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WO2016158019A1 - Batterie à sel solide de vanadium - Google Patents

Batterie à sel solide de vanadium Download PDF

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Publication number
WO2016158019A1
WO2016158019A1 PCT/JP2016/053823 JP2016053823W WO2016158019A1 WO 2016158019 A1 WO2016158019 A1 WO 2016158019A1 JP 2016053823 W JP2016053823 W JP 2016053823W WO 2016158019 A1 WO2016158019 A1 WO 2016158019A1
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WO
WIPO (PCT)
Prior art keywords
vanadium
electrode
ion exchange
water retention
solid salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/053823
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English (en)
Japanese (ja)
Inventor
吉田　茂樹
則彦 丹野
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Brother Industries Ltd
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Brother Industries Ltd
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Filing date
Publication date
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Ceased legal-status Critical Current

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a vanadium solid salt battery that contains vanadium ions or ions containing vanadium as an active material, and performs charge / discharge using an oxidation-reduction reaction by the active material.
  • Batteries are widely used in digital home appliances, electric vehicles, hybrid vehicles, solar power generation facilities, and the like.
  • Examples of the battery include a lithium ion secondary battery and a vanadium solid salt battery (Patent Document 1).
  • Vanadium solid salt batteries charge and discharge using an oxidation-reduction reaction by an active material.
  • the active material vanadium ions or ions containing vanadium are used.
  • a vanadium solid salt battery includes an electrode unit including an electrode having an active material and an acidic electrolyte, and a conductor such as copper facing the electrode, with electrodes having different polarities facing each other through an ion exchange membrane. It is configured by arranging them side by side and storing them in an exterior bag. The vanadium solid salt battery may be further housed in a case.
  • the thickness of the conventional ion exchange membrane is as thick as 150 ⁇ m, for example, and it is desired to further reduce the thickness of the ion exchange membrane.
  • the ion exchange membrane is thinned, the absolute amount of moisture contained in the ion exchange membrane is reduced.
  • the present invention has been made in view of such circumstances, and when the ion exchange membrane is thinned, the resistance value related to ion migration of the ion exchange membrane does not increase, and vanadium having good charge / discharge performance.
  • An object is to provide a solid salt battery.
  • the vanadium solid salt battery according to the present invention is a positive electrode including a current collector and a positive electrode including a positive electrode active material, and the positive electrode active material is oxidized between pentavalent and tetravalent by an oxidation-reduction reaction.
  • a positive electrode containing a positive electrode, a current collector, and a negative electrode active material the vanadium ion containing a vanadium ion containing a vanadium ion containing a vanadium ion, or an ion containing vanadium whose oxidation number changes between pentavalent and tetravalent
  • the negative electrode active material contains vanadium ions whose oxidation number changes between divalent and trivalent or vanadium whose oxidation number changes between divalent and trivalent by an oxidation-reduction reaction.
  • the vanadium solid salt battery of the present invention since the water retention membrane is provided between the ion exchange membrane and the positive electrode or the negative electrode, when water is supplied to the ion exchange membrane and the thickness of the ion exchange membrane is reduced, It is suppressed that the resistance value regarding ion movement increases. Therefore, the vanadium solid salt battery of the present invention has good charge / discharge performance and a high battery capacity.
  • FIG. 1 is a schematic plan view showing a vanadium solid salt battery 1 according to Embodiment 1 of the present invention.
  • FIG. 2 is a schematic cross-sectional view taken along the line II-II in FIG. It is typical sectional drawing which shows the vanadium solid salt battery 11 which concerns on Embodiment 2 of this invention.
  • It is a graph which shows the relationship between vanadium density
  • the vanadium solid salt battery 1 includes an outer bag 2, a positive electrode terminal 3 and a negative electrode terminal 4 protruding from a part of the peripheral edge of the outer bag 2, and an electrode unit 5 constituting a negative electrode. And an electrode unit 6 constituting the positive electrode.
  • the positive electrode terminal 3 and the negative electrode terminal 4 protrude from a part of the peripheral edge portion of the outer bag 2 in a state where the base end side is covered with the sealing materials 30 and 40.
  • the vanadium solid salt battery 1 alone or a combination of the vanadium solid salt battery 1 and another vanadium solid salt battery may be housed in a case (not shown).
  • the electrode unit 5 includes an electrode 50 that is a negative electrode, a conductor 51, a coating film 52, a sealant 54, a water retention film 55, and an ion exchange membrane 56.
  • the conductor 51 has a rectangular flat plate shape and is disposed on the upper surface of the lower half 22 in FIG. 2 of the outer bag 2, and the upper surface of the conductor 51 is covered with a coating film 52. Inside the peripheral edge of the upper surface of the coating film 52, a square plate-like electrode 50 having an active material and an electrolytic solution is provided.
  • a water retention film 55 having a larger planar area than the electrode 50 is provided on the electrode 50, and an ion exchange membrane 56 having a larger planar area than the water retention film 55 is provided on the water retention film 55.
