WO2020179645A1 - Électrode négative et batterie métal-air - Google Patents

Électrode négative et batterie métal-air Download PDF

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Publication number
WO2020179645A1
WO2020179645A1 PCT/JP2020/008201 JP2020008201W WO2020179645A1 WO 2020179645 A1 WO2020179645 A1 WO 2020179645A1 JP 2020008201 W JP2020008201 W JP 2020008201W WO 2020179645 A1 WO2020179645 A1 WO 2020179645A1
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Prior art keywords
negative electrode
case
positive electrode
metal
opening
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PCT/JP2020/008201
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English (en)
Japanese (ja)
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俊輔 佐多
宏隆 水畑
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シャープ株式会社
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Priority to JP2021504036A priority Critical patent/JP7223114B2/ja
Publication of WO2020179645A1 publication Critical patent/WO2020179645A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • 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 disclosure relates to a negative electrode and a metal-air battery.
  • the present application claims priority based on Japanese Patent Application No. 2019-039922 filed in Japan on March 5, 2019, the content of which is incorporated herein by reference.
  • a metal-air battery has a positive electrode (air electrode), a negative electrode (metal negative electrode), and an electrolyte (electrolyte solution) and has a high energy density. Therefore, development and research for practical use and secondary battery development have been carried out. It is being advanced.
  • an insulating separator is interposed between the positive electrode and the negative electrode and is housed in an outer container.
  • the metal contained in the negative electrode becomes metal ions during discharge, diffuses into the electrolyte, and becomes needle-like and deposits during charging. Therefore, in the metal-air battery, there is a risk that dendrites (needle-shaped metal deposits) grown by repeated charging/discharging may penetrate the separator and short-circuit the positive electrode and the negative electrode.
  • Patent Document 1 by providing an anion conductive film as a separator between a positive electrode and a negative electrode of a metal-air battery, a metal is obtained while ensuring good permeability of anions necessary for an electrode reaction.
  • a configuration is disclosed in which the growth of dendrite that causes a short circuit between the positive electrode and the negative electrode is suppressed while suppressing the diffusion of ions.
  • the negative electrode is pressure-bonded to the positive electrode via the anion conductive film that is the separator. This is intended to prevent the negative electrode active material from sliding off from the surface of the negative electrode that is in close contact with the positive electrode via the separator due to the action of gravity.
  • friction is generated between the anion conductive film and the positive electrode because the positive electrode is pressure-bonded to the anion conductive film.
  • the anion conductive membrane may be pressed against the positive electrode. Due to such friction and pressure, the anion conductive film is likely to be damaged or burst, and dendrite is generated, which causes a short circuit between the positive electrode and the negative electrode.
  • the present disclosure has been made in view of the above-mentioned conventional problems, and an object thereof is a negative electrode suitable for suppressing the growth of dendrites and suppressing a short circuit between electrodes, and a negative electrode thereof. Is to provide a metal-air battery equipped with.
  • a negative electrode of the present disclosure for achieving the above object is a negative electrode current collector including a resin case having at least one opening, a portion housed in the case, and a portion extended from the case.
  • the negative electrode active material is housed in the case and the slippage is suppressed.
  • the first porous membrane is arranged between the anion conducting membrane and the opening of the case, it is possible to prevent the anion conducting membrane from being damaged. By preventing damage to the anion-conducting membrane, it is possible to eliminate the path through which dendrites grow. Therefore, the growth of dendrites can be effectively suppressed, and short circuits between the electrodes can be prevented.
  • the opening is preferably covered with the first porous film inside the case.
  • the negative electrode expands due to repeated charging and discharging, and the space between the opening peripheral edge of the case and the anion conductive film, which tends to be a growth path for dendrites, can be reinforced by the first porous film. It is possible to prevent damage/damage to the anion-conductive membrane or peeling of the anion-conductive membrane from the opening peripheral portion of the case.
  • the integrity of the case and the first porous film is enhanced, the growth path of dendrites is blocked, and a short circuit between the electrodes can be prevented.
  • the case and the first porous film are welded.
  • each component of the case and the first porous membrane is melted, and the pores of the first porous membrane can be closed. Therefore, even in the peripheral portion of the first porous film, which is likely to become a growth path for dendrites, the growth path for dendrites can be blocked and a short circuit between electrodes can be prevented.
  • the anion conductive film is in contact with the inner surface of the case.
  • the growth path of dendrites can be narrowed while maintaining the distance between the positive electrode and the negative electrode, so that it becomes possible to further prevent a short circuit between the electrodes.
  • the anion conductive film is covered with the first porous film from the inside of the case and extends outward from a peripheral portion of the first porous film. .. Even with such a configuration, the growth path of the dendrite can be narrowed, so that short circuits between the electrodes can be further prevented.
  • the anion conductive membrane in the negative electrode having the above-mentioned configuration is configured to include a polymer containing an anion exchange group or a layered double hydroxide.
  • the anion conductive film is preferably configured so as to suppress the permeation of zincate ions and allow the permeation of hydroxide ions. With such a configuration, the anion conductive film can be provided with good anion permeation performance.
  • the air permeability of the first porous film in the negative electrode having the above-mentioned structure is preferably 0.1 to 1000 seconds in terms of Gurley value.
  • the first porous membrane has a large number of micropores having communication, and the average pore diameter of the micropores is 0.1 to 100 ⁇ m.
  • the negative electrode having the above configuration may be configured to include a second porous film between the anion conductive film and the negative electrode active material layer. This makes it possible to further prevent damage to the anion conductive film and the like.
  • the case contains an electrolyte.
  • the electrolyte can be held in the case and the charge/discharge reaction can be efficiently performed.
  • the metal air cell of the present disclosure includes a negative electrode, a positive electrode, and an electrolyte, and the negative electrode is housed in a resin case having at least one opening and the case, and is extended from the case.
