WO2012111134A1 - Filter and air cell - Google Patents

Filter and air cell Download PDF

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Publication number
WO2012111134A1
WO2012111134A1 PCT/JP2011/053421 JP2011053421W WO2012111134A1 WO 2012111134 A1 WO2012111134 A1 WO 2012111134A1 JP 2011053421 W JP2011053421 W JP 2011053421W WO 2012111134 A1 WO2012111134 A1 WO 2012111134A1
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WO
WIPO (PCT)
Prior art keywords
acid
film
filter
chelate
positive electrode
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PCT/JP2011/053421
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French (fr)
Japanese (ja)
Inventor
匡昭 佐々
吉田　賢介
山本　保
田中　努
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富士通株式会社
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Priority to PCT/JP2011/053421 priority Critical patent/WO2012111134A1/en
Publication of WO2012111134A1 publication Critical patent/WO2012111134A1/en

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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
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
    • 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 relates to a filter and an air battery having the filter.
  • lithium ion secondary batteries are used as storage batteries for mobile phones, mobile personal computers, electric vehicles, etc., but when considering the energy density and volumetric energy density, the energy density is still not sufficient. Therefore, a metal-air secondary battery that can make the theoretical capacity of the battery larger than that of the lithium ion secondary battery has attracted attention.
  • each of the positive electrode and the negative electrode includes an active material that is a source of an oxidation-reduction reaction.
  • Each active material of the positive electrode and the negative electrode undergoes a chemical reaction to release energy. By taking out the released energy as electric energy, the function as a battery is developed.
  • the metal-air secondary battery has a metal as a negative electrode active material in the negative electrode, but utilizes oxygen in the atmosphere existing outside the battery as the positive electrode active material. For this reason, the weight of the positive electrode active material is zero despite the infinite number of positive electrode active materials. Accordingly, the metal-air secondary battery can significantly increase the weight energy density and the volume energy density compared to the conventional battery such as a lithium ion secondary battery, thereby making the battery lighter and smaller. Is possible.
  • the metal-air secondary battery uses oxygen as a positive electrode active material, oxygen needs to enter and exit inside and outside the battery. For this reason, a gas exchange port is provided in a portion of the battery that faces the atmosphere of the positive electrode. However, not only can air be taken in, but the electrolyte inside the battery can leak. Further, metal ions constituting the catalyst are dissolved in the leaked electrolyte. The metal ions block the gas exchange port (hereinafter also referred to as “air hole”), leading to deterioration of the performance of the air battery. Therefore, for example, in order to prevent leakage from the inside of the battery, a method of pressure bonding a multilayer film made of a fluororesin has been proposed (see Patent Document 1). However, in this proposal, in the unlikely event that the liquid leaks, the electrolyte solution contains metal ions, which may block the gas exchange port and cause a failure. Furthermore, there is a problem that metal ions have an adverse effect on the human body and the environment.
  • an object of the present invention is to provide a filter capable of reliably trapping metal ions and preventing leakage of metal ions even when electrolyte solution leaks from the inside of the battery, and an air battery having the filter.
  • the disclosed filter includes a chelate film containing a chelate substance capable of forming a complex with a metal ion contained in a battery electrolyte; An adsorbing film containing an adsorbing material capable of adsorbing a complex formed from the metal ion and the chelating substance, and an acidic solid substance capable of lowering the hydrogen ion concentration of the electrolytic solution by reacting with the electrolytic solution And at least one of a solid film.
  • the disclosed air battery has the disclosed filter.
  • the disclosed filter it is possible to solve the above-described problems and achieve the above-mentioned object, and even if the electrolyte leaks from the inside of the battery, the metal ions are reliably trapped to prevent the metal ions from leaking out. can do.
  • FIG. 1 is a schematic cross-sectional view showing an example of the air battery of the present invention.
  • the filter of the present invention includes a chelate film and at least one of an adsorption film and an acidic solid film, and further includes other members as necessary.
  • the filter preferably includes the adsorption film and the chelate film, and has the adsorption film, the chelate film, and the acidic solid film in terms of the trap effect of metal ions in the electrolyte of the air battery. More preferably, it is particularly preferable to have the adsorption film, the chelate film, and the acidic solid film in this order from the outside (from the positive electrode case side when mounted in an air battery). Since the air battery is a battery using oxygen in the air as a positive electrode active material, a gas exchange port for taking air into the positive electrode surface of the battery is provided in the positive electrode case. However, not only can air be taken in from the gas exchange port, but the electrolyte inside the battery can also leak.
  • metal ions constituting the positive electrode catalyst and the like are dissolved.
  • the metal ions block the gas exchange port and lead to deterioration of the performance of the air battery.
  • Metal ions also have an adverse effect on the human body and the environment.
  • a filter is provided inside the gas exchange port inside the battery, that is, in the path through which the electrolyte solution leaks, and the filter is externally connected to the positive electrode (when installed in an air battery) in terms of the trap effect of metal ions. It is particularly preferable to have the adsorption film, the chelate film, and the acidic solid film in this order from the case side.
  • the chelate film contains a chelate substance, and further contains other components as necessary.
  • the chelate film preferably has a base material.
  • the chelating substance is not particularly limited as long as it is a substance capable of forming a complex with a metal ion contained in an electrolyte solution of an air battery, and can be appropriately selected depending on the purpose.
  • ASDA L-asparagine Acid-N, N-2acetic acid
  • CyDTA trans-cyclohexanediaminetetraacetic acid
  • CP carbboxymethylpolyethyleneimine
  • DTPA diethylenetriaminehexaacetic acid
  • DPTA-OH (1,3-diamino-2-hydroxypropane4)
  • Acetic acid DHEG (dihydroxyethyl glycine), DHEDDA (dihydroxyethyl ethylenediamine diacetic acid), EDTA (ethylenediamine tetraacetic acid), EDTMP (ethylenediamine 4-methylene phosphoric acid), GEDTA (glycol ether diamine tetraacetic acid), HEDP (hydroxye
  • EDTA ethylenediaminetetraacetic acid
  • the chelate substance such as EDTA causes a complex formation reaction with the metal ion M n + in the electrolytic solution as shown in the following reaction formula to form a metal chelate complex, and the ion radius of the metal ion is increased. Further, the metal chelate complex is safer to the human body than the metal ion. Therefore, even if the electrolyte containing the metal chelate complex leaks out of the battery system, it is safer than the electrolyte containing the metal ions themselves.
  • the other components are not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include solvents and dispersants.
  • examples of the solvent include water, methanol, ethanol, propanol and the like.
  • paper such as filter paper, kraft paper, vinylon mixed paper, synthetic pulp mixed paper, synthetic paper, cellophane, polyethylene graft
  • examples include membranes, polyolefin nonwoven fabrics such as polypropylene melt blown nonwoven fabric, polyamide nonwoven fabrics, glass fiber nonwoven fabrics, and synthetic resin sheets (films).
  • the average thickness of the substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 10 ⁇ m to 500 ⁇ m.
  • the base material such as filter paper
  • the base material is a solution in which a chelating substance such as EDTA is dissolved in a solvent such as ethanol. It can be made by impregnation and drying.
  • the average thickness of the chelate film is preferably 50 ⁇ m to 500 ⁇ m, more preferably 100 ⁇ m to 400 ⁇ m. If the average thickness is less than 50 ⁇ m, the chelate film is too thin and the amount of chelate substance decreases, so that a sufficient chelate effect may not be obtained. If the average thickness exceeds 500 ⁇ m, the chelate film is too thick. , May block the passage of air.
  • the adsorbing film contains an adsorbing substance, and further contains other components as necessary.
  • the adsorption film preferably has a base material.
  • the adsorbing substance is not particularly limited as long as at least one of the surface and the inside of the substance has a porous structure, and can be an organic substance or an inorganic substance that can adsorb the complex formed from the metal ion and the chelate substance. It can be appropriately selected depending on the purpose, and examples thereof include activated carbon, zeolite, silica gel and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, activated carbon is particularly preferable because it has high adsorption power and is inexpensive. Since the diameter of the metal chelate complex formed from the chelate substance and metal ions is about 0.5 nm, it is easily adsorbed by an adsorbent such as activated carbon. On the other hand, since the metal ion has a small diameter of 0.1 nm to 0.2 nm, it is not adsorbed by an adsorbent such as activated carbon.
  • the other components are not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include solvents and dispersants.
  • examples of the solvent include water, methanol, ethanol, propanol and the like.
  • the same one as the chelate film can be used.
  • the method for producing the adsorption film is not particularly limited and can be appropriately selected according to the purpose.
  • a slurry in which a substrate such as filter paper is dissolved in an adsorbent such as activated carbon in a solvent such as propanol can be prepared by applying and drying.
  • the average thickness of the adsorption film is preferably 50 ⁇ m to 500 ⁇ m, more preferably 100 ⁇ m to 400 ⁇ m. If the average thickness is less than 50 ⁇ m, the adsorbing film is too thin and the amount of adsorbing material decreases, so that a sufficient adsorbing effect may not be obtained. If the average thickness exceeds 500 ⁇ m, the adsorbing film is too thick. , May block the passage of air.
  • the acidic solid film contains an acidic solid substance, and further contains other components as necessary.
  • the acidic solid film preferably has a base material.
  • the acidic solid substance is a substance that can react with the electrolytic solution of the air battery to lower the hydrogen ion concentration of the electrolytic solution, and can be reduced to a hydrogen ion concentration of less than 7 when dissolved in an aqueous solution.
  • the substance is not particularly limited as long as it is a substance composed of a weak base and a strong acid, and can be appropriately selected according to the purpose. Examples thereof include ammonium chloride, ammonium sulfate, ammonium nitrate, and ⁇ -alumina / silica. These may be used individually by 1 type and may use 2 or more types together.
  • ammonium chloride is particularly preferable because it has a high effect of reducing the hydrogen ion concentration and can be obtained at low cost.
  • the acidic solid membrane reacts with the electrolytic solution in the air battery, and the hydrogen ion concentration of the electrolytic solution decreases.
  • the other components are not particularly limited and may be appropriately selected depending on the intended purpose.
  • examples thereof include solvents and dispersants.
  • examples of the solvent include water, methanol, ethanol, propanol and the like.
  • the same one as the chelate film can be used.
  • the method for producing the acidic solid film is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a base material such as filter paper is dissolved, and an acidic solid substance such as ammonium chloride is dissolved in a solvent such as water. It can be prepared by impregnating with an aqueous solution and drying.
  • the average thickness of the acidic solid film is preferably 50 ⁇ m to 500 ⁇ m, more preferably 100 ⁇ m to 400 ⁇ m. When the average thickness is less than 50 ⁇ m, the acidic solid film is too thin and the amount of the acidic solid substance is reduced, so that a sufficient hydrogen ion concentration lowering effect may not be obtained. The solid film may be too thick and block the air passage.
  • the filter of the present invention is produced by superposing the adsorption film, the chelate film, and the acidic solid film.
  • the adsorption film, the chelate film, and the acidic solid film are disposed so as to overlap with the positive electrode case.
  • the adsorption film, the chelate film, and the acidic solid film are overlapped, it is not necessary to bond them with an adhesive or the like, but they may be bonded using an adhesive or the like as necessary. Absent.
  • the average thickness of the filter is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100 ⁇ m to 1,500 ⁇ m.
  • the filter of the present invention can be used in various air batteries because it can reliably trap metal ions and prevent metal ions from leaking out even when electrolyte solution leaks from the inside of the air battery. It is particularly preferably used as an industrial filter.
  • the air battery of the present invention includes the filter of the present invention, and further includes other members as necessary.
  • the air battery may be an air primary battery or an air secondary battery, but an air secondary battery is particularly preferable from the viewpoint of charge and discharge.
  • the air battery preferably includes a positive electrode case, a positive electrode catalyst, a separator, a negative electrode active material, and a negative electrode case, and the filter of the present invention is provided between the positive electrode case and the positive electrode catalyst. It is particularly preferable in terms of the trapping effect of metal ions that the filter is arranged so that the adsorption film, the chelate film, and the acidic solid film are arranged in this order from the positive electrode case side.