  • the sealant 54 has a frame shape having an edge portion (hereinafter sometimes referred to as a “frame shape”), is bonded to the peripheral edge portion and the half body 22, and the conductor 51 is formed by the half body 22 and the covering portion 52. Seal
  • the half 22 is electrolyte impermeable.
  • the half 22 is preferably composed of a laminate sheet containing a synthetic resin layer and a metal layer.
  • the material for the synthetic resin layer include polypropylene, polyethylene, polyamide such as nylon 6, nylon 66, and the like.
  • the thickness of the synthetic resin layer is preferably 5 to 200 ⁇ m. In this case, the battery has good airtightness.
  • the material for the metal layer include aluminum, aluminum alloy, copper, copper alloy, iron, stainless steel, titanium, and titanium alloy.
  • the thickness of the metal layer is preferably 5 to 100 ⁇ m.
  • the thickness of the half body 22 is not particularly limited, but is preferably 15 to 250 ⁇ m. When the thickness is 15 to 250 ⁇ m, the battery has sufficient strength and the battery becomes compact.
  • the planar area of the conductor 51 is smaller than the planar area of the half body 22.
  • the conductor 51 is preferably made of a metal foil such as copper, aluminum, or nickel.
  • the thickness is preferably 5 to 100 ⁇ m. When the thickness is 100 ⁇ m or less, the battery is lightweight and downsized.
  • the conductor 51 has a tab (not shown) protruding from a part of the peripheral edge, and the tip of the tab is connected to the negative electrode terminal 4.
  • the coating film 52 is formed by coating the upper surface of the conductor 51 with graphite, and has conductivity and electrolyte solution impermeability.
  • the thickness of the coating film 52 is preferably 1 to 100 ⁇ m. In this case, the electrical conductivity between the electrode 50 and the conductor 51 is not lowered, and the internal resistance of the battery can be reduced.
  • the conductor 51 is not limited to the case where the conductor 51 is covered with the coating film 52 formed by coating with graphite.
  • the covering material of the conductor 51 should just be electroconductivity and electrolyte solution non-permeable, and can be covered with an electroconductive film, a sheet-like electroconductive rubber, a graphite sheet, etc.
  • the graphite sheet may be arranged on one surface of the conductor 51 through a conductive adhesive sheet.
  • the protective layer 52 may not be provided.
  • “the conductor 51 (or 61) and the coating film 52 (or 62)” or “the conductor 51 (or 61) alone” means the current collector.
  • the electrode 50 is provided inside the peripheral edge of the upper surface of the coating film 52, that is, at a portion other than the peripheral edge of the upper surface of the coating film 52.
  • the electrode 50 has vanadium ions whose oxidation number changes between divalent and trivalent or ions containing vanadium whose oxidation number changes between divalent and trivalent due to an oxidation-reduction reaction.
  • a precipitate containing a solid compound containing the contained vanadium solid salt as a negative electrode active material is supported.
  • the electrode 50 preferably contains vanadium ions whose oxidation number changes between divalent and trivalent by an oxidation-reduction reaction.
  • vanadium ions whose oxidation number varies between divalent and trivalent include V 2+ (II) and V 3+ (III).
  • vanadium compound that is an active material for the negative electrode include vanadium sulfate (II) (VSO 4 ⁇ nH 2 O) and vanadium sulfate (III) (V 2 (SO 4 ) 3 ⁇ nH 2 O). Mixtures of these can be used.
  • n represents 0 or an integer of 1 to 10.
  • the coating film 52 is dried by applying or impregnating the coating film 52 with a solution, semi-solid material, or solid material containing a vanadium compound, and drying the coating film 52.
  • the semi-solid material include a slurry material obtained by adding an aqueous sulfuric acid solution to a vanadium compound, and a gel material obtained by adding silica or the like to a vanadium compound.
  • the electrode 50 is formed by applying a slurry, which is a semi-solid material containing an active material, a binder, and carbon, to the coating film 52 and drying.
  • a precipitate containing a solid compound containing an active material by applying or impregnating a solution containing a vanadium compound, a semi-solid product, or a solid product to a carbon material such as carbon felt or drying. May be obtained, and the carbon material may be provided on the coating film 52.
  • the electrolyte contained in the electrode 50 is preferably an aqueous sulfuric acid solution.
  • the sulfuric acid aqueous solution for example, sulfuric acid having a sulfuric acid concentration of less than 90% by mass can be used.
  • the amount of the electrolyte is not excessive or deficient so that the SOC of the battery can be taken from 0 to 100%.
  • the amount of the electrolytic solution is, for example, 70 mL of 2M (mol / L) sulfuric acid with respect to 100 g of the vanadium compound.
  • the water retention film 55 provided on the electrode 50 is electrolyte permeable.
  • the water retaining film 55 is preferably made of a porous material. In this case, water retention is good.
  • Specific examples of the water retention film 55 include a porous glass separator, a porous PTFE separator, and carbon paper.