  • An anion conductive film is provided between the film and the negative electrode active material layer, and the positive electrode is provided so as to face the opening.
  • a metal-air battery having a structure capable of suppressing the growth of dendrites in the negative electrode and preventing a short circuit between the electrodes.
  • the positive electrode includes a first positive electrode for discharging and a second positive electrode for charging, and the first positive electrode, the second positive electrode, the negative electrode, It is preferable that they are arranged in the order of.
  • first openings and second openings are provided as the openings on both sides of the negative electrode active material layer in the thickness direction, respectively, and the positive electrode is a first for discharge.
  • the metal-air battery can effectively block the growth path of dendrites and prevent short circuits between electrodes.
  • the negative electrode and the metal-air battery including the negative electrode according to the present disclosure it is possible to prevent damage and breakage of the anion conductive membrane, suppress growth of dendrites that cause a short circuit between the electrodes, and improve battery performance. Can be made.
  • FIG. 1 It is sectional drawing which shows typically the negative electrode which concerns on Embodiment 1 of this disclosure. It is a perspective view which shows the negative electrode. It is a perspective view which shows the metal-air battery which concerns on Embodiment 1 of this disclosure. It is a perspective view which shows the negative electrode which concerns on Embodiment 2.
  • FIG. 2 It is a partially enlarged sectional view which shows the negative electrode schematically. It is sectional drawing which shows typically the negative electrode which concerns on Embodiment 3. It is sectional drawing which shows typically the negative electrode which concerns on Embodiment 4.
  • FIG. It is sectional drawing which shows typically the metal-air battery which concerns on Embodiment 5. It is sectional drawing which shows typically the metal-air battery which concerns on Embodiment 6.
  • FIG. 1 is a cross-sectional view schematically showing a negative electrode 1 according to the first embodiment of the present disclosure.
  • FIG. 2 is a perspective view showing the negative electrode 1 according to the first embodiment.
  • the upper part in the drawing in FIG. 1 will be described below assuming that the negative electrode 1 and the metal-air battery 10 provided with the negative electrode 1 are above.
  • the negative electrode 1 contains a metal serving as an electrode active material, constitutes a metal-air battery 10 together with a positive electrode 8 and a battery case 9, and extracts electrical energy obtained in the process of converting a metal into a metal oxide by an electrochemical reaction. ..
  • the negative electrode 1 includes a resin negative electrode case (case) 2, a negative electrode current collector 3, a negative electrode active material layer 4, a first porous film 5, and an anion conductive film 6.
  • the negative electrode case 2 of the negative electrode 1 is provided with at least one opening 20 and houses the negative electrode current collector 3 inside.
  • the negative electrode case 2 is formed by, for example, folding and joining one or a plurality of sheet-shaped insulating film materials.
  • the negative electrode case 2 is provided with the openings 20 penetrating in and out so that both the one surface and the other surface of the negative electrode current collector 3 are opposed to each other. That is, the openings 20 are formed in the negative electrode case 2 on the surfaces facing each other with the negative electrode current collector 3 interposed therebetween.
  • the size of each opening 20 is smaller than the size of either surface of the negative electrode current collector 3 housed in the negative electrode case 2.
  • the dendrite easily grows at the end of the negative electrode current collector 3 or the negative electrode active material layer 4. Therefore, by making the size of each opening 20 smaller than the size of one of the surfaces of the negative electrode current collector 3, the electrode reaction is less likely to occur at the end of the negative electrode current collector 3 or the negative electrode active material layer 4. Therefore, the growth of dendrite can be suppressed.
  • the negative electrode current collector 3 is made of a porous material having electronic conductivity.
  • a material having a high hydrogen overvoltage or a material obtained by plating a metal material surface such as stainless steel with a material having a high hydrogen overvoltage is used.
  • the negative electrode current collector 3 may be formed of a mesh, an expanded metal, a punching metal, a sintered body of metal particles or metal fibers, a foam metal, or the like.
  • the negative electrode current collector 3 has a lead portion 31 extending as a negative electrode terminal so that it can be electrically connected to an external circuit.
  • the negative electrode current collector 3 is housed in the negative electrode case 2 with the lead portion 31 extending from the upper portion of the negative electrode case 2. As a result, it is possible to transfer the electric charge consumed or generated by the negative electrode 1 to an external circuit (not shown).
  • the negative electrode active material layer 4 is arranged in the negative electrode case 2 so as to be in contact with both surfaces of the negative electrode current collector 3, and has a negative electrode active material containing a metal element as an electrode active material.
  • a metal element zinc, lithium, sodium, calcium, magnesium, aluminum, iron and the like are preferable.
  • the negative electrode active material layer 4 may be a layer made of a metal in a reduced state or a layer made of a metal in an oxidized state.
  • particulate zinc or zinc oxide can be used for the negative electrode active material layer 4.
  • the metallic element is zinc, it is metallic zinc in the reduced state and zinc oxide in the oxidized state.
  • the negative electrode 1 containing zinc can be taken out from the battery case 9 after discharging, and zinc oxide can be reduced to zinc.
  • the metal element is zinc
  • an oxidation reaction of metallic zinc occurs during discharge. That is, as a result of oxidation of zinc, zinc oxide may be dissolved in the electrolytic solution as zincate ions, or zinc oxide or zinc hydroxide may be directly produced.
  • a reduction reaction to metallic zinc occurs. That is, zinc may be produced by reduction of zincate ions dissolved in the electrolytic solution, or zinc oxide or zinc hydroxide may be directly reduced to zinc.
  • First porous membrane 5 Each of the two openings 20 of the negative electrode case 2 is provided with a first porous film 5 having an insulating porous structure, and these openings 20 are covered.
  • the first porous film 5 is housed inside the negative electrode case 2, and is arranged so as to cover the opening 20 from the inside of the negative electrode case 2.