  • the positive electrode case of the present invention has a metal member in which an air hole through which air enters and exits is formed, and further includes other members as necessary.
  • the positive electrode case also serves as a positive electrode terminal.
  • the metal member is not particularly limited as long as it is a metal member in which air holes through which air enters and exits are formed, and can be appropriately selected according to the purpose.
  • Examples of the material of the metal member include a metal obtained by plating copper, stainless steel, stainless steel, or iron with nickel or the like.
  • Examples of the shape of the metal member include a shallow dish shape with a curved base, a bottomed cylindrical shape, and a bottomed prismatic shape.
  • the size of the metal member is not particularly limited as long as it is a size that can be used for an air battery, and can be appropriately selected according to the purpose.
  • the structure of the metal member may be a single layer structure or a laminated structure.
  • the metal member usually has the air holes at the bottom.
  • the number of the air holes may be one or plural.
  • size of the opening part of the said air hole According to the objective, it can select suitably.
  • the method for producing the air holes in the metal member is not particularly limited and may be appropriately selected depending on the purpose. For example, a method for producing an air hole by punching a metal member with a mold, a metal wire A method of simultaneously producing a metal member having a predetermined shape and an air hole by weaving and forming a mesh.
  • ⁇ Cathode catalyst> There is no restriction
  • the material of the positive electrode catalyst include pyrochlore type metal oxides, oxygen-deficient pyrochlore type metal oxides, acetylene black, ketjen black, and mixtures of activated carbon and manganese oxides such as manganese dioxide.
  • pyrochlore type metal oxides and oxygen-deficient pyrochlore type metal oxides are preferable, and pyrochlore type metal oxides are particularly preferable.
  • the pyrochlore-type metal oxide is not particularly limited and may be appropriately selected depending on the purpose, for example, Bi 2 Ru 2 O 7, Pb 2 Ru 2 O 6, and Pb 2 Ir 2 O 6.5 At least one selected from is preferred.
  • the shape of the positive electrode catalyst includes, for example, a sheet shape.
  • the method for forming the positive electrode catalyst into a sheet is not particularly limited and can be appropriately selected depending on the purpose.
  • Examples include a method in which manganese oxide, expanded graphite as a conductive material, and polytetrafluoroethylene powder as a binder are mixed and molded into a sheet shape.
  • Electrolyte solution containing an organic solvent and electrolyte, an ionic liquid, etc. are mentioned.
  • the electrolytic solution a non-aqueous electrolytic solution containing no water is preferable.
  • Organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples thereof include carbonate organic solvents such as cyclic carbonates and chain carbonates, ester organic solvents such as cyclic esters and chain esters,
  • Examples include ether organic solvents such as cyclic ethers and chain ethers. These may be used individually by 1 type and may use 2 or more types together. Among these, carbonate-based organic solvents are preferable in terms of high electrolyte dissolving power.
  • the cyclic carbonate include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), and the like.
  • Examples of the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate.
  • Examples of the cyclic ester include ⁇ -butyrolactone ( ⁇ BL), 2-methyl- ⁇ -butyrolactone, acetyl- ⁇ -butyrolactone, and ⁇ -valerolactone.
  • Examples of the chain ester include propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester.
  • Examples of the cyclic ether include tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, 1,4-dioxolane and the like.
  • Examples of the chain ether include 1,2-dimethoxyethane (DME), diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, and tetraethylene glycol dialkyl ether.
  • the electrolyte is not particularly limited and may be appropriately selected depending on the purpose.
  • an alkaline aqueous solution such as a potassium hydroxide aqueous solution or a sodium hydroxide aqueous solution containing zinc oxide is used.
  • An aqueous solution containing zinc chloride or zinc perchlorate may be used, a non-aqueous solvent containing zinc perchlorate, or a non-aqueous solvent containing zinc bis (trifluoromethylsulfonyl) imide.
  • a lithium salt is preferable in that the ion size is small and the system becomes simple when lithium is used for the negative electrode active material.
  • lithium salt examples include lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium arsenic hexafluoride (LiAsF 6 ), and trifluorometasulfone.
  • lithium acid LiCF 3 SO 3
  • lithium bistrifluoromethylsulfonylimide LiN (C 2 F 5 SO 2 ) 2
  • lithium bisfurfluoroethylsulfonylimide LiN (CF 2 F 5 SO 2 ) 2
  • the concentration of the electrolyte is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 mol / L to 3 mol / L in terms of ionic conductivity in the organic solvent. .
  • the ionic liquid is not particularly limited as long as it is an ionic substance in a molten state at room temperature (25 ° C.), and can be appropriately selected according to the purpose.
  • the ionic liquid is a salt of a cation and an anion.
  • the cation include imidazolium, ammonium, pyridinium, piperidinium, and the like.
  • the imidazolium include 1-ethyl-3-methylimidazolium (EMI), 1-methyl-3-octylimidazolium (MOI), and the like.
  • Examples of the ammonium include tetrabutylammonium.
  • Examples of the pyridinium include 1-butyl-3-methylpyridinium and 1-butylpyridinium.
  • Examples of the piperidinium include 1-ethyl-1-methylpiperidinium.
  • Examples of the anions include imide anions such as bis (trifluoromethylsulfonyl) imide (TFSI) and bis (pentafluoroethylsulfonyl) imide (BETI), and inorganic anions such as tetrafluoroborate, perchlorate, and halogen anions. Can be mentioned.
  • the material of the current collector is not particularly limited as long as it is formed of a conductive material, and can be appropriately selected according to the purpose. Examples thereof include stainless steel, nickel, aluminum, and copper. It is done.
  • the shape of the current collector is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a net-like or mesh-like porous body from the viewpoint of promptly diffusing oxygen.
  • the size of the current collector is not particularly limited as long as it is a size that can be used for the air battery, and can be appropriately selected according to the purpose.
  • the structure of the current collector is preferably a structure in which the surface thereof is coated with a coating of an oxidation-resistant metal or alloy from the viewpoint of suppressing oxidation.
  • the negative electrode active material is not particularly limited as long as it can occlude and release metal ions. It can be appropriately selected according to the purpose.
  • the metal ions are preferably alkali metal ions or alkaline earth metal ions, Zn ions, Al ions, and Fe ions.
  • the alkali metal ions include Li ions, Na ions, K ions, and the like.
  • the alkaline earth metal ions include Mg ions and Ca ions.
  • Zn ions are particularly preferable.
  • the negative electrode active material examples include simple metals, alloys, metal oxides, and metal nitrides.
  • the negative electrode layer may contain only the negative electrode active material, or may contain at least one of a conductive material and a binder in addition to the negative electrode active material.
  • a negative electrode layer containing only the negative electrode active material can be obtained.
  • a negative electrode layer having at least one of a conductive material and a binder can be obtained.
  • the conductive material include a carbon material. Examples of the carbon material include graphite, acetylene black, carbon nanotube, carbon fiber, and mesoporous carbon.
  • the binder is not particularly limited and may be appropriately selected depending on the intended purpose.
  • fluorine-based binders such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), and polytetrafluoroethylene (PTFE).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVdF Polyvinylidene fluoride
  • EPBR ethylene-propylene-butadiene rubber
  • SBR styrene-butadiene rubber
  • CMC carboxymethylcellulose
  • fluorine-based binders such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE) are particularly preferable.
  • ⁇ Negative electrode case> There is no restriction
  • the material of the negative electrode case include copper, stainless steel, stainless steel, or metal obtained by plating nickel or the like on iron.
  • Examples of the shape of the negative electrode case include a shallow dish having a curved base, a bottomed cylindrical shape, and a bottomed prismatic shape.
  • the size of the negative electrode case is not particularly limited as long as it is a size that can be used for the air battery, and can be appropriately selected according to the purpose.
  • the negative electrode case may have a single layer structure or a laminated structure. Examples of the laminated structure include a three-layer structure of nickel, stainless steel, and copper.
  • ⁇ Separator> There is no restriction
  • the material of the separator include paper such as kraft paper, vinylon mixed paper and synthetic pulp mixed paper, cellophane, polyethylene graft film, polyolefin nonwoven fabric such as polypropylene melt blown nonwoven fabric, polyamide nonwoven fabric, and glass fiber nonwoven fabric.
  • Examples of the shape of the separator include a sheet shape.
  • the size of the separator is not particularly limited as long as it is a size that can be used for the air battery, and can be appropriately selected according to the purpose.
  • the separator may have a single layer structure or a laminated structure.
  • the gasket is not particularly limited as long as it is a material that can maintain insulation between the positive electrode case and the negative electrode case, and can be appropriately selected according to the purpose.
  • a polyester resin such as polyethylene terephthalate
  • fluorine resins such as polytetrafluoroethylene, polyphenylene sulfide resins, polyetherimide resins, and polyamide resins.
  • FIG. 1 is a schematic sectional view showing a coin-shaped air battery 20.
  • the air battery 20 includes a positive electrode case 1 having an air hole 10, the filter 11 (adsorption film 4, chelate film 5, acidic solid film 6) of the present invention, a positive electrode catalyst 7, a separator 8, a negative electrode active material 9, and a negative electrode.
  • the case 3 is overlapped, and the positive electrode case 1 and the negative electrode case 3 are sealed with a gasket 2.
  • the filter 11, the positive electrode catalyst 7, the separator 8, and the negative electrode active material 9 are immersed in an electrolytic solution (not shown).
  • the shape of the air battery of the present invention is not particularly limited and can be appropriately selected depending on the purpose.
  • the air battery of the present invention can reliably trap metal ions and prevent the metal ions from leaking even if the electrolyte leaks from the inside of the battery, it can be used for mobile devices such as mobile phones and laptop computers. It can be widely used in small electronic devices, hearing aids, hybrid vehicles, electric vehicles, distributed household power supplies, distributed business power supplies, power storage batteries, and the like.
  • Example 1 -Preparation of filter- Apply a slurry of 10% by mass normal propyl alcohol (manufactured by Kanto Chemical Co., Inc.) of activated carbon (trade name: Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.) to filter paper (thickness 0.1 mm, diameter 18 mm), and dry. An adsorption film having an average thickness of 350 ⁇ m was produced. Filter paper (thickness 0.1 mm, diameter 18 mm) was impregnated with a 1% by mass ethanol solution of EDTA (manufactured by Kanto Chemical Co., Ltd.) and dried to produce a chelate film having an average thickness of 350 ⁇ m.
  • EDTA manufactured by Kanto Chemical Co., Ltd.
  • a filter paper (thickness 0.1 mm, diameter 18 mm) was impregnated with a 1% by weight aqueous solution of ammonium chloride (manufactured by Kanto Chemical Co., Ltd.) and dried to prepare an acidic solid film having an average thickness of 350 ⁇ m.
  • the produced adsorption film, chelate film, and acidic solid film were superposed in this order to produce the filter of Example 1.
  • Example 2 Preparation of filter-
  • a filter of Example 2 composed of a chelate film and an acidic solid film was produced in the same manner as Example 1 except that it did not have an adsorption film.
  • Example 3 Preparation of filter-
  • a filter of Example 3 comprising an adsorption film and a chelate film was produced in the same manner as in Example 1 except that the acidic solid film was not provided.
  • Example 4 Preparation of filter-
  • the filter of Example 4 was produced in the same manner as in Example 1 except that the activated carbon in the adsorption film was replaced with zeolite (trade name: Molecular Sieve 5A, manufactured by Wako Pure Chemical Industries, Ltd.). .
  • zeolite trade name: Molecular Sieve 5A, manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 5 Preparation of filter- Example 5 was the same as Example 1 except that EDTA in the chelate film was changed to ASDA (trade names: L-aspartic acid N, N-2 acetic acid, manufactured by Mitsubishi Rayon Co., Ltd.). A filter was prepared.
  • ASDA trade names: L-aspartic acid N, N-2 acetic acid, manufactured by Mitsubishi Rayon Co., Ltd.
  • Example 6 Preparation of filter- A filter of Example 6 was produced in the same manner as in Example 1 except that ammonium chloride in the acidic solid film was replaced with ammonium sulfate (trade name: ammonium sulfate, manufactured by Kanto Chemical Co., Inc.).
