WO2012035968A1 - Élément secondaire à hydrogène/air - Google Patents

Élément secondaire à hydrogène/air Download PDF

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Publication number
WO2012035968A1
WO2012035968A1 PCT/JP2011/069549 JP2011069549W WO2012035968A1 WO 2012035968 A1 WO2012035968 A1 WO 2012035968A1 JP 2011069549 W JP2011069549 W JP 2011069549W WO 2012035968 A1 WO2012035968 A1 WO 2012035968A1
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Prior art keywords
electrolyte
air
negative electrode
hydrogen
electrode
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PCT/JP2011/069549
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English (en)
Japanese (ja)
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正嗣 盛満
浩二 高野
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学校法人同志社
九州電力株式会社
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Publication of WO2012035968A1 publication Critical patent/WO2012035968A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention uses oxygen in the atmosphere as a positive electrode active material, hydrogen in a hydrogen storage alloy as a negative electrode active material, and an alkaline aqueous solution as an electrolytic solution.
  • the present invention relates to an air secondary battery.
  • the air battery is a battery using air in the atmosphere as a positive electrode active material, and a commercially available zinc / air primary battery is well known.
  • air batteries having a structure similar to that of a zinc / air primary battery, there are batteries using aluminum or iron as a negative electrode active material, all of which have been confirmed to function as primary batteries, but have not yet been put into practical use.
  • air batteries are not yet put into practical use as secondary batteries except for mechanically charged zinc / air secondary batteries.
  • a mechanical rechargeable zinc / air secondary battery is one that only discharges as a reaction inside the battery, and can be reused by taking out the zinc negative electrode after discharge and replacing it with a new zinc negative electrode. .
  • an air battery using an alkaline aqueous solution as an electrolyte a battery using hydrogen as a negative electrode active material has been developed.
  • the present inventors have disclosed an air secondary battery including an air electrode obtained by mixing nickel powder, a pyrochlore oxide containing iridium, and a binder, and a negative electrode using a hydrogen storage alloy (patent) Document 1) and (Non-Patent Document 1).
  • this secondary battery is referred to as a hydrogen / air secondary battery.
  • the charge / discharge reaction of the hydrogen / air secondary battery is expressed by the following equation.
  • M is a hydrogen storage alloy
  • MH means a hydrogen storage alloy in a state of storing hydrogen.
  • hydrogen is released from the hydrogen storage alloy at the negative electrode, and oxygen is reduced at the air electrode to produce water.
  • water increases in the alkaline aqueous solution used for the electrolytic solution.
  • in charging water in the alkaline aqueous solution is decomposed, hydrogen is occluded in the negative electrode, and oxygen is generated in the air electrode.
  • the hydrogen / air secondary battery is a secondary battery using only water as an active material, and is characterized in that the amount of water in the electrolytic solution changes depending on the amount of charge / discharge electricity. This is a battery reaction peculiar to hydrogen / air secondary batteries.
  • Patent Document 2 to Patent Document 4 disclose air batteries, which use an organic solvent or an ionic liquid as an electrolytic solution, or use lithium as a negative electrode active material.
  • the hydrogen / air secondary battery of Patent Document 1 has a simple configuration that can be charged and discharged with an air electrode, a negative electrode, and an alkaline aqueous solution, has a high energy density and a high output density, and has a large capacity by stacking. Is easy.
  • the inventors of this patent have conducted various studies. As a result, in this battery, water in the electrolytic solution is reduced by charging, so that the amount of the electrolytic solution between the air electrode and the negative electrode is small, or a so-called battery separator.
  • the conventional hydrogen / air secondary battery has a problem that when charging / discharging is repeated, the discharge voltage decreases or the charging voltage increases, making subsequent charging / discharging difficult. Further, when the discharge current is increased, the discharge capacity becomes extremely small, and when the charge current is increased, there is a problem that the charge voltage becomes high and the charge cannot be continued at a stage before full charge. Furthermore, there has been a problem that when the discharge is performed at a very high current, the electrolyte leaks through the air electrode. In particular, when the electrode area is increased or the battery capacity is increased, there is a problem that the charge / discharge characteristics are deteriorated.
  • the hydrogen / air secondary battery of the present invention has the following configuration.
  • the hydrogen / air secondary battery according to claim 1 of the present invention uses an air electrode disposed in a battery container and a hydrogen storage alloy disposed in the battery container so as to face the air electrode.
  • a hydrogen / air secondary battery comprising a negative electrode and an electrolytic solution holding body that is disposed between the air electrode and the negative electrode and holds an electrolytic solution, wherein the electrolytic solution is reduced by a charging reaction
  • the electrolyte solution storage part which stores the electrolyte solution which increases by discharge reaction in the said battery container, At least one part of the said electrolyte solution holding body is immersed in the said electrolyte solution in the said electrolyte solution storage part have.
  • the battery container has an electrolyte solution storage unit that supplies an electrolyte solution that decreases due to a charging reaction or stores an electrolyte solution that increases due to a discharge reaction, and at least a part of the electrolyte solution holder is in the electrolyte solution storage unit.
