attached to each of the holes in the flow path on the side of the electrode. The carbon dioxide concentration measured when this was attached was 0.4% (4000 ppm). Then, by adjusting the power supply, negative electrode and the above positive electrode The discharge characteristics of the carbon dioxide adsorption battery were measured by charging at a constant current of 0.25 mA between 0.1 V and 1.0 V (between 0.1 V and 1.0 V) until the voltage reached 4 V, and then discharging to 3 V. Specifically, the discharge characteristics of the carbon dioxide adsorption battery were measured (evaluation of discharge rate characteristics) as follows.

[0142] Discharge rate characteristic evaluation Using a charge / discharge tester (TOSCAT manufactured by Toyo Systems Co., Ltd.), the carbon dioxide adsorption battery was charged at a constant current of 2.5 mA until the voltage reached 4 V, and then continuously charged at a constant voltage of 4 V until the voltage reached 0.25 mA. Subsequently, the battery was discharged at a constant current of 1 C (2.5 mA), and the discharge capacity (mAh / g) was measured. The discharge capacity was calculated as the capacity per weight of the radical material to facilitate comparison of the efficiency of the radical materials.

[0143] When this discharge rate characteristic evaluation was measured, after the end of the charge, negative electrode ( Anode during discharge The residual carbon dioxide concentration (CO2 concentration after charging) was measured using a portable carbon dioxide concentration meter (CGP-31 manufactured by DKK-TOA Corporation) attached to the hole of the flow path on the side of the side electrode. negative electrode ( Anode during discharge The carbon dioxide concentration (CO2 concentration after discharge) was measured using a portable carbon dioxide concentration meter attached to the hole in the flow path on the side of the electrode. positive electrode It was confirmed that no gas was leaking from the flow path formed on the side.

[0144] These results are shown in Table 1.

[0145] [Example 2] A carbon dioxide adsorption battery was manufactured in the same manner as in Example 1, except that 42.9 g of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonylimide) was used instead of poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidinyloxy radical) as the electrolyte (ionic liquid) capable of dissolving carbon dioxide. Then, the obtained carbon dioxide adsorption battery was used to carry out the same evaluation as in Example 1. positive electrode It was confirmed that no gas was leaking from the flow path formed on the side.

[0146] These results are shown in Table 1.

[0147] [Example 3] The aforementioned positive electrode As, positive electrodeEquipped with a main body and a gas permeation barrier positive electrode Instead of negative electrode The same electrode (a conductive copper foil tape (used as a tab) attached to one side of the cut carbon paper) was used, i.e., positive electrode A carbon dioxide adsorption battery was manufactured in the same manner as in Example 1, except that the carbon dioxide adsorption battery was not provided with a gas permeation blocking portion. Then, the obtained carbon dioxide adsorption battery was subjected to the same evaluation as in Example 1. positive electrode It was confirmed that no gas was leaking from the flow path formed on the side.

[0148] These results are shown in Table 1.

[0149] [Example 4] The aforementioned negative electrode Instead of pasting conductive copper foil tape (used as a tab) on one side of the cut carbon paper, negative electrode A carbon dioxide adsorption battery was manufactured in the same manner as in Example 1, except that the carbon dioxide adsorption battery was used. The obtained carbon dioxide adsorption battery was then evaluated in the same manner as in Example 1. positive electrode It was confirmed that no gas was leaking from the flow path formed on the side.

[0150] These results are shown in Table 1.

[0151] Activated carbon (YP-50 manufactured by Kuraray Co., Ltd.), styrene-butadiene rubber (SBR) (TRD2001 manufactured by JSR Corporation), carboxymethyl cellulose (CMC) (Cellogen BSH manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and carbon black (Super-P manufactured by TIMCAL Graphite & Carbon Co., Ltd.) were mixed with water in a mass ratio of activated carbon:SBR:CMC:carbon black = 90:3:2:5 to obtain a slurry. Instead of carbon paper, a stainless steel mesh (stainless steel mesh manufactured by Kureha Co., Ltd., stainless steel 304, mesh number 635) was used. The obtained slurry was applied to this stainless steel mesh using a bar coater, and then dried in a glass tube oven at 150°C for 7 hours under reduced pressure to obtain an activated carbon-coated electrode (activated carbon thickness 150 μm). This electrode was negative electrode It was used as.

