Device for adsorbing and emitting carbon dioxide

Adsorption and the discharge device of carbon dioxide

0001The present invention relates to the device which can adsorb and emit carbon dioxide electrochemically.

0002Carbon dioxide is a substance which occupies 0.04% in the atmosphere and which exists widely on the earth. It is the compound used widely industrially. Supposing it gives the example of industrial use of carbon dioxide, the gas for foaming, such as a carbonated drink, bath salts, extinguishing media, or dry ice for cooling, and the air for an urgent supplement of a bicycle will be mentioned. The carbon dioxide of a supercritical state is used as an extracting solvent of caffeine, and is used also for the carbon dioxide laser further used as the laser used for processing in the industrial field, or a laser surgical unit for medical science. It is CO as substitution of a chlorofluocarbon system refrigerant._２It is used for the refrigerant compressor etc.

0003In agriculture, carbon dioxide is used for the carbon dioxide fertilization which accelerates growth of plants, such as forced agriculture of a strawberry, and a seaweed of the tank for admiration, and is used also for the CA storage (controlled*atomosphere*storage) of Fresh produce.

0004Thus, it is although it is the carbon dioxide generally used widely, the compression adsorption art of carrying out compression adsorption of the carbon dioxide using zeolite as shown in patent documents 1 as art of storing carbon dioxide conventionally -- or The thing to which carbon dioxide is made to stick using alkaline fluid and half fluid as shown in patent documents 2 is in use, and the device which is low energy consumption and can perform adsorption and desorption of carbon dioxide without needing a large-scale device did not exist.

<p num="0005"><patcit num="1"><text>JP,7-39752,A</text></patcit><patcit num="2"><text>JP,11-114353,A</text></patcit></p>

<p num="0006">In the solutions reported by the above-mentioned prior art document, big energy, such as applying heat, is required in the case of adsorption and desorption, and adsorption desorption performance and low energy consumption had the problem of being incompatible.</p><p num="0007">The present invention is made in view of the above-mentioned reason, and an object of the present invention is to have high adsorption ability and to provide carbon dioxide adsorption / discharge device with little energy expenditure at the time of adsorption desorption.</p>