  • the amount of electrolyte increased by the discharge between the air electrode and the negative electrode via the electrolyte holder is increased by the pressure increase caused by the water generated between the air electrode and the negative electrode during discharge.
  • the amount of electrolyte to be adjusted can be adjusted by changing the porosity and thickness of the electrolyte holder, and the required optimum amount of electrolyte is always maintained between the air electrode and the negative electrode regardless of the charge / discharge capacity of the battery. can do.
  • At least one pair of an air electrode and a negative electrode is disposed in the battery container.
  • the air electrode and the negative electrode may be disposed horizontally or vertically.
  • an electrolytic solution holder that holds an electrolytic solution that is an alkaline aqueous solution is disposed between the air electrode and the negative electrode.
  • On the opposite side of the air electrode from the electrolyte holder there is an air passage formed in the battery container so that oxygen necessary for discharging can be taken into the air electrode or oxygen generated by charging can be dissipated from the air electrode. is there.
  • This vent path may simply be an opening formed in the battery container.
  • the battery container is provided with an electrolytic solution storage part, and a part of the electrolytic solution holding body is immersed in the electrolytic solution in the electrolytic solution storage part.
  • the electrolytic solution storage section has a volume suitable for the charge / discharge capacity of the battery so that the electrolytic solution that decreases by the charging reaction can be supplied or the electrolytic solution that increases by the discharging reaction can be stored. Furthermore, the flow of the electrolytic solution is ensured between the electrolytic solution storage unit and the electrolytic solution holding body, and this increases the electrolytic solution by water generated between the air electrode and the negative electrode during discharge.
  • the electrolyte is stored in the electrolyte storage unit via the liquid holder, and the electrolyte is reduced by the decomposition of water between the air electrode and the negative electrode during charging. To be replenished between the air electrode and the negative electrode.
  • the air electrode is basically composed of a conductive substance that imparts conductivity to the air electrode, a catalyst, and a binder. These are integrally formed in a mixed state, and are further formed integrally with a current collector for outputting electric power to the outside during discharging and facilitating input of electric power from an external power source during charging.
  • a conductive substance that imparts conductivity to the air electrode, a catalyst, and a binder. These are integrally formed in a mixed state, and are further formed integrally with a current collector for outputting electric power to the outside during discharging and facilitating input of electric power from an external power source during charging.
  • Carbon, metal, or the like can be used as the conductive material, but those that are stable against oxygen reduction and oxygen generation in an alkaline aqueous solution are preferable. Examples of the carbon material include graphite, glassy carbon, fullerene, carbon nanotube, carbon having other structures, and graphite having excellent oxidation resistance that is heat-treated at high temperature is particularly preferable.
  • nickel
  • a catalyst having activity for oxygen reduction and oxygen generation is used.
  • precious metals such as platinum and silver, metal oxides, metal sulfides, metal nitrides, metal carbides, metal oxides, metal sulfides, metal carbides, metal carbide oxides, etc. with nitrogen substitution, Metal, oxygen, nitrogen, and carbon composite oxide (MeC x N y O z : Me is a metal or alloy, C is carbon, N is nitrogen, O is oxygen, and x, y, and z indicate the composition ratio. ) And other oxygen reduction catalysts that have catalytic activity for oxygen reduction, and oxide activity such as iridium oxide and ruthenium oxide, metal sulfides, and metal composite oxides.
  • the oxygen generation catalyst having the same can be used together to impart oxygen reduction activity and oxygen generation activity to the air electrode.
  • a bifunctional metal, alloy, or compound having both oxygen reduction activity and oxygen generation activity can be used. Examples of such dual functional materials include complex oxides classified into pyrochlore type, perovskite type, spinel type, and the like.
  • the binder has water repellency with respect to the electrolyte so that an air flow path can be formed inside the air electrode, and allows air to flow through the gap while binding the conductive substances to each other.
  • Resin-based materials such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and ethylene / vinyl acetate copolymer (EVA) can be used.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • EVA ethylene / vinyl acetate copolymer
  • a dispersion solution in which such a binder is dispersed in an appropriate solution may be used as a starting material. it can.
  • the current collector can be made of various shapes of metal, such as mesh, fiber, or porous material, or conductive organic matter. However, the shape needs to have an opening for taking in oxygen in the atmosphere. is there.
  • the material for the current collector is preferably nickel. Note that the materials, structures, and shapes used for the conductive material, catalyst, binder, and current collector are particularly limited to those listed above as long as they exhibit their respective functions as described above. It is not something.
  • a method generally used for producing an air electrode such as a press method or an extrusion method can be used.
  • the conductive substance, the catalyst, and the binder are in the form of powder or particles, they can be produced by mixing them in a dry or wet manner and then forming them into a thin plate using a roll press. Moreover, it can be produced by putting a mixture in a specific mold and molding it.
  • the conductive material is a porous body such as nickel foam
  • the catalyst and the binder can be introduced into the porous body, and then the entire conductive material can be pressurized to be integrally molded. .