  • Comparative Example 1 Preparation of filter- Carbon paper (manufactured by Toray International Co., Ltd., TGP-H-120, thickness 350 ⁇ m) was used as the filter of Comparative Example 1.
  • Comparative Example 2 (Comparative Example 2) -Preparation of filter-
  • a filter of Comparative Example 2 consisting only of a chelate film was produced in the same manner as Example 1 except that it did not have an adsorption film and an acidic solid film.
  • Example 7 -Fabrication of air battery- A coin battery (air battery) (size 2032, made of stainless steel) shown in FIG. 1 was produced using the filter of Example 1. - cathode catalyst as Bi 2 Ru 2 O 7 was used (high purity Chemical Co., Ltd.). An anion exchange membrane (manufactured by Tokuyama Corporation) was used as a separator. -As a positive electrode cover, four air holes with a diameter of 1 mm for gas exchange ports were provided. -Zinc paste (a mixture of 66 mass% Zn powder and KOH electrolyte) was used as the negative electrode active material.
  • the air battery 20 includes a positive electrode case 1 having an air hole 10, a filter 11 (adsorption film 4, chelate film 5, and acidic solid film 6), a positive electrode catalyst 7, a separator 8, a negative electrode active material 9, and a negative electrode case. 3 were stacked and the positive electrode case 1 and the negative electrode case 3 were sealed with a gasket (O-ring) 2 to assemble the air battery 20.
  • a gasket O-ring
  • Example 8 to 14 and Comparative Examples 3 to 6 -Fabrication of air battery- In Example 7, coin batteries (air batteries) of Examples 8 to 14 and Comparative Examples 3 to 6 were obtained in the same manner as Example 7 except that the combinations of the filter and the positive electrode catalyst were changed to those shown in Table 2. Produced.
  • the air cells of Examples 7 and 10 to 14 using the three-layer filter composed of the adsorption film of Example 1 and Examples 4 to 6, the chelate film, and the acidic solid film are Metal ions were not contained in the electrolyte solution after the accelerated deterioration test.
  • the air batteries of Comparative Examples 3 to 6 using the filters of Comparative Examples 1 and 2 were found to contain metal ions in the electrolytic solution after the accelerated deterioration test.
  • the air batteries of Examples 8 and 9 using the two-layer filter of Examples 2 and 3 are accelerated and deteriorated as compared with the air batteries of Comparative Examples 3 to 6 using the filters of Comparative Examples 1 and 2. It turned out that the density
  • the filter and air battery of the present invention can reliably trap metal ions and prevent leakage of metal ions even when electrolyte solution leaks from the inside of the air battery. It can be widely used for mobile devices, memory backup batteries, small electronic devices, hearing aids, hybrid vehicles, electric vehicles, distributed household power sources, distributed business power sources, power storage batteries, and the like.

Abstract

Provided is a filter, comprising: a chelate film, including a chelate capable of forming, with metallic ions included in an electrolyte in a battery, a complex; and at least either an adsorbent film including an adsorbent substance capable of adsorbing the complex formed by the metallic ions and the chelate, or an acidic solid film including an acidic solid substance capable of reacting with the electrolyte and reducing the concentration of hydrogen ions in the electrolyte. An embodiment comprising the adsorbent film, the chelate film, and the acidic solid film is preferred.

Description

フィルタ及び空気電池Filter and air battery
　本発明は、フィルタ及び該フィルタを有する空気電池に関する。 The present invention relates to a filter and an air battery having the filter.
　現在、携帯電話、モバイルパソコン、電気自動車等の蓄電池として、リチウムイオン二次電池が使用されているが、重量エネルギー密度や体積エネルギー密度を考慮した場合、エネルギー密度はまだまだ十分とはいえない。そこで、電池の理論容量をリチウムイオン二次電池よりも大きくすることが可能とされている金属空気二次電池が注目を集めている。 Currently, lithium ion secondary batteries are used as storage batteries for mobile phones, mobile personal computers, electric vehicles, etc., but when considering the energy density and volumetric energy density, the energy density is still not sufficient. Therefore, a metal-air secondary battery that can make the theoretical capacity of the battery larger than that of the lithium ion secondary battery has attracted attention.
　リチウムイオン二次電池等の従来の電池では、正極及び負極のそれぞれの電極には、酸化還元反応の素となる活物質が内包されている。正極及び負極のそれぞれの活物質は化学反応を起こすことでエネルギーが放出される。放出されたエネルギーを電気エネルギーとして取り出すことで、電池としての機能が発現している。一方、金属空気二次電池は、負極には負極活物質として、金属を有しているが、正極活物質として、電池の外部に存在する大気中の酸素を利用している。このため、無限に正極活物質が存在するにもかかわらず正極活物質の重量はゼロである。これに従い、金属空気二次電池は、リチウムイオン二次電池等の従来の電池と比べて、重量エネルギー密度及び体積エネルギー密度を大幅に向上させることが可能となり、電池をより軽量かつ小型にすることが可能となる。 In a conventional battery such as a lithium ion secondary battery, each of the positive electrode and the negative electrode includes an active material that is a source of an oxidation-reduction reaction. Each active material of the positive electrode and the negative electrode undergoes a chemical reaction to release energy. By taking out the released energy as electric energy, the function as a battery is developed. On the other hand, the metal-air secondary battery has a metal as a negative electrode active material in the negative electrode, but utilizes oxygen in the atmosphere existing outside the battery as the positive electrode active material. For this reason, the weight of the positive electrode active material is zero despite the infinite number of positive electrode active materials. Accordingly, the metal-air secondary battery can significantly increase the weight energy density and the volume energy density compared to the conventional battery such as a lithium ion secondary battery, thereby making the battery lighter and smaller. Is possible.
　前記金属空気二次電池は、酸素を正極活物質として用いるため、電池の内部と外部で、酸素の出入りが必要となる。このため、電池の正極の大気に面している部分には、ガス交換口が設けられている。しかし、空気を取り込むだけでなく、電池内部の電解液が漏液することも起こりえる。更に、漏液した電解液中には、触媒を構成する金属イオンが溶解している。金属イオンがガス交換口（以下、「空気孔」と称することもある）を塞いでしまい、空気電池の性能の劣化に繋がる。
　そこで、例えば、電池内部からの漏液を防止するために、フッ素樹脂からなる多層膜を圧着する方法が提案されている（特許文献１参照）。しかし、この提案では、万が一漏液した場合には、電解液中には金属イオンが含まれているため、ガス交換口を塞いでしまい障害が発生するおそれがある。更に、金属イオンは人体や環境に対しても悪影響を与えてしまうという課題がある。 Since the metal-air secondary battery uses oxygen as a positive electrode active material, oxygen needs to enter and exit inside and outside the battery. For this reason, a gas exchange port is provided in a portion of the battery that faces the atmosphere of the positive electrode. However, not only can air be taken in, but the electrolyte inside the battery can leak. Further, metal ions constituting the catalyst are dissolved in the leaked electrolyte. The metal ions block the gas exchange port (hereinafter also referred to as “air hole”), leading to deterioration of the performance of the air battery.
Therefore, for example, in order to prevent leakage from the inside of the battery, a method of pressure bonding a multilayer film made of a fluororesin has been proposed (see Patent Document 1). However, in this proposal, in the unlikely event that the liquid leaks, the electrolyte solution contains metal ions, which may block the gas exchange port and cause a failure. Furthermore, there is a problem that metal ions have an adverse effect on the human body and the environment.
特開平８－２２２２３１号公報JP-A-8-222231
　本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、電池内部から電解液が漏洩しても金属イオンを確実にトラップして金属イオンの漏れ出しを防止することができるフィルタ、及び該フィルタを有する空気電池を提供することを目的とする。 This invention makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, an object of the present invention is to provide a filter capable of reliably trapping metal ions and preventing leakage of metal ions even when electrolyte solution leaks from the inside of the battery, and an air battery having the filter. And
　開示のフィルタは、電池の電解液中に含まれる金属イオンと錯体を形成可能なキレート物質を含むキレート膜と、
　前記金属イオンと前記キレート物質から形成された錯体を吸着可能な吸着物質を含む吸着膜、及び前記電解液と反応して該電解液の水素イオン濃度を下げることが可能な酸性固体物質を含む酸性固体膜の少なくともいずれかとを有する。
　開示の空気電池は、開示のフィルタを有する。 The disclosed filter includes a chelate film containing a chelate substance capable of forming a complex with a metal ion contained in a battery electrolyte;
An adsorbing film containing an adsorbing material capable of adsorbing a complex formed from the metal ion and the chelating substance, and an acidic solid substance capable of lowering the hydrogen ion concentration of the electrolytic solution by reacting with the electrolytic solution And at least one of a solid film.
The disclosed air battery has the disclosed filter.
　開示のフィルタによれば、従来における前記諸問題を解決し、前記目的を達成することができ、電池内部から電解液が漏洩しても金属イオンを確実にトラップして金属イオンの漏れ出しを防止することができる。 According to the disclosed filter, it is possible to solve the above-described problems and achieve the above-mentioned object, and even if the electrolyte leaks from the inside of the battery, the metal ions are reliably trapped to prevent the metal ions from leaking out. can do.
図１は、本発明の空気電池の一例を示す概略断面図である。FIG. 1 is a schematic cross-sectional view showing an example of the air battery of the present invention.
（フィルタ）
　本発明のフィルタは、キレート膜と、吸着膜及び酸性固体膜の少なくともいずれかとを有してなり、更に必要に応じてその他の部材を有してなる。 (filter)
The filter of the present invention includes a chelate film and at least one of an adsorption film and an acidic solid film, and further includes other members as necessary.
　前記フィルタとしては、前記吸着膜と前記キレート膜を有することが好ましく、空気電池の電解液中の金属イオンのトラップ効果の点で、前記吸着膜と前記キレート膜と前記酸性固体膜を有することがより好ましく、外界から（空気電池内に装着した場合には正極ケース側から）、前記吸着膜と前記キレート膜と前記酸性固体膜とをこの順に有することが、特に好ましい。
　これは、空気電池は、正極活物質として空気中の酸素を用いた電池であるため、電池の正極面に空気を取り込むためのガス交換口が正極ケースに設けられている。しかし、前記ガス交換口から、空気を取り込むだけでなく、電池内部の電解液が漏液することも起こり得る。漏液した電解液中には、正極触媒等を構成する金属イオンが溶解している。金属イオンはガス交換口を塞ぎ、空気電池の性能の劣化に繋がる。また、金属イオンは人体や環境に対しても悪影響を与える。
　したがって、電池内部のガス交換口の内側、即ち、電解液が漏れる経路にフィルタを設けると共に、前記フィルタは、金属イオンのトラップ効果の点で、外界から（空気電池内に装着した場合には正極ケース側から）、前記吸着膜と前記キレート膜と前記酸性固体膜とをこの順に有することが特に好ましい。 The filter preferably includes the adsorption film and the chelate film, and has the adsorption film, the chelate film, and the acidic solid film in terms of the trap effect of metal ions in the electrolyte of the air battery. More preferably, it is particularly preferable to have the adsorption film, the chelate film, and the acidic solid film in this order from the outside (from the positive electrode case side when mounted in an air battery).
Since the air battery is a battery using oxygen in the air as a positive electrode active material, a gas exchange port for taking air into the positive electrode surface of the battery is provided in the positive electrode case. However, not only can air be taken in from the gas exchange port, but the electrolyte inside the battery can also leak. In the leaked electrolyte, metal ions constituting the positive electrode catalyst and the like are dissolved. The metal ions block the gas exchange port and lead to deterioration of the performance of the air battery. Metal ions also have an adverse effect on the human body and the environment.
Accordingly, a filter is provided inside the gas exchange port inside the battery, that is, in the path through which the electrolyte solution leaks, and the filter is externally connected to the positive electrode (when installed in an air battery) in terms of the trap effect of metal ions. It is particularly preferable to have the adsorption film, the chelate film, and the acidic solid film in this order from the case side.
