WO2010041396A1 - Pompe à oxygène, procédé de fabrication d’une pompe à oxygène, et entrepôt de stockage comprenant une pompe à oxygène - Google Patents

Pompe à oxygène, procédé de fabrication d’une pompe à oxygène, et entrepôt de stockage comprenant une pompe à oxygène Download PDF

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WO2010041396A1
WO2010041396A1 PCT/JP2009/005097 JP2009005097W WO2010041396A1 WO 2010041396 A1 WO2010041396 A1 WO 2010041396A1 JP 2009005097 W JP2009005097 W JP 2009005097W WO 2010041396 A1 WO2010041396 A1 WO 2010041396A1
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Prior art keywords
oxygen
electrode
negative electrode
positive electrode
oxygen concentration
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PCT/JP2009/005097
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English (en)
Japanese (ja)
Inventor
梅田章広
貫名康之
中川雅至
橋田卓
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パナソニック株式会社
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Priority claimed from JP2008259254A external-priority patent/JP2010089975A/ja
Priority claimed from JP2008266005A external-priority patent/JP2010095743A/ja
Priority claimed from JP2008322158A external-priority patent/JP2010144992A/ja
Priority claimed from JP2008322160A external-priority patent/JP2010144994A/ja
Priority claimed from JP2009059123A external-priority patent/JP2010208916A/ja
Priority claimed from JP2009059122A external-priority patent/JP2010209442A/ja
Priority claimed from JP2009095842A external-priority patent/JP2010248534A/ja
Priority claimed from JP2009095841A external-priority patent/JP2010248533A/ja
Priority claimed from JP2009097855A external-priority patent/JP2010248555A/ja
Application filed by パナソニック株式会社 filed Critical パナソニック株式会社
Publication of WO2010041396A1 publication Critical patent/WO2010041396A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen

Definitions

  • the present invention relates to an oxygen pump using an electrochemical reaction.
  • the oxygen pump is one that takes in oxygen from one electrode and releases oxygen from the other electrode.
  • the oxygen pump is constituted by an electrochemical cell in which an electrolyte is sandwiched between a pair of electrodes. By direct current flowing between both electrodes, oxygen is electrochemically taken into the cell from the negative electrode, and oxygen is supplied to the positive electrode. It is an oxygen transfer means that releases oxygen.
  • Patent Document 1 discloses an oxygen pump using an aqueous electrolyte.
  • an oxygen pump using a water-based electrolyte is excellent in that it operates at room temperature and normal pressure.
  • a large amount of acidic solution or alkaline solution is held in an electrochemical cell, and a large capacity and structure for holding the oxygen pump are required.
  • Strength is required. Therefore, the degree of freedom as a structure of the oxygen pump and the degree of freedom of the space for incorporating the oxygen pump are remarkably deteriorated. Furthermore, there is a risk that these solutions will flow out upon breakage.
  • oxygen is a substance that is considerably inactive to the electrode, and the negative electrode reaction is slow, so that an electrode catalyst such as platinum is required.
  • Patent Document 2 is an example of using a ceramic-based solid electrolyte.
  • a solid electrolyte uses a high operating temperature of 700 to 1000 ° C. and consumes a large amount of power, although there is no deterioration in performance due to leakage of the electrolyte.
  • the solid electrolyte itself is thin, hard and brittle, it is not suitable for increasing the oxygen carrying capacity by increasing the area.
  • each oxygen pump has its merits and demerits, operates at room temperature and normal pressure, can easily provide a large oxygen carrying capacity, and has not been found an oxygen pump that has no fear of electrolyte leakage.
  • the present invention has been made in view of the above points, and provides an oxygen pump that operates at room temperature and normal pressure, can easily provide a large oxygen carrying capacity, and suppresses electrolyte leakage due to breakage or the like. It is.
  • the oxygen pump of the present invention includes an external DC power source for taking in an electric current from the outside, a negative electrode having a porous gas exchange property, a positive electrode having a porous gas exchange property, A porous separator sandwiched between a negative electrode and a positive electrode, impregnated with an electrolyte containing metal ions, and connected to an external current power source, and a negative collector electrode provided outside the negative electrode And a positive current collecting electrode connected to an external direct current power source and provided outside the positive electrode, and by supplying power to the negative current collecting electrode and the positive current collecting electrode by the external direct current power source, Oxygen is transferred from the gas phase to the positive electrode side gas phase.
  • the oxygen pump of the present invention uses an electrolytic solution, so operates at room temperature and normal pressure, does not require a large amount of electrolytic solution, and has a structure that is difficult to break, so it has a large area and a large oxygen carrying capacity. Can be put out easily. Furthermore, since a large amount of electrolyte is not required, leakage of the electrolyte due to breakage or the like can be suppressed.
  • FIG. 1 is a cross-sectional view illustrating a configuration example of the oxygen pump according to the first to seventh embodiments.
  • FIG. 2 is a cross-sectional view showing the configuration of the oxygen pump in the experimental examples of the first to seventh embodiments.
  • FIG. 3 is a cross-sectional view showing the storage of the eighth embodiment.
  • FIG. 4 is a diagram showing the procedure of adjusting the oxygen concentration in the eighth embodiment.
  • FIG. 5 is a cross-sectional view showing the oxygen concentration adjusting unit of the eighth embodiment.
  • FIG. 6 is a diagram showing the procedure of adjusting the oxygen concentration according to the ninth embodiment.
  • FIG. 7 is a diagram showing a change in oxygen concentration in the ninth embodiment.
  • FIG. 8 is a cross-sectional view showing the storage of the tenth embodiment.
  • FIG. 9A is a cross-sectional view showing the oxygen concentration adjustment tray of the tenth embodiment.
  • FIG. 9B is a cross-sectional view showing the oxygen concentration adjustment tray of the tenth embodiment.
  • FIG. 10 is a cross-sectional view showing the storage of the eleventh embodiment.
  • FIG. 11 is a cross-sectional view showing the oxygen concentration adjusting unit of the eleventh embodiment.
  • FIG. 12 is a cross-sectional view showing the relationship between the oxygen concentration adjusting unit and the oxygen concentration adjusting tray of the eleventh embodiment.
  • FIG. 13A is a cross-sectional view showing the oxygen concentration adjustment tray of the thirteenth embodiment.
  • FIG. 13B is a cross-sectional view showing the oxygen concentration adjustment tray of the thirteenth embodiment.
  • FIG. 14A is a cross-sectional view showing the oxygen concentration adjustment tray of the eleventh embodiment.
  • FIG. 14B is a cross-sectional view showing the oxygen concentration adjustment tray of the eleventh embodiment.
  • FIG. 15 is a cross-sectional view showing the oxygen concentration adjusting unit of the twelfth embodiment.
  • FIG. 16A is a cross-sectional view showing the oxygen concentration adjustment tray of the thirteenth embodiment.
  • FIG. 16B is a cross-sectional view showing the oxygen concentration adjustment tray of the thirteenth embodiment.
  • FIG. 17 is a cross-sectional view showing an oxygen concentration adjustment tray according to the fourteenth embodiment.
  • FIG. 18 is a cross-sectional view showing the storage of the fifteenth embodiment.
  • FIG. 1 shows a cross-sectional view of an oxygen pump.
  • a positive electrode 2 and a negative electrode 3 configured by applying fine carbon powder are disposed on both sides of a separator 1 impregnated with an electrolyte solution.
  • the positive electrode side collector electrode 4 and the negative electrode side collector electrode 5 are configured by closely attaching a carbon cloth to the outside.
  • the separator 1, the positive electrode 2, the negative electrode 3, the positive electrode side current collecting electrode 4 and the negative electrode side current collecting electrode 5 are laminated, and then the end portion in the surface direction of the laminated structure is impregnated with an adhesive.
  • each structure is connected and integrated as a mold part 8.
  • the positive electrode side electrode extraction part 6 and the negative electrode side electrode extraction part 7 with respect to the outside are configured by pulling out carbon fibers of the carbon cloth from the mold part 8, and are connected to an external DC power source (not shown).
  • the separator 1 may be made of a material having a porous membrane having a gap penetrating the front and back, and a battery separator, an electrolytic partition, an ultrafiltration membrane, a filter paper, a nonwoven fabric, and the like can be used.
  • the separator of the first embodiment has a function of performing gas separation in addition to insulation of electronic conduction between both the positive electrode 2 and the negative electrode 3 and blocking gas phase communication between the negative electrode 3 side and the positive electrode 2 side. Is responsible. Accordingly, the gap inside the separator 1 must be filled with the electrolyte solution and cannot pass through the gas. For this reason, materials that are water-repellent and repel the electrolyte cannot be used. Accordingly, water-repellent materials such as polyethylene and polytetrafluorocarbon can be used as long as they have been subjected to hydrophilic treatment.
  • a material with a large mesh opening is desirable because even if it is a hydrophilic material, the liquid phase runs out and the gas phase communicates.
  • Any film having an opening of about 3 micrometers or less can be used.
  • the carbon fine powder of the electrode material of the positive electrode 2 and the negative electrode 3 can be carbon black, graphite carbon powder, activated carbon powder, or the like.
  • a fine layer that does not peel off when applied to the separator 1 is preferable, and the particle size is preferably 10 micrometers or less.
  • Carbon black acetylene black is favorable because it is available in stable and fine particulate form.
  • the carbon fine particles have good conductivity, and an electrode in close contact with the separator can be easily formed.
  • Carbon cloth is a cloth made of plain carbon fiber bundles. Carbon fibers are classified into raw materials by PAN, pitch, rayon, etc., and there are various mechanical properties such as elastic modulus. It doesn't matter. Since the carbon cloth is soft and strong, an oxygen pump having a large area can be made and the oxygen carrying capacity can be increased. Furthermore, by pulling out the carbon fiber bundle of the carbon cloth, binding it with a crimp terminal, and taking out the terminal, the connection with the external power supply circuit can be facilitated.
  • the peripheral ends of the laminated film-like separator 1, the positive electrode 2, the negative electrode 3, the positive electrode side collector electrode 4 and the negative electrode side collector electrode 5 are molded with an adhesive, and the surface direction
  • the gas escape to the gas and the gas sneaking between the positive electrode and the negative electrode are regulated.
  • the adhesive that can be used as an adhesive, rubber paste in which rubber such as neoprene is dissolved in a solvent, silicon corn sealing agent, and the like can be used, and any adhesive that is resistant to the water of the electrolytic solution may be used.
  • the mold portion 8 regulates gas escape in the surface direction and gas wraparound between the positive electrode 2 and the negative electrode 2.
  • the solution to be impregnated in the separator 1 uses an aqueous solvent that operates at room temperature and normal pressure. Since an extremely small amount of electrolyte is impregnated and held, there is no fear of leakage of the electrolyte. Therefore, the oxygen pump of Embodiment 1 is structurally thin and soft, and can have a large area to increase the oxygen carrying capacity.
  • ferrous chloride and calcium chloride aqueous solutions are used as the electrolyte.
  • the blending ratio is 0.2 to 2 mol equivalent to anhydrous ferrous chloride and 4 to 15 mol of water per mol of calcium chloride anhydride.
  • the mixture of ferrous chloride and calcium chloride on the separator 1 has strong deliquescence, absorbs water vapor from the atmosphere, falls within 4 to 15 moles of water per mole of calcium chloride anhydride, and returns to its original wet state. Within this range, the electrolytic solution becomes a non-volatile solution and does not dry out. Further, not only the separator 1 but also surrounding carbon fine powder and carbon cloth hold the aqueous solution. Therefore, when the aqueous solution drips or leaks, the aqueous solution is not lost and the surroundings are not soiled.
  • the current is transmitted from the positive electrode extraction part 6 to the positive electrode 2 via the positive electrode collecting electrode 4.
  • the current is exchanged with the electrolyte solution on the surface of the fine carbon powder of the positive electrode 2 to generate oxygen, and then is transferred through the electrolyte impregnated in the separator by ionic conduction to the fine carbon powder surface of the negative electrode 3.