  • the current collector may be integrated with the air electrode as described above, or may be further integrated with the current collector after the conductive material, the catalyst, and the binder are integrally formed. Furthermore, when producing an air electrode, you may heat-process after the process of the above shaping
  • the hydrogen storage alloy used for the negative electrode is La-Ni alloy, La-Nd-Ni alloy, La-Gd-Ni alloy, La-Y-Ni alloy, La-Co-Ni alloy, La-Ce. -Ni alloy, La-Ni-Ag alloy, La-Ni-Fe alloy, La-Ni-Cr alloy, La-Ni-Pd alloy, La-Ni-Cu alloy, La-Ni-Al Alloy, La-Ni-Mn alloy, La-Ni-In alloy, La-Ni-Sn alloy, La-Ni-Ga alloy, La-Ni-Si alloy, La-Ni-Ge alloy La-Ni-Al-Co alloy, La-Ni-Al-Mn alloy, La-Ni-Al-Cr alloy, La-Ni-Al-Cu alloy, La-Ni-Al-Si alloy La-Ni-Al-Ti alloys, La-Ni-Al-Zr alloys Gold, La—
  • Alloys composed of combinations of two or more of Ti, Fe, Mn, Al, Ce, Ca, Mg, Zr, Nb, V, Co, Ni, and Cr elements
  • Metals that form hydrides such as Ti, V, Zr, La, Pd, and Pt (having hydrogen storage properties) or hydrides of the above alloys and metals (substances that store hydrogen) ) Can be used, but hydrogen storage and release If possible materials, but it is not particularly limited to the above composition.
  • Batteries using an alkaline aqueous solution as the electrolytic solution holder such as zinc / air primary batteries, nickel / hydrogen secondary batteries, alkaline batteries, alkaline manganese batteries, nickel / cadmium batteries, etc.
  • a separator material or the like can be used.
  • Such materials are disclosed in, for example, Japanese Patent Application Laid-Open Nos. 7-272771, 11-293564, 2007-154402, 2007-284845, 2009-224100, and Japanese Patent Publication. This is disclosed in Japanese Patent Application Laid-Open No. 2009-516781 and Japanese Patent Application Laid-Open No. 2010-70870.
  • ion permeable films such as cellophane, films such as polypropylene and polyethylene, polyvinyl alcohol fibers, cellulose fibers, polyamide fibers, polyolefin fibers, and ethylene-vinyl alcohol copolymer fibers.
  • ultrafine fibers, core-sheath type composite fibers, those subjected to hydrophilic treatment, and the like are also used.
  • the electrolytic solution holding body only needs to have a function of isolating the air electrode and the negative electrode and holding the electrolytic solution. Therefore, the electrolytic solution holding body has ion conductivity or ion permeability while holding the electrolytic solution, and has alkali resistance and electrolysis.
  • the liquid is not particularly limited as long as it has liquid absorption.
  • a metal or alloy other than a hydrogen storage alloy is used for the negative electrode. Since a short circuit does not occur, so-called separation property, which is a function intended for this, is not necessarily required for the electrolyte solution holder of the hydrogen / air secondary battery of the present invention.
  • the invention according to claim 2 is the hydrogen / air secondary battery according to claim 1, wherein the air electrode contains nickel, a pyrochlore oxide containing iridium, and a binder. It has the composition which becomes. With this configuration, in addition to the operation obtained in the first aspect, the following operation can be obtained. (1) High catalytic ability for oxygen generation and oxygen reduction is obtained by electronic and chemical interaction between the pyrochlore oxide containing iridium and nickel. Can also proceed smoothly. (2) The combination of iridium-containing pyrochlore oxide and nickel suppresses the oxidation and reduction of nickel that may occur as a side reaction at the air electrode, thereby reducing nickel consumption and carbon powder.
  • the pyrochlore oxide containing iridium is a B site in A 2 B 2 O 7-x (where ⁇ 1 ⁇ x ⁇ 1), which is a general expression representing the molar composition of the pyrochlore oxide.
  • a site element include bismuth and lead.
  • Pyrochlore oxide containing iridium is supported on nickel and / or in contact with nickel against both alkaline aqueous solution and air, and is a high catalyst for both oxygen reduction and oxygen generation Has activity.
  • a third aspect of the present invention is the hydrogen / air secondary battery according to the second aspect, wherein the pyrochlore oxide containing the iridium is a bismuth iridium oxide.
  • the pyrochlore oxide containing the iridium is a bismuth iridium oxide.
  • Bismuth iridium oxide is a simple process in which a bismuth compound such as bismuth nitrate and an iridium compound such as chloroiridic acid are used as starting materials, and a precursor material is synthesized by a method called a coprecipitation method, followed by heat treatment. Therefore, a highly active catalyst constituting the air electrode can be easily obtained.
  • the bismuth iridium oxide is an oxide represented by Bi 2 Ir 2 O 7-x in the composition formula of the pyrochlore oxide shown above.
  • those in which bismuth at the A site and / or iridium at the B site are partially substituted with other elements are also included.
  • a fourth aspect of the present invention is the hydrogen / air secondary battery according to any one of the first to third aspects, wherein the two air electrodes are disposed so as to face the negative electrode.
  • the electrolyte solution holding body is configured to be disposed between the negative electrode and each air electrode.