＜キレート膜＞
　前記キレート膜は、キレート物質を含んでなり、更に必要に応じて、その他の成分を含有してなる。前記キレート膜は、基材を有することが好ましい。 <Chelate film>
The chelate film contains a chelate substance, and further contains other components as necessary. The chelate film preferably has a base material.
－キレート物質－
　前記キレート物質としては、空気電池の電解液中に含まれる金属イオンと錯体を形成可能な物質であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、ＡＳＤＡ（Ｌ－アスパラギン酸－Ｎ，Ｎ－２酢酸）、ＣｙＤＴＡ（ｔｒａｎｓ－シクロヘキサンジアミン４酢酸）、ＣＰ(カルボキシメチルポリエチレンイミン)、ＤＴＰＡ（ジエチレントリアミン６酢酸）、ＤＰＴＡ－ＯＨ（１，３－ジアミノ－２－ヒドロキシプロパン４酢酸）、ＤＨＥＧ（ジヒドロキシエチルグリシン）、ＤＨＥＤＤＡ（ジヒドロキシエチルエチレンジアミン２酢酸）、ＥＤＴＡ(エチレンジアミン４酢酸)、ＥＤＴＭＰ（エチレンジアミン４メチレンリン酸）、ＧＥＤＴＡ（グリコールエーテルジアミン４酢酸）、ＨＥＤＰ（ヒドロキシエチリデン２リン酸）、ＨＥＤＴＡ（ヒドロキシエチルエチレンジアミン３酢酸）、ＨＩＤＡ（ヒドロキシエチルイミノ２酢酸）、ＮＴＭＰ（ニトリロ３メチレンリン酸）、ＮＴＡ（ニトリロ３酢酸）、ＰＤＴＡ（１，３－プロパンジアミン４酢酸）、ＰＢＴＣ（ホスフォノブタントリカルボン酸）、ＴＴＨＡ（トリエチレンテトラアミン６酢酸）、などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、キレート効果が高く、安価な点で、ＥＤＴＡ(エチレンジアミン４酢酸)が特に好ましい。
　前記ＥＤＴＡ等のキレート物質は、電解液中の金属イオンＭｎ＋と下記反応式で示すように錯体形成反応を起こし、金属キレート錯体を形成し、金属イオンのイオン半径が大きくなる。また、金属キレート錯体は、金属イオンに比べて人体に安全なものである。したがって、万が一、金属キレート錯体を含む電解液が電池系外に漏液した場合でも金属イオンそのものを含む電解液よりも安全である。
Figure JPOXMLDOC01-appb-C000001
 -Chelating substances-
The chelating substance is not particularly limited as long as it is a substance capable of forming a complex with a metal ion contained in an electrolyte solution of an air battery, and can be appropriately selected depending on the purpose. For example, ASDA (L-asparagine Acid-N, N-2acetic acid), CyDTA (trans-cyclohexanediaminetetraacetic acid), CP (carboxymethylpolyethyleneimine), DTPA (diethylenetriaminehexaacetic acid), DPTA-OH (1,3-diamino-2-hydroxypropane4) Acetic acid), DHEG (dihydroxyethyl glycine), DHEDDA (dihydroxyethyl ethylenediamine diacetic acid), EDTA (ethylenediamine tetraacetic acid), EDTMP (ethylenediamine 4-methylene phosphoric acid), GEDTA (glycol ether diamine tetraacetic acid), HEDP (hydroxyethylidene 2 Acid), HEDTA (hydroxyethyl ethylenediamine triacetic acid), HIDA (hydroxyethylimino diacetic acid), NTMP (nitrilo 3 methylene phosphoric acid), NTA (nitrilo triacetic acid), PDTA (1,3-propanediamine tetraacetic acid), PBTC (phosphonobutane tricarboxylic acid), TTHA (triethylenetetraamine 6 acetic acid), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, EDTA (ethylenediaminetetraacetic acid) is particularly preferable because of its high chelating effect and low cost.
The chelate substance such as EDTA causes a complex formation reaction with the metal ion M n + in the electrolytic solution as shown in the following reaction formula to form a metal chelate complex, and the ion radius of the metal ion is increased. Further, the metal chelate complex is safer to the human body than the metal ion. Therefore, even if the electrolyte containing the metal chelate complex leaks out of the battery system, it is safer than the electrolyte containing the metal ions themselves.
Figure JPOXMLDOC01-appb-C000001
　前記その他の成分としては、特に制限はなく、目的に応じて適宜選択することができ、例えば溶媒、分散剤などが挙げられる。前記溶媒としては、例えば水、メタノール、エタノール、プロパノールなどが挙げられる。 The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include solvents and dispersants. Examples of the solvent include water, methanol, ethanol, propanol and the like.
－基材－
　前記基材の形状、構造、大きさ、材質等については特に制限はなく、目的に応じて適宜選択することができ、前記形状としては、例えば、膜状、シート状などが挙げられる。前記構造としては、単層構造、積層構造などが挙げられる。前記大きさとしては、用途等に応じて適宜選択することができる。
　前記基材の材質としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ろ紙、クラフト紙、ビニロン混抄紙、合成パルプ混抄紙等の紙、合成紙、セロハン、ポリエチレングラフト膜、ポリプロピレンメルトブロー不織布等のポリオレフィン不織布、ポリアミド不織布、ガラス繊維不織布、合成樹脂製シート（フィルム）、などが挙げられる。
　前記基材の平均厚みとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、１０μｍ～５００μｍが好ましい。 -Base material-
There is no restriction | limiting in particular about the shape, structure, magnitude | size, material, etc. of the said base material, According to the objective, it can select suitably, For example, a film | membrane form, a sheet form, etc. are mentioned. Examples of the structure include a single layer structure and a laminated structure. The size can be appropriately selected according to the application.
The material of the base material is not particularly limited and can be appropriately selected depending on the purpose. For example, paper such as filter paper, kraft paper, vinylon mixed paper, synthetic pulp mixed paper, synthetic paper, cellophane, polyethylene graft Examples include membranes, polyolefin nonwoven fabrics such as polypropylene melt blown nonwoven fabric, polyamide nonwoven fabrics, glass fiber nonwoven fabrics, and synthetic resin sheets (films).
The average thickness of the substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 10 μm to 500 μm.
　前記キレート膜の製造方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ろ紙等の基材を、ＥＤＴＡ等のキレート物質をエタノール等の溶媒に溶解させた溶液で含浸し、乾燥させて、作製することができる。 There is no restriction | limiting in particular as a manufacturing method of the said chelate film | membrane, According to the objective, it can select suitably, For example, the base material, such as filter paper, is a solution in which a chelating substance such as EDTA is dissolved in a solvent such as ethanol. It can be made by impregnation and drying.
　前記キレート膜の平均厚みは、５０μｍ～５００μｍが好ましく、１００μｍ～４００μｍがより好ましい。前記平均厚みが、５０μｍ未満であると、キレート膜が薄すぎて、キレート物質の量が少なくなるため、十分なキレート効果が得られないことがあり、５００μｍを超えると、キレート膜が厚すぎて、空気の通り道を塞いでしまうことがある。 The average thickness of the chelate film is preferably 50 μm to 500 μm, more preferably 100 μm to 400 μm. If the average thickness is less than 50 μm, the chelate film is too thin and the amount of chelate substance decreases, so that a sufficient chelate effect may not be obtained. If the average thickness exceeds 500 μm, the chelate film is too thick. , May block the passage of air.
＜吸着膜＞
　前記吸着膜は、吸着物質を含み、更に必要に応じて、その他の成分を含んでなる。前記吸着膜は、基材を有することが好ましい。 <Adsorption film>
The adsorbing film contains an adsorbing substance, and further contains other components as necessary. The adsorption film preferably has a base material.
　前記吸着物質としては、物質の表面及び内部の少なくともいずれかが多孔質構造を有し、前記金属イオンと前記キレート物質から形成された錯体を吸着可能な有機物又は無機物であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、活性炭、ゼオライト、シリカゲルなどが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、吸着力が高く、安価である点から、活性炭が特に好ましい。
　前記キレート物質と金属イオンから形成された金属キレート錯体の直径は０．５ｎｍ程度であるため、活性炭等の吸着物質で容易に吸着される。これに対し、金属イオンは、直径が０．１ｎｍ～０．２ｎｍと小さいため、活性炭等の吸着物質で吸着されない。 The adsorbing substance is not particularly limited as long as at least one of the surface and the inside of the substance has a porous structure, and can be an organic substance or an inorganic substance that can adsorb the complex formed from the metal ion and the chelate substance. It can be appropriately selected depending on the purpose, and examples thereof include activated carbon, zeolite, silica gel and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, activated carbon is particularly preferable because it has high adsorption power and is inexpensive.
Since the diameter of the metal chelate complex formed from the chelate substance and metal ions is about 0.5 nm, it is easily adsorbed by an adsorbent such as activated carbon. On the other hand, since the metal ion has a small diameter of 0.1 nm to 0.2 nm, it is not adsorbed by an adsorbent such as activated carbon.
　前記その他の成分としては、特に制限はなく、目的に応じて適宜選択することができ、例えば溶媒、分散剤などが挙げられる。前記溶媒としては、例えば水、メタノール、エタノール、プロパノールなどが挙げられる。 The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include solvents and dispersants. Examples of the solvent include water, methanol, ethanol, propanol and the like.
－基材－
　前記基材としては、前記キレート膜と同様なものを用いることができる。 -Base material-
As the substrate, the same one as the chelate film can be used.
　前記吸着膜の製造方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ろ紙等の基材を、活性炭等の吸着物質をプロパノール等の溶媒に溶解させたスラリーを塗布し、乾燥させて、作製することができる。 The method for producing the adsorption film is not particularly limited and can be appropriately selected according to the purpose. For example, a slurry in which a substrate such as filter paper is dissolved in an adsorbent such as activated carbon in a solvent such as propanol. It can be prepared by applying and drying.
　前記吸着膜の平均厚みは、５０μｍ～５００μｍが好ましく、１００μｍ～４００μｍがより好ましい。前記平均厚みが、５０μｍ未満であると、吸着膜が薄すぎて、吸着物質の量が少なくなるため、十分な吸着効果が得られないことがあり、５００μｍを超えると、吸着膜が厚すぎて、空気の通り道を塞いでしまうことがある。 The average thickness of the adsorption film is preferably 50 μm to 500 μm, more preferably 100 μm to 400 μm. If the average thickness is less than 50 μm, the adsorbing film is too thin and the amount of adsorbing material decreases, so that a sufficient adsorbing effect may not be obtained. If the average thickness exceeds 500 μm, the adsorbing film is too thick. , May block the passage of air.
＜酸性固体膜＞
　前記酸性固体膜は、酸性固体物質を含み、更に必要に応じて、その他の成分を含有してなる。前記酸性固体膜は、基材を有することが好ましい。 <Acid solid film>
The acidic solid film contains an acidic solid substance, and further contains other components as necessary. The acidic solid film preferably has a base material.
　前記酸性固体物質としては、空気電池の電解液と反応し該電解液の水素イオン濃度を下げることが可能で、水溶液等に溶解した場合、水素イオン濃度を７よりも小さくできる物質であり、一般的には、弱塩基と強酸からなる物質であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、塩化アンモニウム、硫酸アンモニウム、硝酸アンモニウム、γ－アルミナ・シリカ、などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、水素イオン濃度を下げる効果が高く、安価に入手できる点で、塩化アンモニウムが特に好ましい。
　前記酸性固体膜と空気電池中の電解液が反応し、電解液の水素イオン濃度が下がる。電解液の水素イオン濃度が高い場合には、キレート膜における、水酸化物イオンとキレート物質と金属イオンとの錯体形成反応を妨害してしまう。前記電解液の水素イオン濃度としてはｐＨ＝９前後が好ましい。 The acidic solid substance is a substance that can react with the electrolytic solution of the air battery to lower the hydrogen ion concentration of the electrolytic solution, and can be reduced to a hydrogen ion concentration of less than 7 when dissolved in an aqueous solution. Specifically, the substance is not particularly limited as long as it is a substance composed of a weak base and a strong acid, and can be appropriately selected according to the purpose. Examples thereof include ammonium chloride, ammonium sulfate, ammonium nitrate, and γ-alumina / silica. These may be used individually by 1 type and may use 2 or more types together. Among these, ammonium chloride is particularly preferable because it has a high effect of reducing the hydrogen ion concentration and can be obtained at low cost.