  • the thickness of the water retaining film 55 is preferably 50 ⁇ m or more and 135 ⁇ m or less.
  • the thickness of the water retention film 55 is not less than 50 ⁇ m and not more than 135 ⁇ m, when the ion exchange membrane 56 is thinned, an increase in resistance due to a decrease in moisture in the ion exchange membrane 56 can be suppressed, and charge / discharge performance is good. .
  • the increase in the total thickness of the ion exchange membrane 56 and the water retention membrane 55 can be suppressed, and the vanadium solid salt battery 1 can be made thinner.
  • the lower limit of the thickness is more preferably 55 ⁇ m, still more preferably 65 ⁇ m, and particularly preferably 75 ⁇ m.
  • the water retaining film 55 is impregnated with water or an aqueous solution.
  • the aqueous solution can contain vanadium or sulfur.
  • the theoretical capacity of the vanadium solid salt battery 1 can be increased.
  • the water retention amount of the water retention film 55 when the size of the water retention film 55 is 27 ⁇ m ⁇ 27 ⁇ m ⁇ 55 ⁇ m, it may be 100 ⁇ l or more.
  • the vanadium element concentration in the water retaining film 55 is preferably 5 mol / L or less. In this case, the charge / discharge performance of the vanadium solid salt battery 1 is good.
  • the vanadium element concentration in the water retaining film 55 is more preferably 4.8 mol / L or less, and further preferably 4.5 mol / L or less. In this case, the charge / discharge performance of the vanadium solid salt battery 1 is good.
  • the sulfur element concentration in the water retaining film 55 is 8 mol / L or less. In this case, the charge / discharge performance of the vanadium solid salt battery 1 is good, and the output capacity and input capacity are good.
  • the sulfur element concentration in the water retaining film 55 is more preferably 7.8 mol / L or less, and further preferably 7.5 mol / L or less.
  • the sealant 54 has a frame shape as described above, and includes an inner edge portion 54a projecting inwardly at the upper end portion of the rectangular tube-shaped frame body, and an outer edge portion 54b projecting outwardly at the lower end portion of the frame body.
  • the sealant 54 is configured such that the outer edge portion 54b is positioned outside the inner edge portion 54a (the outer portion of the electrode 50) in plan view.
  • the inner edge 54 a of the sealant 54 is bonded to the peripheral edge of the upper surface of the coating film 52, and the upper part of the inner side surface of the inner edge 54 a is bonded to the side surface of the water retention film 55.
  • the outer edge portion 54 b is bonded to the outer surface of the conductor 51 on the surface of the half body 22 on the conductor 51 side.
  • the conductor 51 and the coating film 52 are sandwiched between the half body 22 and the sealant 54. That is, the conductor 51 is fixed to the half body 22 in a state where the conductor 51 is sealed by the half body 22, the coating film 52, and the sealant 54.
  • the side surface of the conductor 51 may be bonded to the sealant 54, or may not be bonded.
  • Examples of the material of the sealant 54 include polypropylene or polyethylene. By using polypropylene or polyethylene, the conductor 51 can be easily sealed by heat welding.
  • the ion exchange membrane 56 covers the water retention membrane 55 and is bonded to the upper surface of the inner edge portion 54 a of the sealant 54.
  • the ion exchange membrane 56 can pass hydrogen ions (protons) or sulfate ions.
  • the vanadium solid salt battery 1 according to the present embodiment has a water retention membrane 55 and can supply moisture to the ion exchange membrane 56. Even if the thickness of the ion exchange membrane 56 is reduced, the ion of the ion exchange membrane 56 is reduced. Since an increase in resistance related to movement can be suppressed, the thickness of the conventional ion exchange membrane is approximately 150 ⁇ m, and can be set to, for example, 10 ⁇ m and 20 ⁇ m.
  • the electrode unit 6 has the same configuration as the electrode unit 5, and includes an electrode 60 that is a positive electrode, a conductor 61, a coating film 62, and a sealant 64.
  • the conductor 61 has a rectangular flat plate shape and is disposed on the lower surface of the half body 21 of the outer bag 1 in FIG. 2, and the lower surface of the conductor 61 is covered with a coating film 62.
  • a square plate electrode 60 having an active material and an electrolytic solution is provided.
  • the sealant 64 has a frame shape, and includes an inner edge portion 64a projecting inward at the lower end portion of the rectangular tube-shaped frame body, and an outer edge portion 64b projecting outward at the upper end portion of the frame body.
  • the inner edge portion 64 a is bonded to the peripheral edge portion
  • the outer edge portion 64 b is bonded to the half body 21, and the sealant 64 seals the conductor 61 with the half body 21 and the covering portion 62.
  • the conductor 61 of the electrode unit 6 has a tab (not shown) protruding from a part of the peripheral edge, and the tip of the tab is connected to the positive electrode terminal 3.
  • the conductor 61, the coating film 62, and the sealant 64 of the electrode unit 6 are made of the same material as that of the electrode unit 5.