  • a fifth aspect of the present invention is the hydrogen / air secondary battery according to the fourth aspect, wherein at least a part of the plurality of electrolytic solution holders is immersed in the electrolytic solution in the common electrolytic solution storage unit. It has the composition which has. With this configuration, in addition to the operation obtained in the fourth aspect, the following operation can be obtained. (1) Since at least some of the plurality of electrolytic solution holders are immersed in the electrolytic solution in the common electrolytic solution storage unit, the structure of the electrolytic solution storage unit in the battery container can be simplified (2 ) Compared to the case where the electrolyte storage part is not common and is arranged for each electrolyte holder, the volume of the electrolyte storage part can be reduced, and the volume of the entire battery container is also reduced. The hit energy density and output density can be improved.
  • a sixth aspect of the present invention is the hydrogen / air secondary battery according to the fifth aspect, wherein a plurality of the electrolytic solution holders are connected in the common electrolytic solution storage unit. Yes.
  • the following operation can be obtained. (1) Since a plurality of electrolyte holders are connected in a common electrolyte storage part, the plurality of electrolyte holders are integrated with each other with respect to two or more air electrodes via the electrolyte storage part. The number of members of the electrolytic solution holder can be reduced.
  • a seventh aspect of the present invention is the hydrogen / air secondary battery according to any one of the first to sixth aspects, wherein the negative electrode and one or two of the air electrodes facing the negative electrode are provided.
  • a plurality of pairs of electrodes whose longitudinal directions are arranged in parallel with the horizontal direction are stacked in the battery container.
  • the invention according to claim 8 is the hydrogen / air secondary battery according to any one of claims 1 to 6, wherein the negative electrode and one or two of the air electrodes facing the negative electrode are provided.
  • a plurality of pairs of electrodes whose longitudinal directions are arranged in parallel with the vertical direction are arranged in parallel in the battery container.
  • the following action is obtained.
  • a plurality of electrode pairs, in which the longitudinal direction of one or two air electrodes facing the negative electrode and the negative electrode is arranged in parallel with the vertical direction, are arranged in parallel in the battery container. Maximum dischargeable current, power density, and energy density can be improved.
  • the volume occupied by the whole battery can be reduced as compared with the case where a plurality of batteries each made up of a single electrode pair are connected.
  • the electrolyte holder between the air electrode and the negative electrode from the electrolyte storage part corresponds to the decrease / increase in water between the air electrode and the negative electrode during charge / discharge.
  • the electrolyte can be supplied at a more appropriate timing, or the electrolyte can be stored at a more appropriate timing from the electrolyte holder between the air electrode and the negative electrode to the electrolyte reservoir.
  • the following advantageous effects can be obtained.
  • the first aspect of the invention the following advantageous effects can be obtained. (1) Since the increase or decrease in the amount of the electrolyte between the air electrode and the negative electrode can be adjusted by the electrolyte holder and the electrolyte storage unit, the amount of the electrolyte between the air electrode and the negative electrode can always be kept constant.
  • the battery resistance is increased by increasing the electrode reaction resistance of the negative electrode and the air electrode due to the decrease in the amount of the electrolyte between the air electrode and the negative electrode during charging, and the non-uniform reaction distribution on the electrode And a decrease in the amount of hydrogen stored in the hydrogen storage alloy of the negative electrode can be suppressed.
  • the battery resistance is increased by increasing the electrode reaction resistance of the negative electrode and the air electrode due to the decrease in the amount of the electrolyte between the air electrode and the negative electrode during charging, and the non-uniform reaction distribution on the electrode And a decrease in the amount of hydrogen stored in the hydrogen storage alloy of the negative electrode can be suppressed.
  • the density can be improved.
  • the leakage of the electrolyte and the heat generation associated with the battery reaction are suppressed, and the safety of the battery can be improved.
  • the following advantageous effects can be obtained.
  • the resistance of the air electrode during charging and discharging can be reduced as compared to the case where a pyrochlore type oxide is used.
  • bismuth iridium oxide has particularly high catalytic activity for oxygen generation and oxygen reduction, and has a high air electrode for charge / discharge cycles even at high current density and high temperature operation. Since it has durability, it becomes possible to improve the maximum current that can be charged and discharged of the battery, and it is possible to widen the operating temperature range.
  • the maximum current that can be charged / discharged by the battery is improved, so that the maximum output of the battery can be further increased.
  • a secondary battery with high safety and recyclability in a life cycle can be provided in a power source for a mobile body, a power source for an electric vehicle / hybrid vehicle, a power source for an electric motorcycle, and the like.
  • a secondary battery with high safety can be provided even when used as a power source for devices used near the human body, such as a power source for hearing aids or a power source for mobile devices.
  • a single battery can be charged / discharged at a higher current, and the polarization at the time of charging / discharging can be reduced. Therefore, the maximum current that can be charged / discharged is improved, and the energy density and output density of the battery are increased. Can be high.
  • the dead space inside the battery can be reduced compared to the case where one air electrode is disposed opposite to the negative electrode, so that the energy density and output density of the battery can be further increased. Can be improved.
  • the following advantageous effect can be obtained. (1) Since the structure of the electrolyte storage part in the battery container can be simplified and the volume thereof can be reduced, the overall volume of the battery is also reduced, and the energy density and output density per volume are high, so that it can be mounted at a high density. And high output performance.