The acidic solid membrane reacts with the electrolytic solution in the air battery, and the hydrogen ion concentration of the electrolytic solution decreases. When the hydrogen ion concentration of the electrolytic solution is high, the complex formation reaction between the hydroxide ion, the chelate substance, and the metal ion in the chelate film is hindered. The hydrogen ion concentration of the electrolytic solution is preferably about pH = 9.
　前記その他の成分としては、特に制限はなく、目的に応じて適宜選択することができ、例えば溶媒、分散剤などが挙げられる。前記溶媒としては、例えば水、メタノール、エタノール、プロパノールなどが挙げられる。 The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include solvents and dispersants. Examples of the solvent include water, methanol, ethanol, propanol and the like.
－基材－
　前記基材としては、前記キレート膜と同様なものを用いることができる。 -Base material-
As the substrate, the same one as the chelate film can be used.
　前記酸性固体膜の製造方法としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、ろ紙等の基材を、塩化アンモニウム等の酸性固体物質を水等の溶媒に溶解させた水溶液で含浸し、乾燥させて、作製することができる。 The method for producing the acidic solid film is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a base material such as filter paper is dissolved, and an acidic solid substance such as ammonium chloride is dissolved in a solvent such as water. It can be prepared by impregnating with an aqueous solution and drying.
　前記酸性固体膜の平均厚みは、５０μｍ～５００μｍが好ましく、１００μｍ～４００μｍがより好ましい。前記平均厚みが、５０μｍ未満であると、酸性固体膜が薄すぎて、酸性固体物質の量が少なくなるため、十分な水素イオン濃度低下効果が得られないことがあり、５００μｍを超えると、酸性固体膜が厚すぎて、空気の通り道を塞いでしまうことがある。 The average thickness of the acidic solid film is preferably 50 μm to 500 μm, more preferably 100 μm to 400 μm. When the average thickness is less than 50 μm, the acidic solid film is too thin and the amount of the acidic solid substance is reduced, so that a sufficient hydrogen ion concentration lowering effect may not be obtained. The solid film may be too thick and block the air passage.
　本発明のフィルタは、前記吸着膜と、前記キレート膜と、前記酸性固体膜とを重ね合わせることにより、作製される。前記吸着膜、前記キレート膜、及び前記酸性固体膜は、空気電池を組み立てる際に、正極ケースに重ね合わせて配置される。なお、前記吸着膜と、前記キレート膜と、前記酸性固体膜とを重ね合わせる際には、接着剤などで張り合わせる必要はないが、必要に応じて接着剤などを用いて貼り合せても構わない。
　前記フィルタの平均厚みは、特に制限はなく、目的に応じて適宜選択することができるが、１００μｍ～１，５００μｍが好ましい。 The filter of the present invention is produced by superposing the adsorption film, the chelate film, and the acidic solid film. When the air battery is assembled, the adsorption film, the chelate film, and the acidic solid film are disposed so as to overlap with the positive electrode case. In addition, when the adsorption film, the chelate film, and the acidic solid film are overlapped, it is not necessary to bond them with an adhesive or the like, but they may be bonded using an adhesive or the like as necessary. Absent.
The average thickness of the filter is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100 μm to 1,500 μm.
　本発明のフィルタは、空気電池内部から電解液が漏洩しても金属イオンを確実にトラップして金属イオンの漏れ出しを防止できるので、各種空気電池に用いることができ、空気電池の金属イオントラップ用フィルタとして特に好適に用いられる。 The filter of the present invention can be used in various air batteries because it can reliably trap metal ions and prevent metal ions from leaking out even when electrolyte solution leaks from the inside of the air battery. It is particularly preferably used as an industrial filter.
（空気電池）
　本発明の空気電池は、本発明の前記フィルタを有してなり、更に必要に応じてその他の部材を有してなる。
　前記空気電池としては、空気一次電池であっても空気二次電池であってもよいが、充放電可能な点から、空気二次電池が特に好ましい。
　前記空気電池は、正極ケースと、正極触媒と、セパレータと、負極活物質と、負極ケースとを有し、前記正極ケースと前記正極触媒の間に、本発明の前記フィルタを有することが好ましく、前記フィルタが、前記正極ケース側から、吸着膜と、キレート膜と、酸性固体膜とをこの順となるように配置することが、金属イオンのトラップ効果の点で特に好ましい。 (Air battery)
The air battery of the present invention includes the filter of the present invention, and further includes other members as necessary.
The air battery may be an air primary battery or an air secondary battery, but an air secondary battery is particularly preferable from the viewpoint of charge and discharge.
The air battery preferably includes a positive electrode case, a positive electrode catalyst, a separator, a negative electrode active material, and a negative electrode case, and the filter of the present invention is provided between the positive electrode case and the positive electrode catalyst. It is particularly preferable in terms of the trapping effect of metal ions that the filter is arranged so that the adsorption film, the chelate film, and the acidic solid film are arranged in this order from the positive electrode case side.
＜正極ケース＞
　本発明の正極ケースは、空気が出入りする空気孔が形成された金属部材を有し、更に必要に応じて、その他の部材を有する。前記正極ケースは、正極端子を兼ねている。 <Positive electrode case>
The positive electrode case of the present invention has a metal member in which an air hole through which air enters and exits is formed, and further includes other members as necessary. The positive electrode case also serves as a positive electrode terminal.
－金属部材－
　前記金属部材は、空気が出入りする空気孔が形成された金属部材であれば、その材質、形状、大きさ、構造としては、特に制限はなく、目的に応じて適宜選択することができる。
　前記金属部材の材質としては、例えば、銅、ステンレス鋼、ステンレス鋼又は鉄にニッケルなどのめっきを施した金属などが挙げられる。
　前記金属部材の形状としては、例えば、周囲が反り上がった底の浅い皿状、有底円筒形、有底角柱状などが挙げられる。
　前記金属部材の大きさとしては、空気電池に使用可能な大きさであれば、特に制限はなく、目的に応じて適宜選択することができる。
　前記金属部材の構造は、単層構造であってもよく、積層構造であってもよい。前記積層構造としては、例えば、ニッケル、ステンレス鋼、及び銅の三層構造などが挙げられる。
　前記金属部材は、通常、底部に前記空気孔を有している。前記空気孔の数は、１つであってもよく、複数であってもよい。前記空気孔の開口部の形状としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、円形状、楕円形状、正方形状、長方形状、菱形状などが挙げられる。前記空気孔の開口部の大きさとしては、特に制限はなく、目的に応じて適宜選択することができる。
　前記金属部材における前記空気孔の作製方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、金属部材を金型により打抜き加工して空気孔を作製する方法、金属線を織って網目状にすることで、所定の形状の金属部材と空気孔を同時に作製する方法などが挙げられる。 -Metal parts-
The metal member is not particularly limited as long as it is a metal member in which air holes through which air enters and exits are formed, and can be appropriately selected according to the purpose.
Examples of the material of the metal member include a metal obtained by plating copper, stainless steel, stainless steel, or iron with nickel or the like.
Examples of the shape of the metal member include a shallow dish shape with a curved base, a bottomed cylindrical shape, and a bottomed prismatic shape.
The size of the metal member is not particularly limited as long as it is a size that can be used for an air battery, and can be appropriately selected according to the purpose.
The structure of the metal member may be a single layer structure or a laminated structure. Examples of the laminated structure include a three-layer structure of nickel, stainless steel, and copper.
The metal member usually has the air holes at the bottom. The number of the air holes may be one or plural. There is no restriction | limiting in particular as a shape of the opening part of the said air hole, According to the objective, it can select suitably, For example, circular shape, elliptical shape, square shape, rectangular shape, rhombus shape etc. are mentioned. There is no restriction | limiting in particular as a magnitude | size of the opening part of the said air hole, According to the objective, it can select suitably.
The method for producing the air holes in the metal member is not particularly limited and may be appropriately selected depending on the purpose. For example, a method for producing an air hole by punching a metal member with a mold, a metal wire A method of simultaneously producing a metal member having a predetermined shape and an air hole by weaving and forming a mesh.
＜正極触媒＞
　前記正極触媒の材質、形状、大きさ、構造としては、特に制限はなく、目的に応じて適宜選択することができる。
　前記正極触媒の材質としては、例えば、パイロクロア型金属酸化物、酸素欠陥パイロクロア型金属酸化物、アセチレンブラック、ケッチェンブラック、活性炭と二酸化マンガン等のマンガン酸化物との混合物などが挙げられる。これらの中でも、パイロクロア型金属酸化物、酸素欠陥パイロクロア型金属酸化物が好ましく、パイロクロア型金属酸化物が特に好ましい。
　前記パイロクロア型金属酸化物としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、Ｂｉ２Ｒｕ２Ｏ７、Ｐｂ２Ｒｕ２Ｏ６、及びＰｂ２Ｉｒ２Ｏ６．５から選択される少なくとも１種が好ましい。 <Cathode catalyst>
There is no restriction | limiting in particular as a material of the said positive electrode catalyst, a shape, a magnitude | size, and a structure, According to the objective, it can select suitably.
Examples of the material of the positive electrode catalyst include pyrochlore type metal oxides, oxygen-deficient pyrochlore type metal oxides, acetylene black, ketjen black, and mixtures of activated carbon and manganese oxides such as manganese dioxide. Among these, pyrochlore type metal oxides and oxygen-deficient pyrochlore type metal oxides are preferable, and pyrochlore type metal oxides are particularly preferable.
Examples of the pyrochlore-type metal oxide is not particularly limited and may be appropriately selected depending on the purpose, for example, Bi 2 Ru 2 O 7, Pb 2 Ru 2 O 6, and Pb 2 Ir 2 O 6.5 At least one selected from is preferred.
　前記正極触媒の形状としては、例えば、シート状が挙げられる。前記正極触媒をシート状にする方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、活性炭とマンガン酸化物との混合物を正極触媒とする場合には、活性炭と、マンガン酸化物と、導電性材料としての膨張化黒鉛と、結着剤としてポリテトラフルオロエチレン粉末とを混合し、シート状に成型する方法が挙げられる。 The shape of the positive electrode catalyst includes, for example, a sheet shape. The method for forming the positive electrode catalyst into a sheet is not particularly limited and can be appropriately selected depending on the purpose. For example, when a mixture of activated carbon and manganese oxide is used as the positive electrode catalyst, Examples include a method in which manganese oxide, expanded graphite as a conductive material, and polytetrafluoroethylene powder as a binder are mixed and molded into a sheet shape.
＜電解液＞
　前記電解液としては、特に制限はなく、適宜目的に応じて選択することができ、例えば、有機溶媒及び電解質を含有する電解液、イオン液体などが挙げられる。
　前記電解液としては、水を含まない非水電解液が好ましい。 <Electrolyte>
There is no restriction | limiting in particular as said electrolyte solution, According to the objective, it can select suitably, For example, the electrolyte solution containing an organic solvent and electrolyte, an ionic liquid, etc. are mentioned.
As the electrolytic solution, a non-aqueous electrolytic solution containing no water is preferable.