  • a first porous film 5 is arranged between an anion conductive film 6 described later and an opening 20. Further, the positive electrode 8 described later is closely arranged in the first porous film 5 through the opening 20 of the negative electrode case 2.
  • the first porous film 5 covers the opening 20 of the negative electrode case 2, is interposed between the internal and external constituent members of the negative electrode case 2, and acts as a buffer layer for these components. That is, the first porous membrane 5 prevents the anion conductive membrane 6 arranged in the negative electrode case 2 from coming into contact with the edge portion of the opening 20.
  • the positive electrode 8 arranged outside the negative electrode case 2 comes into contact with the opening 20 but does not come into contact with the anion conductive film 6 and is arranged.
  • FIG. 1 shows a configuration in which the first porous film 5 is arranged from the inside of the negative electrode case 2 so as to cover the opening 20, the first porous film 5 is provided from the outside of the negative electrode case 2 to the opening 20. You may arrange so that it may be covered. Even in such an arrangement form, it is possible to prevent the positive electrode 8 arranged outside the negative electrode case 2 from coming into contact with the anion conductive film 6.
  • the disposition of covering the opening 20 from the inside of the negative electrode case 2 is more desirable than the disposition of covering the opening 20 from the outside. This is because when the first porous film 5 is arranged so as to cover the opening 20 from the inside of the negative electrode case 2, it is possible to prevent the edge portion of the opening 20 and the positive electrode 8 from contacting the anion conductive film. ..
  • the first porous membrane 5 is responsible for ionic conductivity between the positive electrode 8 and the negative electrode 1, it is formed of a porous member capable of holding an electrolyte in the pores, and a non-woven fabric made of polyolefin, filter paper, or the like may be used. it can.
  • the first porous membrane 5 may contain, for example, an inorganic substance such as titanium oxide, niobium oxide, and tantalum oxide.
  • the first porous membrane 5 preferably has an air permeability represented by a Garley value of 0.1 to 1000 seconds.
  • the Garley value is an index showing the ease of passage of gas, and the larger the value, the more difficult it is for gas to pass through.
  • the Garley value of the first porous membrane 5 can be easily measured by the measuring method specified in JIS P8117.
  • the Garley value in the first porous membrane 5 is preferably 0.1 seconds or more.
  • the Garley value is preferably up to 1000 seconds, and the upper limit is more preferably 100 seconds.
  • the Gurley value is less than 0.1 seconds, there are too many voids, the strength required as a buffer layer is insufficient, and the first porous film 5 may be damaged. If the Gurley value is greater than 1000 seconds, the voids are too small, which hinders ionic conduction and causes an increase in battery resistance.
  • the average pore diameter of these micropores is 0.1 to 100 ⁇ m.
  • the average pore diameter of the micropores is 1 to 50 ⁇ m.
  • the first porous membrane 5 has a non-uniform pore size in the case of a non-woven fabric or a woven fabric, but it is preferable to configure the average pore size within the above range.
  • An anion conducting film 6 is arranged between the first porous film 5 and the negative electrode active material layer 4.
  • the anion conductive film 6 enables the movement of anions between these members while ensuring the insulating property between the positive electrode 8 and the negative electrode 1, and prevents a short circuit due to the formation of an electron conduction path between the electrodes.
  • the anion conductive film 6 is a film that permeates anions such as hydroxide ions (OH ⁇ ) involved in the battery reaction, and contains organic substances and inorganic substances.
  • the anion conductive membrane 6 has conductivity of hydroxide ions and allows the penetration of hydroxide ions. On the other hand, it is preferable that the anion conductive film 6 suppresses the permeation of zincate ions and inhibits the diffusion of zincate ions.
  • the anion conductive film 6 has the selectivity of the permeating anion due to the action of an inorganic substance or the like described later.
  • the selectivity of the anion is such that, for example, an anion such as a hydroxide ion easily permeates, and even an anion has a large ionic radius and sufficiently prevents the permeation of a metal-containing ion derived from an active material.
  • the anion conduction in the anion-conducting membrane 6 means that anions having a small ionic radius such as hydroxide ions sufficiently permeate, and have anion permeability. Anions having a large ionic radius, such as metal-containing ions, are more difficult to permeate and do not have to permeate at all.
  • the inorganic substances contained in the anion conductive film 6 include alkali metals, alkaline earth metals, Mg, Sc, Y, lanthanoids, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe and Ru. , Co, Ni, Pd, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, C, Si, Ge, Sn, Pb, N, P, Sb, Bi, S, Se, Te It is preferable that at least one element selected from the group consisting of F, Cl, and Br is included.
  • the inorganic substance examples include layered inorganic compounds such as oxides, composite oxides and layered compound hydroxides, hydroxides, clay compounds, solid solutions, alloys, zeolites, halides, carboxylate compounds, carbonate compounds and hydrogen carbonates.
  • layered inorganic compounds such as oxides, composite oxides and layered compound hydroxides, hydroxides, clay compounds, solid solutions, alloys, zeolites, halides, carboxylate compounds, carbonate compounds and hydrogen carbonates.
  • oxides, composite oxides, layered double hydroxides such as hydrotalcite, hydroxides, clay compounds, solid solutions, zeolites, fluorides, phosphoric acid compounds, boric acid compounds, silicic acid compounds, aluminate compounds, Salt is preferred.
  • the oxide for example, cerium oxide and zirconium oxide are preferable. More preferably, it is cerium oxide.
  • the cerium oxide may be, for example, one doped with a metal oxide such as samarium oxide, gadolinium oxide, or bismuth oxide, or a solid solution with a metal oxide such as zirconium oxide.
  • the oxide may have an oxygen defect.
  • As the hydroxide for example, magnesium hydroxide, cerium hydroxide, and zirconium hydride are preferable.
  • the layered inorganic compound constituting the anion conductive film 6 may have only one layer or two or more layers laminated.