  • the current exchanges the charge again to take in oxygen into the electrolytic solution, and further returns to the external DC power source through the negative electrode side collecting electrode 5 and the negative electrode side electrode take-out unit 7 to constitute a closed circuit as a whole.
  • gaseous oxygen is taken into the electrolytic solution from the negative electrode-side gas phase 10 on the surface of the fine carbon powder of the negative electrode 3, is transmitted through the electrolytic solution in accordance with ionic conduction, and returns to oxygen on the surface of the fine carbon powder of the positive electrode 2. , And discharged to the positive electrode side gas phase 9. In this way, the function of oxygen transfer as an oxygen pump is exhibited.
  • the divalent iron of ferrous chloride is reduced on the surface of the negative electrode 3 to generate zero-valent iron and the divalent iron of ferrous chloride is oxidized on the surface of the positive electrode 2 in accordance with energization. Trivalent iron is produced. Therefore, the electric charge is consumed by the reaction inside the electrolyte, and no charge is received from or transferred to the external oxygen. Thereafter, when energization is continued, zero-valent iron receives oxygen in the gas phase and hydrogen ions in the electrolyte on the surface of the negative electrode 3 to become divalent iron hydroxide, and the hydroxyl group of the divalent iron hydroxide substitutes for chlorine ions. Thus, hydroxide ions are brought into the electrolyte.
  • the divalent iron is reduced again by charge exchange and returns to zero-valent iron. Therefore, iron works catalytically to take up oxygen.
  • the liberated hydroxide ions brought into the electrolyte move in the electrolyte solution in the separator 1 and collect charges on the surface of the positive electrode 2 to generate oxygen and hydrogen ions.
  • the transfer is complete.
  • ozone and hydrogen peroxide are not detected. Therefore, it is expected that iron works as a catalyst for decomposing ozone and hydrogen peroxide.
  • Hydrogen ions generated by the reaction in the positive electrode 2 move to the negative electrode 3 and participate in the next oxygen uptake reaction. As described above, the reaction is continuous.
  • a pre-operation is carried out in the forward direction, the iron on the surface of the negative electrode 3 is reduced to zero valence, and the iron on the surface of the positive electrode 2 is trivalent. It needs to be oxidized.
  • Calcium chloride that is not directly involved in oxygen transport also has several functions. First, the presence of a large amount of calcium ions suppresses the generation of hydrogen gas from the negative electrode 3. Calcium ions are electrically adsorbed on the surface of the negative electrode 3, and the surface of the electrode is maintained on the alkali side due to pH buffering of calcium ions, so that the equilibrium potential for hydrogen generation is lowered and hydrogen gas is hardly emitted. Second, the solubility of iron involved in the reaction can be increased. Since the separator 1 cannot be impregnated with an iron salt that does not dissolve, if the iron salt is charged at a high concentration, the solubility must be increased. Calcium chloride co-dissolves with ferrous chloride and helps dissolve ferrous chloride.
  • calcium chloride is a source of chloride ions.
  • Trivalent iron ions are liable to form insoluble hydroxides, and the hydroxides are irreversibly changed to iron oxide (iron trioxide).
  • iron oxide iron trioxide
  • the chlorine ions coordinate with the iron ions and compete with the hydroxide ions, so that irreversible iron oxide production can be prevented.
  • FIG. 2 shows the configuration of the oxygen pump used in the experiment.
  • the separator 1 a polyethylene hydrophilic separator having a thickness of 0.38 mm (manufactured by Nippon Sheet Glass Co., Ltd.) was used. Both electrodes of the positive electrode 2 and the negative electrode 3 were composed of acetylene black (manufactured by Wako Pure Chemical Industries, Ltd.) and carbon cloth (manufactured by Mitsubishi Rayon Co., Ltd.).
  • the mold part 8 was configured with a circular effective diameter of 30 millimeters (effective area of 7.0 square centimeters) using a silicone sealant (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a positive electrode case 11 having a gas outlet 12 was attached, and a thin film micro flow meter was connected to the gas outlet 12 so that the flow rate could be observed.
  • the experiment was conducted at room temperature (about 25 ° C), 2.4 V was applied, 1.4 ampere of current flowed, 0.044 ml / s of gas flowed out of the positive electrode, and the stoichiometry of current and gas flow rate. Relationship was confirmed.
  • Electrolyte used is an aqueous solution of ferric chloride and calcium chloride.
  • the mixing ratio is 0.2 to 2 mol equivalent to anhydrous ferric chloride and 4 to 15 mol of water per mol of calcium chloride anhydride.
  • the separator 1 containing the electrolytic solution is dried.
  • the separator 1 impregnated with the electrolytic solution, the positive electrode 2, the negative electrode 3, the positive electrode side current collecting electrode 4 and the negative electrode side current collecting electrode 5 are laminated, and then an adhesive is applied to the end portion in the plane direction of the laminated structure. Impregnation is then performed, and the structure is connected and integrated as a mold portion 8. In addition, it is difficult to make a mold part with a wet separator that is not dried.
  • the mixture of ferric chloride and calcium chloride on the separator 1 has strong deliquescence, absorbs water vapor from the atmosphere, falls within 4 to 15 moles of water per mole of calcium chloride anhydride, and is originally wet. Return to state. Within this range, the electrolytic solution becomes a non-volatile solution and does not dry out. In addition to the separator 1, the surrounding carbon fine powder and carbon cloth hold the aqueous solution. Therefore, when the aqueous solution drips or leaks, the aqueous solution is not lost, and the surroundings are not soiled.
  • gaseous oxygen is taken into the electrolytic solution from the negative electrode-side gas phase 10 on the surface of the fine carbon powder of the negative electrode 3, is transmitted through the electrolytic solution in accordance with ionic conduction, and returns to oxygen on the surface of the fine carbon powder of the positive electrode 2. , And discharged to the positive electrode side gas phase 9. In this way, the function of oxygen transfer as an oxygen pump is exhibited.
  • trivalent iron ions of ferric chloride on the surface of the negative electrode 3 receive electrons from the negative electrode 3 and are reduced to divalent iron ions.
  • the divalent iron ions are auto-oxidized with oxygen to return to trivalent iron ions, and water is generated from the hydrogen ions in the solution, and oxygen is taken into the electrolyte.
  • Embodiment 2 oxygen can be efficiently taken in by introducing divalent iron ions to be auto-oxidized. Since iron ions are electrode active, it is easy to receive charges from the electrodes. Trivalent iron ions are an oxidized form of divalent iron ions that are auto-oxidized.
  • calcium chloride not directly involved in oxygen transport also has several functions.
  • chlorine ions act to promote oxygen auto-oxidation of divalent iron ions, and oxygen uptake at the negative electrode 3 is accelerated.
  • iron ions are also supplied in the form of chlorides.
  • by adding calcium chloride oxygen auto-oxidation of divalent iron ions is further accelerated.
  • Calcium ions are electrically adsorbed on the surface of the negative electrode 3, and the surface of the electrode is maintained on the alkali side due to pH buffering of calcium ions, so that the equilibrium potential for hydrogen generation is lowered and hydrogen gas is hardly emitted.
  • the solubility of iron involved in the reaction can be increased. Since it is impossible to impregnate the separator with an iron salt that does not dissolve, if the iron salt is charged at a high concentration, the solubility must be increased.
  • Calcium chloride co-dissolves with ferrous chloride and helps dissolve ferrous chloride.
  • calcium chloride is a source of chloride ions.
  • Trivalent iron ions are liable to form insoluble hydroxides, and the hydroxides are irreversibly changed to iron oxide (iron trioxide).
  • iron oxide iron trioxide
  • the chlorine ions coordinate with the iron ions and compete with the hydroxide ions, so that irreversible iron oxide production can be prevented.
  • FIG. 2 shows the configuration of the oxygen pump used in the experiment.
  • the separator 1 a polyethylene hydrophilic separator having a thickness of 0.38 mm (manufactured by Nippon Sheet Glass Co., Ltd.) was used.
  • the positive electrode 2 and the negative electrode 3 were composed of acetylene black (manufactured by Wako Pure Chemical Industries, Ltd.) and carbon cloth (manufactured by Mitsubishi Rayon Co., Ltd.).
  • the mold part 8 was configured with a circular effective diameter of 30 millimeters (effective area of 7.0 square centimeters) using a silicone sealant (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a positive electrode case 11 having a gas outlet 12 was attached, and a thin film micro flow meter was connected to the gas outlet 12 so that the flow rate could be observed.
  • the experiment was conducted at room temperature (about 25 ° C), 2.1 V was applied, a current of 1.4 amperes flowed, 0.044 ml / sec of gas flowed out from the positive electrode 2, and the stoichiometry of current and gas flow rate. A logical relationship was confirmed.
  • Electrolyte solution is an aqueous solution of nickel chloride or calcium chloride.
  • the mixing ratio is 0.2 to 2 moles equivalent to anhydrous nickel chloride and 4 to 15 moles of water per mole of calcium chloride anhydride.
  • the separator 1 containing the electrolytic solution is dried.
  • the separator 1 impregnated with the electrolytic solution, the positive electrode 2, the negative electrode 3, the positive electrode side collector electrode 4 and the negative electrode side collector electrode 5 are laminated, and then the adhesive is applied to the end portion in the plane direction of the laminated structure.
  • the mold part 8 is piled up to make the mold part 8 and integrated.
  • the mixture of nickel chloride and calcium chloride on the separator 1 has strong deliquescence, absorbs water vapor from the atmosphere, falls within 4 to 15 moles of water per mole of calcium chloride anhydride, and returns to its original wet state. Return. Within this range, the electrolytic solution becomes a non-volatile solution and does not dry out. In addition to the separator 1, the surrounding carbon fine powder and carbon cloth hold the aqueous solution. Therefore, when the aqueous solution drips or leaks, the aqueous solution is not lost and the surroundings are not soiled.
  • the current is transmitted from the positive electrode extraction part 6 to the positive electrode 2 via the positive electrode collecting electrode 4.
  • the current is exchanged with the electrolyte solution on the surface of the fine carbon powder of the positive electrode 2 to generate oxygen, and then is transferred through the electrolyte impregnated in the separator by ionic conduction to the fine carbon powder surface of the negative electrode 3.
  • the current exchanges the charge again to take in oxygen into the electrolytic solution, and further returns to the external DC power source through the negative electrode side collecting electrode 5 and the negative electrode side electrode take-out unit 7 to constitute a closed circuit as a whole.
  • gaseous oxygen is taken into the electrolytic solution from the negative electrode-side gas phase 10 on the surface of the fine carbon powder of the negative electrode 3, is transmitted through the electrolytic solution in accordance with ionic conduction, and returns to oxygen on the surface of the fine carbon powder of the positive electrode 2. , And discharged to the positive electrode side gas phase 9. In this way, the function of oxygen transfer as an oxygen pump is exhibited.
  • the divalent nickel ion of nickel chloride on the surface of the negative electrode 3 receives electrons from the negative electrode and is reduced to become metallic nickel.
  • the metallic nickel is auto-oxidized with oxygen to return to divalent nickel ions, and water is generated from hydrogen ions in the solution, and oxygen is taken into the electrolytic solution.
  • oxygen can be efficiently taken in by introducing nickel that is auto-oxidized.
  • Nickel is electrode active and it is easy to accept charges from the electrode.
  • the divalent nickel ion is an oxidized form of metallic nickel that is auto-oxidized.
  • Calcium chloride which is not directly involved in oxygen transport, also has several functions.
  • calcium chloride has strong deliquescence, excellent water retention, and difficult to dry. Therefore, drying of the electrolytic solution is suppressed, and the electrolytic solution is not cut and ion conduction is not lost.
  • the chlorine ions promote the oxygen auto-oxidation of nickel metal, and the oxygen uptake at the anode 3 is accelerated.
  • nickel is also supplied in the form of chloride.
  • oxygen auto-oxidation of metallic nickel is further accelerated.
  • the presence of a large amount of calcium ions suppresses the generation of hydrogen gas from the negative electrode 3.
  • Calcium ions are electrically adsorbed on the surface of the negative electrode 3, and the surface of the electrode is maintained on the alkali side due to pH buffering of calcium ions, so that the equilibrium potential for hydrogen generation is lowered and hydrogen gas is hardly emitted.