  • the following advantageous effect is obtained.
  • the number of members of the electrolytic solution holder is small, and the amount of electrolytic solution in the electrolytic solution holder can be kept uniform with respect to the space between the plurality of air electrodes and the negative electrode. It is possible to prevent the balance of the amount of the existing electrolyte from being lost, to suppress the difference in the voltage between the electrodes, and to achieve excellent output uniformity and stability.
  • FIG. 2 is a schematic cross-sectional view of the main part of the hydrogen / air secondary battery according to Embodiment 1 of the present invention.
  • Cross-sectional schematic diagram of relevant parts of a modification of the hydrogen / air secondary battery of Embodiment 1 of the present invention Sectional schematic diagram of relevant parts of the hydrogen / air secondary battery of Embodiment 2 of the present invention
  • Sectional schematic diagram of relevant parts of a modification of the hydrogen / air secondary battery of Embodiment 2 of the present invention Cross-sectional schematic diagram of relevant parts of a hydrogen / air secondary battery according to Embodiment 3 of the present invention
  • Sectional schematic diagram of relevant parts of a hydrogen / air secondary battery according to Embodiment 4 of the present invention Sectional schematic diagram of relevant parts of a hydrogen / air secondary battery according to Embodiment 5 of the present invention
  • Sectional schematic diagram of relevant parts of a hydrogen / air secondary battery according to Embodiment 6 of the present invention The figure which shows the cycle dependence of the charge / discharge voltage of
  • FIG. 1 is a schematic cross-sectional view of the relevant part of a hydrogen / air secondary battery according to Embodiment 1 of the present invention.
  • 1 is a hydrogen / air secondary battery according to Embodiment 1 of the present invention
  • 1a is a battery container of the hydrogen / air secondary battery 1
  • 2 is bismuth iridium, which is a pyrochlore oxide containing nickel and iridium.
  • the air electrode 3 formed by mixing the oxide and the binder and horizontally disposed in the battery container 1 a is disposed horizontally in the battery container 1 a so as to face the air electrode 2.
  • Negative electrode 4 using hydrogen storage alloy, 4 is disposed between air electrode 2 and negative electrode 3, and is an electrolytic solution holder that holds an electrolytic solution that is an alkaline aqueous solution, and 5 is opposite to electrolytic solution holder 4 of air electrode 2.
  • an air passage formed in the battery case 1a so that oxygen necessary for discharge can be taken into or discharged from the air electrode 2 is formed in the battery case 1a.
  • An electrolyte storage part formed at one end in the longitudinal direction of the electrolyte holder 4 Part is immersed in the electrolyte in the electrolytic solution reservoir 6, between the electrolyte storage unit 6 and the electrolytic solution holding body 4 to flow of the electrolyte is ensured.
  • the electrolyte is increased by the water generated between the air electrode 2 and the negative electrode 3 at the time of discharge, but this is stored in the electrolyte storage unit 6 via the electrolyte holder 4, and the air is charged at the time of charging.
  • the electrolytic solution decreases due to the decomposition of water between the electrode 2 and the negative electrode 3, but this is replenished from the electrolytic solution storage unit 6 through the electrolytic solution holder 4.
  • the amount of the electrolyte solution held in the electrolyte solution holder 4 is always kept constant.
  • the electrolytic solution storage unit 6 supplies sufficient electrolytic solution to the electrolytic solution holder 4 in which the electrolytic solution decreases due to the charging reaction, and can reliably store the electrolytic solution that increases in the electrolytic solution holder 4 due to the discharge reaction. Furthermore, the volume is suitable for the charge / discharge capacity of the battery.
  • the ventilation path 5 may simply be an opening formed in the battery container 1.
  • FIG. 2 is a schematic cross-sectional view of an essential part of a modification of the hydrogen / air secondary battery according to Embodiment 1 of the present invention.
  • the hydrogen / air secondary battery 1A in the modification of the first embodiment is different from that of the first embodiment in that the two ends of the electrolytic solution holder 4 are immersed in the electrolytic solution in the battery container 1a.
  • One electrolyte storage part 6 is formed.
  • an electrolyte holding body is used at the time of discharge by utilizing a pressure increase caused by water generated between the air electrode 2 and the negative electrode 3 due to discharge and a pressure drop caused by water decreasing between the air electrode 2 and the negative electrode 3 due to charging.
  • 4 can be stored in the electrolyte storage units 6 at both ends, and the amount of electrolyte decreased by the electrolyte holder 4 can be supplied from the electrolyte storage units 6 at both ends during charging. Can do.
  • the amount of the electrolyte solution held in the electrolyte solution holder 4 is always kept constant.
  • the hydrogen / air secondary battery according to Embodiment 1 configured as described above has the following effects.
  • the battery container has an electrolyte solution storage unit that supplies an electrolyte solution that decreases due to a charging reaction or stores an electrolyte solution that increases due to a discharge reaction, and at least a part of the electrolyte solution holder is in the electrolyte solution storage unit.
  • the amount of electrolyte increased by the discharge between the air electrode and the negative electrode via the electrolyte holder is increased by the pressure increase caused by the water generated between the air electrode and the negative electrode during discharge.