  • Examples of the layered inorganic compound include layered double hydroxides. This layered double hydroxide has the following formula: [M 1 1 - x M 2 x (OH) 2] (A n-) x / n ⁇ mH 2 O (M 1 represents a divalent metal ion which is any one of Mg, Fe, Zn, Ca, Li, Ni, Co, Cu and Mn. M 2 represents Al, Fe, Mn, Co, Cr and In.
  • a n- represents a monovalent to trivalent anion such as OH ⁇ , Cl ⁇ , NO 3 ⁇ , CO 3 2 ⁇ , COO ⁇ , and m is 0 or more.
  • N is a number of 1 to 3.
  • x is a number of 0.20 to 0.40).
  • a n ⁇ is a divalent or less anion.
  • the anion conductive film 6 is composed of the layered double hydroxide
  • Examples of the organic substance contained in the anion conductive film 6 include hydrocarbon site-containing polymers typified by polyolefins such as polyethylene and polypropylene, aromatic group-containing polymers typified by polystyrene and the like; alkylene glycols such as polyethylene oxide and polypropylene oxide.
  • Typical ether group-containing polymers for polyvinyl alcohol, poly ( ⁇ -hydroxymethylacrylate), cellulose, methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyalkyl cellulose (for example, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), etc.
  • hydroxyl group-containing polymer amide bond-containing polymer represented by polyamide, nylon, polyacrylamide, polyvinylpyrrolidone, N-substituted polyacrylamide, etc .; imide bond-containing polymer represented by polymaleimide, polyimide, etc.; (meth) acrylic (Meth)acrylic polymer containing a monomer unit derived from an acid alkyl ester monomer as a main component; poly(meth)acrylic acid (salt), polymaleic acid (salt), polyitaconic acid (salt), polymethylene glutaric acid (salt), Carboxy group-containing polymers typified by carboxymethyl cellulose (including metal salts of carboxy groups (alkali metals, etc.), ammonium salts, etc.); poly (meth) acrylate, polymaleate, polyitaconate, polymethyleneglutaric acid Carboxylate-containing polymers typified by salts; halogen atom-containing polymers such as polyvinyl chloride
  • R 1 , R 2 and R 3 are the same or different. Represents an alkyl group having 1 to 7 carbon atoms, a hydroxyalkyl group, an alkylcarboxyl group, and an aromatic ring group. R 1 , R 2 , and R 3 may be bonded to form a ring structure).
  • a quaternary ammonium salt or a quaternary phosphonium salt-containing polymer typified by a polymer to which the groups to be bonded; an ion-exchangeable polymer used for a cation / anion exchange film, etc .; a main component of natural rubber, artificial rubber, etc.
  • Rubbery polymers with unsaturated carbon bonds in the chain cellulose acetate, chitin, chitosan, a Sugars typified by ruginic acid (salt); amino group-containing polymers typified by polyethyleneimine; carbamate group-containing polymers; carbamide group-site-containing polymers; epoxy group-site-containing polymers; heterocycles and / or ionized Examples thereof include a heterocyclic site-containing polymer; a polymer alloy; a heteroatom-containing polymer; a low molecular weight surfactant, and one or more of these can be used.
  • An electrolyte is housed in the negative electrode case 2 containing the negative electrode current collector 3, the negative electrode active material layer 4, the anion conductive film 6, and the first porous film 5.
  • the electrolyte is not particularly limited as long as it is usually used as an electrolyte for a battery, and examples thereof include a water-containing electrolyte and an organic solvent-based electrolyte, and a water-containing electrolyte is more preferable.
  • the water-containing electrolytic solution refers to an electrolytic solution that uses only water as a solvent raw material (aqueous electrolytic solution) or an electrolytic solution that uses a liquid obtained by adding an organic solvent to water as a solvent raw material.
  • aqueous electrolyte examples include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, lithium hydroxide aqueous solution, zinc sulfate aqueous solution, zinc nitrate aqueous solution, zinc phosphate aqueous solution, zinc acetate aqueous solution, and the like.
  • the electrolyte is not particularly limited, but when an aqueous electrolytic solution is used, it is preferably a compound that generates a hydroxide ion responsible for ion conduction in the system. From the viewpoint of ionic conductivity, an aqueous potassium hydroxide solution is more preferable.
  • the aqueous electrolytic solution may be one type or two or more types.
  • the electrolytic solution immerses the negative electrode 1 and the positive electrode 8 in the battery case 9.
  • the negative electrode 1 (and the metal-air battery 10) according to the first embodiment there is no liquid layer of the electrolytic solution, and the negative electrode 1 and the positive electrode 8 are immersed in the electrolytic solution in a wet state. ..
  • an alkaline aqueous solution such as an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide can be used as the electrolytic solution.
  • a sodium chloride aqueous solution can be used as the electrolytic solution
  • an organic electrolytic solution can be used.
  • An organic additive or an inorganic additive other than the electrolyte may be added to the electrolytic solution, or it may be gelled with a polymer additive.
  • the negative electrode current collector 3, the negative electrode active material layer 4, the anion conductive film 6, and the first porous film 5 are contained in the negative electrode case 2 and housed in the battery case 9 constituting the metal-air battery 10.
  • the negative electrode case 2 ensures the insulation between the negative electrode current collector 3 and the positive electrode 8 in the battery case 9.
  • the negative electrode case 2 is formed in the shape of a bag with a bottom and an open top before being stored in the battery case 9. You can The negative electrode case 2 has a margin for heat fusion secured on the upper side, and the upper side may be heat fused and sealed after the injection of the electrolytic solution.
  • the material of the negative electrode case 2 is not particularly limited as long as it is made of a material that can prevent the permeation of the electrolytic solution required for this type of metal-air battery 10 and can function as an insulating member.
  • it is formed of a thermoplastic resin material having good insulating properties, less likely to cause wrinkles, and high heat resistance.