  • the solubility of nickel involved in the reaction can be increased. Since the separator cannot be impregnated with a nickel salt that does not dissolve, if the nickel salt is charged at a high concentration, the solubility must be increased. Calcium chloride co-dissolves with nickel chloride to help dissolve the nickel chloride.
  • FIG. 2 shows the configuration of the oxygen pump used in the experiment.
  • the separator 1 a polyethylene hydrophilic separator having a thickness of 0.38 mm (manufactured by Nippon Sheet Glass Co., Ltd.) was used.
  • the positive electrode 2 and the negative electrode 3 were composed of acetylene black (manufactured by Wako Pure Chemical Industries) and carbon cloth (manufactured by Mitsubishi Rayon Co., Ltd.).
  • the mold part 8 was configured with a circular effective diameter of 30 millimeters (effective area of 7.0 square centimeters) using a silicone sealant (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a positive electrode case 11 having a gas outlet 12 was attached, and a thin film micro flow meter was connected to the gas outlet 12 so that the flow rate could be observed.
  • the experiment was performed at room temperature (about 25 ° C), 1.5 V was applied, 1.5 ampere current flowed, 0.017 ml / s gas flowed out of the positive electrode, and the stoichiometry of current and gas flow rate. Relationship was confirmed.
  • Electrolytic solution is an aqueous solution of cobalt chloride and calcium chloride.
  • the mixing ratio is 0.2 to 2 mol equivalent to anhydrous cobalt chloride and 4 to 15 mol of water per mol of calcium chloride anhydride.
  • a positive electrode 2 and a negative electrode 2 configured by applying carbon fine powder are disposed on both surfaces of a separator 1 impregnated with an electrolyte solution. Furthermore, the positive electrode side collector electrode 4 and the negative electrode side collector electrode 5 are configured by closely attaching a carbon cloth to the outside.
  • the separator 1, the positive electrode 2, the negative electrode 3, the positive electrode side collector electrode 4, and the negative electrode side collector electrode 5 are laminated, and then the end portion in the plane direction of the laminated structure is impregnated with an adhesive, Then, each structure is connected and integrated as a mold part 8. It is difficult to make the mold part 8 with a wet separator that is not dry.
  • the mixture of cobalt chloride and calcium chloride on the separator has strong deliquescence, absorbs water vapor from the atmosphere, fits in 4 to 15 moles of water per mole of calcium chloride anhydride, and returns to the original wet state. .
  • the electrolytic solution becomes a non-volatile solution and does not dry out.
  • not only the separator 1 but also surrounding carbon fine powder and carbon cloth hold the aqueous solution. Therefore, when the aqueous solution drips or leaks, the aqueous solution is not lost and the surroundings are not soiled.
  • the current is transmitted from the positive electrode extraction part 6 to the positive electrode 2 via the positive electrode collecting electrode 4.
  • the current is exchanged with the electrolyte solution on the surface of the fine carbon powder of the positive electrode 2 to generate oxygen, and then is transferred through the electrolyte impregnated in the separator by ionic conduction to the fine carbon powder surface of the negative electrode 3.
  • the current exchanges the charge again to take in oxygen into the electrolytic solution, and further returns to the external DC power source through the negative electrode side collecting electrode 5 and the negative electrode side electrode take-out unit 7 to constitute a closed circuit as a whole.
  • gaseous oxygen is taken into the electrolytic solution from the negative electrode-side gas phase 10 on the surface of the fine carbon powder of the negative electrode 3, is transmitted through the electrolytic solution in accordance with ionic conduction, and returns to oxygen on the surface of the fine carbon powder of the positive electrode 2. , And discharged to the positive electrode side gas phase 9. In this way, the function of oxygen transfer as an oxygen pump is exhibited.
  • the divalent cobalt ions of cobalt chloride on the surface of the negative electrode 3 receive electrons from the negative electrode 3 and are reduced to become metallic cobalt.
  • Embodiment 4 oxygen can be efficiently taken in by bringing cobalt to be auto-oxidized.
  • Cobalt is electrode active and charge collection with the electrode is easy.
  • the divalent cobalt ion is an oxidized form of metallic cobalt that undergoes auto-oxidation.
  • Calcium chloride which is not directly involved in oxygen transport, also has several functions.
  • calcium chloride has strong deliquescence, excellent water retention, and difficult to dry. Therefore, drying of the electrolytic solution is suppressed, and the electrolytic solution is not cut and ion conduction is not lost.
  • the chlorine ions promote the oxygen auto-oxidation of metallic cobalt, and the oxygen uptake at the negative electrode 3 is accelerated.
  • cobalt is also supplied in the form of chloride.
  • oxygen autooxidation of metallic cobalt is further accelerated.
  • the presence of a large amount of calcium ions suppresses the generation of hydrogen gas from the negative electrode 3.
  • Calcium ions are electrically adsorbed on the surface of the negative electrode 3, and the surface of the electrode is maintained on the alkali side due to pH buffering of calcium ions, so that the equilibrium potential for hydrogen generation is lowered and hydrogen gas is hardly emitted.
  • the solubility of cobalt involved in the reaction can be increased. Since the separator cannot be impregnated with a cobalt salt that does not dissolve, the only way to increase the solubility of the cobalt salt is to increase the concentration of the cobalt salt. Calcium chloride co-dissolves with cobalt chloride to help dissolve cobalt chloride.
  • FIG. 2 shows the configuration of the oxygen pump used in the experiment.
  • the separator 1 a polyethylene hydrophilic separator having a thickness of 0.38 mm (manufactured by Nippon Sheet Glass Co., Ltd.) was used. Both electrodes of the positive electrode 2 and the negative electrode 3 were composed of acetylene black (manufactured by Wako Pure Chemical Industries, Ltd.) and carbon cloth (manufactured by Mitsubishi Rayon Co., Ltd.).
  • the mold part 8 was composed of a silicone sealant (manufactured by Shin-Etsu Chemical Co., Ltd.) and a circular effective diameter of 30 millimeters (effective area of 7.0 square centimeters).
  • a positive electrode case 11 having a gas outlet 12 was attached, and a thin film micro flow meter was connected to the gas outlet 12 so that the flow rate could be observed.
  • 2V is applied, 1.3 ampere current flows, 0.075 ml / sec gas flows out from the positive electrode, and stoichiometric relationship between current and gas flow rate was confirmed.
  • the negative electrode 3 was formed by applying fine carbon powder whose surface was iron-plated, and the positive electrode 2 was formed by applying fine carbon powder.
  • the electrolyte solution is a saturated aqueous solution of potassium fluoride.
  • the separator 1 containing the electrolytic solution is dried.
  • the positive electrode 2, the negative electrode 3, the positive electrode side collector electrode 4, and the negative electrode side collector electrode 5 are laminated, and then the end portion in the plane direction of the laminated structure is impregnated with an adhesive, and then is built up.
  • the mold part 8 is made to be integrated.
  • potassium fluoride on the separator 1 has strong deliquescence, absorbs water vapor from the atmosphere, and returns to its original wet state. Therefore, the electrolytic solution becomes a non-volatile solution and does not dry out.
  • the surrounding carbon fine powder and carbon cloth hold the aqueous solution. Therefore, when the aqueous solution drips or leaks, the aqueous solution is not lost, and the surroundings are not soiled.
  • gaseous oxygen is taken into the electrolytic solution from the negative electrode-side gas phase 10 on the surface of the fine carbon powder of the negative electrode 3, is transmitted through the electrolytic solution in accordance with ionic conduction, and returns to oxygen on the surface of the fine carbon powder of the positive electrode 2. , And discharged to the positive electrode side gas phase 9. In this way, the function of oxygen transfer as an oxygen pump is exhibited.
  • metallic iron is auto-oxidized with oxygen on the surface of the negative electrode 3 to form divalent iron ions, and water is generated from hydrogen ions in the solution, and oxygen is taken into the electrolytic solution.
  • the divalent iron ions on the surface of the negative electrode 3 receive electrons from the negative electrode 3 and are reduced to return to metallic iron.
  • oxygen can be efficiently taken in by introducing iron that is auto-oxidized. Iron is electrode active and it is easy to receive charges with the electrode. Further, divalent iron ions are an oxidized form of metallic iron that undergoes auto-oxidation.
  • potassium fluoride which is not directly involved in oxygen transport, also has several functions.
  • potassium fluoride has strong deliquescence, excellent water retention, and difficult to dry. Therefore, drying of the electrolytic solution is suppressed, and the electrolytic solution is not cut and ion conduction is not lost. This is a common effect for salts with high solubility and strong deliquescence.
  • alkali halides such as calcium chloride, lithium chloride, and lithium bromide.
  • bromide cannot be used because it reacts earlier to produce bromine at a lower potential than oxygen is produced from water at the positive electrode.
  • Chloride reacts at a higher potential than oxygen is produced from water, but the potential is close and there is a risk of producing chlorine at the same time. In this respect, the fluoride reacts at a much higher potential than oxygen is produced from water, and there is no danger of producing fluorine.
  • fluorine ions promote the oxygen auto-oxidation of metallic iron, and oxygen uptake at the negative electrode 3 is accelerated.
  • the electrode material of the negative electrode 3 is obtained by depositing and coating iron metal on a fine carbon powder by electroless plating, and an electrode in close contact with the separator 1 can be easily formed.
  • Electroless plating can be performed by using an iron salt such as iron sulfate or iron chloride as an iron raw material and allowing a reducing agent such as hypophosphite, borohydride, or hydrazine to act under alkaline conditions. At this time, if a small amount of a metal salt having a noble potential such as copper sulfate or nitrosoparadium is added, it is reduced prior to iron to form a reduced nucleus, which acts as a catalyst and iron plating proceeds. , Iron plating of carbon fine powder becomes easy.
  • carbonyl iron can be immersed and absorbed, and this can be thermally decomposed to deposit metallic iron.
  • Carbon black, graphite carbon powder, activated carbon powder, etc. can be used as the carbon fine powder.
  • a fine layer that does not peel off when applied to the separator 1 is preferable, and its particle size is 10 micrometers or less.
  • the carbon fine powder of the positive electrode 2 can be carbon black, graphite carbon powder, activated carbon powder or the like.
  • a fine layer that does not peel off when applied to the separator 1 is preferable, and its particle size is 10 micrometers or less.
  • Carbon black acetylene black is favorable because it is available in stable and fine particulate form.
  • the carbon fine particles have good conductivity, and an electrode in close contact with the separator 1 can be easily formed.
  • FIG. 2 shows the configuration of the oxygen pump used in the experiment.
  • the separator 1 a hydrophilized filter paper made of polytetrafluoroethylene having a thickness of 0.5 millimeters and a pore diameter of 0.1 micrometers (manufactured by Advantech Toyo Co., Ltd.) was used.
  • the positive electrode 2 was made of carbon graphite (manufactured by Wako Pure Chemical Industries, Ltd.), and the negative electrode 3 was made of carbon graphite (made by Wako Pure Chemical Industries, Ltd.) by iron plating.
  • the iron raw material was iron carbonyl, which was absorbed by carbon graphite and thermally decomposed.
  • the positive electrode side collecting electrode 4 and the negative electrode side collecting electrode 5 were made of carbon cloth (manufactured by Mitsubishi Rayon Co., Ltd.).
  • the mold part 8 is a silicone sealant (manufactured by Shin-Etsu Chemical Co., Ltd.), and has a circular effective diameter of 30 millimeters (effective area of 7.0 square centimeters). Furthermore, a positive electrode case having a gas outlet 12 was attached, and a thin film micro flow meter was connected to the gas outlet 12 so that the flow rate could be observed.
  • the negative electrode 3 was formed by applying a fine nickel-plated carbon powder, and the positive electrode 2 was formed by applying a fine carbon powder.
  • the electrolyte solution is a saturated aqueous solution of potassium fluoride.
  • the separator 1 containing the electrolytic solution is dried.