  • the electrode 60 has vanadium ions whose oxidation number changes between pentavalent and tetravalent or ions containing vanadium whose oxidation number changes between pentavalent and tetravalent due to an oxidation-reduction reaction.
  • a precipitate containing a solid compound containing the contained vanadium solid salt as a positive electrode active material is supported.
  • the vanadium ion or the ion containing vanadium contained in the electrode 60 is preferably an ion containing vanadium whose oxidation number changes between pentavalent and tetravalent by an oxidation-reduction reaction.
  • the ion containing pentavalent and tetravalent vanadium oxidation number changes between, VO 2+ (IV), VO 2 + (V) are exemplified.
  • the vanadium compound supported on the carbon material is vanadium oxide (IV) (VOSO 4 ⁇ nH 2 O), vanadium oxide (V) ((VO 2 ) 2 SO 4 ⁇ nH 2 O). Can be mentioned. Mixtures of these may be used. n represents 0 or an integer of 1 to 5.
  • the electrode 60 is formed by applying a slurry, which is a semi-solid material containing a positive electrode active material, a binder, and carbon, to the coating film 62 and drying.
  • a slurry which is a semi-solid material containing a positive electrode active material, a binder, and carbon
  • a precipitate containing a solid compound containing an active material by applying or impregnating a solution containing a vanadium compound, a semi-solid product, or a solid product to a carbon material such as carbon felt or drying. May be obtained, and the carbon material may be provided on the coating film 62.
  • the halves 21 and 22 to which the conductors 61 and 51 are fixed are aligned so that the inside faces each other, and the positive electrode terminal 3 and the negative electrode terminal 4 protrude from a part of the peripheral edge of the halves 21 and 22.
  • the outer bag 2 is formed by pressure-contacting and bonding the peripheral edge portion, and the vanadium solid salt battery 1 is obtained.
  • the halves 21 and 22 may be integrated from the beginning.
  • the charge and discharge of the vanadium solid salt battery using the vanadium solid salt battery 1 is performed using the reactions of the above formulas (1) and (2). At this time, charging / discharging is performed with an external load or a charger via the positive terminal 3 and the negative terminal 4. In the reaction of the formulas (1) and (2), protons move between the electrodes 50 and 60 through the ion exchange membrane 56.
  • the vanadium solid salt battery 1 according to the present embodiment configured as described above has the water retention film 55 between the ion exchange membrane 56 and the negative electrode 50, the thickness of the ion exchange membrane 56 is reduced. In this case, the water retention amount of the ion exchange membrane 56 is improved. Therefore, by making the ion exchange membrane 56 thinner, the absolute amount of moisture contained in the ion exchange membrane 56 is reduced, and the ion exchange membrane 56 and the electrode 50 are changed by the change in the ion concentration in the electrode 50 accompanying the charge / discharge reaction during use.
  • the vanadium solid salt battery 1 When the osmotic pressure is generated between the two, the moisture in the ion exchange membrane 56 is lost, the permeability of ions containing hydrogen ions is deteriorated, and the resistance value of the ion exchange membrane 56 relating to ion migration is suppressed from increasing. ing. Therefore, the vanadium solid salt battery 1 according to the present embodiment has good charge / discharge performance and a high battery capacity.
  • the plane area of the water retention film 55 is equal to or larger than the plane area of the electrode 50, a portion where osmotic pressure is generated between the ion exchange membrane 56 and the electrode 50 when the vanadium solid salt battery 1 is used is covered by the water retention film 55. In other words, it is possible to prevent the moisture in the ion exchange membrane 56 from being lost when the osmotic pressure is generated.
  • the planar area of the electrode 50 is larger than the planar area of the water retention film 55, the water content of the water retention film 55 decreases.
  • the plane area of the water retention membrane 55 is less than or equal to the plane area of the ion exchange membrane 56, a portion where osmotic pressure is generated between the ion exchange membrane 56 and the electrode 50 when the vanadium solid salt battery 1 is used is formed by the water retention membrane 55.
  • the water retention film 55 does not become unnecessarily large, and the planar area of the vanadium solid salt battery 1 is prevented from becoming large.
  • the conductor 51 is sealed by the sealant 54, the coating film 52, and the half body 22, and the electrode 50 is surrounded by the water retention film 55, the ion exchange membrane 56, and the sealant 54a. Therefore, the acidic substance related to the electrolytic solution contained in the electrode 50 does not react with the conductor 51, and corrosion of the conductor 51 is prevented.
  • the conductor 61 is sealed by the sealant 64, the coating film 62, and the half body 21, and the electrode 60 is surrounded by the ion exchange film 56 and the sealant 64a. The acidic substance related to the liquid does not react with the conductor 61, and corrosion of the conductor 61 is prevented.
  • the water retention film 55 is provided so as to contact the negative electrode 50 so as to contact the negative electrode 50.
  • the present invention is not limited to this and is provided on the positive electrode 60 side. May be.