  • the bismuth iridium oxide forming the air electrode is a catalytic activity for oxygen generation during charging and oxygen reduction during discharge in the air electrode, particularly in combination with nickel among pyrochlore oxides containing iridium.
  • Bismuth iridium oxide is a simple process in which a bismuth compound such as bismuth nitrate and an iridium compound such as chloroiridic acid are used as starting materials, a precursor material is synthesized by a method called a coprecipitation method, and then heat treatment is performed. Therefore, a highly active catalyst constituting the air electrode can be easily obtained.
  • FIG. 3 is a schematic cross-sectional view of the main part of the hydrogen / air secondary battery according to Embodiment 2 of the present invention
  • FIG. 4 is a cross-sectional view of the main part of a modification of the hydrogen / air secondary battery according to Embodiment 2 of the present invention. It is a schematic diagram. In FIG.
  • the hydrogen / air secondary battery 1B of the second embodiment is different from that of the first embodiment in that the air electrode 2, the negative electrode 3, and the electrolyte holding body 4 are arranged in the vertical direction.
  • the electrolyte solution storage part 6 is arrange
  • Embodiment 2 also includes an arrangement in which the electrolyte storage unit 6 is turned upside down in FIG.
  • the hydrogen / air secondary battery 1C according to the modification of the second embodiment is different from the second embodiment in that both ends of the electrolytic solution holder 4 are immersed in the electrolytic solution in the battery container 1a.
  • two electrolyte storage parts 6 are formed, which corresponds to a vertical arrangement of the hydrogen / air secondary battery 1A in the modification of the first embodiment.
  • the following functions are provided.
  • the electrolyte holder between the air electrode and the negative electrode from the electrolyte storage part corresponds to the decrease / increase in water between the air electrode and the negative electrode during charge / discharge.
  • the electrolyte can be supplied at a more appropriate timing, or the electrolyte can be stored at a more appropriate timing from the electrolyte holder between the air electrode and the negative electrode to the electrolyte reservoir.
  • FIG. 5 is a schematic cross-sectional view of the relevant part of a hydrogen / air secondary battery according to Embodiment 3 of the present invention.
  • the hydrogen / air secondary battery 1D of the third embodiment is different from the modification of the second embodiment in that two air electrodes 2 are arranged opposite to both sides of the negative electrode 3 to hold the electrolyte solution.
  • the body 4 is disposed between the negative electrode 3 and each air electrode 2.
  • the air passage 5 can be shared between the adjacent air electrodes 2.
  • the negative electrode 3, the air electrode 2, and the electrolytic solution holding body 4 are arranged in the vertical direction in the battery container 1a.
  • the structure may be arranged in the horizontal direction as in the first embodiment.
  • FIG. 6 is a schematic cross-sectional view of the relevant part of a hydrogen / air secondary battery according to Embodiment 4 of the present invention.
  • the hydrogen / air secondary battery 1E of the fourth embodiment is different from that of the third embodiment in that both ends of the two electrolyte holding bodies 4a and 4b are electrolyzed in a common electrolyte storage section 6. It is a point immersed in the liquid.
  • the air passage 5 can be shared between the adjacent air electrodes 2.
  • the negative electrode 3, the air electrode 2, and the electrolyte solution holders 4a and 4b are arranged in the vertical direction in the battery container 1a.
  • the structure may be arranged in the horizontal direction. Good.
  • FIG. 7 is a schematic cross-sectional view of the relevant part of a hydrogen / air secondary battery according to Embodiment 5 of the present invention.
  • the hydrogen / air secondary battery 1 ⁇ / b> F of the fifth embodiment is different from the fourth embodiment in that two electrolyte solution holders 4 a and 4 b are connected by a connecting portion 4 c in a common electrolyte storage unit 6. It is an integrated point.
  • the electrolytic solution holders 4a and 4b and the connection portion 4c may be integrated as a matter of course.
  • the structure of FIG. 7 can be set as one set, and a plurality of sets can be arranged in parallel in one battery container 1a.
  • the air passage 5 can be shared between the adjacent air electrodes 2.
  • the negative electrode 3, the air electrode 2, and the electrolytic solution holders 4a and 4b are arranged in the vertical direction in the battery container 1a.
  • the structure may be arranged in the horizontal direction. Good.
  • the hydrogen / air secondary battery in the fifth embodiment configured as described above, in addition to the functions in the fourth embodiment, the following functions are provided.
  • FIG. 8 is a schematic cross-sectional view of the relevant part of a hydrogen / air secondary battery according to Embodiment 6 of the present invention.
  • the hydrogen / air secondary battery 1G of the sixth embodiment is different from that of the fifth embodiment in that the two airs facing the negative electrode 3 and the negative electrode 3 in the hydrogen / air secondary battery 1F of the fifth embodiment.
  • all the electrolytic solution holders 4a and 4b are connected by the connecting portions 4c and 4d, and are immersed in the electrolytic solution by the common electrolytic solution storage unit 6.