  • the separator 1 impregnated with the electrolytic solution, the positive electrode 2, the negative electrode 3, the positive electrode side collecting electrode 4 and the negative electrode side collecting electrode are laminated, and then an adhesive is applied to the end portion in the plane direction of the laminated structure. It is impregnated, and then integrated by forming the mold part 8 by overlaying.
  • potassium fluoride on the separator 1 has strong deliquescence, absorbs water vapor from the atmosphere, and returns to its original wet state. Therefore, the electrolytic solution becomes a non-volatile solution and does not dry out.
  • the surrounding carbon fine powder and carbon cloth hold the aqueous solution. Therefore, when the aqueous solution drips or leaks, the aqueous solution is not lost and the surroundings are not soiled.
  • the current is transmitted from the positive electrode extraction part 6 to the positive electrode 2 via the positive electrode collecting electrode 4.
  • the current is exchanged with the electrolyte solution on the surface of the fine carbon powder of the positive electrode 2 to generate oxygen, and then is transferred through the electrolyte impregnated in the separator by ionic conduction to the fine carbon powder surface of the negative electrode 3.
  • the current exchanges the charge again to take in oxygen into the electrolytic solution, and further returns to the external DC power source through the negative electrode side collecting electrode 5 and the negative electrode side electrode take-out unit 7 to constitute a closed circuit as a whole.
  • gaseous oxygen is taken into the electrolytic solution from the negative electrode-side gas phase 10 on the surface of the fine carbon powder of the negative electrode 3, is transmitted through the electrolytic solution in accordance with ionic conduction, and returns to oxygen on the surface of the fine carbon powder of the positive electrode 2. , And discharged to the positive electrode side gas phase 9. In this way, the function of oxygen transfer as an oxygen pump is exhibited.
  • the nickel metal is auto-oxidized with oxygen on the surface of the negative electrode 3 to form divalent nickel ions, and water is generated from hydrogen ions in the solution, and oxygen is taken into the electrolyte.
  • the divalent nickel ions on the surface of the negative electrode 3 receive electrons from the negative electrode 3 and are reduced to return to metallic nickel.
  • Ni 2+ + 2e ⁇ ⁇ Ni Therefore, in the entire reaction of the negative electrode 3, oxygen and hydrogen ions receive electrons from the negative electrode and water is generated.
  • oxygen can be efficiently taken in by bringing nickel to be auto-oxidized.
  • Nickel is electrode active and it is easy to accept charges from the electrode.
  • the divalent nickel ion is an oxidized form of metallic nickel that is auto-oxidized.
  • potassium fluoride which is not directly involved in oxygen transport, also has several functions.
  • potassium fluoride has strong deliquescence, excellent water retention, and difficult to dry. Therefore, drying of the electrolytic solution is suppressed, and the electrolytic solution is not cut and ion conduction is not lost. This is a common effect for salts with high solubility and strong deliquescence.
  • alkali halides such as calcium chloride, lithium chloride, and lithium bromide.
  • bromide cannot be used because it reacts first at a lower potential than oxygen is produced from water at the positive electrode 2 to produce bromine.
  • Chloride reacts at a higher potential than oxygen is produced from water, but the potential is close and there is a risk of producing chlorine at the same time. In this respect, the fluoride reacts at a much higher potential than oxygen is produced from water, and there is no danger of producing fluorine.
  • the fluorine ions promote the oxygen auto-oxidation of nickel metal, and the oxygen uptake at the anode 3 is accelerated.
  • the electrode material of the negative electrode 3 is obtained by depositing and coating nickel metal on a fine carbon powder by electroless plating, and an electrode in close contact with the separator can be easily formed.
  • Electroless plating can be performed by using a nickel salt such as nickel sulfate or nickel chloride as a nickel raw material and allowing a reducing agent such as hypophosphite, borohydride, or hydrazine to act under alkaline conditions.
  • a nickel salt having a noble potential such as copper sulfate or nitrosoparadium
  • the nickel plating of the carbon fine powder becomes easy. Carbon black, graphite carbon powder, activated carbon powder, etc. can be used as the carbon fine powder.
  • a fine layer that does not peel off when applied to the separator 1 is preferable, and its particle size is 10 micrometers or less.
  • the carbon fine powder of the positive electrode 2 can be carbon black, graphite carbon powder, activated carbon powder or the like.
  • a fine layer that does not peel off when applied to the separator 1 is preferable, and its particle size is 10 micrometers or less.
  • Carbon black acetylene black is favorable because it is available in stable and fine particulate form.
  • the carbon fine particles have good conductivity, and an electrode in close contact with the separator can be easily formed.
  • FIG. 2 shows the configuration of the oxygen pump used in the experiment.
  • the separator 1 was a polytetrafluoroethylene hydrophilized filter paper having a thickness of 0.5 mm and a pore diameter of 0.1 micrometers (manufactured by Advantech Toyo Co., Ltd.).
  • the positive electrode 2 was made of nickel-plated carbon graphite (manufactured by Wako Pure Chemical Industries) and the negative electrode 3 was made of nickel-plated carbon graphite (manufactured by Wako Pure Chemical Industries).
  • Nickel sulfate was used as the nickel raw material
  • hydrazine monohydrate was used as the reducing agent
  • potassium hydroxide was used as the alkali.
  • the positive electrode side collecting electrode 4 and the negative electrode side collecting electrode 5 carbon cloth (manufactured by Mitsubishi Rayon Co., Ltd.) was used.
  • the mold part 8 was made of a silicone sealant (manufactured by Shin-Etsu Chemical Co., Ltd.) and had a circular effective diameter of 30 millimeters (effective area of 7.0 square centimeters).
  • a positive electrode case 11 having a gas outlet 12 was attached, and a thin film micro flow meter was connected to the gas outlet 12 so that the flow rate could be observed.
  • the experiment was performed at room temperature (about 25 ° C.), 2.6 V was applied, 1.1 ampere current flowed, 0.064 ml / sec gas flowed out from the positive electrode, and the stoichiometry of current and gas flow rate. Relationship was confirmed.
  • the negative electrode 3 was constituted by applying a fine carbon powder having a cobalt plating surface, and the positive electrode 2 was constituted by applying a fine carbon powder.
  • the electrolyte solution is a saturated aqueous solution of potassium fluoride.
  • the separator 1 containing the electrolytic solution is dried.
  • the separator 1 impregnated with the electrolytic solution, the positive electrode 2, the negative electrode 3, the positive electrode side collector electrode 4 and the negative electrode side collector electrode 5 are laminated, and then the adhesive is applied to the end portion in the plane direction of the laminated structure.
  • the mold part 8 is piled up to make the mold part 8 and integrated.
  • potassium fluoride on the separator 1 has strong deliquescence, absorbs water vapor from the atmosphere, and returns to its original wet state. Therefore, the electrolytic solution becomes a non-volatile solution and does not dry out.
  • the surrounding carbon fine powder and carbon cloth hold the aqueous solution. Therefore, when the aqueous solution drips or leaks, the aqueous solution is not lost and the surroundings are not soiled.
  • the current is transmitted from the positive electrode extraction part 6 to the positive electrode 2 via the positive electrode collecting electrode 4.
  • the current exchanges electric charge with the electrolyte solution on the surface of the carbon fine powder of the positive electrode 2 to generate oxygen, and then is transmitted through the electrolytic solution impregnated in the separator by ionic conduction to reach the surface of the carbon fine powder of the negative electrode 3.
  • the current exchanges the charge again to take in oxygen into the electrolyte, and further returns to the external DC power source via the negative electrode side collecting electrode 5 and the negative electrode side electrode take-out part 7 to constitute a closed circuit as a whole. .
  • gaseous oxygen is taken into the electrolytic solution from the negative electrode-side gas phase 10 on the surface of the fine carbon powder of the negative electrode 3, is transmitted through the electrolytic solution in accordance with ionic conduction, and returns to oxygen on the surface of the fine carbon powder of the positive electrode 2. , And discharged to the positive electrode side gas phase 9. In this way, the function of oxygen transfer as an oxygen pump is exhibited.
  • metallic cobalt is auto-oxidized with oxygen on the surface of the negative electrode 3 to form divalent cobalt ions, and water is generated from hydrogen ions in the solution, and oxygen is taken into the electrolytic solution.
  • the divalent cobalt ions on the surface of the negative electrode 3 receive electrons from the negative electrode 3 and are reduced to return to metallic cobalt.
  • Embodiment 7 oxygen can be efficiently taken in by bringing cobalt to be auto-oxidized.
  • Cobalt is electrode active and charge collection with the electrode is easy.
  • the divalent cobalt ion is an oxidized form of metallic cobalt that undergoes auto-oxidation.
  • potassium fluoride which is not directly involved in oxygen transport, also has several functions.
  • potassium fluoride has strong deliquescence, excellent water retention, and difficult to dry. Therefore, drying of the electrolytic solution is suppressed, and the electrolytic solution is not cut and ion conduction is not lost. This is a common effect for salts with high solubility and strong deliquescence.
  • alkali halides such as calcium chloride, lithium chloride, and lithium bromide.
  • bromide cannot be used because it reacts first at a lower potential than oxygen is produced from water at the positive electrode 2 to produce bromine.
  • Chloride reacts at a higher potential than oxygen is produced from water, but the potential is close and there is a risk of producing chlorine at the same time. In this respect, the fluoride reacts at a much higher potential than oxygen is produced from water, and there is no danger of producing fluorine.
  • fluorine ions promote the oxygen auto-oxidation of metallic cobalt, and oxygen uptake at the negative electrode 3 is accelerated.
  • the electrode material of the negative electrode 3 is obtained by depositing and coating cobalt metal on a fine carbon powder by electroless plating, and an electrode in close contact with the separator can be easily formed.
  • Electroless plating can be performed by using a cobalt salt such as cobalt sulfate or cobalt chloride as a cobalt raw material, and allowing a reducing agent such as hydrazine to act under hypophosphite, borohydride, or alkali.
  • a metal salt having a noble potential such as copper sulfate or nitrosoparadium
  • Cobalt plating of carbon fine powder becomes easy.
  • Carbon black, graphite carbon powder, activated carbon powder, etc. can be used as the carbon fine powder.
  • a fine layer that does not peel off when applied to the separator 1 is preferable, and its particle size is 10 micrometers or less.
  • the carbon fine powder of the positive electrode 2 can be carbon black, graphite carbon powder, activated carbon powder or the like.
  • a fine layer that does not peel off when applied to the separator 1 is preferable, and its particle size is 10 micrometers or less.
  • Carbon black acetylene black is favorable because it is available in stable and fine particulate form.
  • the carbon fine particles have good conductivity, and an electrode in close contact with the separator can be easily formed.
  • FIG. 2 shows the configuration of the oxygen pump used in the experiment.
  • the separator 1 is a hydrophilized filter paper made of polytetrafluoroethylene, having a thickness of 0.5 millimeters and a pore diameter of 0.1 micrometers (manufactured by Advantech Toyo Co., Ltd.).
  • the positive electrode 2 was a carbon graphite (manufactured by Wako Pure Chemical Industries) and the negative electrode 3 was a carbon graphite (manufactured by Wako Pure Chemical Industries) plated with cobalt.
  • the cobalt raw material was cobalt sulfate, the reducing agent was hydrazine monohydrate, and the alkali was potassium hydroxide.
  • the mold part 8 is a silicone sealant (manufactured by Shin-Etsu Chemical Co., Ltd.), and has a circular effective diameter of 30 millimeters (effective area of 7.0 square centimeters). Furthermore, a positive electrode case 11 having a gas outlet 12 was attached, and a thin film micro flow meter was connected to the gas outlet 12 so that the flow rate could be observed.
  • FIG. 3 is a cross-sectional view showing a food storage space capable of adjusting the oxygen concentration in the refrigerator as a storage in the eighth embodiment.
  • FIG. 3 shows one of a plurality of storage rooms extracted from a refrigerator as a storage.
  • Deoxygenation assistance that forms a deoxygenation auxiliary space with a food storage container 39 whose interior is a food storage space 40 in a space formed by the front storage chamber door 31, the upper and lower heat insulating partition walls 32, and the partition plate 34
  • the container 38 is connected and arranged.