[0152] [Comparative Example 1] 28.4 g of a compound [poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidinyloxy radical)] (non-volatile) obtained by polymerizing a redox compound, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidinyloxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) as a monomer using a conventional anionic polymerization method was dissolved in 30.0 g of toluene. The solution thus obtained was dropped onto the entire surface of a glass fiber filter paper (GC50 manufactured by Advantec). Thereafter, the glass fiber filter paper onto which the solution had been dropped was dried under a nitrogen atmosphere. By doing so, the toluene was removed and a solid electrolyte layer was obtained. A device was manufactured in the same manner as in Example 1 except that this solid electrolyte layer was used. Then, the obtained device was used and evaluated in the same manner as in Example 1. positive electrode It was confirmed that no gas was leaking from the flow path formed on the side. Furthermore, this device does not adsorb carbon dioxide or store electricity, so it is simply called a device.

[0153] These results are shown in Table 1.

[0154] Comparative Example 2 A carbon dioxide adsorption battery was manufactured in the same manner as in Example 1, except that no redox compound was added. Then, the obtained carbon dioxide adsorption battery was used to carry out the same evaluation as in Example 1. positive electrode It was confirmed that no gas was leaking from the flow path formed on the side. Furthermore, this device does not adsorb carbon dioxide or store electricity, so it is simply called a device.

[0155] These results are shown in Table 1.

[0156] In Table 1, "-" in the discharge capacity column indicates that electricity could not be stored (the charged state could not be maintained).

[0157] [Table 1]

[0158] Comparative Example 3 The aforementioned positive electrode As, positive electrode Equipped with a main body and a gas permeation barrier positive electrode Instead of negative electrode A device was produced in the same manner as in Example 1, except that the same electrodes (conductive copper foil tape (used as a tab) attached to one side of the cut-out carbon paper) were used and a separator was not provided. Note that this device does not adsorb carbon dioxide or store electricity, and is therefore referred to as a carbon dioxide separation device.

[0159] First, the carbon dioxide separator is placed in an environment at room temperature (28°C), Anode during discharge A gas bag filled with carbon dioxide is placed in the hole of the flow path on the side electrode. Cathode during discharge A gas pack filled with nitrogen was attached to the hole in the side channel. Anode during discharge The hole in the flow path on the side electrode and Cathode during dischargeThe portable carbon dioxide concentration meter was attached to each of the holes in the flow path on the side electrode. The carbon dioxide concentration measured at this time was 0.4% (4000 ppm). Then, the power supply was adjusted to apply a constant current of 0.25 mA between the electrodes until a voltage of 4 V was reached.

[0160] The carbon dioxide separator is configured to: Anode during discharge The carbon dioxide concentration measured by the carbon dioxide concentration meter on the side decreases, Cathode during discharge The concentration measured by the carbon dioxide gas concentration meter on the side began to rise. After that, after applying voltage for 2 hours, the voltage application was stopped and the current was stopped. The voltage between the two electrodes quickly dropped, and it was confirmed that the device was not being charged. Anode during discharge The carbon dioxide concentration measured by the carbon dioxide concentration meter on the side was 270 ppm. Cathode during discharge The concentration measured by the carbon dioxide gas concentration meter on the side was 3520 ppm. During charging From the cathode side During charging Carbon dioxide was able to pass through to the anode side, but charging was not possible.

[0161] As can be seen from Table 1, negative electrode , the above positive electrode In the carbon dioxide adsorption batteries (Examples 1 to 4) comprising the separator and the electrolyte layer, the electrolyte layer contained an electrolyte solution capable of dissolving carbon dioxide and a redox compound having an N-oxy radical group in the molecule, and the carbon dioxide adsorption batteries according to Examples 1 to 4 were chargeable. negative electrode It was confirmed that carbon dioxide was adsorbed, as the carbon dioxide concentration on the side of the battery decreased. negative electrode The carbon dioxide concentration on the side of the electrode returned to almost the same level as before charging, confirming that the adsorbed carbon dioxide was released.