  • FIG. The vanadium solid salt battery 11 according to Embodiment 2 includes an outer bag 2, a positive terminal and a negative terminal (not shown) protruding from a part of the peripheral edge of the outer bag 2, and two electrode units 7 constituting the negative electrode. And three electrode units 8 constituting the positive electrode and two electrode units 9 constituting the negative electrode.
  • An electrode unit 8, an electrode unit 9, an electrode unit 8, an electrode unit 9, an electrode unit 8, and an electrode unit 7 are sequentially stacked on the lower electrode unit 7 in FIG. 3.
  • the electrode unit 8 is provided on the inner side of the peripheral portion of the surface of each of the coating films 83, 83, 83 covering the both sides of the rectangular plate-shaped conductor 82, the conductors 82, and the surface of each coating film 83.
  • the electrodes 80 and 81, the conductor 82, and the coating film 83 of the electrode unit 8 are made of the same material as the electrode 50, the conductor 51, and the coating film 52 of the electrode unit 5 according to Embodiment 1, It has the same configuration.
  • the sealant 84 has a frame shape as described above, and is formed by adhering the upper half 84a and the lower half 84b.
  • the half body 84a includes an inner edge portion 84c projecting inward at the upper end portion of the rectangular tube-shaped frame main body, and an outer edge portion 84d projecting outward at the lower end portion of the frame main body.
  • the half body 84b includes an inner edge portion 84e projecting inwardly at the lower end portion of the rectangular tube-shaped frame body, and an outer edge portion 84f projecting outward at the upper end portion of the frame body.
  • the inner edge portions 84c and 84e of the sealant 84 are bonded to the peripheral edge portions of the surfaces of the coating films 83 and 83, and the outer edge portions 84d and 84f are bonded together.
  • the conductor 82 is sealed with coating films 83 and 83 and a sealant 84. Note that the side surface of the conductor 82 may or may not be bonded to the sealant 84.
  • Sealant 84 is impermeable to electrolyte solution, and examples of the material include polypropylene or polyethylene. By using polypropylene or polyethylene, the conductor 82 can be easily sealed by heat welding.
  • the ion exchange membranes 85 and 86 are such that the electrode unit 7 and the electrode unit 9 have a water retention membrane 75 and water retention membranes 95 and 95, and can supply moisture to the ion exchange membranes 85 and 86. Even if 86 is made thinner, an increase in resistance value related to ion movement can be suppressed, so that the thickness of the ion exchange membranes 85 and 86 can be made thinner, for example, 10 ⁇ m, 20 ⁇ m, and the like.
  • the electrode unit 9 includes electrodes 90 and 91, a conductor 92, coating films 93 and 93, a sealant 94, and water retention films 95 and 95.
  • the conductor 92 has a rectangular plate shape, and both planes of the conductor 92 are covered with coating films 93 and 93.
  • Square plate electrodes 90 and 91 each having an active material and an electrolytic solution are provided inside the peripheral edge portions of the surfaces of the coating films 93 and 93.
  • water retention films 95 and 95 having a larger plane area than the electrodes 90 and 91 are provided on the electrodes 90 and 91.
  • the water retention membrane 95 in contact with the electrode 90 is in contact with the ion exchange membrane 86 of the electrode unit 8
  • the water retention membrane 95 in contact with the electrode 91 is in contact with the ion exchange membrane 85 of the electrode unit 8.
  • the sealant 94 includes an upper half 94a and a lower half 94b. Like the sealant 84, the sealant 94 has a frame shape so as to sandwich the coating films 93 and the conductors 92. It is glued to. The upper part of the inner side surface of the inner edge part of the half body 94a of the sealant 94 and the lower part of the inner side surface of the inner edge part of the half body 94b are bonded to the side surfaces of the water retention films 95 and 95.
  • the electrodes 90 and 91, the conductor 92, the coating film 93, the sealant 94, and the water retention film 95 of the electrode unit 9 are made of the same material as that of the electrode unit 5 according to the first embodiment.
  • the electrode unit 7 has the same configuration as that of the electrode unit 9.
  • the electrode unit 7 has a rectangular flat conductor 72, coating films 73 and 73 that cover both surfaces of the conductor 72, and each coating film 73 and conductor 72. And a sealant 74 that is bonded to the peripheral edge of each covering portion 73.
  • the sealant 74 includes an upper half 74 a and a lower half 74 b and has the same configuration as the sealant 84.
  • the upper electrode unit 7 in FIG. 3 is provided on the inner side of the peripheral portion of the lower surface of the lower coating film 73, and has a square plate electrode 70 having an active material and an electrolytic solution. No electrode is provided on the upper surface of the upper coating film 73. On the lower surface of the electrode 70, a water retention film 75 having a larger planar area than the electrode 70 is provided.
  • the upper surface of the half 74 a of the sealant 74 of the upper electrode unit 7 is bonded to the half 21 of the outer bag 2.
  • the lower part of the inner side surface of the inner edge of the half body 74 b of the sealant 74 is bonded to the side surface of the water retention film 75.