  • a deoxygenation gas introduction unit 36 is disposed at a connection portion between the food storage container 39 and the deoxygenation auxiliary container 38, and the deoxygenation auxiliary container 38 includes an external gas replacement unit 37 and an oxygen concentration adjustment unit (oxygen pump). 35.
  • a cooler, a fan, etc. are installed in the space between the partition plate 34 and the main body heat insulation wall 33 or the space connected thereto, and cool air is supplied to the storage room.
  • Equipment, fans, etc. are omitted.
  • FIG. 4 shows a procedure for deoxidizing the food storage space of the eighth embodiment.
  • an outline of a specific method of adjusting the oxygen concentration and the function of each unit will be described with reference to FIGS. 3 and 4.
  • Deoxidation of the food storage space 39 proceeds in three steps shown in FIG.
  • the first step is “substitution of the gas in the deoxygenation auxiliary container with an external gas”.
  • This step is performed by the external gas replacement unit 37 included in the deoxygenation auxiliary container 38.
  • the external gas replacement unit 37 is a kind of opening / closing device, and first performs an operation of opening the opening / closing device. As a result, the gas inside the deoxygenation auxiliary container 38 is released to the outside, and the external gas is introduced into the deoxygenation auxiliary container 38.
  • the purpose of this step is to maintain the oxygen concentration of the gas in the deoxygenation auxiliary container 38 at about 21%, which is the same as that in the atmosphere, prior to step 2 by the above replacement. If the oxygen concentration is kept at a constant value of 21%, the volume of the deoxygenation auxiliary container 38 is constant, so that the total oxygen amount in the deoxygenation auxiliary container 38 becomes constant. As a result, as will be described below, in step 2, hydrogen ions and oxygen react without excess and deficiency, and hydrogen generation does not proceed.
  • the second step is “deoxygenation in the deoxygenation auxiliary vessel”.
  • deoxidation in the deoxygenation auxiliary container 38 is performed by applying a voltage to the oxygen concentration adjusting unit (oxygen pump) 35 of the deoxygenation auxiliary container 38.
  • oxygen concentration adjusting unit (oxygen pump) 35 the electric charge that flows when voltage is applied to the oxygen concentration adjusting unit (oxygen pump) 35
  • the electric charge corresponding to the total amount of oxygen in the deoxygenation auxiliary vessel 38 (the electric charge that flows when voltage is applied to the oxygen concentration adjusting unit (oxygen pump) 35) is controlled to flow by voltage application. It is to be. This generates hydrogen ions equivalent to the charges, which react with oxygen and are removed.
  • both the external gas replacement part 37, which is a kind of opening / closing mechanism, and the deoxygenation gas introduction part 36, which is also a kind of opening / closing mechanism, are closed, and the deoxygenation auxiliary container is isolated. To do.
  • the operation of the deoxygenated gas introducing section 36 will be described in the third step.
  • the third step is “introduction of gas in the deoxygenation auxiliary container into the food storage space”.
  • the deoxygenated gas introduction part 36 which is a kind of opening / closing mechanism is opened.
  • the deoxygenated gas in the deoxygenation auxiliary container 38 is introduced into the food storage space 40 that has not been deoxygenated and becomes uniform. In this way, the oxygen concentration in the food storage space 40 is reduced by introducing the deoxygenated gas.
  • the amount of oxygen to be always removed is constant, and the charge corresponding to the amount of oxygen is expressed as oxygen.
  • Control is performed so as to flow when a voltage is applied to the concentration adjusting unit (oxygen pump) 35.
  • step 3 gas diffusion is promoted to replace the gas in the deoxygenation auxiliary container 38 with external gas (step 1), the introduction of the deoxygenated gas in the deoxygenation auxiliary container 38 into the food storage space 40, and uniform
  • a fan As a place to install, the inside of the deoxidation auxiliary container 38 is preferable.
  • step 2 since the inside of the deoxygenation auxiliary container 38 is depressurized by deoxygenation, the deoxygenation auxiliary container 38 needs to have a strength that can withstand the pressure difference, and is a thick resin container or metal container. Etc. are used.
  • the deoxygenation auxiliary container 38, the external gas replacement unit 37, and the deoxygenation gas introduction unit 36 have high hermeticity, a tighter synthetic container is required.
  • the deoxygenation auxiliary container 38, the external gas replacement unit 37, and the deoxygenation gas introduction unit 36 are reduced in the sealing property, or the deoxygenation auxiliary container 8 is provided with a pinhole, so that the deoxygenation auxiliary container The inside of 38 is not decompressed, and it is also possible to use a resin case having a normal strength with a small thickness.
  • FIG. 5 is a cross-sectional view of the oxygen concentration adjusting unit (oxygen pump) 35 in the eighth embodiment.
  • the oxygen concentration adjusting unit (oxygen pump) 35 has a polymer solid electrolyte membrane (separator) 42 at the center, a negative electrode 43 on the left side, and a positive electrode 44 on the right side.
  • a supply electrode (a negative electrode side collector electrode and a positive electrode side collector electrode) 45 is provided outside, and these are fixed by a frame 41.
  • the oxygen concentration adjusting unit (oxygen pump) 35 has a negative electrode 43 inside the deoxygenation auxiliary hand container 38 and a positive electrode 44 outside the deoxygenation auxiliary container 38 in order to deoxygenate the inside of the deoxygenation auxiliary container 38. It is arranged to become.
  • the voltage application to the oxygen concentration adjusting unit (oxygen pump) 35 is performed by voltage application to two supply electrodes (a negative electrode side collector electrode and a positive electrode side collector electrode) 45.
  • a negative electrode side collector electrode and a positive electrode side collector electrode By this voltage application, water vapor in the air is electrolyzed on the positive electrode 44 side to generate oxygen, and simultaneously generated hydrogen ions are passed through the polymer solid electrolyte membrane (separator) 42 by the applied voltage.
  • To the negative electrode 43 Since water is supplied as water vapor from the space on the positive electrode 44 side, the humidity in the space on the positive electrode 44 side decreases.
  • the oxygen concentration in the negative electrode 43 side space decreases and the oxygen concentration on the positive electrode 44 side increases, so that oxygen is pumped from the negative electrode 43 side to the positive electrode 44 side.
  • the water vapor is pumped from the positive electrode 44 side to the negative electrode 43 side.
  • the polymer solid electrolyte membrane (separator) 42 used in Embodiment 8 for example, a perfluorocarbon sulfonic acid membrane (film thickness: several tens of micrometers to several hundreds of micrometers) is used.
  • a porous electrode is used which has a suitable water repellency by pressure molding a mixture of carbon powder carrying a catalyst such as platinum and fluororesin powder.
  • a carbon cloth, carbon paper, or the like is used for the power feeding body (negative electrode side collecting electrode and positive electrode side collecting electrode) 45.
  • the positive electrode 44 be formed as a positive electrode 44 by directly forming a platinum layer on the polymer solid electrolysis (separator) 42 without using carbon powder that is easily oxidized by voltage application as a carrier such as platinum.
  • the positive electrode-side supply electrode (positive electrode-side collector electrode) 45 mesh-like titanium whose surface is platinum-plated is used instead of the carbon paper or carbon cloth.
  • the external gas replacement unit 37 and the deoxygenated gas introduction unit 36 used in the eighth embodiment are the open / close mechanisms already described, and an electromagnetic valve, a valve using air pressure, a switch or the like is used.
  • the oxygen concentration in the food storage space can be safely reduced without generating hydrogen, and the food can be safely stored for a long period of time with high quality. Become.
  • the polymer solid electrolyte membrane (separator) 42 of the oxygen concentration adjusting section (oxygen pump) 35 a perfluorocarbon sulfonic acid membrane having a thickness of about 200 microns was used.
  • the negative electrode 43 a porous electrode having a suitable water repellency by pressure-molding a mixture of a carbon powder carrying platinum on its surface and a fluororesin powder was used.
  • the positive electrode 44 used was a platinum black layer formed directly on the polymer solid electrolyte membrane (separator) 42.
  • the power supply body 45 a cloth made of carbon fiber was used for the negative electrode, and mesh-like titanium whose surface was plated with platinum was used for the positive electrode.
  • This oxygen concentration adjusting unit (oxygen pump) 35 is capable of removing about 170 ml of oxygen on the negative electrode 43 side per hour in an atmosphere of temperature 25 ° C. and humidity 60% and simultaneously generating the same amount of oxygen on the positive electrode 44 side. Had. This capability is achieved by connecting both sides of the oxygen concentration adjusting unit (oxygen pump) 35 to two bags having gas barrier properties, and applying a voltage of 2.8 V to the supply electrode (negative electrode side collector electrode and positive electrode side collector electrode) 45. It was confirmed by measuring the oxygen concentration in the two bags when applied. The oxygen concentration was determined by quantifying the amount of oxygen using a gas chromatogram.
  • the food storage container 39 shown in FIG. 3 has an internal volume of 1 L, and the deoxygenation auxiliary container 38 has an internal volume of 3 L.
  • the deoxygenation auxiliary container 38 has a structure having a thickness so that it can withstand the pressure load due to the reduced pressure during deoxygenation.
  • Step 1 With the above configuration, 200 ml of beef minced meat is put in the food storage space and stored in an atmosphere of 5 ° C., the external gas replacement unit 37 is opened, and the deoxygenation auxiliary container with external air 38 was replaced.
  • Step 2 the external gas replacement unit 37 was closed, and a voltage of 2.8 V was applied to the negative electrode 43 and the positive electrode 44 of the oxygen concentration adjusting unit (oxygen pump) 35.
  • This time was determined from the charge amount as follows.
  • the inside of the deoxygenation auxiliary container 38 is deoxygenated in advance under the above voltage condition, the sum of the current values (charge amount) at which the oxygen concentration becomes 2% is obtained, and the voltage application is stopped at the time when the charge amount is reached. .
  • the voltage application was canceled when the same amount of electric charge was reached even in the following changes in the amount of beef minced meat.
  • the deoxygenated gas introduction section 36 is opened, and the deoxygenated auxiliary oxygen container 38 is introduced into the food storage space 40 and homogenized, and then the oxygen concentration and hydrogen concentration are adjusted to the gas chromatograph. Measured by togram.
  • the oxygen concentration adjustment unit is directly placed on the food storage container of the same volume as the experimental example, and the deoxygenation of the food storage space in the food storage container is directly performed. Carried out.
  • the charge amount at the time of deoxygenation does not depend on the amount of beef minced meat.
  • the charge amount when the oxygen concentration reaches 2% is used as a standard.
  • the voltage application to the oxygen concentration adjusting unit was released.
  • a pinhole having a diameter of 1 mm was opened in the food storage container so that the inside was not depressurized, and sampling at the time of gas chromatogram measurement was also performed from this pinhole.
  • the structure has a thickness so as to withstand the pressure load caused by the reduced pressure during deoxygenation.
  • a structure having a pinhole with a diameter of 1 mm may be used so as not to reduce the pressure during deoxygenation.
  • the sealing property is lowered by such a pinhole or the like, it is difficult to control the degree of sealing property or a fine pinhole, and in many cases, intrusion of oxygen that cannot be permitted from the outside may occur.
  • periodic deoxygenation can compensate for the decrease in sealing, and by reducing the pressure applied to the container, destruction or the like does not occur. Deoxygenation can be performed with improved reliability.
  • the structural feature of the ninth embodiment is that when the oxygen concentration is adjusted, the number of introductions of the deoxygenated gas into the space for storing the food is made plural.
  • the oxygen concentration adjusting method according to the ninth embodiment will be described with reference to FIG. 3 and FIG.
  • the first to third steps are the same as those in FIG. 4, and the first to third steps are repeated a plurality of times as necessary.
  • FIG. 7 shows the number of step repetitions on the horizontal axis and the change in oxygen concentration at that time on the vertical axis. Specifically, when the volume of the deoxygenation auxiliary container 38 indicated by the solid line is equal to the volume of the food storage space 40, the volume of the deoxygenation auxiliary container 38 indicated by the broken line is three times the volume of the food storage space 40. It is related to some cases. In each case, the oxygen concentration change in the food storage space 40 is plotted against the number of repetitions of the first to third steps.