  • polyolefin-based resin materials such as polyethylene (PE) and polypropylene (PP) can be preferably used.
  • the thickness of the polyolefin-based resin material is preferably 0.2 mm or less, more preferably 30 to 150 ⁇ m, and more preferably 50 to 100 ⁇ m.
  • the negative electrode 1 has a structure in which the negative electrode active material and the electrolyte serving as a conduction path for hydroxide ions (OH ⁇ ) are efficiently in contact with each other. By doing so, the electrolytic solution permeates into the voids between the particles of the active material particles. As a result, the contact interface between the active material particles and the electrolytic solution can be widened.
  • the negative electrode active material layer 4 may be configured to include a binder, and by including the binder, the negative electrode active materials can be bound to each other.
  • FIG. 3 is a perspective view showing the metal-air battery 10 according to the first embodiment.
  • the metal-air battery 10 includes a battery case 9, a negative electrode 1, and a positive electrode 8.
  • the positive electrodes 8 constituting the metal-air battery 10 are a discharge positive electrode (air electrode) 81 which is a first positive electrode for discharge and a charging positive electrode which is a second positive electrode for charging. 82 and.
  • a discharge positive electrode 81 is arranged on one surface of the negative electrode case 2 of the negative electrode 1, and a charging positive electrode 82 is arranged on the other surface.
  • the battery case 9 is an outer container that houses the negative electrode 1, the discharging positive electrode 81, and the charging positive electrode 82.
  • the battery case 9 is arranged outside the negative electrode case 2 and is configured to include the negative electrode 1.
  • the first case 91 arranged to face one opening 20 of the negative electrode case 2 and the second case 92 arranged to face the other opening 20 of the negative electrode case 2 are provided. , Are formed by being bonded to each other with the negative electrode 1 included inside.
  • the opening is the air intake port 93.
  • the opening is a gas discharge port 94.
  • the battery case 9 is capable of taking in air through these air intake ports 93, and at the same time, through the gas exhaust port 94, gas such as oxygen generated at the time of charging and accumulated in the vicinity of the charging electrode is collected. It is possible to discharge to the outside.
  • the first case 91 and the second case 92 are arranged to face each other and are fused at the outer peripheral portion.
  • the upper end of the battery case 9 can be used as an injection port for injecting the electrolytic solution.
  • the upper end of the battery case 9 is sealed by heat fusion after injecting the electrolytic solution.
  • the upper end of the battery case 9 is preferably sealed with the negative electrode case 2 sandwiched between the first case 91 and the second case 92.
  • the material forming the battery case 9 is preferably a material having corrosion resistance to an electrolytic solution, and also having heat resistance and heat fusion resistance.
  • the material of the battery case 9 is preferably polyvinyl chloride (PVC), polyvinyl acetate, ABS resin, vinylidene chloride, polyacetal, polyethylene, polypropylene, polyisobutylene, fluororesin, epoxy resin and the like.
  • the negative electrode 1 As the metal-air battery 10, the negative electrode 1, the positive electrode 81 for discharging, and the positive electrode 82 for charging are immersed in the electrolytic solution (electrolyte) in the battery case 9.
  • electrolytic solution electrolytic solution
  • An example is a three-pole secondary battery arranged in parallel.
  • the discharge positive electrode 81 is an electrode that has a catalyst and serves as a positive electrode when the metal-air battery 10 is discharged.
  • the discharge positive electrode 81 when an alkaline aqueous solution is used as the electrolytic solution, water supplied from the electrolytic solution or the like reacts with oxygen gas supplied from the atmosphere and electrons on the catalyst to cause hydroxide ions (OH ⁇ . A discharge reaction occurs. In the discharge positive electrode 81, the discharge reaction proceeds at the three-phase interface where oxygen (gas phase), water (liquid phase), and electron conductor (solid phase) coexist.
  • the discharge positive electrode 81 is provided so that oxygen gas contained in the atmosphere can diffuse.
  • the discharge positive electrode 81 is provided so that at least a part of the surface of the discharge positive electrode 81 is exposed to the atmosphere.
  • oxygen gas contained in the atmosphere is diffused into the discharge positive electrode 81 via the multiple air intake ports 93 of the battery case 9.
  • the discharge positive electrode 81 may include a discharge positive electrode current collector, a discharge positive electrode catalyst layer containing a catalyst, and a water repellent film.
  • the positive electrode current collector for discharge is preferably a material having porosity and electron conductivity.
  • an alkaline aqueous solution is used as the electrolytic solution, from the viewpoint of corrosion resistance, it is desirable to use a material obtained by plating the surface of nickel or a metal material such as stainless steel with nickel.
  • the positive electrode current collector for discharge can be made porous by using a mesh, an expanded metal, a punching metal, a sintered body of metal particles or metal fibers, a foam metal, or the like.
  • the positive electrode current collector for discharge may function as a gas diffusion layer.
  • the positive electrode current collector for electric discharge is a carbon paper or carbon cloth surface-treated with a water-repellent resin, or a porous sheet made of carbon black and a water-repellent resin.
  • the water-repellent resin is provided to prevent the electrolytic solution from leaking from the battery case 9, has a gas-liquid separation function, and does not hinder the supply of oxygen gas to the catalyst layer.
  • the water-repellent film is a porous material containing a water-repellent resin, and is arranged on the side opposite to the negative electrode 1. By disposing the water-repellent film, leakage of the electrolytic solution can be suppressed.
  • PTFE polytetrafluoroethylene
  • the discharge positive electrode 81 can be electrically connected to the discharge positive electrode terminal (air electrode terminal), and enables the charge generated in the catalyst layer to be taken out to an external circuit (not shown).
  • the charging positive electrode 82 is a porous electrode that acts as a charging positive electrode.
  • a reaction occurs in which oxygen, water, and electrons are generated from hydroxide ions (OH ⁇ ) (charging reaction). That is, in the charging positive electrode 82, the charging reaction proceeds at the three-phase interface where oxygen (gas phase), water (liquid phase), and electron conductor (solid phase) coexist.