<p num="0008">Carbon dioxide adsorption / discharge device which starts the present invention that the above-mentioned subject should be solved, Electrolysis solution 3 with which it filled up between a pair of electrodes 1 and 2 countered and provided, and a pair of each electrodes 1 and 2 of an electrode, It is carbon dioxide adsorption / discharge device which has porous body 4 provided on a pair of one electrodes 1 of an electrode, and electrolysis solution 3 is, By absorbing carbon dioxide and making it dissolve in the electrolysis solution concerned, carbonic acid ion or carbonated water matter ion can be formed, and it is by the above-mentioned porous body 4, The surface of porous body 4 is electrostatically adsorbed in carbonic acid ion or carbonated water matter ion at the time of the forward direction voltage impression to an above-mentioned pair of electrodes 1 and 2, and the above-mentioned carbonic acid ion or carbonated water matter ion is electrostatically emitted from the surface of porous body 4 at the time of the opposite direction voltage impression to an above-mentioned pair of electrodes.</p><p num="0009">A pair of electrodes 1 and 2 provided in forward direction voltage impression face to face here, In carbon dioxide adsorption / discharge device which has electrolysis solution 3 with which it filled up among a pair of each electrodes 1 and 2 of an electrode, and porous body 4 provided on a pair of one electrodes 1 of an electrode, it means connecting the anode of a direct-current power supply to electrode 1, connecting the cathode of a direct-current power supply to electrode 2, and impressing voltage. On the other hand, opposite direction voltage impression means connecting the cathode of a direct-current power supply to electrode 1, connecting the anode of a direct-current power supply to electrode 2, and impressing voltage in the above-mentioned composition.</p><p num="0010">As for porous body 4, in carbon dioxide adsorption / discharge device concerning the present invention, it is preferred that they are organic polymers from which either the oxidization object of unit A or a reduced form will be in a cation state reversibly by voltage impression to a pair of electrodes 1 and 2 including unit A in which oxidation reduction is possible.</p><p num="0011">As for porous body 4, in carbon dioxide adsorption / discharge device concerning the present invention, it is preferred that it is the polymer gel which swells to an electrolysis solution.</p><p num="0012">In carbon dioxide adsorption / discharge device which starts the present invention especially, it is preferred that unit A is shown with the following structural formulae (Turn 1 or Turn 2) in porous body 4 which comprises above-mentioned polymer gel.<br /><chemistry num="1"><img file="WO2012144189A1_D0001.tif" /></chemistry><chemistry num="2"><img file="WO2012144189A1_D0002.tif" /></chemistry></p><p num="0013">The above-mentioned porous body 4 is shown by the following structural formulae (Turn 3 or Turn 4) in carbon dioxide adsorption / discharge device concerning the present invention.<br /><chemistry num="3"><img file="WO2012144189A1_D0003.tif" /></chemistry><chemistry num="4"><img file="WO2012144189A1_D0004.tif" /></chemistry></p><p num="0014">In carbon dioxide adsorption / discharge device concerning another mode of the present invention, the above-mentioned porous body 4 is a conductive polymer porous body.</p><p num="0015">In carbon dioxide adsorption / discharge device which starts the present invention especially, it is preferred in the above-mentioned porous body 4 that unit A is poly aniline shown with the following structural formulae (Turn 5).<br /><chemistry num="5"><img file="WO2012144189A1_D0005.tif" /></chemistry></p><p num="0016">In carbon dioxide adsorption / discharge device concerning another mode of the present invention, the above-mentioned porous body 4 is a conductive inorganic matter porous body.</p><p num="0017">In the inorganic porous body of carbon dioxide adsorption / discharge device which starts the present invention especially, it is preferred that the above-mentioned unit A is graphene.</p><p num="0018">The above-mentioned conductive inorganic matter porous body comprises at least one chosen from the group which consists of graphite, a carbon nanotube, and carbon fiber (carbon fiber).</p><p num="0019">In carbon dioxide adsorption / discharge device concerning the present invention, it is preferred that the densities of unit A included in porous body 4 are 0.0002 mol/g - 0.02 mol/g.</p><p num="0020">In carbon dioxide adsorption / discharge device concerning the present invention, the solvent of the above-mentioned electrolysis solution is water.</p><p num="0021">In carbon dioxide adsorption / discharge device concerning the present invention, the above-mentioned electrolysis solution contains support salt.</p><p num="0022">In carbon dioxide adsorption / discharge device concerning the present invention, it is preferred that the cations of the above-mentioned support salt are 1000 or more molecular weights.</p><p num="0023">In carbon dioxide adsorption / discharge device concerning the present invention, it is preferred that the anions of the above-mentioned support salt are 1000 or more molecular weights.</p>

<p num="0024">It has an electrolysis solution filled up with the present invention between a pair of electrodes provided face to face, and an above-mentioned pair of each electrodes of an electrode, and the porous body provided on an above-mentioned pair of one electrodes of an electrode, and an electrolysis solution absorbs carbon dioxide and carbon dioxide is dissolved in the electrolysis solution concerned. Therefore, carbonic acid ion or carbonated water matter ion can be formed, and it is the above-mentioned porous body, The above-mentioned carbonic acid ion or carbonated water matter ion adsorbs electrostatically on the surface of a porous body at the time of forward direction voltage impression to an above-mentioned pair of electrodes, Since the above-mentioned carbonic acid ion or carbonated water matter ion is electrostatically emitted from the surface of a porous body at the time of opposite direction voltage impression to an above-mentioned pair of electrodes, storage and discharge of carbon dioxide are electrochemically controlled by impressing forward direction voltage and opposite direction voltage to electrodes 1 and 2. Adsorption and discharge of carbon dioxide are performed by impression of voltage, and since big energy, such as applying heat, is not needed, the adsorption desorption performance which is low energy and was excellent is demonstrated.<br />Therefore, according to the present invention, it is high adsorption ability and can provide carbon dioxide adsorption / discharge device with little energy expenditure at the time of adsorption desorption.</p>

0025<figref num="1">It is a sectional view of an outline showing one embodiment of the present invention.</figref>

0026An example of carbon dioxide adsorption / discharge device is shown in Drawing 1. Carbon dioxide adsorption / discharge device is provided with a pair of electrodes (electrode 1, electrode 2), electrolysis solution 3, and porous body 4. Electrode 1 and electrode 2 are estranged [ they counter them and ] and arranged, and electrolysis solution 3 and porous body 4 exist between electrode 1 and electrode 2. Electrolysis solution 3 and porous body 4 touch, as for electrode 2 and porous body 4, it touches and electrolysis solution 3 exists so that transfer of electrode 1, and an electron and an electron hole can be performed.