  • the adjusted oxygen concentration in the deoxygenation auxiliary container 38 in the second step was set to 4%.
  • the adjusted oxygen concentration is 4% here, but can be arbitrarily set between 0 and 21%.
  • the oxygen concentration in the oxygen auxiliary container 38 converges to 4%.
  • the volume of the deoxygenation auxiliary container 38 is three times the volume of the food storage space 40, the number of repetitions of the first to third steps is 0 to 2, and the inside of the deoxygenation auxiliary container 38 in the second step.
  • the adjusted oxygen concentration converges to around 4%.
  • the volume of the original deoxygenation auxiliary container 38 is three times the above (when the food storage space 40 and the deoxygenation auxiliary container 38 are equal in volume)
  • the number of repetitions of the first to third steps should be the same.
  • the amount of deoxygenation is three times the above (when the volume of the food storage space 40 and the deoxygenation auxiliary container 38 is equal), and deoxidation requires three times as much time.
  • the amount of deoxygenated is equal to the volume of the food storage space 40 and the volume of the deoxygenation auxiliary container 38, and the number of repetitions of the first to third steps is 3, and the volume of the deoxygenation auxiliary container 38 is equal to the volume of the food storage space 40.
  • the number of repetitions of the first to third steps is 1 at 3 times the volume, it is equal. Comparing the two cases in FIG. 7, the oxygen concentration is lower when the volume of the deoxygenation auxiliary container is smaller and the number of repetitions of the first to third steps is larger, and the food storage space is deoxygenated more efficiently. I understand that.
  • a low oxygen concentration can be realized more efficiently in a short time, and food can be stored more efficiently and for a long time with high quality. This is because the smaller the volume of the auxiliary oxygen storage container, the smaller the loss due to substitution with external gas (increase in oxygen concentration) in step 1.
  • Embodiment 10 Next, Embodiment 10 will be described.
  • the same configuration as in the eighth and ninth embodiments has the same effect, and the same reference numerals are given and the description is omitted. Therefore, only different parts will be described.
  • the structural feature of the tenth embodiment lies in how the food storage space 40 is formed, and the other configuration is the same as that of the eighth embodiment.
  • the same oxygen concentration adjusting unit (oxygen pump) as that used in the eighth embodiment is used.
  • the procedure similar to that described in the eighth and ninth embodiments is used for the procedure of the oxygen concentration adjustment method.
  • FIG. 8 shows a cross-sectional view of one of a plurality of storage rooms in a refrigerator that is a storage similar to FIG. 3 differs from FIG. 3 of the eighth embodiment in that the food storage space 40 is formed by the food storage container 39 in FIG. 3, whereas in the tenth embodiment, the food is placed on the oxygen concentration adjusting tray 46. The space formed by covering this with the gas barrier film 48 is the food storage space 40.
  • the oxygen concentration adjustment is performed by repeating the first to third steps once or a plurality of times as in the eighth or ninth embodiment.
  • the food storage space 40 is significantly reduced. This is because the space occupied by other than food is extremely reduced by covering the food with the gas barrier film 48 in contact with the food. As a result, the volume of the gas to be deoxygenated is reduced, the food storage space 40 can be efficiently deoxygenated in a short time, and many foods can be stored with high quality. In addition, since the volume of the gas to be deoxygenated is reduced, the size of the oxygen concentration adjusting unit (oxygen pump) 35 can be reduced. By doing so, it is possible to obtain an effect that enables food to be stored in high quality at low cost.
  • the gas barrier film used in the tenth embodiment is a transparent film having a low oxygen permeability and a flexibility, and the oxygen permeability needs to be about 20000 mL / m 2 ⁇ day ⁇ atm or less.
  • a film of a hydrocarbon-based organic polymer such as polyethylene or a film obtained by depositing an inorganic substance such as silica on the organic polymer film is used.
  • the oxygen permeability is preferably 1000 mL / m 2 ⁇ day ⁇ atm or less.
  • a polyvinylidene chloride film having an oxygen transmission rate as low as 55 mL / m 2 ⁇ day ⁇ atm is used.
  • the container when using food storage containers made of plastic or metal, the container is not sufficiently transparent, so it is necessary to open the container to check the contents of the stored food.
  • the problem was that the concentration would increase.
  • the gas barrier membrane is highly transparent, it is possible to check the contents from the outside without releasing the sealing of the food storage space except for the membrane, which has the effect of greatly improving usability. is there.
  • the oxygen concentration adjusting tray 46 is connected to the deoxygenation auxiliary container 38 by the deoxygenation auxiliary container connection part 47 so that there is no gas leakage.
  • auxiliary oxygen depletion container 38 and the oxygen concentration adjusting tray 46 are detachable and fitted, and if necessary, a sealing material, packing, or the like can be used to eliminate leakage at the connecting portion. .
  • the oxygen concentration adjusting tray 46 is removed from the deoxygenation auxiliary container 38 and taken out of the refrigerator, and then the food is placed on the oxygen concentration adjusting tray 46. Thereafter, after the food is covered with a gas barrier film, it can be connected to the deoxidation auxiliary container 38 and used. Thus, since food is put out and put on the outside, an effect of greatly improving usability can be obtained.
  • FIGS. 9A and 9B are cross-sectional views of the oxygen concentration adjusting tray in the tenth embodiment.
  • FIG. 9A is a cross-sectional view in the direction of connection with the deoxygenation auxiliary container 38.
  • the arrow in FIG. 9A represents the connection direction with a deoxidation auxiliary container.
  • 9B is a cross-sectional view taken along line 9B-9B in FIG. 9A.
  • the deoxygenation auxiliary container connecting portion 47 of the oxygen concentration adjusting tray 46 has a large opening on the side connected to the deoxygenation auxiliary container 38 as shown in FIG. 9B. Through the opening, the deoxygenated gas can be efficiently supplied to the food storage space 40 by passing the deoxygenated auxiliary container 38 through the deoxygenated gas introduction section 36.
  • the ventilation groove in the lower part or the side part of the oxygen concentration adjusting tray 46.
  • a uniform oxygen concentration can be achieved in a short time through the ventilation groove, and the food can be stored in a high quality state uniformly. The effect becomes.
  • the ventilation groove extends from the vicinity of the deoxygenation auxiliary container connecting portion 47 to the end opposite to the deoxygenation auxiliary container 38.
  • the oxygen concentration adjusting tray 46 which is the gas barrier film and the food holding unit. It is possible to use a holding member for pressing the gas barrier film against the food storage space in order to improve the airtightness of the food storage space and prevent the gas inside and outside the food storage space 40 from entering and exiting.
  • the holding member is preferably configured to hold the gas barrier film between the oxygen concentration adjusting tray and the holding material.For example, a frame that closes the gas barrier film from the outside or a fixing device on the belt is used. Can be used.
  • this invention is not limited by this experimental example.
  • the oxygen concentration in the food storage space in FIG. 8 was lowered using the oxygen concentration adjusting tray 46 and the gas barrier film 48 in FIG. 8 of the tenth embodiment.
  • the oxygen concentration adjusting tray 46 shown in FIG. 8 was taken out, beef minced meat was placed thereon, covered with a gas barrier film 48, and this was connected to the deoxygenation auxiliary container 38. Thereafter, as in the experimental example shown in the eighth embodiment, the oxygen concentration in the food storage space 40 was adjusted according to the operation, and the oxygen concentration and the hydrogen concentration were measured.
  • the oxygen concentration was lower than that in the experimental example shown in the eighth embodiment. Further, as in the experimental example shown in the eighth embodiment, generation of hydrogen was avoided.
  • the generation of hydrogen was avoided because, as in the experimental example shown in the eighth embodiment, deoxygenation is always a certain amount of oxygen in the deoxygenation auxiliary container. This is probably because the corresponding hydrogen ions were supplied and no excess hydrogen ions were generated.
  • the reason why the oxygen concentration is low is considered to be as follows. By covering the beef minced meat with a gas barrier membrane, the volume to be deoxygenated (the volume of the food storage space) is greatly reduced. For this reason, when the deoxygenated gas is introduced from the deoxygenation auxiliary container, the influence of the food storage space 40 is reduced, and becomes almost equal to the oxygen concentration in the deoxygenation auxiliary container.
  • FIG. 10 is a cross-sectional view showing a food storage space capable of adjusting the oxygen concentration in the refrigerator as a storage in the eleventh embodiment.
  • FIG. 10 shows one extracted from a plurality of storage rooms of a refrigerator as a storage.
  • An oxygen concentration adjusting tray 56 covered with a gas barrier film 57 in a space formed by the storage chamber door 51 on the entire surface, the heat insulating partition walls 52 on the upper and lower surfaces, and the partition plate 54 is an oxygen concentration adjusting unit (oxygen pump). 55 is connected and installed.
  • a sealed space formed by connecting the oxygen concentration adjusting tray 56 with a gas barrier film 57 to an oxygen concentration adjusting portion (oxygen pump) 55 is a food storage space 70.
  • the volume variable section is an oxygen concentration adjusting tray 56 that is a food holding section that forms at least the bottom surface of the food storage space 70, and the gas barrier property provided on the oxygen concentration adjusting tray 56.
  • the film 57 is formed.
  • a cooler, a fan, etc. are installed in the space between the partition plate 54 and the main body heat insulating wall 53 or the space connected thereto, and cool air is supplied to the storage room.
  • Equipment, fans, etc. are omitted.
  • a sealed food storage space 70 formed by an oxygen concentration adjusting tray 56, a gas barrier film 57 covering the oxygen concentration adjusting tray 56, and an oxygen concentration adjusting unit (oxygen pump) 55 connected thereto an oxygen concentration adjusting unit (oxidygen removal is performed by an oxygen pump 55. Thereby, the oxygen concentration in the food storage space 70 is adjusted to be reduced.
  • the oxygen concentration can be reduced to about 0% to 10%, and the amount of gas in the food storage space 70 decreases accordingly.
  • the gas barrier film 57 since the gas barrier film 57 has flexibility, the gas barrier film 57 is deformed so as to decrease in volume as the gas decreases. As a result, no pressure difference is generated inside and outside the food storage space 70, and the inside and outside of the food storage space 70 are in substantially the same pressure state.
  • the gas barrier film 57 is a transparent film having a low oxygen permeability and a flexibility, and requires an oxygen permeability of about 20000 mL / m 2 ⁇ day ⁇ atm or less, and is a hydrocarbon-based material such as polyethylene.
  • An organic polymer film or a film obtained by depositing an inorganic substance such as silica on the organic polymer film is used.
  • the oxygen permeability is preferably 1000 mL / m 2 ⁇ day ⁇ atm or less.
  • a polyvinylidene chloride film having an oxygen transmission rate as low as 55 mL / m 2 ⁇ day ⁇ atm is used.
  • the gas barrier film 57 is transparent, so that there is an effect that the contents can be confirmed from the outside without releasing the sealing, improving the user-friendliness and reducing the number of times the sealing is released, The freshness can be further improved.
  • FIG. 11 is a cross-sectional view of oxygen concentration adjusting unit (oxygen pump) 55 in the eleventh embodiment.
  • the oxygen concentration adjusting unit (oxygen pump) 55 has a polymer solid electrolyte membrane (separator) 59 at the center, a negative electrode 60 on the left side, and a positive electrode 61 on the right side.
  • a supply electrode (a negative electrode side collector electrode and a positive electrode side collector electrode) 62 is provided outside, and these are fixed by a frame 58.
  • a tray connecting portion 63 for connecting to the oxygen concentration adjusting tray 56 is provided at the right end.
  • oxygen concentration adjusting unit (oxygen pump) 55 is described with reference to FIG.
  • Oxygen is generated by electrolysis of water on the positive electrode 61 side by applying a voltage to the supply electrode (negative electrode side collecting electrode and positive electrode side collecting electrode) 62, and simultaneously generated hydrogen ions are polymerized by the applied voltage.