－有機溶媒－
　前記有機溶媒としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、環状カーボネート、鎖状カーボネート等のカーボネート系有機溶媒、環状エステル、鎖状エステル等のエステル系有機溶媒、環状エーテル、鎖状エーテル等のエーテル系有機溶媒などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
　これらの中でも、カーボネート系有機溶媒が、電解質の溶解力が高い点で好ましい。
　前記環状カーボネートとしては、例えば、プロピレンカーボネート（ＰＣ）、エチレンカーボネート（ＥＣ）、ブチレンカーボネート（ＢＣ）、ビニレンカーボネート（ＶＣ）などが挙げられる。
　前記鎖状カーボネートとしては、例えば、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、メチルエチルカーボネートなどが挙げられる。
　前記環状エステルとしては、例えば、γ－ブチロラクトン（γＢＬ）、２－メチル－γ－ブチロラクトン、アセチル－γ－ブチロラクトン、γ－バレロラクトンなどが挙げられる。
　前記鎖状エステルとしては、例えば、プロピオン酸アルキルエステル、マロン酸ジアルキルエステル、酢酸アルキルエステルなどが挙げられる。
　前記環状エーテルとしては、例えば、テトラヒドロフラン、アルキルテトラヒドロフラン、アルコキシテトラヒドロフラン、ジアルコキシテトラヒドロフラン、１，３－ジオキソラン、アルキル－１，３－ジオキソラン、１，４－ジオキソランなどが挙げられる。
　前記鎖状エーテルとしては、例えば、１，２－ジメトシキエタン（ＤＭＥ）、ジエチルエーテル、エチレングリコールジアルキルエーテル、ジエチレングリコールジアルキルエーテル、トリエチレングリコールジアルキルエーテル、テトラエチレングリコールジアルキルエーテルなどが挙げられる。 -Organic solvent-
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carbonate organic solvents such as cyclic carbonates and chain carbonates, ester organic solvents such as cyclic esters and chain esters, Examples include ether organic solvents such as cyclic ethers and chain ethers. These may be used individually by 1 type and may use 2 or more types together.
Among these, carbonate-based organic solvents are preferable in terms of high electrolyte dissolving power.
Examples of the cyclic carbonate include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), and the like.
Examples of the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate.
Examples of the cyclic ester include γ-butyrolactone (γBL), 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, and γ-valerolactone.
Examples of the chain ester include propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester.
Examples of the cyclic ether include tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, 1,4-dioxolane and the like.
Examples of the chain ether include 1,2-dimethoxyethane (DME), diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, and tetraethylene glycol dialkyl ether.
－電解質－
　前記電解質としては、特に制限はなく、目的に応じて適宜選択することができ、負極が亜鉛又はその合金の場合には、酸化亜鉛を含む水酸化カリウム水溶液、水酸化ナトリウム水溶液などのアルカリ水溶液を用いてもよいし、塩化亜鉛や過塩素酸亜鉛を含む水溶液を用いてもよいし、過塩素酸亜鉛を含む非水系溶媒、亜鉛ビス（トリフルオロメチルスルフォニル）イミドを含む非水系溶媒を用いてもよい。
　また、イオンサイズが小さい点、及び負極活物質にリチウムを用いる場合に系が単純になる点でリチウム塩が好ましい。前記リチウム塩としては、例えば、過塩素酸リチウム（ＬｉＣｌＯ４）、ヘキサフルオロリン酸リチウム（ＬｉＰＦ６）、ホウ弗化リチウム（ＬｉＢＦ４）、六弗化砒素リチウム（ＬｉＡｓＦ６）、トリフルオロメタスルホン酸リチウム（ＬｉＣＦ３ＳＯ３）、リチウムビストリフルオロメチルスルホニルイミド（ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２）、リチウムビスファーフルオロエチルスルホニルイミド（ＬｉＮ（ＣＦ２Ｆ５ＳＯ２）２）などが挙げられる。前記電解質は、１種単独で使用してもよいし、２種以上を併用してもよい。
　前記電解質の濃度としては、特に制限はなく、目的に応じて適宜選択することができるが、前記有機溶媒中に、０．５ｍｏｌ／Ｌ～３ｍｏｌ／Ｌであることがイオン伝導度の点で好ましい。 -Electrolytes-
The electrolyte is not particularly limited and may be appropriately selected depending on the purpose. When the negative electrode is zinc or an alloy thereof, an alkaline aqueous solution such as a potassium hydroxide aqueous solution or a sodium hydroxide aqueous solution containing zinc oxide is used. An aqueous solution containing zinc chloride or zinc perchlorate may be used, a non-aqueous solvent containing zinc perchlorate, or a non-aqueous solvent containing zinc bis (trifluoromethylsulfonyl) imide. Also good.
In addition, a lithium salt is preferable in that the ion size is small and the system becomes simple when lithium is used for the negative electrode active material. Examples of the lithium salt include lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium arsenic hexafluoride (LiAsF 6 ), and trifluorometasulfone. Examples include lithium acid (LiCF 3 SO 3 ), lithium bistrifluoromethylsulfonylimide (LiN (C 2 F 5 SO 2 ) 2 ), lithium bisfurfluoroethylsulfonylimide (LiN (CF 2 F 5 SO 2 ) 2 ), and the like. It is done. The said electrolyte may be used individually by 1 type, and may use 2 or more types together.
The concentration of the electrolyte is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 mol / L to 3 mol / L in terms of ionic conductivity in the organic solvent. .
－イオン液体－
　前記イオン液体としては、常温（２５℃）において溶融状態にあるイオン性物質であれば、特に制限はなく、目的に応じて適宜選択することができる。
　前記イオン液体は、カチオンとアニオンとの塩である。
　前記カチオンとしては、例えば、イミダゾリウム、アンモニウム、ピリジニウム、ピペリジニウムなどが挙げられる。
　前記イミダゾリウムとしては、例えば、１－エチル－３－メチルイミダゾリウム（ＥＭＩ）、１－メチル－３－オクチルイミダゾリウム（ＭＯＩ）などが挙げられる。
　前記アンモニウムとしては、例えば、テトラブチルアンモニウムなどが挙げられる。
　前記ピリジニウムとしては、例えば、１－ブチル－３－メチルピリジニウム、１－ブチルピリジニウムなどが挙げられる。
　前記ピペリジニウムとしては、例えば、１－エチル－１－メチルピペリジニウムなどが挙げられる。
　前記アニオンとしては、例えば、ビス（トリフルオロメチルスルフォニル）イミド（ＴＦＳＩ）、ビス（ペンタフルオロエチルスルフォニル）イミド（ＢＥＴＩ）等のイミドアニオン、テトラフルオロボレート、パークロレート、ハロゲンアニオン等の無機アニオンなどが挙げられる。 -Ionic liquid-
The ionic liquid is not particularly limited as long as it is an ionic substance in a molten state at room temperature (25 ° C.), and can be appropriately selected according to the purpose.
The ionic liquid is a salt of a cation and an anion.
Examples of the cation include imidazolium, ammonium, pyridinium, piperidinium, and the like.
Examples of the imidazolium include 1-ethyl-3-methylimidazolium (EMI), 1-methyl-3-octylimidazolium (MOI), and the like.
Examples of the ammonium include tetrabutylammonium.
Examples of the pyridinium include 1-butyl-3-methylpyridinium and 1-butylpyridinium.
Examples of the piperidinium include 1-ethyl-1-methylpiperidinium.
Examples of the anions include imide anions such as bis (trifluoromethylsulfonyl) imide (TFSI) and bis (pentafluoroethylsulfonyl) imide (BETI), and inorganic anions such as tetrafluoroborate, perchlorate, and halogen anions. Can be mentioned.
＜集電体＞
　前記集電体の材質、形状、大きさ、構造としては、特に制限はなく、目的に応じて適宜選択することができる。
　前記集電体の材質としては、導電性材料で形成されたものであれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、ステンレス鋼、ニッケル、アルミニウム、銅などが挙げられる。
　前記集電体の形状としては、特に制限はなく、目的に応じて適宜選択することができるが、酸素の拡散を速やかに行わせる点から、網状、メッシュ状などの多孔体であることが好ましい。
　前記集電体の大きさとしては、前記空気電池に使用可能な大きさであれば、特に制限はなく、目的に応じて適宜選択することができる。
　前記集電体の構造としては、酸化を抑制する点から、その表面に耐酸化性の金属及び合金のいずれかの被膜を被覆した構造が好ましい。 <Current collector>
There is no restriction | limiting in particular as a material, a shape, a magnitude | size, and a structure of the said electrical power collector, According to the objective, it can select suitably.
The material of the current collector is not particularly limited as long as it is formed of a conductive material, and can be appropriately selected according to the purpose. Examples thereof include stainless steel, nickel, aluminum, and copper. It is done.
The shape of the current collector is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a net-like or mesh-like porous body from the viewpoint of promptly diffusing oxygen. .
The size of the current collector is not particularly limited as long as it is a size that can be used for the air battery, and can be appropriately selected according to the purpose.
The structure of the current collector is preferably a structure in which the surface thereof is coated with a coating of an oxidation-resistant metal or alloy from the viewpoint of suppressing oxidation.
－負極活物質－
　前記負極活物質としては、金属イオンを吸蔵放出できるものであれば特に制限はなく。目的に応じて適宜選択することができる。これらの中でも、金属イオンは、アルカリ金属イオン又はアルカリ土類金属イオン、Ｚｎイオン、Ａｌイオン、Ｆｅイオンが好ましい。前記アルカリ金属イオンとしては、例えばＬｉイオン、Ｎａイオン、Ｋイオンなどが挙げられる。前記アルカリ土類金属イオンとしては、Ｍｇイオン、Ｃａイオンなどが挙げられる。これらの中でも、Ｚｎイオンが特に好ましい。 -Negative electrode active material-
The negative electrode active material is not particularly limited as long as it can occlude and release metal ions. It can be appropriately selected according to the purpose. Among these, the metal ions are preferably alkali metal ions or alkaline earth metal ions, Zn ions, Al ions, and Fe ions. Examples of the alkali metal ions include Li ions, Na ions, K ions, and the like. Examples of the alkaline earth metal ions include Mg ions and Ca ions. Among these, Zn ions are particularly preferable.
　前記負極活物質としては、例えば金属単体、合金、金属酸化物、金属窒化物などが挙げられる。
　前記負極層は、負極活物質のみを含有するものであってもよく、負極活物質の他に、導電性材料及びバインダーの少なくとも一方を含有するものであってもよい。例えば、負極活物質が箔状である場合は、負極活物質のみを含有する負極層とすることができる。一方、負極活物質が粉末状である場合は、導電性材料及びバインダーの少なくとも一方を有する負極層とすることができる。
　前記導電性材料としては、例えば、カーボン材料などが挙げられる。前記カーボン材料としては、例えば、グラファイト、アセチレンブラック、カーボンナノチューブ、カーボンファイバー、メソポーラスカーボンなどが挙げられる。
　前記バインダーとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素系バインダー、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶｄＦ）、エチレン－プロピレン－ブタジエンゴム（ＥＰＢＲ）、スチレン－ブタジエンゴム（ＳＢＲ）、カルボキシメチルセルロース（ＣＭＣ）などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素系バインダーが特に好ましい。 Examples of the negative electrode active material include simple metals, alloys, metal oxides, and metal nitrides.
The negative electrode layer may contain only the negative electrode active material, or may contain at least one of a conductive material and a binder in addition to the negative electrode active material. For example, when the negative electrode active material is in the form of a foil, a negative electrode layer containing only the negative electrode active material can be obtained. On the other hand, when the negative electrode active material is in a powder form, a negative electrode layer having at least one of a conductive material and a binder can be obtained.
Examples of the conductive material include a carbon material. Examples of the carbon material include graphite, acetylene black, carbon nanotube, carbon fiber, and mesoporous carbon.
The binder is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fluorine-based binders such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), and polytetrafluoroethylene (PTFE). Polyvinylidene fluoride (PVdF), ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), carboxymethylcellulose (CMC) and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, fluorine-based binders such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE) are particularly preferable.
＜負極ケース＞
　前記負極ケースの材質、形状、大きさ、構造としては、特に制限はなく、目的に応じて適宜選択することができる。
　前記負極ケースの材質としては、例えば、銅、ステンレス鋼、ステンレス鋼、又は鉄にニッケルなどのめっきを施した金属などが挙げられる。
　前記負極ケースの形状としては、例えば、周囲が反り上がった底の浅い皿状、有底円筒形、有底角柱状などが挙げられる。
　前記負極ケースの大きさとしては、前記空気電池に使用可能な大きさであれば、特に制限はなく、目的に応じて適宜選択することができる。
　前記負極ケースの構造は、単層構造であってもよく、積層構造であってもよい。前記積層構造としては、例えば、ニッケルとステンレス鋼と銅の３層構造などが挙げられる。 <Negative electrode case>
There is no restriction | limiting in particular as a material, a shape, a magnitude | size, and a structure of the said negative electrode case, According to the objective, it can select suitably.