  • the charging positive electrode 82 is provided so that a gas such as oxygen gas generated by the progress of the charging reaction can be diffused.
  • the charging positive electrode 82 is provided so that at least a part thereof communicates with the outside air.
  • gas such as oxygen gas generated by the charging reaction is discharged from the charging positive electrode 82 via the multiple gas discharge ports 94 of the battery case 9.
  • the charging positive electrode 82 is preferably a material having porosity and electron conductivity.
  • nickel or a material obtained by plating the surface of a metal material such as stainless steel with nickel may be used. desirable.
  • the charging positive electrode 82 can be made porous by using a mesh, an expanded metal, a punching metal, a sintered body of metal particles or metal fibers, a foam metal, or the like as the charging positive electrode 82.
  • the charging positive electrode 82 may be provided with oxygen evolution catalyst particles that promote the charging reaction on the surface. Further, the charging positive electrode 82 may be configured to include a charging positive electrode current collector (not shown).
  • the charging positive electrode 82 may be provided with a water repellent film. By disposing the water-repellent film, it is possible to suppress leakage of the electrolytic solution through the charging positive electrode 82, separate gas such as oxygen gas generated by the charging reaction from the electrolytic solution, and the battery case 9 It is possible to discharge to the outside of.
  • the charging positive electrode 82 can be electrically connected to the charging positive electrode terminal, and makes it possible to supply the charge required for the charging reaction from an external circuit (not shown).
  • the negative electrode 1 including the negative electrode case 2 is arranged in the battery case 9, and the lead portion 31 of the negative electrode current collector 3 is connected to the negative electrode case 2. It is formed by pulling it out from the upper part of the battery case 9 in a stretched state. Further, referring to FIG. 1, the constituent members of the negative electrode 1 such as the negative electrode current collector 3 do not come into contact with the battery case 9, and the insulating property between the negative electrode current collector 3 and the inner surface of the battery case 9 is ensured. Has been done.
  • the positive electrode 8 is arranged so as to be insulated from the negative electrode current collector 3 by the negative electrode case 2 and not to contact with it.
  • the anion conductive film 6 is interposed between the negative electrode 1 and the positive electrode 8 (the discharging positive electrode 81 and the charging positive electrode 82). Ion conduction occurs between these electrodes through the first porous film 5, and the charge reaction and the discharge reaction of the metal-air battery 10 are enabled.
  • the anion conductive film 6 enables the movement of anions while ensuring the insulation between the positive electrode 8 and the negative electrode 1, and prevents the formation of an electron conduction path. Therefore, the metal-air battery 10 has a structure that can suppress the growth of dendrites and can prevent a short circuit between the electrodes.
  • the negative electrode active material layer 4 may expand or contract with charge/discharge cycles.
  • the anion conductive film 6 and the first porous film 5 that compose the negative electrode 1 including the negative electrode active material layer 4 are housed in the negative electrode case 2.
  • the negative electrode 1 and the positive electrode 8 are closely arranged in the battery case 9 and have a structure in which there is no liquid layer of the electrolytic solution between the electrodes. As a result, expansion and the like accompanying the charge / discharge cycle are suppressed, and a structure in which the volume does not change easily is realized.
  • the first porous film 5 is interposed between the anion conductive film 6 and the negative electrode case 2 (or between the anion conductive film 6 and the positive electrode 8). Since it serves as a buffer layer, it is possible to prevent the anion conductive film 6 from being pressed and damaged.
  • the sheet material of the single-layer structure or the multi-layer structure which constitutes the negative electrode case 2 is formed into a bottomed bag shape by heat fusion, and the two openings 20 are opposed to the side surfaces. It is opened to form the negative electrode case 2.
  • a first porous film 5 is applied to each opening 20 from the inside, and the opening 20 is closed from the inside of the negative electrode case 2.
  • the negative electrode current collector 3, the negative electrode active material layer 4, and the anionic conductive film 6 are inserted into the negative electrode case 2. Since the first porous film 5 is interposed between the anion conductive film 6 and the negative electrode case 2, the anion conductive film 6 may come into contact with the opening 20 of the negative electrode case 2 or the positive electrode 8. It is prevented. As a result, the anion conductive film 6 can be arranged in the negative electrode case 2 without being damaged, and the anion conductive film 6 can be sufficiently functioned.
  • the negative electrode case 2 is housed in the battery case 9, and the positive electrode 8 is arranged between the negative electrode case 2 and the battery case 9. Further, the electrolytic solution is injected into the negative electrode case 2 and the battery case 9 (between the inner surface of the battery case 9 and the outer surface of the negative electrode case 2), and the battery case 9 and the negative electrode case 2 are sealed by heat fusion. This makes it possible to block the growth path of dendrites and prevent short circuits between the electrodes.
  • the metal-air battery 10 can be applied to, for example, a zinc-air battery, a lithium-air battery, a sodium-air battery, a calcium-air battery, a magnesium-air battery, an aluminum-air battery, an iron-air battery, and the like, and in particular, a metal as a negative electrode 1. It can be suitably used for a zinc-air battery in which the negative electrode is a zinc type. Unlike lithium-air batteries, zinc-air batteries do not need to use a flammable electrolyte (electrolyte), and can use an alkaline electrolyte (electrolyte), so they have the advantage of high safety. is there. Further, the zinc-air battery has an advantage that the capacity can be easily increased because the negative electrode can be manufactured at a lower cost than the lithium-air battery.
  • a three-pole type metal-air secondary battery is illustrated as the metal-air battery 10, but the metal-air battery 10 is a primary battery and the charging positive electrode 82 is omitted. May be.
  • the metal-air battery 10 may have a form in which the positive electrode is provided with a catalyst having an oxygen reducing ability and an oxygen generating ability, and the positive electrode that can be used during both charging and discharging is used.