[0162] In contrast, when a solid electrolyte layer made of a redox compound having an N-oxy radical group in its molecule and not containing an electrolyte capable of dissolving carbon dioxide was used (Comparative Example 1), charging and storage of electricity were not possible. negative electrode It was confirmed that the carbon dioxide concentration on the electrode side did not decrease, and carbon dioxide was not adsorbed. Furthermore, when an electrolyte layer containing an electrolyte solution capable of dissolving carbon dioxide but not containing a redox compound having an N-oxy radical group in the molecule was used (Comparative Example 2), charging and storage were not possible, as with the device according to Comparative Example 1. Furthermore, the device according to Comparative Example 2 was unable to charge even when a voltage was applied between the electrodes in an attempt to charge it. negative electrode It was confirmed that the carbon dioxide concentration on the electrode side did not decrease, and carbon dioxide was not adsorbed. The reason why these devices could not be charged and carbon dioxide was not adsorbed even when a voltage was applied between the electrodes to charge them is thought to be because carbon dioxide could not be bound to the redox compound even when a voltage was applied between the electrodes to charge them.

[0163] Furthermore, when no separator was provided (Comparative Example 3), charging and storage of electricity were not possible. When a voltage was applied between the electrodes to charge the device according to Comparative Example 3, negative electrode The carbon dioxide concentration on the side of the electrode decreased, and it was confirmed that carbon dioxide was adsorbed. This is thought to be due to the carbon dioxide being bound to the redox compound. On the other hand, while applying a voltage between the electrodes to charge the electrode, During charging The carbon dioxide concentration on the anode side increased, which confirmed that carbon dioxide was being released from the electrode. This indicates that the redox compound to which carbon dioxide is bound is During charging It is believed that the carbon dioxide reaches the anode electrode, where it is released from the redox compound. For this reason, it is believed that the device according to Comparative Example 3 cannot be charged or store electricity.

[0164] This application is based on Japanese Patent Application No. 2021-034204, filed on March 4, 2021, the contents of which are incorporated herein by reference.

[0165] In order to express the present invention, the present invention has been properly and sufficiently described through the embodiments in the above, but it should be recognized that those skilled in the art can easily change and / or improve the above-mentioned embodiments. Therefore, unless the changes or improvements made by those skilled in the art are at a level that causes departure from the scope of the claims described in the claims, such changes or improvements are interpreted as being included in the scope of the claims. [Industrial Applicability]

[0166] According to the present invention, there is provided a carbon dioxide adsorption battery that can be charged while easily adsorbing carbon dioxide from a gas containing carbon dioxide. Also, according to the present invention, there is provided a charge / discharge device including the carbon dioxide adsorption battery.

Claims

1. a negative electrode; A positive electrode and a separator disposed between the negative electrode and the positive electrode; an electrolyte layer disposed between the negative electrode and the separator and between the positive electrode and the separator, the negative electrode is a gas-permeable electrode, the positive electrode is provided with a gas permeation blocking portion that blocks gas permeation, the electrolyte layer contains an electrolyte solution capable of dissolving carbon dioxide and a redox compound having an N-oxy radical group in the molecule; the separator inhibits permeation of the redox compound and allows permeation of the electrolyte; A carbon dioxide adsorption battery, characterized in that the thickness of the electrolyte layer is 0.1 μm to 2 mm.

2. 2. The carbon dioxide adsorption battery according to claim 1, wherein the positive electrode is configured so as not to come into contact with outside air.

3. 3. The carbon dioxide adsorption battery according to claim 1, which adsorbs carbon dioxide during charging and releases carbon dioxide during discharging.

4. 4. The carbon dioxide adsorption battery according to claim 1, wherein the redox compound is a compound in which two quaternary carbons are bonded to the N-oxy radical group.

5. The carbon dioxide adsorption battery according to any one of claims 1 to 4, wherein the redox compound is a compound represented by the following formula (1) or a compound having a group in which one hydrogen atom has been eliminated from a compound represented by the following formula (1): 【Chemistry 1】 [In formula (1), Z is —CR ５ R ６ CR ７ R ８ -, -CR ９ R １０ CR １１ R １２ CR １３ R １４ -, - (CR １５ R １６ ) O-, -(CR １７ R １８ ) NR ２７ -, - (CR １９ R ２０ ) O (CR ２１ R ２２ ) - or - (CR ２３ R ２４ ) NR ２８ (CR ２５ R ２６ )-, R １ ~R ２８ each independently represents a hydrogen atom or a substituent.

6. 6. The carbon dioxide adsorption battery according to claim 1, wherein the negative electrode is made of a conductive material containing at least one selected from the group consisting of graphite, carbon nanotubes, activated carbon, and carbon fibers.

7. A charge / discharge device comprising two or more carbon dioxide adsorption batteries according to any one of claims 1 to 6.

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