0027Electrode 1 is connected with electric devices, such as an external power supply, a rechargeable battery, and a capacitor. Electric discharge charge processing can be performed now to this carbon dioxide adsorption / discharge device. Electrode 1 functions as a cathode (anode) of carbon dioxide adsorption / discharge device.

0028Electrode 1 and electrode 2 may be formed with the independent film of the conductive material, or a conductive material may be laminated on a substrate. As a desirable example of a conductive material, they are platinum, gold, silver, copper, and aluminum, Metal, such as rhodium and indium; carbon; indium tin compound oxide, Conductive metal oxides, such as tin oxide by which antimony was doped, and tin oxide by which fluoride was doped; the compound thing of the above-mentioned metal or a compound; the material etc. to which the coat of oxidization silicon, tin oxide, titanium oxide, a zirconium dioxide, the aluminum oxide, etc. was carried out are mentioned on the above-mentioned metal or a compound.

0029Although the surface resistance of electrode 1 is so good that it is low, the surface resistance concerned is below 200ohms / , more preferably below 50ohms / preferably. A voltage loss with electrode 1 in the device of the present invention can become low, and it can make a device drive on low voltage, when surface resistance is below 200ohms / . In particular, when surface resistance is below 50ohms / , the above-mentioned effect further improves and a device drive on lower voltage is attained. Although there is no restriction in particular in the minimum of this surface resistance, they are usually 0.1ohm/. When surface resistance is 0.1ohm / more than , the low-voltage drive of the ease of receiving of an electrode and a device is compatible.

0030When electrode 1 is formed by making transparent conductive oxides, such as indium oxide, tin oxide, a zinc oxide, deposit on a substrate, for example on a substrate, vacuum processes, such as the sputtering method and the vapor-depositing method, are adopted. Wet process, such as a spin coat method, the spraying method, and the screen-stenciling method, may be adopted.

0031Electrode 2 functions as an anode (cathode) of carbon dioxide adsorption / discharge device. Electrode 2 may be formed by the same method as the case of electrode 1, for example of the same material as the case of electrode 1.

0032In order for electrode 2 to act efficiently as an anode of carbon dioxide adsorption / discharge device, it is preferred that electrode 2 comprises a material which has a catalytic action which gives an electron to the reduced form in electrolysis solution 3. As such a material, they are platinum, gold, silver, copper, aluminum, and rhodium, Metal, such as indium; carbon materials, such as carbon which supported graphite, a carbon nanotube, and platinum; indium tin compound oxide, Conductive metal oxides, such as tin oxide which doped antimony, and tin oxide which doped fluoride; conductive polymers, such as polyethylene dioxythiophene, polypyrrole, and poly aniline, etc. are mentioned. Platinum, graphite, especially polyethylene dioxythiophene, etc. are preferred among these materials.

0033Electrolysis solution 3 is constituted including a solvent and an electrolyte. As for an electrolyte, it is preferred to exist in the state where it is dissolving in the solvent. Added [ and ] in order that an electrolyte may improve the ion conduction nature of a solvent, a solvent dissolves carbon dioxide and serves as a medium for the adsorption and desorption to porous body 4. A solvent fills up or swells to porous body 4, and constitutes a device.

0034The stable thing of a solvent been a compound with a large potential window is electrochemically preferred. As a solvent, both a water solvent and an organic solvent can be used. For example, water; dimethyl carbonate, diethyl carbonate, methylethyl carbonate, Carbonate compounds, such as ethylene carbonate and propylene carbonate; acetic acid methyl, Ester compounds, such as methyl propionate and gamma-butyrolactone; diethylether, 1, 2-dimethoxyethane, 1, 3-dioxo Silane, a tetrahydro franc, Ether compounds, such as 2-methyl tetrahydro franc; 3-methyl 2-Oxazodi linon, Heterocyclic compounds, such as 2-methyl pylori boss; nitryl compounds, such as an acetonitrile, methoxy acetonitrile, and Propi demon trill; aprotic polar compounds, such as Sour Follain, Dimethyl sulfoxide, and Dimethylform amide, etc. are mentioned. These can also be used independently, respectively, and can also mix and use two or more kinds. Carbonate compounds especially, such as ethylene carbonate and propylene carbonate, Nitryl compounds, such as a heterocyclic compound [, such as gamma-butyrolactone, 3-methyl 2-Oxazodi linon, and 2-methyl pylori boss, ], acetonitrile, methoxy acetonitrile, and Propi demon trill, a 3-methoxy Propi demon trill, and Valeric acid nitril, are preferred. When two or more sorts of these solvents are mixed, it is preferred that water is mixed from a viewpoint of generation of a carbonated water matter anion.