  • FIG. 4 is a perspective view of the negative electrode 1 according to the second embodiment.
  • FIG. 5 is an enlarged cross-sectional view schematically showing the negative electrode 1 according to the second embodiment, and the portion corresponding to the A1 portion in FIG. 1 is enlarged and shown. Since the second to sixth embodiments described below are common to the first embodiment in the basic configuration, the configurations specific to each embodiment will be described in detail, and the other configurations are common to the first embodiment. The description is omitted by using the reference numeral.
  • the opening 20 provided in the negative electrode case 2 of the negative electrode 1 is covered with the first porous film 5 from the inside of the negative electrode case 2.
  • the negative electrode 1 is further characterized in that the first porous film 5 covering the opening 20 from the inside of the negative electrode case 2 is welded to the negative electrode case 2.
  • the opening 20 is covered with the first porous film 5 from the inside of the negative electrode case 2, and the negative electrode case 2 and the first porous film 5 are welded to each other to form a welded region 23.
  • the welding region 23 is provided along the peripheral edge of the opening 20 in the negative electrode case 2.
  • the first porous film 5 is fixed to the peripheral edge of the opening 20 and integrated with the negative electrode case 2.
  • the anionic conductive film 6 interferes with the opening 20 of the negative electrode case 2. It can be prevented from being caught or caught, and the anion conductive film 6 can be smoothly inserted. This not only improves workability in manufacturing the negative electrode 1, but also prevents damage to the anion conductive film 6.
  • the negative electrode case 2 and the first porous film 5 are closely arranged without any gap. This makes it possible to block the path where the dendrite grows toward the positive electrode 8, which is even more preferable in preventing a short circuit between the electrodes.
  • the first porous film 5 is welded to the negative electrode case 2 so that the micropores of the first porous film 5 are closed in the vicinity of the welded region 23. Therefore, in the welding region 23, the inside and outside of the negative electrode case 2 (negative electrode 1) are blocked, and the growth path of dendrites can be blocked.
  • FIG. 6 is a cross-sectional view schematically showing the negative electrode 1 according to the third embodiment, and is a diagram corresponding to FIG. 1 in the first embodiment.
  • the negative electrode 1 according to the third embodiment is characterized by an anion conductive film 6, and other configurations are common to those of the first or second embodiment.
  • the anion conductive film 6 is provided between the negative electrode active material layer 4 and the first porous film 5 so as to contact the inner surface of the negative electrode case 2.
  • the anion conducting membrane 6 is larger than the size of the first porous membrane 5 that covers the opening 20, and has a size that extends outwardly beyond the outer edge portion of the overlapping first porous membrane 5. ing.
  • the gap formed between the anion conductive film 6 and the negative electrode case 2 with the anion conductive film 6 arranged in the negative electrode case 2 is smaller than that shown in FIG. Therefore, it becomes possible to lengthen and block the path through which the dendrite grows toward the positive electrode 8, which is even more preferable in preventing a short circuit between the electrodes.
  • FIG. 6 shows a state in which the lower end of the anion conductive membrane 6 is in contact with the inner surface of the negative electrode case 2 and the upper end is not in contact with the inner surface of the negative electrode case 2.
  • the arrangement form of the anion conducting film 6 in the negative electrode 1 is not limited to this, and if the anion conducting film 6 has a size larger than that of the first porous film 5, it should be in contact with the inner surface of the negative electrode case 2.
  • the contact form between the negative electrode case 2 and the anion conductive film 6 may be any shape.
  • FIG. 7 is a cross-sectional view schematically showing the negative electrode 1 according to the fourth embodiment, and is a diagram corresponding to FIG. 1 in the first embodiment.
  • the negative electrode 1 according to the fourth embodiment is further provided with a second porous film 7 in addition to the configuration shown in the third embodiment.
  • the negative electrode 1 includes a second porous film 7 between the anion conductive film 6 and the negative electrode active material layer 4.
  • the second porous film 7 may be a member having ion conductivity between the positive electrode 8 and the negative electrode 1, and may be a nonwoven fabric made of polyolefin or the like, a first filter paper or the like.
  • a member common to the porous film 5 can be used.
  • the size and thickness of the second porous membrane 7 can also be the same as that of the first porous membrane 5.
  • the second porous membrane 7 Since the second porous membrane 7 has a porous structure, it can be placed in the negative electrode case 2 to hold the electrolytic solution in the negative electrode case 2.
  • the negative electrode active material layer 4 may expand or contract with charge/discharge cycles, but the second porous film 7 is formed on the negative electrode active material layer 4. It is possible to prevent the electrolyte solution of the negative electrode active material layer 4 from being deficient by being closely stacked.
  • the second porous film 7 is interposed between the negative electrode active material layer 4 and the anion conductive film 6, the second porous film 7 is on the side opposite to the first porous film 5 side in the anion conductive film 6, This prevents damage to the anion conductive film 6.
  • the second porous film 7 acts as a buffer layer between the negative electrode active material layer 4 and the anion conductive film 6, and the dendrite is used. It prevents the anion conductive membrane 6 from being damaged.
  • FIG. 8 is a cross-sectional view schematically showing the metal-air battery 10 according to the fifth embodiment.
  • the discharge positive electrode 81 is arranged on one of the negative electrodes 1
  • the charging positive electrode 82 is arranged on the other side.
  • the discharging positive electrode 81 and the charging positive electrode 82 are arranged adjacent to each other.
  • the negative electrode 1 of the metal-air battery 10 the one having the configuration shown in the fourth embodiment is provided.