  • the lower electrode unit 7 in FIG. 3 is provided on the inner side of the peripheral edge of the upper surface of the upper coating film 73 and has a square plate-like electrode 71 having an active material and an electrolytic solution. No electrode is provided on the lower surface of the lower coating film 73. On the upper surface of the electrode 71, a water retention film 75 having a larger planar area than the electrode 71 is provided. The lower surface of the half 74 b of the sealant 74 of the lower electrode unit 7 is bonded to the half 22 of the outer bag 2. The upper part of the inner side surface of the inner edge of the half body 74 a of the sealant 74 is bonded to the side surface of the water retention film 75.
  • the electrodes 70 and 71, the conductor 72, the coating film 73, the sealant 74, and the water retention film 75 of the electrode unit 7 are made of the same material as the electrode unit 9.
  • the conductors 72 and 92 of the electrode units 7 and 9 have tabs (not shown), and the tips of the tabs are connected to the negative terminal in a state where they are overlapped with each other.
  • the tips of tabs (not shown) of the conductors 82 of the electrode units 8 are connected to the positive terminal in a state where they are overlapped with each other.
  • the halves 21 and 22 to which the conductors 72 and 72 are fixed are aligned so that the inner sides are opposed to each other, and the positive electrode terminal and the negative electrode terminal protrude from a part of the rim part of the halves 21 and 22.
  • the outer bag 2 is formed by pressure-contacting and bonding, and the vanadium solid salt battery 11 is obtained.
  • the halves 21 and 22 may be integrated from the beginning.
  • the reaction of the above formulas (1) and (2) occurs between the electrodes of the vanadium solid salt battery 11.
  • Charging / discharging of the vanadium solid salt battery using the vanadium solid salt battery 11 is performed using the reactions of the above-described formulas (1) and (2). At this time, charging / discharging is performed with an external load or a charger via the positive terminal 3 and the negative terminal 4.
  • protons move between the electrodes via the ion exchange membranes 85 and 86.
  • the electrode units 7 and 7 of the vanadium solid salt battery 11 according to the present embodiment configured as described above have water retention films 75 and 75 that are in contact with the ion exchange membranes 85 and 86 of the electrode units 8 and 8. Since the electrode unit 9 has the water retention membranes 95 and 95 that come into contact with the ion exchange membranes 85 and 86 of the electrode unit 8, when the thickness of the ion exchange membranes 85 and 86 is reduced, water is supplied to the ion exchange membranes 85 and 86. can do.
  • the thinning of the ion exchange membranes 85 and 86 reduces the absolute amount of moisture contained in the ion exchange membranes 85 and 86, and the ion exchange is caused by the change in the ion concentration in the corresponding electrode during charge / discharge reaction during use.
  • osmotic pressure is generated between the membranes 85 and 86 and the electrodes, moisture in the ion exchange membranes 85 and 86 is lost, and the permeability of ions including hydrogen ions is deteriorated. It is suppressed that the resistance value regarding ion movement increases. Therefore, the vanadium solid salt battery 11 according to the present embodiment has good charge / discharge performance and a high battery capacity.
  • the plane area of the water retention membranes 75 and 75 is more than the plane area of the electrodes 70 and 71, osmotic pressure is generated between the ion exchange membranes 86 and 85 and the electrodes 70 and 71 when the vanadium solid salt battery 11 is used.
  • the portion to be covered can be covered with the water retention membranes 75, 75, and the water content of the ion exchange membranes 86, 85 is prevented from being reduced by the osmotic pressure.
  • the plane area of the water retention membranes 75 and 75 is less than or equal to the plane area of the ion exchange membranes 86 and 85, an osmotic pressure is generated between the ion exchange membranes 86 and 85 and the electrodes 70 and 71 when the vanadium solid salt battery 11 is used.
  • the generated portion can be covered with the water retaining films 75 and 75, and the water retaining film 75 does not become unnecessarily large.
  • the planar area of the water retention membranes 95 and 95 is equal to or larger than the planar area of the electrodes 90 and 91, a portion where osmotic pressure is generated between the ion exchange membranes 86 and 85 and the electrodes 90 and 91 when the vanadium solid salt battery 11 is used. Can be covered by the water retention membranes 95, 95, and the water content of the ion exchange membranes 86, 85 is prevented from being reduced by the osmotic pressure.
  • the plane area of the water retention membranes 95 and 95 is equal to or less than the plane area of the ion exchange membranes 86 and 85, an osmotic pressure is generated between the ion exchange membranes 86 and 85 and the electrodes 90 and 91 when the vanadium solid salt battery 11 is used.
  • the generated portion can be covered by the water retention films 95 and 95, and the water retention films 95 and 95 are not unnecessarily large. As described above, the planar area of the vanadium solid salt battery 11 is prevented from increasing.
  • the conductor 72 of the electrode unit 7 is sealed with the sealant 74, the coating films 73 and 73, and the half body 21 (or 22), and the electrode 70 (or 71) is the water retention film.