0035a solvent may contain ionic liquid (ionic liquid) -- it carries out or consists only of ionic liquid -- it may be. In this case, the fixity of electrolysis solution 3, fire retardancy, etc. improve. Although the ionic liquid of the example of the publicly known public at large is mentioned as ionic liquid, For example, an imidazolium system, a pyridine system, an alicyclic amine system, an aliphatic amine system, Azo Ni amine system ionic liquid and the European patent No. 718288 specification, The 95th/of international publication the pamphlet of 18456 No., the electrochemistry 65th volume 923 pages (1997), [ No. 11 ] J. The ionic liquid of the structure indicated to *Electrochem.*Soc.*143 volume, *10 No., *3099page* (1996), and Inorg.*Chem.* 35 * 1168-page * (1996) is mentioned. Thus, when it has ion conduction nature with a sufficient solvent, the electrolyte does not need to exist.

0036The electrolyte may be gelled or fixed and may be formed from the gelled electrolyte (gelling electrolyte) or a polymer electrolyte. As a gelling agent for gelling an electrolyte, the gelling agent using techniques, such as polymer and polymer crosslinking reaction, polymerization polyfunctional monomer, an oil gelling agent, etc. are mentioned. Although the substance generally used may be applied as a gelling electrolyte and a polymer electrolyte, For example, acrylic acid series polymers, such as vinylidene fluoride system polymers, such as polyvinylidene fluoride, and polyacrylic acid, The compound etc. which have amide structure in polyether system polymers, such as acrylonitrile series polymers, such as polyacrylonitrile, and polyethylene oxide, and structure are preferred.

0037Electrolysis solution 3 may contain the redox system structure material in which oxidation reduction is stably possible. Redox system structure material means a pair of substances which exist in the form of an oxidization object and a reduced form reversibly in an oxidation-reduction reaction. As redox system structure material, conductive polymers, such as amine derivatives, such as p-type semiconductors, such as a solid electrolyte like solution and fusion salt which dissolved the oxidation reduction pair into the solvent, and copper iodide, and Torife nil amine, polyacetylene, poly aniline, and the poly Thiophene, etc. are mentioned.

0038As an example of redox system structure material, it is chlorine compound-chlorine, for example, Iodine compound-iodine, bromine compound-bromine, thallium ion (III)-thallium ion (I), Mercury ion (II)-mercury ion (I), ruthenium ion (III)-ruthenium ion (II), Although copper ion (II)-copper ion (I), ferric iron (III)-ferric iron (II), nickel ion (II)-nickel ion (III), vanadium ion (III)-vanadium ion (II), manganic acid ion permanganic acid ion, etc. are mentioned, Limitation is not carried out to these. In this case, these redox system structure material is distinguished and functions as the oxidation reduction part in porous body 4.

0039This redox system structure material may be fixed on electrode 2. As the method of fixation, the carbon electrodes used with the rechargeable battery etc., the method of making the above-mentioned structure material contain in polymer gel, etc. are mentioned.

0040When oxidation reduction structure material does not exist, the electrode reaction by disassembly of a solvent occurs and supply of a solvent at any time is needed. In this case, as for a solvent, it is preferred that it is water which exists widely in the atmosphere.

0041If it is water, a Peltier device etc. will be used, for example and the method of supplying the water in the atmosphere will be mentioned.

0042An electrolyte dissolves in a solvent, and it is added in order to raise the ion conduction nature of electrolysis solution 3.

0043As an electrolyte, alkali metal salt, such as ammonium salt, such as perchloric acid tetrabutylammonium, 6 phosphorus-fluoride acid tetraethyl ammonium, imidazolium salt, and pyridinium salt, lithium perchlorate, and 4 boron-fluoride potassium, etc. are preferred, for example. Alkaline metals, such as lithium, sodium, potassium, and calcium, or alkaline-earth metals, and the organic compound that has an amino group are used as a cation, and the salt which uses halogen ions, such as chlorine and bromine, or sulfonium as an anion is mentioned.

0044As for electrolytic support salt, it is more preferred to stabilize carbonic acid ion or carbonated water matter ion, and to have pH buffering ability. Supposing it gives an example, sodium bicarbonate, sodium carbonate, acetic acid, acetic acid sodium, etc. will be mentioned. These electrolytes may contain plurality simultaneously.