Examples of the material of the negative electrode case include copper, stainless steel, stainless steel, or metal obtained by plating nickel or the like on iron.
Examples of the shape of the negative electrode case include a shallow dish having a curved base, a bottomed cylindrical shape, and a bottomed prismatic shape.
The size of the negative electrode case is not particularly limited as long as it is a size that can be used for the air battery, and can be appropriately selected according to the purpose.
The negative electrode case may have a single layer structure or a laminated structure. Examples of the laminated structure include a three-layer structure of nickel, stainless steel, and copper.
＜セパレータ＞
　前記セパレータの材質、形状、大きさ、構造としては、特に制限はなく、目的に応じて適宜選択することができる。
　前記セパレータの材質としては、例えば、クラフト紙、ビニロン混抄紙、合成パルプ混抄紙等の紙、セロハン、ポリエチレングラフト膜、ポリプロピレンメルトブロー不織布等のポリオレフィン不織布、ポリアミド不織布、ガラス繊維不織布などが挙げられる。
　前記セパレータの形状としては、例えば、シート状が挙げられる。
　前記セパレータの大きさとしては、前記空気電池に使用可能な大きさであれば、特に制限はなく、目的に応じて適宜選択することができる。
　前記セパレータの構造は、単層構造であってもよく、積層構造であってもよい。 <Separator>
There is no restriction | limiting in particular as a material of the said separator, a shape, a magnitude | size, and a structure, According to the objective, it can select suitably.
Examples of the material of the separator include paper such as kraft paper, vinylon mixed paper and synthetic pulp mixed paper, cellophane, polyethylene graft film, polyolefin nonwoven fabric such as polypropylene melt blown nonwoven fabric, polyamide nonwoven fabric, and glass fiber nonwoven fabric.
Examples of the shape of the separator include a sheet shape.
The size of the separator is not particularly limited as long as it is a size that can be used for the air battery, and can be appropriately selected according to the purpose.
The separator may have a single layer structure or a laminated structure.
＜ガスケット＞
　前記ガスケットとしては、前記正極ケースと前記負極ケースとの絶縁を保つことができる材質であれば、特に制限はなく、目的に応じて適宜選択することができ、例えば、ポリエチレンテレフタレート等のポリエステル樹脂、ポリテトラフルオロエチレン等の弗素樹脂、ポリフェニレンサルファイド樹脂、ポリエーテルイミド樹脂、ポリアミド樹脂などが挙げられる。 <Gasket>
The gasket is not particularly limited as long as it is a material that can maintain insulation between the positive electrode case and the negative electrode case, and can be appropriately selected according to the purpose. For example, a polyester resin such as polyethylene terephthalate, Examples thereof include fluorine resins such as polytetrafluoroethylene, polyphenylene sulfide resins, polyetherimide resins, and polyamide resins.
　図１は、コイン形の空気電池２０を表す概略断面図である。空気電池２０は、空気孔１０を有する正極ケース１に、本発明の前記フィルタ１１（吸着膜４、キレート膜５、酸性固体膜６）、正極触媒７、セパレータ８、負極活物質９、及び負極ケース３を重ね合わせ、前記正極ケース１と前記負極ケース３との間をガスケット２で封止した構造となっている。なお、前記フィルタ１１、前記正極触媒７、前記セパレータ８、及び前記負極活物質９は、電解液（不図示）に浸っている。 FIG. 1 is a schematic sectional view showing a coin-shaped air battery 20. The air battery 20 includes a positive electrode case 1 having an air hole 10, the filter 11 (adsorption film 4, chelate film 5, acidic solid film 6) of the present invention, a positive electrode catalyst 7, a separator 8, a negative electrode active material 9, and a negative electrode. The case 3 is overlapped, and the positive electrode case 1 and the negative electrode case 3 are sealed with a gasket 2. The filter 11, the positive electrode catalyst 7, the separator 8, and the negative electrode active material 9 are immersed in an electrolytic solution (not shown).
－形状－
　本発明の空気電池の形状は、特に制限はなく、目的に応じて適宜選択することができ、例えば、コイン型空気電池、ボタン型空気電池、シート型空気電池、積層型空気電池、円筒型空気電池、偏平型空気電池、角型空気電池などが挙げられる。 -shape-
The shape of the air battery of the present invention is not particularly limited and can be appropriately selected depending on the purpose. For example, a coin-type air battery, a button-type air battery, a sheet-type air battery, a stacked air battery, a cylindrical air Examples thereof include a battery, a flat air battery, and a square air battery.
－用途－
　本発明の空気電池は、電池内部から電解液が漏洩しても金属イオンを確実にトラップして金属イオンの漏れ出しを防止することができるので、例えば、携帯電話、ノートパソコン等のモバイル機器用途、小型電子機器、補聴器、ハイブリッド自動車、電気自動車、分散型家庭用電源、分散型事業用電源、電力貯蔵用電池などに幅広く利用可能である。 -Applications-
Since the air battery of the present invention can reliably trap metal ions and prevent the metal ions from leaking even if the electrolyte leaks from the inside of the battery, it can be used for mobile devices such as mobile phones and laptop computers. It can be widely used in small electronic devices, hearing aids, hybrid vehicles, electric vehicles, distributed household power supplies, distributed business power supplies, power storage batteries, and the like.
　以下、実施例を挙げて本発明をより具体的に説明するが、本発明は、これらの実施例に何ら制限されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
－フィルタの作製－
　ろ紙（厚み０．１ｍｍ、直径１８ｍｍ）に、活性炭（商品名：電化ブラック、電気化学工業社製）の１０質量％ノルマルプロピルアルコール（関東化学株式会社製）のスラリーを塗布し、乾燥させて、平均厚み３５０μｍの吸着膜を作製した。
　ろ紙（厚み０．１ｍｍ、直径１８ｍｍ）に、ＥＤＴＡ(関東化学株式会社製)の１質量％エタノール溶液を含浸させ、乾燥させて、平均厚み３５０μｍのキレート膜を作製した。
　ろ紙（厚み０．１ｍｍ、直径１８ｍｍ）に、塩化アンモニウム（関東化学株式会社製）の１質量％水溶液を含浸させ、乾燥させて、平均厚み３５０μｍの酸性固体膜を作製した。
　作製した吸着膜と、キレート膜と、酸性固体膜とをこの順に重ね合わせて、実施例１のフィルタを作製した。 Example 1
-Preparation of filter-
Apply a slurry of 10% by mass normal propyl alcohol (manufactured by Kanto Chemical Co., Inc.) of activated carbon (trade name: Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.) to filter paper (thickness 0.1 mm, diameter 18 mm), and dry. An adsorption film having an average thickness of 350 μm was produced.
Filter paper (thickness 0.1 mm, diameter 18 mm) was impregnated with a 1% by mass ethanol solution of EDTA (manufactured by Kanto Chemical Co., Ltd.) and dried to produce a chelate film having an average thickness of 350 μm.
A filter paper (thickness 0.1 mm, diameter 18 mm) was impregnated with a 1% by weight aqueous solution of ammonium chloride (manufactured by Kanto Chemical Co., Ltd.) and dried to prepare an acidic solid film having an average thickness of 350 μm.
The produced adsorption film, chelate film, and acidic solid film were superposed in this order to produce the filter of Example 1.
（実施例２）
－フィルタの作製－
　実施例１において、吸着膜を有さない以外は、実施例１と同様にして、キレート膜と酸性固体膜とからなる実施例２のフィルタを作製した。 (Example 2)
-Preparation of filter-
In Example 1, a filter of Example 2 composed of a chelate film and an acidic solid film was produced in the same manner as Example 1 except that it did not have an adsorption film.
（実施例３）
－フィルタの作製－
　実施例１において、酸性固体膜を有さない以外は、実施例１と同様にして、吸着膜とキレート膜からなる実施例３のフィルタを作製した。 (Example 3)
-Preparation of filter-
In Example 1, a filter of Example 3 comprising an adsorption film and a chelate film was produced in the same manner as in Example 1 except that the acidic solid film was not provided.
（実施例４）
－フィルタの作製－
　実施例１において、吸着膜における活性炭を、ゼオライト（商品名：モレキュラーシーブ５Ａ、和光純薬工業株式会社製）に代えた以外は、実施例１と同様にして、実施例４のフィルタを作製した。 Example 4
-Preparation of filter-
In Example 1, the filter of Example 4 was produced in the same manner as in Example 1 except that the activated carbon in the adsorption film was replaced with zeolite (trade name: Molecular Sieve 5A, manufactured by Wako Pure Chemical Industries, Ltd.). .
（実施例５）
－フィルタの作製－
　実施例１において、キレート膜におけるＥＤＴＡを、ＡＳＤＡ（商品名：Ｌ－アスパラギン酸Ｎ，Ｎ－２酢酸、三菱レイヨン株式会社製）に代えた以外は、実施例１と同様にして、実施例５のフィルタを作製した。 (Example 5)
-Preparation of filter-
Example 5 was the same as Example 1 except that EDTA in the chelate film was changed to ASDA (trade names: L-aspartic acid N, N-2 acetic acid, manufactured by Mitsubishi Rayon Co., Ltd.). A filter was prepared.
（実施例６）
－フィルタの作製－
　実施例１において、酸性固体膜における塩化アンモニウムを、硫酸アンモニウム（商品名：硫酸アンモニウム、関東化学株式会社製）に代えた以外は、実施例１と同様にして、実施例６のフィルタを作製した。 (Example 6)
-Preparation of filter-
A filter of Example 6 was produced in the same manner as in Example 1 except that ammonium chloride in the acidic solid film was replaced with ammonium sulfate (trade name: ammonium sulfate, manufactured by Kanto Chemical Co., Inc.).
（比較例１）
－フィルタの作製－
　カーボンペーパー（東レインターナシャナル株式会社製、ＴＧＰ－Ｈ－１２０、厚み３５０μｍ）を比較例１のフィルタとして用いた。 (Comparative Example 1)
-Preparation of filter-
Carbon paper (manufactured by Toray International Co., Ltd., TGP-H-120, thickness 350 μm) was used as the filter of Comparative Example 1.
（比較例２）
－フィルタの作製－
　実施例１において、吸着膜及び酸性固体膜を有さない以外は、実施例１と同様にして、キレート膜のみからなる比較例２のフィルタを作製した。 (Comparative Example 2)
-Preparation of filter-
In Example 1, a filter of Comparative Example 2 consisting only of a chelate film was produced in the same manner as Example 1 except that it did not have an adsorption film and an acidic solid film.
　次に、実施例１～６及び比較例１～２のフィルタの内容について、表１にまとめて記載した。
Figure JPOXMLDOC01-appb-T000002
 Next, the contents of the filters of Examples 1 to 6 and Comparative Examples 1 and 2 are summarized in Table 1.
Figure JPOXMLDOC01-appb-T000002
（実施例７）
－空気電池の作製－
　実施例１のフィルタを用い、図１に示すコイン電池（空気電池）（サイズ２０３２、ステンレス製）を作製した。
　・正極触媒としてＢｉ２Ｒｕ２Ｏ７(高純度化学株式会社製)を用いた。
　・セパレータとしてアニオン交換膜（トクヤマ株式会社製)を用いた。
　・正極カバーとしてガス交換口用の直径１ｍｍの空気孔を４つ設けた。
　・負極活物質として亜鉛ペースト（６６質量％のＺｎ粉末、ＫＯＨ電解液の混合物）を用いた。
　そして、空気電池２０は、空気孔１０を有する正極ケース１に、フィルタ１１（吸着膜４、キレート膜５、及び酸性固体膜６）、正極触媒７、セパレータ８、負極活物質９、及び負極ケース３を重ね合わせ、前記正極ケース１と前記負極ケース３との間をガスケット（Ｏリング）２で封止して、空気電池２０を組み立てた。 (Example 7)
-Fabrication of air battery-
A coin battery (air battery) (size 2032, made of stainless steel) shown in FIG. 1 was produced using the filter of Example 1.