  • the solid electrolyte membrane (separator) 59 moves from the positive electrode 61 to the negative electrode 60. Since water is supplied as water vapor from the space on the positive electrode 61 side, the humidity in the space on the positive electrode 61 side decreases.
  • oxygen in the negative electrode 60 side space reacts with hydrogen ions moved to the negative electrode 60 side or hydrogen gas generated by reduction of hydrogen ions, and is taken into the electrolyte membrane as water. At this time, a part of the water is discharged to the negative electrode 60 side space and increases the humidity of the corresponding space. Some water moves to the positive electrode 61 side and is used for electrolysis.
  • oxygen in the negative electrode 60 side space is pumped to the positive electrode 61 side.
  • water vapor is pumped from the positive electrode 61 side to the negative electrode 60 side.
  • the polymer solid electrolyte membrane (separator) 59 for example, a perfluorocarbon sulfonic acid membrane (film thickness: several tens of microns to several hundreds of microns) is used.
  • a porous electrode having a suitable water repellency by pressure molding a mixture of carbon powder carrying platinum on the surface thereof and a fluororesin powder is used.
  • the power supply body 62 is preferably made of a metal that is not easily oxidized, and mesh-like titanium or the like whose surface is platinum plated is used.
  • FIG. 12 is a cross-sectional view showing the relationship between the oxygen concentration adjusting unit (oxygen pump) 55 and the oxygen concentration adjusting tray 56 in the eleventh embodiment.
  • the oxygen concentration adjusting tray 56 is connected to the tray connecting portion 63 of the oxygen concentration adjusting portion (oxygen pump) 55 by the oxygen concentration adjusting portion connecting portion 64 so as not to leak gas. Yes.
  • the oxygen concentration adjusting tray 56 is connected to the negative electrode 60 side of the oxygen concentration adjusting unit (oxygen pump) 55, and oxygen diffused from the food storage space 70 reacts with hydrogen ions or hydrogen gas at the negative electrode 60. Thus, the oxygen concentration in the food storage space 70 is reduced by generating water.
  • the oxygen concentration adjusting unit connecting part 64 and the tray connecting part 63 are, for example, a fitting type, and seal packing or the like can be used as necessary.
  • FIGS. 13A and 13B are cross-sectional views of oxygen concentration adjusting tray 56 in the eleventh embodiment.
  • FIG. 13A is a cross-sectional view in the direction of connection with the oxygen concentration adjusting unit (oxygen pump).
  • the arrow in FIG. 13A represents the connection direction with a deoxidation auxiliary container.
  • 13B is a cross-sectional view taken along line 13B-13B in FIG. 13A.
  • the oxygen concentration adjusting portion connecting portion 64 of the oxygen concentration adjusting tray 56 has a large opening on the side connected to the oxygen concentration adjusting portion (oxygen pump) 55 as shown in FIG.
  • oxygen can be efficiently supplied to the oxygen concentration adjusting unit (oxygen pump) 55.
  • oxygen that has reached the negative electrode 60 of the oxygen concentration adjusting unit (oxygen pump) 55 becomes water by reacting with hydrogen ions or hydrogen gas, and the oxygen concentration is reduced.
  • FIGS. 14A and 14B are cross-sectional views of oxygen concentration adjusting tray 56 used differently in the eleventh embodiment.
  • FIG. 14A is a cross-sectional view in the direction of connection with the oxygen concentration adjusting portion (oxygen pump) 55 of the oxygen concentration adjusting tray 56.
  • the arrow in FIG. 14B represents the connection direction with a deoxidation auxiliary container.
  • 14B is a cross-sectional view taken along the line 14-14 in FIG. 14A.
  • FIGS. 13A and 13B The difference between FIGS. 13A and 13B and FIGS. 14A and 14B is that a gas barrier film fixing frame 65 is used in FIGS. 14A and 14B5.
  • the gas barrier film fixing frame 65 is in close contact with the gas barrier film 57 covering the oxygen concentration adjusting tray 56.
  • the gas barrier film fixing frame 65 has a function of pressing the gas barrier film 57 against the oxygen concentration adjusting tray 56 from above to improve the adhesion and fix it. For this reason, the intrusion of air from the outside is further suppressed, the oxygen concentration in the food storage space 70 can be reduced more efficiently, and the oxygen concentration that reaches can be reduced. As a result, the effect that the food can be stored for a long period of time with high quality is obtained.
  • the gas barrier film fixing frame 65 only needs to be able to uniformly press the gas barrier film 57 against the oxygen concentration adjusting tray 56 from above, and can be pressed more strongly by using a function of contracting rubber or a spring. It can also be mechanically tightened after installation.
  • the configuration of the eleventh embodiment it is possible to efficiently reduce the oxygen concentration in the food storage space 70, and it is possible to store food in high quality for a long period of time.
  • the configurations and materials of the respective parts described in the eleventh embodiment can be applied to the following embodiments as long as the difference in configuration is not particularly described.
  • the food storage space 70 shown in FIG. 10 is used by using the oxygen concentration adjusting unit (oxygen pump) 55 of FIG. 11 of Embodiment 11 and the oxygen concentration adjusting tray 56 of FIGS. 14A and 14B.
  • the oxygen concentration was reduced.
  • the polymer solid electrolyte membrane (separator) 59 of the oxygen concentration adjusting unit (oxygen pump) 55 a perfluorocarbon sulfonic acid membrane having a thickness of about 100 microns is used, and the positive electrode 61 and the negative electrode 60 are carbons carrying platinum on their surfaces.
  • the power supply body 62 mesh-like titanium whose surface is platinum-plated is used.
  • This oxygen concentration adjusting unit (oxygen pump) 55 has the ability to remove about 200 ml of oxygen on the negative electrode 60 side per hour in an atmosphere of temperature 25 ° C. and humidity 60% and simultaneously generate the same amount of oxygen on the positive electrode side. Had. This capability is achieved by connecting both sides of the oxygen concentration adjusting unit (oxygen pump) 55 to two bags having gas barrier properties, and applying a voltage of 2.8 V to the supply electrode (negative electrode side collector electrode and positive electrode side collector electrode) 62. It was confirmed by measuring the oxygen concentration in the two bags when applied. The oxygen concentration was determined by quantifying the amount of oxygen using a gas chromatogram.
  • the oxygen concentration adjustment tray 56 shown in FIG. 14A and FIG. 14B has an internal volume of about 1 L, and the gas barrier film 57 is a polyvinylidene chloride film having a thickness of 11 ⁇ m. Further, in order to improve the adhesion between the gas barrier film 57 and the oxygen concentration adjusting portion (oxygen pump) 55, a gas barrier film fixing frame 65 made of a belt-like rubber was used.
  • a broccoli having a volume of 150 ml was placed in the food storage space 70 and stored at 5 ° C. by applying a voltage of 2.8 V to the negative electrode 60 and the positive electrode 61 of the oxygen concentration adjusting unit (oxygen pump) 55.
  • the humidity was 60-80%.
  • the gas barrier film 57 has flexibility, when it was put on the oxygen concentration adjusting tray 56, it could be put in accordance with the shape of broccoli as food. For this reason, the volume of the container is about 1 L, but the volume of the food storage space 70 is as small as about 500 ml.
  • the oxygen concentration in the food storage space 70 was measured over time, the oxygen concentration reached 2% after 30 minutes. At this time, the gas barrier film 57 was deformed so that the volume of the food storage space 70 decreased as the oxygen concentration decreased. Subsequently, storage was carried out for 7 days while operating the oxygen concentration adjusting unit (oxygen pump) 55 at a rate of 2 minutes every 4 hours.
  • the upper part of the oxygen concentration adjustment tray 56 was sealed with a polyethylene built-in lid used in Tappaware.
  • the oxygen concentration adjusting unit (oxygen pump) 55 was operated under the same configuration and conditions as in the experimental example. However, the operation conditions were continuous operation.
  • the rate at which the oxygen concentration is decreased is slow and the oxygen concentration to be reached is high, whereas in the experimental example, a low oxygen concentration was realized in a short time. This is considered to be due to the following two reasons.
  • the oxygen concentration adjusting tray 56 is covered with the flexible gas barrier film 57 in the experimental example, it can be covered in accordance with the shape of the food. The volume to be oxygen is reduced.
  • the second reason is as follows.
  • the polypropylene cover is deformed as the food storage space is depressurized, and the portion of the oxygen concentration adjustment tray 56 where the cover is fitted is distorted.
  • the intrusion of air from the outside proceeds from the portion where the distortion occurs, but at this time, the intrusion of air is accelerated because the decompression of the food storage space is not completely eliminated.
  • the oxygen concentration adjusting tray 56 is covered with the flexible gas barrier film 57, so that even if oxygen is removed from the food storage space, the gas barrier film 57 is deformed.
  • the internal pressure is maintained at 1 atm.
  • the adhesion between the gas barrier film 57 and the oxygen concentration adjusting tray 56 is not impaired, air does not enter from the outside.
  • the structural feature of the twelfth embodiment is that the positions of the negative electrode 60 and the positive electrode 61 of the oxygen concentration adjusting unit (oxygen pump) 55 are reversed. Regarding other configurations, the same configurations as those described with reference to FIGS. 10, 12, 13A, and 13B are used. A specific configuration will be described with reference to FIG. 15 showing a cross section of the oxygen concentration adjusting unit (oxygen pump) 55 in the twelfth embodiment.
  • variable volume portion is an oxygen concentration adjusting tray 56 that is a food holding portion that forms at least the bottom surface of the food storage space 70, and a gas barrier film 57 provided on the oxygen concentration adjusting tray 56. It is formed with.
  • the difference from FIG. 11 of the eleventh embodiment is that the positions of the negative electrode 60 and the positive electrode 61 are opposite to the polymer solid electrolyte membrane (separator) 59. .
  • the negative electrode 60 and the positive electrode 61 of the oxygen concentration adjusting unit (oxygen pump) 55 are reversed. Therefore, as shown in FIG. 10, the food storage space 70 formed by covering the oxygen concentration adjusting tray 56 connected to the oxygen concentration adjusting unit (oxygen pump) 55 with the gas barrier film 57 is the oxygen storage space 70 shown in FIG. This leads to the positive electrode 61 of the concentration adjusting unit (oxygen pump) 55. Thereby, as for the food storage space 70, oxygen concentration rises and humidity falls. However, when using it in the refrigerator as a storage, since the temperature is low, the water produced
  • oxymyoglobin which is a red pigment contained in meat and fish when stored in an atmosphere with a high oxygen concentration, can maintain a beautiful red color for a long period of time because the change to brown metmyoglobin is suppressed. .
  • an effect of suppressing the growth of viable bacteria can be obtained.
  • the food storage space 70 of FIG. 10 is used by using the oxygen concentration adjusting unit (oxygen pump) 55 of FIG. 15 of the twelfth embodiment and the oxygen concentration adjusting tray 56 of FIG. 14 of the eleventh embodiment.
  • the oxygen concentration was increased.
  • the oxygen concentration in the food storage space reached 30% 20 minutes later.
  • the gas barrier film 57 swelled from the initial stage. Thereafter, it was operated for 3 minutes every 4 hours and stored for 7 days.
  • the following is a comparative example.
  • the oxygen concentration adjustment tray 56 in place of the oxygen concentration adjustment tray 56, except that 150 ml of beef minced meat is placed on a normal plate and sealed with a gas barrier film 57 from above, and the oxygen concentration is not adjusted. Storage was performed under the same conditions.
  • the degree of color change was measured using a color difference meter (CR-2000, manufactured by Minolta) to measure the a * value indicating red in the color value.
  • a * value indicating red in the color value.
  • the initial a * value was 25.3.
  • the measurement results are 21.0 after 7 days for the example and 11.1 for the comparative example, and the experimental example maintains a red color, has a small degree of discoloration, and can be stored for a long time with high quality. all right.
  • the oxygen concentration in the food storage space can be increased efficiently, discoloration of meat is suppressed, and high-quality storage is possible.
  • Embodiment 13 Next, Embodiment 13 will be described.
  • the same components as those in the eleventh and twelfth embodiments are denoted by the same reference numerals and description thereof is omitted. Therefore, only different parts will be described.