0045Porous body 4 is electrochemically charged in positive charge, and it has the function to make carbonated water matter ion or carbonic acid ion adsorb.

0046(Polymer gel object)<br />As for porous body 4, it is preferred that it is a polymer gel object (gel layer 6) which swells to electrolysis solution 3.

0047In this case, a polymer gel object has a oxidation reduction part and a gel part in that molecule. A oxidation reduction part is the part in which repetition oxidation reduction is possible, i.e., the part which serves as an oxidization object and a reduced form reversibly in an oxidation-reduction reaction. This oxidation reduction part should just comprise a part which constitutes a pair of redox systems which consist of oxidization objects and reduced forms. As for at least 1 side of the oxidization object of a oxidation reduction part, and a reduced form, it is preferred that it is a cationic compound. A gel part is a part which swells including an electrolyte solution and serves as gel. The oxidation reduction part is chemically combined with the gel part. Although the oxidation reduction part within the molecule of an organic compound and the physical relationship in particular of a gel part are not limited, when frames, such as a main chain of a molecule, are formed, for example by a gel part, a oxidation reduction part serves as structure combined with the main chain as a side chain. The part inner rib rank which forms a gel part, and the part inner rib rank which forms a oxidation reduction part may be the structures united by turns. Thus, if the oxidation reduction part and the gel part exist in the same molecule of an organic compound, a oxidation reduction part will become that it is easy to be held within gel layer 6 in the position to which it is easy to convey an electron. Although it is preferred that it is the shape of konnyaku and appearance-shaped [ like an ion-exchange membrane ] as for the state of the gel of gel layer 6, it is not restricted to in particular this, for example. Gel layer 6 can adsorb carbon dioxide in the form of carbonic acid ion or carbonated water matter ion, when it changes into a cation state in either an oxidation state or the reduction state and changes into the cation state in a oxidation reduction process.

0048There is a degree of swelling as a physical index which affects the size of the reaction interface formed in gel layer 6. A degree of swelling is denoted by the following formula.<br />Degree-of-swelling =(weight of gel)/(weight of gel dry object) x100

0049A gel dry object refers to what dried gel layer 6. Dryness of gel layer 6 refers to removal of the solution included by gel layer 6, especially removal of a solvent. As a method of drying gel layer 6, removal etc. of the solution or the solvent in the solution in the inside of heating and vacuum environment or removal of a solvent, and other solvents, included by gel layer 6 are mentioned.

0050The solution or the solvent included on the occasion of removal with other solvents of the solution or the solvent included by gel layer 6, and compatibility are high, and it is preferred that the solvent which is easy to remove in heating and vacuum environment is chosen further because of efficient removal of the solution or the solvent included by gel layer 6.

0051As for the degree of swelling of gel layer 6, it is preferred that it is 110 to 3000%, and it is more preferred that it is 150 to 500%. When this degree of swelling is less than 110%, since the electrolyte composition in the inside of gel layer 6 decreases, there is a possibility that stabilization of a oxidation reduction part may no longer be performed fully. When a degree of swelling exceeds 3000%, there is a possibility that the oxidation reduction part in the inside of gel layer 6 may decrease, and carbon dioxide adsorption capability may decline. For this reason, in any case, the performance of carbon dioxide adsorption / discharge device will fall.

0052The organic compound which has a oxidation reduction part and a gel part in one molecule is denoted, for example by the following general formula.<br />(X_i）_nj:Y_k<br />(X_i）_nA Is gel part is shown and it is X._iThe monomer of the compound which forms a Is gel part is shown. A gel part is formed by a polymer skeleton. Degree of polymerization n of a monomer has the preferred range of n= 10,000-100,000. Y (X)_i）_nThe oxidation reduction part boiled and combined is shown. j and k are contained in one molecule, respectively (X)._i）_nIt is the arbitrary integers showing the number of Y, and all have the preferred range of 10,000-100,000. Oxidation reduction part Y is a gel part (X)._i）_nIt may combine with what kind of part of the polymer skeleton to constitute.

0053More specifically, the oxidation reduction part of a polymer gel structure can mention the structure shown in the following chemical formula (6) and (7).<br /><chemistry num="6"><img file="WO2012144189A1_D0006.tif" /></chemistry><chemistry num="7"><img file="WO2012144189A1_D0007.tif" /></chemistry>

0054Opposite anion A in a chemical formula (6)^－If it carries out, the anion chosen, for example from a bromine ion, chlorine ion, a perchlorate ion, a hexafluoro phosphate ion, and tetrafluoroboric acid ion is mentioned.

