WO2012111134A1 - Filtre et pile à dépolarisation par l'air - Google Patents

Filtre et pile à dépolarisation par l'air 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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WIPO (PCT)
Prior art keywords
acid
film
filter
chelate
positive electrode
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PCT/JP2011/053421
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English (en)
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/fr
Publication of WO2012111134A1 publication Critical patent/WO2012111134A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Hybrid Cells (AREA)

Abstract

La présente invention concerne un filtre comprenant : un film chélaté, comprenant une substance chélatée capable de former un complexe avec des ions métalliques inclus dans un électrolyte dans une batterie ; et au moins soit un film adsorbant comprenant une substance adsorbante capable d'adsorber un complexe formé par les ions métalliques et la substance chélatée ou un film solide acide comprenant une substance solide acide capable de réagir avec l'électrolyte et de réduire la concentration d'ions hydrogène dans l'électrolyte. Un mode de réalisation comprenant le film adsorbant, le film chélaté et le film solide acide est préféré.
PCT/JP2011/053421 2011-02-17 2011-02-17 Filtre et pile à dépolarisation par l'air WO2012111134A1 (fr)

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WO2013161552A1 (fr) * 2012-04-26 2013-10-31 日産自動車株式会社 Pile métal-air et procédé de récupération du métal à partir d'une pile métal-air usagée
JP2014165099A (ja) * 2013-02-27 2014-09-08 Sumitomo Chemical Co Ltd 空気二次電池
JP2015529945A (ja) * 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 金属空気電池用エアーブリージングカソード
JP2020126754A (ja) * 2019-02-04 2020-08-20 Fdk株式会社 空気二次電池用の空気極触媒及び空気二次電池
CN116454287A (zh) * 2023-06-16 2023-07-18 广州纳诺新材料技术有限公司 一种高循环性能锂电池、集流体及其制备方法

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JP2001223015A (ja) * 1999-11-29 2001-08-17 Toyota Central Res & Dev Lab Inc 高耐久性固体高分子電解質及びその高耐久性固体高分子電解質を用いた電極−電解質接合体並びにその電極−電解質接合体を用いた電気化学デバイス
JP2009026484A (ja) * 2007-07-17 2009-02-05 Toyota Motor Corp 固体高分子電解質膜、固体高分子電解質膜の製造方法および燃料電池
JP2010153234A (ja) * 2008-12-25 2010-07-08 Equos Research Co Ltd 空気電池
JP2010244729A (ja) * 2009-04-01 2010-10-28 Toyota Motor Corp 空気電池

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JP2001223015A (ja) * 1999-11-29 2001-08-17 Toyota Central Res & Dev Lab Inc 高耐久性固体高分子電解質及びその高耐久性固体高分子電解質を用いた電極−電解質接合体並びにその電極−電解質接合体を用いた電気化学デバイス
JP2009026484A (ja) * 2007-07-17 2009-02-05 Toyota Motor Corp 固体高分子電解質膜、固体高分子電解質膜の製造方法および燃料電池
JP2010153234A (ja) * 2008-12-25 2010-07-08 Equos Research Co Ltd 空気電池
JP2010244729A (ja) * 2009-04-01 2010-10-28 Toyota Motor Corp 空気電池

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013161552A1 (fr) * 2012-04-26 2013-10-31 日産自動車株式会社 Pile métal-air et procédé de récupération du métal à partir d'une pile métal-air usagée
JP2015529945A (ja) * 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 金属空気電池用エアーブリージングカソード
JP2014165099A (ja) * 2013-02-27 2014-09-08 Sumitomo Chemical Co Ltd 空気二次電池
JP2020126754A (ja) * 2019-02-04 2020-08-20 Fdk株式会社 空気二次電池用の空気極触媒及び空気二次電池
JP7149525B2 (ja) 2019-02-04 2022-10-07 Fdk株式会社 空気二次電池用の空気極触媒及び空気二次電池
CN116454287A (zh) * 2023-06-16 2023-07-18 广州纳诺新材料技术有限公司 一种高循环性能锂电池、集流体及其制备方法
CN116454287B (zh) * 2023-06-16 2023-08-25 广州纳诺新材料技术有限公司 一种高循环性能锂电池、集流体及其制备方法

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