  • the ion exchange membrane 86 (or 85) and the sealant 74 the acidic substance related to the electrolyte contained in the electrode 70 (or 71) does not react with the conductor 72, and the conductor 72 corrosion is prevented.
  • the conductor 92 of the electrode unit 9 is sealed with the sealant 94 and the covering films 93 and 93, and the electrode 90 (or 91) is connected with the water retention film 95 and the ion exchange membrane 86 (or 85) and the sealant 94. Therefore, the acidic substance related to the electrolyte contained in the electrode 90 (or 91) does not react with the conductor 92, and corrosion of the conductor 92 is prevented.
  • the conductor 82 of the electrode unit 8 is sealed by the sealant 84 and the coating films 83 and 83, and the electrode 80 (or 81) is surrounded by the ion exchange membrane 85 (or 86) and the sealant 84. Therefore, the acidic substance related to the electrolyte contained in the electrode 80 (or 81) does not react with the conductor 82, and corrosion of the conductor 82 is prevented.
  • the polarities of the electrodes 70 and 71 of the electrode unit 7, the electrodes 80 and 81 of the electrode unit 8, and the electrodes 90 and 91 of the electrode unit 9 are not limited to the above case.
  • the polarities of the electrodes of the electrode units 7, 8, 9 may be considered so that the polarities of the electrodes facing each other across the ion exchange membranes 85, 86 of the electrode unit 8 are different.
  • the battery capacity is improved and the battery design Diversification can be achieved.
  • the present invention is not limited to this and may be provided on the positive electrode side.
  • Vanadium Element Concentration in Water Retention Film and Battery Performance For each of the vanadium solid salt batteries 1 of Examples 1 to 5 having the configuration of the first embodiment, the element concentration (mol / L) shown in Table 1 below is added to each water retention film 55. ) was evaluated when the battery was impregnated with a water retention film impregnating solution containing vanadium (V) and sulfur (S) during assembly. A porous glass “TGP-015A” manufactured by Nippon Sheet Glass Co., Ltd. was used as the water retention membrane 55, and an anion exchange membrane manufactured by Fumatech was used as the ion exchange membrane 56. The thickness of the water retention membrane 55 and the ion exchange membrane 56 is 82 ⁇ m and 10 ⁇ m, respectively.
  • V [mol / L] (same as V concentration [mol / L] in FIG. 4) and “S [mol / L]” in “Concentration of solution in water retention membrane during operation” in Table 1 are ICP -Concentrations of vanadium and sulfur elements measured using MS [Inductively Coupled Plasma Mass Spectrometer]. "50 mA / cm 2 at the output capacity" of FIG.
  • the “input capacity at cm 2 ” is a discharge capacity when a current value of 50 mA per 1 cm 2 of electrode is inputted and then discharged at a current value of 1.5 mA per 1 cm 2 of electrode.
  • “Rated capacity” was charged at a current value of the electrode 1 cm 2 per 1.5 mA, a discharge capacity when the output current value of the electrode 1 cm 2 per 1.5 mA.
  • FIG. 4 shows that when the vanadium concentration of the water retention film 55 is 5 mol / L or less, both the input capacity and the output capacity at 50 mA / cm @ 2 are good.
  • the vanadium concentration of the water retaining film 55 is more preferably 4.8 mol / L or less, and further preferably 4.5 mol / L or less.
  • FIG. 5 shows that when the sulfur concentration is 8 mol / L or less, both the input capacity and output capacity at 50 mA / cm 2 are good.
  • the sulfur concentration is more preferably 7.8 mol / L or less, and further preferably 7.5 mol / L or less.
  • “Discharge capacity at 50 mA / cm 2 ” refers to the voltage of the battery when the current is discharged at a current density of 50 mA / cm 2 per electrode area from the state where the open circuit voltage (OCV) is 1.45 V. 1. Current capacity when discharge is achieved until 20V is reached.
  • the thickness of the water-holding film 55 is 50 ⁇ m or more 135 ⁇ m or less, it is found that good both 50 mA / cm 2 at the discharge capacity and 50 mA / cm 2 at charge capacity.
  • the lower limit of the thickness is more preferably 55 ⁇ m, still more preferably 65 ⁇ m, and particularly preferably 75 ⁇ m.
  • the vanadium solid salt battery according to the present invention is a positive electrode including a current collector and a positive electrode including a positive electrode active material, and the positive electrode active material is oxidized between pentavalent and tetravalent by an oxidation-reduction reaction.
  • a positive electrode containing a positive electrode, a current collector, and a negative electrode active material the vanadium ion containing a vanadium ion containing a vanadium ion containing a vanadium ion, or an ion containing vanadium whose oxidation number changes between pentavalent and tetravalent
  • the negative electrode active material contains vanadium ions whose oxidation number changes between divalent and trivalent or vanadium whose oxidation number changes between divalent and trivalent by an oxidation-reduction reaction.