0055in the case of the compound shown with a chemical formula (6), by impression of voltage, N+ (nitroglycerine cation) becomes N- (nitroglycerine -- radical), and carbonic acid ion or carbonated water matter ion contains in a polymer gel structure as the opposite anion.

0056in the case of the compound shown with a chemical formula (7), N-0- (nitroglycerine -- radical) is set to N+=0 (nitroglycerine cation), and impression of voltage adsorbs into a polymer gel structure in carbonic acid ion or carbonated water matter ion as the opposite anion.

0057Electrolytic polymerization can be mentioned as a method for compounding the polymer gel shown with a chemical formula (6).

0058If electrode 1 and a counter electrode are immersed in the solution which contains a precursor, for example in composition of the organic compound by an electrolytic polymerization method and voltage is impressed between electrode 1 and a counter electrode in this state, a precursor will polymerize on electrode 1 by an electrochemical reaction, and an organic compound will deposit. this electrolytic polymerization method -- if -- the advanced equipment or art like [ in CVD ] are not needed, but the speed at which an organic compound deposits and yet is quick, the organic compound which moreover deposited becomes difficult to exfoliate from electrode 1, and also elaboration and thin film-ization of it of an organic compound become easy. If an organic compound elaborates, a oxidation reduction part will be densely arranged in porous body 4, and, for this reason, porous body 4 will demonstrate high electron transport property. When the organic compound which constitutes porous body 4 spreads in three dimensions, the stability of this organic compound becomes high. The solubility to the solvent of this organic compound falls, and the width of selection of the solvent of an electrolyte solution spreads.

0059Thus, the organic compound obtained has a pyridium structure unit shown in a chemical formula (6) as a oxidation reduction part. From the part to which this pyridium structure unit has the structure shown in the chemical formula (8) of a precursor by electrolytic polymerization to M (being here M) They are halogen groups, such as fluoride, chlorine, bromine, and iodine, and a cyano group. It is generated because the substitution machine shown Detachments and the positions from which the substitution machine shown by M in this part was desorbed join together.<br /><chemistry num="8"><img file="WO2012144189A1_D0008.tif" /></chemistry>If unit 1 electronic reduction of this pyridium structure is carried out, a pyridium cation radical will be generated, and also a pyridium diradical will be generated if returned by one electron. On the contrary, if one electron of pyridium diradicals oxidize, a pyridium cation radical will be generated, and also if one electron oxidizes, it will return per original pyridium structure. Thus, an organic compound reveals the repeatedly stable oxidation reduction ability. When an organic compound passes through a radical state at the time of oxidation reduction, a very quick self-electron exchange reaction arises and an electron becomes are and receives it easy to be delivered between organic compounds. The radical state at the time of the oxidation reduction of an organic compound is observed by ESR (electron spin resonance) etc.

0060If a precursor carries out two or more owners of the part which has the structure shown in a chemical formula (8) in one molecule, the organic compound of the amount of polymers may be generated by the electrolytic polymerization of a precursor. For polymers quantification of an organic compound, it is desirable in one molecule 2 or more [ more preferably ] and to have three or more in the part which has the structure which a precursor shows in a chemical formula (8).

0061The concrete compound and synthesizing method are indicated to Langmuir*Vol*17, *No.1, and *2001*155-.

0062Porous body 4 is formed because the organic compound generated by the electrolytic polymerization of a precursor accumulates on electrode 1. In formation of porous body 4, electrode 1 is immersed into the solution which contains a precursor first, for example. By a precursor polymerizing on electrode 1 by electrolytic polymerization in this state, and an organic compound being generated, porous body 4 is formed on electrode 1. Electrode potential of electrode 1 at the time of this electrolytic polymerization is made lower than the reduction potential of a precursor. Thereby, within the organic compound which has the character of the n-type semiconductor on electrode 1, movement of an electron is attained and electrolytic polymerization advances.

0063In order that the organic compound generated by electrolytic polymerization may carry out polymers quantification, porous body 4 formed of the electrolytic polymerization of a precursor demonstrates high endurance. This porous body 4 is formed with high density by being formed through electrolytic polymerization. For this reason, it is expected that the carbon dioxide adsorption performance in porous body 4 will improve.

0064As concrete compound and synthesizing method of the polymer gel object which has a oxidation reduction part, the radical compound and synthesizing method of a statement can be used for JP,2007-70384,A.