  • the configurations of 3 to 5 hydrogen / air secondary batteries 1D to 1F may be arranged in the battery container 1a. Further, in the present embodiment, the case where the number of electrode pairs arranged in parallel in the battery container 1a is two has been described, but the number of electrode pairs can be appropriately selected.
  • the negative electrode 3, the air electrode 2, and the electrolyte solution holders 4a and 4b are arranged in the vertical direction in the battery container 1a, the structure may be arranged in the horizontal direction as in the first embodiment.
  • the electrolytic solution holders 4a and 4b and the connection portions 4c and 4d may be integrated as well.
  • the following functions are provided.
  • (1) Maximum discharge as a unit cell is possible by arranging two pairs of electrode pairs in which the negative electrode and the two air electrodes facing the negative electrode are arranged in parallel in the vertical direction in the battery container Current, power density, and energy density can be improved.
  • the pressure increases due to water generated between the air electrode and the negative electrode by discharge, and the pressure decrease due to water that decreases between the air electrode and the negative electrode due to charging, and gravity.
  • the electrolyte holder between the air electrode and the negative electrode from the electrolyte storage part corresponds to the decrease / increase in water between the air electrode and the negative electrode during charge / discharge.
  • the electrolyte can be supplied at a more appropriate timing, or the electrolyte can be stored at a more appropriate timing from the electrolyte holder between the air electrode and the negative electrode to the electrolyte reservoir.
  • Example 1 Bi (NO 3 ) 3 ⁇ 5H 2 O and H 2 IrCl 6 ⁇ 6H 2 O are dissolved in 75 ° C. distilled water so as to have the same concentration, stirred and mixed, and then added with a 2 mol / L NaOH aqueous solution. It was. At that time, the bath temperature was 75 ° C., and the mixture was stirred for 3 days while carrying out oxygen bubbling. The solution containing the precipitate formed thereby was kept at 85 ° C. and evaporated to dryness to obtain a paste. The paste-like material was transferred to an evaporating dish, dried at 120 ° C.
  • the mixture is made into a clay and then dried at room temperature for about 30 minutes, and then pressed into a disk shape (diameter: 13 mm, thickness: 0.3 mm) at 100 kg / cm 2 on a nickel mesh as a current collector. After that, heat treatment was performed in a nitrogen atmosphere at 370 ° C. for 13 minutes to produce an air electrode.
  • Hydrogen storage alloy (MmNi 4.10 Mn 0.40 Al 0.10 Co 0.50 , capacity density 310 mAh / g), nickel powder (purity 99.8%, average particle size 3-7 ⁇ m) and polyethylene in a weight ratio of 2 : 3: After mixing at 0.12, press-molded into a disk shape at 5 t / cm 2 and further heat-treated at 150 ° C. for 60 minutes in a vacuum heating furnace to obtain a negative electrode (theoretical capacity: 31 mAh) having almost the same area as the air electrode. Produced. A nickel ribbon was resistance-welded to the negative electrode as a lead.
  • FIG. 1 A hydrogen / air secondary battery having a structure was prepared using PTFE (polytetrafluoroethylene) as a material for a battery container.
  • PTFE polytetrafluoroethylene
  • a space serving as an electrolytic solution storage unit was disposed, and 5 mL of the electrolytic solution was injected into the space.
  • the area of the electrolytic solution holder is larger than that of the air electrode and the negative electrode, and a part of the electrolytic solution holder is immersed in the electrolytic solution in the electrolytic solution storage unit.
  • a nickel wire was used for the lead of the air electrode.
  • Example 1 The same hydrogen / air secondary battery as that of Example 1 was manufactured except that the battery container was not provided with a space serving as an electrolyte solution storage unit, and the electrolyte solution holding body had almost the same area as the air electrode and the negative electrode. In addition, the electrolyte solution hold
  • FIG. 9 shows the results of charging and discharging the batteries of Example 1 and Comparative Example 1 at room temperature and 2 mA, and recording the battery voltage during charging and discharging.
  • the horizontal axis represents the number of charge / discharge cycles (times), and the vertical axis represents the battery voltage (V) during discharge and charge.
  • charge / discharge of 300 cycles or more was possible, and a stable voltage with an average discharge voltage of 0.9 to 0.73 V (see white circle) and an average charge voltage of 1.5 V (see gray circle) was shown.
  • Comparative Example 1 the initial charge / discharge test showed substantially the same discharge voltage and charge voltage as in Example 1 (see white squares and gray squares), but the charge / discharge was completed in 10 cycles, and 11 cycles.
  • FIG. 2 shows the air electrode and negative electrode, a commercially available alkaline battery separator (manufactured by Yuasa Membrane Systems Co., Ltd., Yumigrapher) and a nonwoven fabric as the electrolyte holder, and a 7 mol / L KOH aqueous solution as the electrolyte.
  • a hydrogen / air secondary battery having the structure described above was fabricated using PTFE (polytetrafluoroethylene) as a material for the battery container.
  • PTFE polytetrafluoroethylene
  • a space serving as an electrolytic solution storage unit was disposed, and 5 mL of the electrolytic solution was injected into the space.
  • the area of the electrolytic solution holder is larger than that of the air electrode and the negative electrode, and a part of the electrolytic solution holder is immersed in the electrolytic solution in the electrolytic solution storage unit.