  • the vanadium solid salt battery of the present invention since the water retention membrane is provided between the ion exchange membrane and the positive electrode or the negative electrode, when water is supplied to the ion exchange membrane and the thickness of the ion exchange membrane is reduced, the ions of the ion exchange membrane An increase in the resistance value related to movement is suppressed. Therefore, the vanadium solid salt battery of the present invention has good charge / discharge performance and high battery capacity (output capacity and input capacity).
  • the vanadium solid salt battery according to the present invention is characterized in that, in the above-described invention, the planar area of the water retention film is equal to or greater than the planar area of the positive electrode or the negative electrode provided with the water retention film.
  • the portion where osmotic pressure is generated between the ion exchange membrane and the electrode when the battery is used can be covered by the water retention membrane, and moisture in the ion exchange membrane may be lost when the osmotic pressure is generated. It is suppressed.
  • the planar area of the electrode is larger than the planar area of the water retention film, the water content of the water retention film decreases.
  • the vanadium solid salt battery according to the present invention is characterized in that, in any one of the above-described inventions, a planar area of the water retention membrane is equal to or less than a planar area of the ion exchange membrane.
  • the planar area of the electrode is smaller than the planar area of the ion exchange membrane, and it is only necessary to cover the portion where osmotic pressure is generated between the ion exchange membrane and the electrode when the battery is used. Is less than or equal to the planar area of the ion exchange membrane. As a result, the water retention film is not unnecessarily increased, and the planar area of the battery is prevented from increasing.
  • the vanadium solid salt battery according to the present invention is characterized in that, in any of the above-mentioned inventions, the water retention film is made of a porous material.
  • the water retention of the water retention film is good.
  • the vanadium solid salt battery according to the present invention is characterized in that, in any one of the above-described inventions, the thickness of the water retention film is 50 ⁇ m or more and 135 ⁇ m or less.
  • the present invention it is possible to improve the charge / discharge performance of the vanadium solid salt battery by suppressing an increase in the resistance value due to the thinning of the ion exchange membrane, and to increase the total thickness of the ion exchange membrane and the water retention membrane. It is possible to reduce the overall thickness of the battery.
  • the vanadium solid salt battery according to the present invention is characterized in that, in any of the above-described inventions, the vanadium element concentration in the water retaining film is 5 mol / L or less, and the sulfur element concentration is 8 mol / L or less. To do.
  • the vanadium solid salt battery has good charge / discharge performance.
  • Electrode unit 50 60, 70, 71, 80, 81, 90, 91 Electrode 51, 61, 72, 82 , 92 Conductor 52, 62, 73, 83, 93 Coating membrane 54, 64, 74, 84, 94 Sealant 55, 75, 95 Water retention membrane 56, 85, 86 Ion exchange membrane

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  • Electrochemistry (AREA)
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Abstract

L'invention fournit une batterie à sel solide de vanadium dont la valeur ohmique relative au déplacement d'ions d'une membrane échangeuse d'ions n'augmente pas en cas d'amincissement de cette membrane échangeuse d'ions, et qui possède des propriétés satisfaisantes de charge et décharge. La batterie à sel solide de vanadium (1) est équipée : d'une unité électrode (5) qui configure une électrode négative, et dans laquelle une électrode (50) qui contient une matière active comprenant des ions vanadium ou des ions à teneur en vanadium, est agencée sur un conducteur (51) avec un film de revêtement (52) pour intermédiaire ; et d'une unité électrode (6) qui configure une électrode positive et dans laquelle une électrode (60) qui contient une matière active comprenant des ions vanadium ou des ions à teneur en vanadium, est agencée sur un conducteur (61) avec un film de revêtement (62) pour intermédiaire. Une membrane de rétention d'eau (55) est agencée à la surface de l'électrode (50) de l'unité électrode (5), la membrane échangeuse d'ions (56) est agencée à la surface de cette membrane de rétention d'eau (55), et les électrodes (50, 60) s'opposent en enserrant la membrane échangeuse d'ions (56).
PCT/JP2016/053823 2015-03-27 2016-02-09 Batterie à sel solide de vanadium Ceased WO2016158019A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011049103A1 (fr) * 2009-10-20 2011-04-28 国立大学法人東北大学 Pile au vanadium
JP2012054035A (ja) * 2010-08-31 2012-03-15 Tomomi Abe バナジウムイオン電池
JP2014127428A (ja) * 2012-12-27 2014-07-07 Tohoku Techno Arch Co Ltd バナジウムレドックス電池
JP2014235833A (ja) * 2013-05-31 2014-12-15 株式会社 東北テクノアーチ バナジウム固体塩電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011049103A1 (fr) * 2009-10-20 2011-04-28 国立大学法人東北大学 Pile au vanadium
JP2012054035A (ja) * 2010-08-31 2012-03-15 Tomomi Abe バナジウムイオン電池
JP2014127428A (ja) * 2012-12-27 2014-07-07 Tohoku Techno Arch Co Ltd バナジウムレドックス電池
JP2014235833A (ja) * 2013-05-31 2014-12-15 株式会社 東北テクノアーチ バナジウム固体塩電池

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