0065When using such a polymer gel structure, it is preferred that the polymer gel object includes to the substance of high conductivity with high percentage of void called a collector.

0066When a collector exists, by securing the low electron transport property of a polymer gel object with a high conductive material, thick film-ization is attained and it becomes possible to raise the amount of carbon dioxide adsorption per one device.

0067As a substance which constitutes a collector, they are platinum, gold, silver, copper, and aluminum, Metal, such as rhodium and indium; graphite, a carbon nanotube, Carbon materials, such as carbon which supported platinum; conductive metal oxides, such as tin oxide which doped an indium tin compound oxide and antimony, and tin oxide which doped fluoride; conductive polymers, such as polyethylene dioxythiophene, polypyrrole, and poly aniline, etc. are mentioned. These particles may be spherical. More preferably an aspect ratio is high and it is constituted. If an aspect ratio is high, it can have a high structure of the current collection effect in the state where percentage of void is high.

0068(Conductive polymer porous body)<br />As for porous body 4, it is preferred that it is a conductive polymer porous body.

0069If it is a porous polymers object, polymers with conductivity will be formed in the porous state on electrode 1, and the cation site which is oxidized or returned and produces will be electrochemically adsorbed in carbonic acid ion or carbonated water matter ion. Conductive polymers, such as poly aniline and polypyrrole, can be mentioned as a porous polymers object. Poly aniline is extremely excellent in stability over air oxidation as compared with polyacetylene of a straight chain conjugated system. For example, practical use is presented as an anode material which makes lithium aluminum of a rechargeable battery the opposite poles. As other uses, they are electrochromic material and a carrier of immobilized enzyme, Various application of the use as the covering material of the semiconductor electrode using the surface covering material, transistor, and electron-transfer-catalysis operation which control the optical dissolution of a semiconductor, the photoelectrical evaporation study reduction catalyst of carbon dioxide, and also an electrode material that shows a photoelectrical response, etc. is considered.

0070As the synthesizing method, the method shown in Japanese Patent Application No. 4-11458 is mentioned.

0071As for the manufacturing method of poly aniline, at this time, it is desirable that it is electrolytic polymerization. If it is the film produced by electrolytic polymerization, where an electric conduction path is secured, film production can progress, and it can consider it as a polyaniline film with all the active aniline sites.

0072A constant potential method or the potential Running method may be sufficient as the method of electrolytic polymerization.

0073As for the opposite anion which secures the cation site of the polymers porous inside of the body in the present invention, it is desirable that they are carbonated water matter ion or carbonic acid ion.

0074The ratio sets the number of sum total Mol of other opposite anions to 1, and to be 10-99, more preferably 100-10000 preferably are desired.

0075(Inorganic porous body)<br />Porous body 4 may be an inorganic porous body.

0076If it is an inorganic porous body, the porous surface is filled up with plus or minus charge at the time of voltage impression, as the opposite anion, an inorganic porous body will be adsorbed in the form of carbonated water matter ion or carbonic acid ion, and carbon dioxide will be desorbed from an inorganic porous body.

0077The carbon system electrode, for example, using activated carbon and carbon fiber as a concrete component, the electrode with high percentage of void using a needlelike electric conduction material, or a carbon nanotube can be mentioned. It may be compounded and these may be used.

0078Such electric conduction materials may be made to support a predetermined catalyst. As a catalyst supported, platinum and ruthenium catalysts, such as a platinum catalyst and a silver catalyst, a cobalt catalyst, etc. are employable, for example.

0079As for the thickness of porous body 4, it is preferred that it is within the limits of 0.001-10 cm. When it is less than this, the amount of carbon dioxide absorption becomes less enough, and when it is more than this, absorption / discharge speed of carbon dioxide may fall.

0080In carbon dioxide adsorption / discharge device constituted like the above explanation, it has the carbon dioxide adsorption performance which was excellent in porous body 4, and restoration of carbonic acid ion or carbonated water matter ion is promptly performed by electrolysis solution 3.

0081Namely, the thing for which voltage is impressed in the situation where electrolysis solution 3 containing carbon dioxide exists, Carbon dioxide is filled up into porous body 4 with the form of carbonated water matter ion or carbonic acid ion, and it adsorbs, and when reverse voltage is impressed next, carbon dioxide discharge is attained by emitting carbon dioxide into electrolysis solution 3 from porous body 4.