- cathode catalyst as Bi 2 Ru 2 O 7 was used (high purity Chemical Co., Ltd.).
An anion exchange membrane (manufactured by Tokuyama Corporation) was used as a separator.
-As a positive electrode cover, four air holes with a diameter of 1 mm for gas exchange ports were provided.
-Zinc paste (a mixture of 66 mass% Zn powder and KOH electrolyte) was used as the negative electrode active material.
The air battery 20 includes a positive electrode case 1 having an air hole 10, a filter 11 (adsorption film 4, chelate film 5, and acidic solid film 6), a positive electrode catalyst 7, a separator 8, a negative electrode active material 9, and a negative electrode case. 3 were stacked and the positive electrode case 1 and the negative electrode case 3 were sealed with a gasket (O-ring) 2 to assemble the air battery 20.
（実施例８～１４及び比較例３～６）
－空気電池の作製－
　実施例７において、フィルタ、及び正極触媒を、表２に示す組み合わせに変えた以外は、実施例７と同様にして、実施例８～１４及び比較例３～６のコイン電池（空気電池）を作製した。 (Examples 8 to 14 and Comparative Examples 3 to 6)
-Fabrication of air battery-
In Example 7, coin batteries (air batteries) of Examples 8 to 14 and Comparative Examples 3 to 6 were obtained in the same manner as Example 7 except that the combinations of the filter and the positive electrode catalyst were changed to those shown in Table 2. Produced.
　次に、作製した実施例７～１４及び比較例３～６の各コイン電池について、以下のようにして、金属イオン濃度、及び導通性を評価した。結果を表２に示す。 Next, for the coin batteries of Examples 7 to 14 and Comparative Examples 3 to 6, the metal ion concentration and conductivity were evaluated as follows. The results are shown in Table 2.
＜金属イオン濃度の測定＞
　温度６０℃で湿度９０％ＲＨの環境下で、作製した各コイン電池を７週間放置する加速劣化試験を行った。
　各コイン電池のガス交換口（空気孔）よりシリンジを用いて、電解液を抜き取った。抜き取った電解液を０．２２μｍ径のテフロン（登録商標）製メンブレンフィルタでろ過し、ろ液を３００倍に純水で希釈して、ＩＣＰ－ＭＳ（高周波誘導結合プラズマ質量分析装置、株式会社島津製作所製、ＩＣＰＭ－８５００）により金属イオン濃度の分析を行った。 <Measurement of metal ion concentration>
An accelerated deterioration test was performed in which each produced coin cell was left for 7 weeks in an environment of a temperature of 60 ° C. and a humidity of 90% RH.
The electrolyte solution was extracted from the gas exchange port (air hole) of each coin battery using a syringe. The extracted electrolyte was filtered through a 0.22 μm-diameter Teflon (registered trademark) membrane filter, and the filtrate was diluted 300-fold with pure water to obtain an ICP-MS (high frequency inductively coupled plasma mass spectrometer, Shimadzu Corporation). The metal ion concentration was analyzed by ICPM-8500 manufactured by Seisakusho.
＜導通性＞
　作製した各空気電池の電圧を、テスター（カスタム社製、ＣＤＭ－２０００Ｄ）を用いて測定した。 <Conductivity>
The voltage of each produced air battery was measured using a tester (Custom, CDM-2000D).
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表２の結果から、実施例１及び実施例４～６の吸着膜とキレート膜と酸性固体膜とからなる３層構成のフィルタを用いた実施例７及び実施例１０～１４の空気電池は、加速劣化試験後の電解液中に金属イオンが含まれていなかった。
　これに対し、比較例１及び２のフィルタを用いた比較例３～６の空気電池は、加速劣化試験後の電解液中に金属イオンが含まれていることが分かった。
　また、実施例２及び３の２層構成のフィルタを用いた実施例８及び９の空気電池は、比較例１及び２のフィルタを用いた比較例３～６の空気電池に比べて、加速劣化試験後の電解液中の金属イオンの濃度が低下していることが分かった。 From the results of Table 2, the air cells of Examples 7 and 10 to 14 using the three-layer filter composed of the adsorption film of Example 1 and Examples 4 to 6, the chelate film, and the acidic solid film are Metal ions were not contained in the electrolyte solution after the accelerated deterioration test.
In contrast, the air batteries of Comparative Examples 3 to 6 using the filters of Comparative Examples 1 and 2 were found to contain metal ions in the electrolytic solution after the accelerated deterioration test.
Further, the air batteries of Examples 8 and 9 using the two-layer filter of Examples 2 and 3 are accelerated and deteriorated as compared with the air batteries of Comparative Examples 3 to 6 using the filters of Comparative Examples 1 and 2. It turned out that the density | concentration of the metal ion in the electrolyte solution after a test is falling.
　本発明のフィルタ及び空気電池は、空気電池内部から電解液が漏洩しても金属イオンを確実にトラップして金属イオンの漏れ出しを防止することができるので、例えば、携帯電話、ノートパソコン等のモバイル機器用途、メモリーバックアップ用電池、小型電子機器、補聴器、ハイブリッド自動車、電気自動車、分散型家庭用電源、分散型事業用電源、電力貯蔵用電池などに幅広く用いることができる。 The filter and air battery of the present invention can reliably trap metal ions and prevent leakage of metal ions even when electrolyte solution leaks from the inside of the air battery. It can be widely used for mobile devices, memory backup batteries, small electronic devices, hearing aids, hybrid vehicles, electric vehicles, distributed household power sources, distributed business power sources, power storage batteries, and the like.
　　　１　　　正極ケース
　　　２　　　ガスケット
　　　３　　　負極ケース
　　　４　　　吸着膜
　　　５　　　キレート膜
　　　６　　　酸性固体膜
　　　７　　　正極触媒層
　　　８　　　セパレータ
　　　９　　　負極活物質
　　１０　　　空気孔
　　１１　　　フィルタ
　　２０　　　空気電池 DESCRIPTION OF SYMBOLS 1 Positive electrode case 2 Gasket 3 Negative electrode case 4 Adsorbed film 5 Chelate film 6 Acidic solid film 7 Positive electrode catalyst layer 8 Separator 9 Negative electrode active material 10 Air hole 11 Filter 20 Air battery

Claims (12)

  1. 　電池の電解液中に含まれる金属イオンと錯体を形成可能なキレート物質を含むキレート膜と、
    　前記金属イオンと前記キレート物質から形成された錯体を吸着可能な吸着物質を含む吸着膜、及び、前記電解液と反応して該電解液の水素イオン濃度を下げることが可能な酸性固体物質を含む酸性固体膜の少なくともいずれかと、を有すること特徴とするフィルタ。     A chelate film containing a chelate substance capable of forming a complex with a metal ion contained in the battery electrolyte;
    An adsorption film including an adsorbent capable of adsorbing a complex formed from the metal ion and the chelate substance, and an acidic solid substance capable of lowering the hydrogen ion concentration of the electrolyte by reacting with the electrolyte A filter comprising at least one of an acidic solid film.
  2. 　吸着膜と、キレート膜と、酸性固体膜と、を有する請求項１に記載のフィルタ。 The filter according to claim 1, comprising an adsorption film, a chelate film, and an acidic solid film.
  3. 　キレート物質が、Ｌ－アスパラギン酸－Ｎ，Ｎ－２酢酸、ｔｒａｎｓ－シクロヘキサンジアミン４酢酸、カルボキシメチルポリエチレンイミン、ジエチレントリアミン６酢酸、１，３－ジアミノ－２－ヒドロキシプロパン４酢酸、ジヒドロキシエチルグリシン、ジヒドロキシエチルエチレンジアミン２酢酸、エチレンジアミン４酢酸、エチレンジアミン４メチレンリン酸、グリコールエーテルジアミン４酢酸、ヒドロキシエチリデン２リン酸、ヒドロキシエチルエチレンジアミン３酢酸、ヒドロキシエチルイミノ２酢酸、ニトリロ３メチレンリン酸、ニトリロ３酢酸、１，３－プロパンジアミン４酢酸、ホスフォノブタントリカルボン酸、及びトリエチレンテトラアミン６酢酸から選択される少なくとも１種である請求項１から２のいずれかに記載のフィルタ。 The chelating substance is L-aspartic acid-N, N-2acetic acid, trans-cyclohexanediaminetetraacetic acid, carboxymethylpolyethyleneimine, diethylenetriaminehexaacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, dihydroxyethylglycine, dihydroxy Ethylethylenediamine diacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetramethylenephosphoric acid, glycol etherdiaminetetraacetic acid, hydroxyethylidene diphosphoric acid, hydroxyethylethylenediaminetriacetic acid, hydroxyethyliminodiacetic acid, nitrilo-3-methylenephosphoric acid, nitrilotriacetic acid, 1 3. At least one selected from 1,3-propanediaminetetraacetic acid, phosphonobutanetricarboxylic acid, and triethylenetetraaminehexaacetic acid. Filter according to.
  4. 　吸着物質が、活性炭、ゼオライト、及びシリカゲルから選択される少なくとも１種である請求項１から３のいずれかに記載のフィルタ。 The filter according to any one of claims 1 to 3, wherein the adsorbing substance is at least one selected from activated carbon, zeolite, and silica gel.
  5. 　酸性固体物質が、塩化アンモニウム、硫酸アンモニウム、硝酸アンモニウム、及びγ－アルミナ・シリカから選択される少なくとも１種である請求項１から４のいずれかに記載のフィルタ。 5. The filter according to claim 1, wherein the acidic solid substance is at least one selected from ammonium chloride, ammonium sulfate, ammonium nitrate, and γ-alumina-silica.
  6. 　キレート膜、吸着膜、及び酸性固体膜の少なくともいずれかが、基材を有する請求項１から５のいずれかに記載のフィルタ。 The filter according to any one of claims 1 to 5, wherein at least one of the chelate film, the adsorption film, and the acidic solid film has a base material.
  7. 　空気電池の金属イオントラップ用である請求項１から６のいずれかに記載のフィルタ。 The filter according to any one of claims 1 to 6, which is used for a metal ion trap of an air battery.
  8. 　請求項１から７のいずれかに記載のフィルタを有することを特徴とする空気電池。 An air battery comprising the filter according to any one of claims 1 to 7.
  9. 　正極ケースと、正極触媒と、セパレータと、負極活物質と、負極ケースとを有してなり、前記正極ケースと前記正極触媒の間にフィルタを有する請求項８に記載の空気電池。 The air battery according to claim 8, comprising a positive electrode case, a positive electrode catalyst, a separator, a negative electrode active material, and a negative electrode case, and having a filter between the positive electrode case and the positive electrode catalyst.
  10. 　フィルタが、正極ケース側から、吸着膜と、キレート膜と、酸性固体膜とをこの順に有する請求項９に記載の空気電池。 10. The air battery according to claim 9, wherein the filter has an adsorption film, a chelate film, and an acidic solid film in this order from the positive electrode case side.
  11. 　正極触媒が、パイロクロア型金属酸化物、及び酸素欠陥パイロクロア型金属酸化物のいずれかからなる請求項９から１０のいずれかに記載の空気電池。 The air battery according to any one of claims 9 to 10, wherein the positive electrode catalyst is composed of either a pyrochlore type metal oxide or an oxygen-deficient pyrochlore type metal oxide.
  12. 　正極触媒が、Ｂｉ２Ｒｕ２Ｏ７、Ｐｂ２Ｒｕ２Ｏ６、及びＰｂ２Ｉｒ２Ｏ６．５から選択される少なくとも１種である請求項９から１１のいずれかに記載の空気電池。 The air battery according to claim 9, wherein the positive electrode catalyst is at least one selected from Bi 2 Ru 2 O 7 , Pb 2 Ru 2 O 6 , and Pb 2 Ir 2 O 6.5 .
PCT/JP2011/053421 2011-02-17 2011-02-17 Filter and air cell WO2012111134A1 (en)

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WO2013161552A1 (en) * 2012-04-26 2013-10-31 日産自動車株式会社 Metal-air cell, and method for recovering metal from used metal- air cell
JP2015529945A (en) * 2012-08-03 2015-10-08 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ Air breathing cathode for metal-air battery
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