  • a nickel wire was used for the lead of the air electrode.
  • Example 2 The same hydrogen / air secondary battery as that of Example 2 was manufactured except that the battery container was not provided with a space serving as an electrolyte solution storage unit, and the electrolyte solution holding body had almost the same area as the air electrode and the negative electrode. In addition, the electrolyte solution hold
  • FIG. 10 shows the results of recording the battery voltage during discharge when the batteries of Example 2 and Comparative Example 2 were charged and discharged at room temperature and a constant current.
  • Example 2 is 50 mA
  • Comparative Example 2 is 30 mA.
  • discharge for 10 hours was possible with respect to discharge at 50 mA, and a stable discharge voltage was obtained.
  • Comparative Example 2 the discharge time was 7.5 hours despite discharge at a lower current than that in Example 2.
  • the discharge electricity amount of Example 2 was 508 mAh
  • the discharge electricity amount of Comparative Example 2 was 219 mAh
  • Example 2 was able to discharge twice or more that of Comparative Example 2.
  • Example 2 The volume energy density was 308 Wh / L in Example 2 and 115 Wh / L in Comparative Example 2. In Example 2, the energy density was improved 2.7 times compared to Comparative Example 2. In addition, as a result of measuring the maximum dischargeable current value with a dischargeable limit voltage at which a stable discharge voltage can be obtained being 0.1 V, Example 2 is 600 mA and Comparative Example 2 is 150 mA. In Example 2, the maximum dischargeable current value was improved four times. Further, the utilization rate of the hydrogen storage alloy for the negative electrode was 84% in Example 2 and 29% in Comparative Example 2, and the utilization rate was improved about 3 times.
  • the present invention suppresses a large change in voltage during charging and discharging, is excellent in charge / discharge cycle characteristics, has no electrolyte leakage, and is excellent in rechargeability and durability.
  • Hydrogen / air secondary with excellent operational stability, high quality, and long life that can perform stable charge and discharge even when the battery capacity is large or when the discharge current or charge current is large.
  • batteries for mobile devices such as personal computers, mobile phones, portable music players, portable video players, and portable book terminals, electric work machines such as electric cars, hybrid cars, electric bikes, electric bicycles, excavators, and electric construction Power or auxiliary batteries for machinery, etc., batteries for power storage and output regulation of fuel cells for automobiles, households, businesses, and industries, solar power generation, wind power generation, hydroelectric power generation, raw power generation It can be used, such as the power storage and output adjustment batteries such as power generation.
  • mobile devices such as personal computers, mobile phones, portable music players, portable video players, and portable book terminals
  • electric work machines such as electric cars, hybrid cars, electric bikes, electric bicycles, excavators, and electric construction Power or auxiliary batteries for machinery, etc.
  • batteries for power storage and output regulation of fuel cells for automobiles, households, businesses, and industries solar power generation, wind power generation, hydroelectric power generation, raw power generation It can be used, such as the power storage and output adjustment batteries such as power generation.

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  • Engineering & Computer Science (AREA)
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  • Chemical & Material Sciences (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne un élément secondaire à air ayant une excellente durabilité et d'excellentes propriétés de cycle de charge/décharge électrique. Un élément secondaire à hydrogène/air comprend : une électrode d'air qui est disposée à l'intérieur d'un conteneur d'élément ; une électrode négative qui est disposée à l'intérieur du conteneur d'élément afin de se trouver en face de l'électrode d'air et qui utilise un alliage absorbant l'hydrogène ; et un corps de rétention d'électrolyte qui est disposé entre l'électrode d'air et l'électrode négative et qui retient l'électrolyte. L'élément secondaire comporte, à l'intérieur du conteneur d'élément, une section de stockage d'électrolyte qui assure une alimentation en électrolyte décroissante du fait d'une réaction de charge et qui assure un stockage d'électrolyte croissant du fait d'une réaction de décharge, au moins une partie du corps de rétention d'électrolyte étant plongée dans l'électrolyte dans la section de stockage d'électrolyte.
PCT/JP2011/069549 2010-09-16 2011-08-30 Élément secondaire à hydrogène/air WO2012035968A1 (fr)

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JP5943194B2 (ja) * 2011-04-27 2016-06-29 住友化学株式会社 空気二次電池用正極触媒及び空気二次電池
GB201213832D0 (en) * 2012-08-03 2012-09-19 Johnson Matthey Plc Cathode
JP6761655B2 (ja) * 2016-03-29 2020-09-30 Fdk株式会社 空気二次電池
JP2018055810A (ja) * 2016-09-26 2018-04-05 Fdk株式会社 空気二次電池用の空気極、この空気極を含む空気−水素二次電池
JP7149525B2 (ja) * 2019-02-04 2022-10-07 Fdk株式会社 空気二次電池用の空気極触媒及び空気二次電池
JP2020202155A (ja) * 2019-06-13 2020-12-17 Fdk株式会社 空気二次電池用の空気極及び空気二次電池
JP7299449B2 (ja) * 2019-11-12 2023-06-28 Fdk株式会社 空気二次電池用の空気極及びこの空気極を含む空気二次電池

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