<p num="0082">Next, an example explains the present invention concretely.<br />[Example 1]<br />1 mm in thickness and the electrically-conductive-glass board (the Asahi Glass make, 10ohm/) of 21mm by 24mm which have a fluoride dope tin oxide film were prepared. This fluoride dope tin oxide film was used as electrode 1. lmum precipitation of the poly aniline was carried out on substrate 1 as porous body 4 using the electrochemistry oxidizing method (electrolytic polymerization method). On the other hand, prepared 1 mm in thickness and the electrically-conductive-glass board (the Asahi Glass make, 10ohm/) of 21mm by 24mm which have a fluoride dope tin oxide film, platinum was made to deposit by the sputtering method on a fluoride dope tin oxide film, and this was made into electrode 2. It has arranged so that porous body 4 and electrode 2 may be countered, and thermally fusible adhesives (1 mm in width and 50 micrometers in thickness) (the E. I. du Pont de Nemours &amp; Co. make, by flannel) were made to be placed between the outer edge parts between both. By pressurizing, while heating these thermally fusible adhesives, porous body 4 and electrode 2 were joined via thermally fusible adhesives. OH-TEMPO (4-hydroxy 2, *2, *6, and *6-tetramethylpiperidine 1-oxyl) was dissolved at the concentration of 0.5M, potassium chloride was dissolved in water at the concentration of 0.5 mol/l, and the electrolyte solution was prepared. This electrolyte solution was poured in between electrode 2 and porous body 4 from the hole for carbon dioxide pouring / discharge. This produced the element. The synthetic method (the electrochemistry oxidizing method) of poly aniline in this case was performed in accordance with the method indicated to E.*M.*Genies, *Mol.*Cryst.*Liq.*Cryst., and 121,181-186* (1985). The carbon dioxide adsorption desorption performance was evaluated about the obtained element.</p><p num="0083">[Example 2]<br />Unlike the composition of Example 1 only in porous body 4, the other composition of Example 2 is the same as that of Example 1.<br />Porous body 4 was produced by the following methods.<br />Electrolysis manganese dioxide (MnO) heat-treated at 400 _２Polyethylene oxide (viscosity average molecular weight 100,000, the product made by Sigma-AIdrich) and LiN (CF) of average molecular weight 100,000 which are quality of cathode active material, acetylene black (electric conduction agent), and a binder_３SO_２）_２Acetonitrile was dissolved or distributed, and it kneaded and prepared the paste-like anode medical mixture. It is here and is MnO._２: Acetylene black: Polymer electrolyte = it blended so that it might become 70 mass %:20 mass %:10 mass %. Mass of the polymer electrolyte was made into the mass of solid content conversion. After applying the anode medical mixture of the shape of an acquired paste to the electrode and drying it at 1200 for 24 hours, porous body 4 was produced by rolling by a roll press. The carbon dioxide adsorption desorption performance was evaluated like [ element / which was obtained ] Example 1.</p><p num="0084">[Comparative example 1]<br />Porous body 4 in Example 1 was formed using zeolite.<br />As zeolite, it is a Ferrier light (the peaks of pole diameter distribution are about 4.5 A and SiO)._２/Al_２O_３The molar ratio used about 90. About this, it is 50g/m on an electrode.^２It was made to come out and support and porous body 4 was formed. The size of porous body 4 and electrodes 1 and 2, the interval of electrode 2 and porous body 4, etc. are the same as that of Example 1.</p><p num="0085">900kPa was impressed and carbon dioxide was made to adsorb about this carbon dioxide adsorption / discharge device 1. The amount of support was 12 wt %/1g zeolite. Next, CO which calcinated at the temperature of 400 and was made to adsorb_２It emitted. The burst size was computed by the following formulas.<br /><br />Burst size = (weight before calcination) - (weight after calcination)</p><p num="0086"><tables num="1"><img file="WO2012144189A1_D0009.tif" /></tables></p><p num="0087">At comparative example 1, it is as it appears in this result, At Examples 1-2, it is to adsorption performance being 63 (ml/g), consumption energy being 131 (mwh/ml), and adsorption performance and consumption energy being incompatible, It is adsorption performance 261 (ml/g), consumption energy 1.1 (mwh/ml) (example 1), adsorption performance 410 (ml/g), and consumption energy 2.1 (mwh/ml) (example 2), and was able to make adsorption performance and low energy consumption make compatible.</p>

00881 Electrode<br />2 Electrode<br />3 Electrolysis Solution<br />4 Porous Body