  • the positive electrode 8 constituting the metal-air battery 10 includes a discharging positive electrode (air electrode) 81 that is a first positive electrode for discharging, and a charging positive electrode 82 that is a second positive electrode for charging. Have and. Both the discharging positive electrode 81 and the charging positive electrode 82 are arranged on both sides of the negative electrode 1. On one surface of the negative electrode case 2 of the negative electrode 1, a charging positive electrode 82 is arranged in contact with the opening 20, and a discharging positive electrode 81 is arranged adjacent to the charging positive electrode 82. A discharge positive electrode 81 is arranged in contact with the inner surface of the battery case 9 from the inside. The other surface of the negative electrode case 2 is similarly provided.
  • the negative electrode 1 is provided substantially in the center between the two discharging positive electrodes 81, and the charging positive electrode 82 is provided between the discharging positive electrode 81 and the negative electrode 1 (both sides of the negative electrode 1). It is configured to be provided in two places).
  • the metal-air battery 10 has a structure capable of suppressing the growth of dendrites on the negative electrode 1 and preventing a short circuit between the electrodes.
  • the negative electrode 1 in the metal-air battery 10 is shown as an example having the configuration shown in the fourth embodiment, but the present invention is not limited to this, and the negative electrode 1 according to another form may be provided. Good.
  • the metal-air battery 10 has a configuration in which a discharging positive electrode 81 and a charging positive electrode 8 are provided on one side of the negative electrode 1 in the battery case 9, and the discharging positive electrode 81, the charging positive electrode 82, and the negative electrode 1 are arranged in this order. Any arrangement may be used as long as they are arranged.
  • a separator for insulating the charging positive electrode 82 and the discharging positive electrode 81 may be provided between the charging positive electrode 82 and the discharging positive electrode 81.
  • FIG. 9 is a cross-sectional view schematically showing the metal-air battery 10 according to the sixth embodiment.
  • the arrangement of the negative electrode 1, the discharging positive electrode 81, and the charging positive electrode 82 in the metal-air battery 10 is not limited to the above-mentioned form.
  • the metal-air battery 10 according to this embodiment includes the negative electrode 1 having the configuration shown in the fourth embodiment, and has a positive electrode 81 for discharging on one side and a positive electrode 82 for charging on the other side of the negative electrode 1. Has been done.
  • the negative electrode case 2 is provided with a first opening 21 and a second opening 22 on both sides of the negative electrode active material layer 4 in the thickness direction.
  • the positive electrode 8 includes a discharge positive electrode 81 that is a first positive electrode and a charging positive electrode 82 that is a second positive electrode, and the discharge positive electrode 81 is arranged facing the first opening 21.
  • a charging positive electrode 82 is arranged so as to face the second opening 22.
  • the metal-air battery 10 configured in this manner, it is possible to suppress damage or damage to the anion conductive film that causes growth of dendrites in the negative electrode 1, and to prevent a short circuit between the electrodes.
  • the anion conductive film 6 is damaged. It is possible to prevent the occurrence of. As a result, in the negative electrode 1 and the metal-air battery 10, it is possible to prevent the generation of dendrite growth paths, prevent short-circuiting between the electrodes, and achieve a long life and high output. ..
  • the negative electrode and the metal-air battery according to the present disclosure can be widely used for the metal-air battery used as one of the power supply devices.

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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)
  • Sealing Battery Cases Or Jackets (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne une électrode négative ayant un boîtier d'électrode négative pourvu d'au moins une ouverture, un collecteur d'électrode négative comprenant une partie logée dans le boîtier d'électrode négative et une partie s'étendant à partir du boîtier d'électrode négative, une couche de matériau actif d'électrode négative qui est logée dans le boîtier d'électrode négative et est en contact avec au moins une partie du collecteur d'électrode négative, une première membrane poreuse qui recouvre l'ouverture, et une membrane conductrice d'anions disposée entre la première membrane poreuse et la couche de matériau actif d'électrode négative.
PCT/JP2020/008201 2019-03-05 2020-02-28 Électrode négative et batterie métal-air WO2020179645A1 (fr)

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WO2014119663A1 (fr) * 2013-02-01 2014-08-07 株式会社日本触媒 Précurseur d'électrode, électrode et batterie
JP2016186895A (ja) * 2015-03-27 2016-10-27 株式会社日本触媒 アニオン伝導性膜、電極及び電池
JP2016225213A (ja) * 2015-06-02 2016-12-28 シャープ株式会社 金属電極カートリッジ、及び、化学電池
WO2017002815A1 (fr) * 2015-07-01 2017-01-05 日本碍子株式会社 Bloc d'éléments de batterie zinc-air et batterie l'utilisant
JP2017079147A (ja) * 2015-10-20 2017-04-27 シャープ株式会社 金属空気電池、電解液槽、及び、金属空気電池の使用方法
WO2018143287A1 (fr) * 2017-02-03 2018-08-09 シャープ株式会社 Pile métal-air

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JP2012178331A (ja) * 2010-11-17 2012-09-13 Fluidic Inc 階層型アノードのマルチモード充電
WO2014119663A1 (fr) * 2013-02-01 2014-08-07 株式会社日本触媒 Précurseur d'électrode, électrode et batterie
JP2016186895A (ja) * 2015-03-27 2016-10-27 株式会社日本触媒 アニオン伝導性膜、電極及び電池
JP2016225213A (ja) * 2015-06-02 2016-12-28 シャープ株式会社 金属電極カートリッジ、及び、化学電池
WO2017002815A1 (fr) * 2015-07-01 2017-01-05 日本碍子株式会社 Bloc d'éléments de batterie zinc-air et batterie l'utilisant
JP2017079147A (ja) * 2015-10-20 2017-04-27 シャープ株式会社 金属空気電池、電解液槽、及び、金属空気電池の使用方法
WO2018143287A1 (fr) * 2017-02-03 2018-08-09 シャープ株式会社 Pile métal-air

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115441124A (zh) * 2021-06-04 2022-12-06 丰田自动车株式会社 锌二次电池
CN115441124B (zh) * 2021-06-04 2024-03-26 丰田自动车株式会社 锌二次电池

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