  • the volume variable section is an oxygen concentration adjusting tray 56 that is a food holding section that forms at least the bottom surface of the food storage space 70, and a gas barrier film 57 provided on the oxygen concentration adjusting tray 56. It is formed with.
  • a structural feature of the thirteenth embodiment resides in a configuration of an oxygen concentration adjusting tray 56 that is a food holding unit. Regarding other configurations, the same configurations as those described with reference to FIGS. 10, 11, 12, 13A, 13B, 14A, 14B, and 15 are used.
  • FIGS. 16A and 16B showing a cross section of the oxygen concentration adjusting tray 56 in the thirteenth embodiment.
  • 16B is a cross-sectional view taken along the line 16B-16B in FIG. 16A.
  • a ventilation portion 66 is provided at the lower portion or the side portion of the oxygen concentration adjusting tray 56.
  • the ventilation portion 66 By providing the ventilation portion 66, even when many foods are placed on the oxygen concentration adjusting tray 56, a uniform oxygen concentration can be quickly realized through the ventilation portion 66, and the food can be stored uniformly in a high quality state. A possible effect is obtained.
  • the ventilation portion 66 preferably extends from the vicinity of the oxygen concentration adjusting portion connecting portion 64 to the opposite end of the oxygen concentration adjusting tray 56.
  • variable volume portion is an oxygen concentration adjusting tray 56 that is a food holding portion that forms at least the bottom surface of the food storage space 70, and a gas barrier film 57 provided on the oxygen concentration adjusting tray 56. It is formed with.
  • the structural feature of the fourteenth embodiment resides in the configuration of an oxygen concentration adjusting tray 56 that is a food holding unit. Regarding other configurations, the same configurations as those described with reference to FIGS. 10, 11, 12, 13A, 13B, 14A, 14B, 15, 16A, and 16B are used. A specific configuration will be described with reference to FIG. 17 showing a cross section of the oxygen concentration adjusting tray 56 according to the fourteenth embodiment.
  • a water reservoir 67 is provided below the oxygen concentration adjusting tray 56.
  • the humidity of the food storage space 70 increases, and the humidity near the oxygen concentration adjusting part (oxygen pump) 55 also increases.
  • the necessary oxygen concentration can be realized more quickly, the high humidity can be maintained and the food can be prevented from drying, and it can be stored for a long time in a high quality state. .
  • the water storage unit 67 is preferably provided near the oxygen concentration adjusting unit (oxygen pump) 55 that consumes water from the viewpoint of efficient supply of water vapor.
  • variable volume portion different from the variable volume portion described in the eleventh to fourteenth embodiments is used. Therefore, the description will be focused on that part.
  • FIG. 18 is a diagram in which the movable wall 71 is used as a volume variable portion that changes the volume of the food storage space.
  • a movable wall 71 is used as a volume variable portion that changes the volume of the food storage space 70, and the movable wall 71 is provided with an opening / closing portion 72 that can be opened and closed in part. Yes, the volume of the food storage space 70 is changed by opening / closing the opening / closing portion 72.
  • a first food storage space 74 and a second food storage space 75 are provided as the food storage space 70, and the first food storage space 74 and the second food storage space 75 are provided.
  • An opening / closing part 72 is provided between the two.
  • the opening / closing part 72 becomes an opening, and the first food storage space 74 and the second food storage space 75 communicate with each other to form a large-volume food storage space 70.
  • An oxygen concentration adjusting unit (oxygen pump) 55 that adjusts the amount of oxygen with respect to the food storage space 70 having a volume is operated.
  • the volume of the storage chamber capable of reducing the oxygen concentration is only the volume of the first food storage space 74, so the volume is reduced to adjust the oxygen amount.
  • the oxygen concentration adjusting unit (oxygen pump) 55 can be operated, and the food storage space for storing food can be used properly so as to be convenient.
  • variable volume lever (not shown) that allows the user to open and close the openable / closable portion 72 provided on the movable wall 71.
  • the volume of the food storage space changes according to the needs of the user. Therefore, since the usability can be further improved according to the needs of the user, the volume of the food storage space can be changed as necessary, and the food storage space can be efficiently deoxygenated. As a result, it is possible to obtain an effect that the food can be stored in a high quality state for a long period of time efficiently and at low cost.
  • the volume variable section is provided with the opening / closing section 72 in a part of the movable wall 71 in which at least a part of the food storage space is movable to change the volume of the food storage space.
  • a configuration in which the entire wall 71 is movable may be used. In that case, the size of the food storage space can be changed according to the needs of the user, and the food storage space can be set flexibly, so a storage room with improved user convenience can be provided. It becomes possible to provide.
  • the present invention provides an external DC power source for taking in an electric current from the outside, a negative electrode having a porous gas exchange property, a positive electrode having a porous gas exchange property, and a negative electrode and a positive electrode.
  • a porous separator impregnated with an electrolytic solution containing metal ions connected to an external current power source, connected to a negative current collecting electrode provided outside the negative electrode, and connected to an external DC power source
  • a positive current collecting electrode provided outside the positive electrode and by supplying power to the negative current collecting electrode and the positive current collecting electrode by an external DC power source, Perform oxygen transfer to Accordingly, since an extremely small amount of electrolyte is impregnated and retained using an aqueous solvent that operates at normal temperature and pressure, a large amount of electrolyte leakage can be suppressed.
  • the structure can be made thin and soft, the area can be easily increased, and the oxygen carrying capacity can be increased.
  • the metal ion is made of at least one of iron, cobalt, and nickel. Therefore, since these metals exert a large catalytic action on the absorption of oxygen, the oxygen carrying capacity can be increased.
  • the negative electrode has a metal surface. Accordingly, since an extremely small amount of electrolyte is impregnated and retained using an aqueous solvent that operates at normal temperature and pressure, a large amount of electrolyte leakage can be suppressed. Further, since it can be structurally thinned and softened, the area can be easily increased, and the oxygen carrying capacity can be further increased.
  • the metal surface is constituted by electroless plating. Therefore, since the metal can be formed only on the surface where the electrode reaction proceeds, the usage fee and the weight are reduced, and since the adhesion with the electrode is good, the oxygen carrying capacity can be increased. .
  • the metal on the metal surface is made of at least one of iron, cobalt, and nickel.
  • the inclusion of these metals on the metal surface has a large catalytic effect on oxygen absorption, so that the oxygen carrying capacity can be further increased.
  • the positive electrode and the negative electrode contain fine carbon powder. Therefore, it can apply
  • the electrolytic solution contains a deliquescent salt. This prevents the moisture in the electrolyte from decreasing due to drying.
  • the deliquescent salt is potassium fluoride. Therefore, generation
  • the negative electrode side collecting electrode and the positive electrode side collecting electrode are carbon cloth. As a result, it is possible to make an oxygen pump having a large area with flexibility, and the oxygen carrying capacity can be increased. Further, by pulling out the carbon fiber, connection with an external power supply circuit becomes easy.
  • a mold part is provided at the peripheral ends of the negative electrode, the positive electrode, the separator, the negative electrode side collecting electrode, and the positive electrode side collecting electrode.
  • a food storage space that is formed in a sealed space for storing food, and a deoxygenation auxiliary space that is continuous with the food storage space via the oxygen pump, by supplying power from an external DC power source It is a storage that adjusts the oxygen concentration in the food storage space. As a result, high-quality long-term storage of vegetables, meat and the like is possible in a safe state.
  • the food storage space is made of a food holding part and a gas barrier film so that the volume is variable. As a result, an extra space other than food is reduced, so that the food storage space can be efficiently deoxygenated.
  • the present invention also includes a step of impregnating an electrolytic solution to form a porous separator, a step of drying the separator, and laminating a negative electrode, a positive electrode, a negative electrode side collector electrode, and a positive electrode side collector electrode on the porous separator. And a step of adjusting the concentration of the electrolytic solution by applying water vapor to the laminate.
  • a step of impregnating an electrolytic solution to form a porous separator
  • a step of drying the separator and laminating a negative electrode, a positive electrode, a negative electrode side collector electrode, and a positive electrode side collector electrode on the porous separator.
  • a step of adjusting the concentration of the electrolytic solution by applying water vapor to the laminate.
  • the oxygen pump of the present invention operates at room temperature and normal pressure, can easily provide a large oxygen carrying capacity, and there is no problem of accidents such as electrolyte leakage. It can be applied to the fields of combustion, fish farming, medical treatment, etc., foods requiring low oxygen conditions, and food storage.

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Abstract

La présente invention a pour objet une pompe à oxygène comprenant une alimentation en courant continu externe qui reçoit du courant de l’extérieur, une électrode poreuse négative (3) ayant une propriété d’échange de gaz, une électrode poreuse positive (2) ayant une propriété d’échange de gaz, un séparateur poreux (1) qui est maintenu entre l’électrode négative (3) et l’électrode positive (2) et a été imprégné d’une solution d’électrolyse contenant des ions métalliques, une électrode de collecte de courant (5) côté électrode négative qui est connectée à l’alimentation en courant continu externe et est prévue à l’extérieur de l’électrode négative (3), et une électrode de collecte de courant (4) côté électrode positive qui est connectée à l’alimentation en courant continu externe et est prévue à l’extérieur de l’électrode positive (2). Un courant électrique est amené par l’alimentation en courant continu externe à l’électrode de collecte de courant (5) côté électrode négative et à l’électrode de collecte de courant (4) côté électrode positive pour permettre à l’oxygène de migrer d’une phase gazeuse (10) côté électrode négative dans une phase gazeuse (9) côté électrode positive. Un solvant aqueux qui est actif à des températures et pressions ordinaires est utilisé, et une très petite quantité d’un électrolyte est imprégnée et maintenue. En conséquence, la pompe à oxygène est avantageusement exempte, par exemple, de fuite d’électrolyte et peut avoir une grande surface pour augmenter une capacité oxyphorique.
PCT/JP2009/005097 2008-10-06 2009-10-02 Pompe à oxygène, procédé de fabrication d’une pompe à oxygène, et entrepôt de stockage comprenant une pompe à oxygène WO2010041396A1 (fr)

Applications Claiming Priority (18)

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JP2008-259254 2008-10-06
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012202575A (ja) * 2011-03-24 2012-10-22 Toshiba Corp 冷蔵庫

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Publication number Priority date Publication date Assignee Title
JPS56152978A (en) * 1980-04-25 1981-11-26 Matsushita Electric Ind Co Ltd Electrochemical oxygen pump device
JPS62153568U (fr) * 1986-03-20 1987-09-29
JPH0919621A (ja) * 1995-07-06 1997-01-21 Matsushita Electric Ind Co Ltd 脱酸素装置
JP2001176554A (ja) * 1999-12-16 2001-06-29 Nitto Denko Corp 電気化学素子の製造方法
JP2003289839A (ja) * 2002-04-08 2003-10-14 Asahi Kasei Corp 食品包装体
JP2005207690A (ja) * 2004-01-23 2005-08-04 Toshiba Corp 冷蔵庫
JP2007163169A (ja) * 2005-12-09 2007-06-28 Tokyo Metropolitan Univ エタノールガス検知組成物および検知方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56152978A (en) * 1980-04-25 1981-11-26 Matsushita Electric Ind Co Ltd Electrochemical oxygen pump device
JPS62153568U (fr) * 1986-03-20 1987-09-29
JPH0919621A (ja) * 1995-07-06 1997-01-21 Matsushita Electric Ind Co Ltd 脱酸素装置
JP2001176554A (ja) * 1999-12-16 2001-06-29 Nitto Denko Corp 電気化学素子の製造方法
JP2003289839A (ja) * 2002-04-08 2003-10-14 Asahi Kasei Corp 食品包装体
JP2005207690A (ja) * 2004-01-23 2005-08-04 Toshiba Corp 冷蔵庫
JP2007163169A (ja) * 2005-12-09 2007-06-28 Tokyo Metropolitan Univ エタノールガス検知組成物および検知方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012202575A (ja) * 2011-03-24 2012-10-22 Toshiba Corp 冷蔵庫

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