WO2020111084A1 - Électrode pour batterie redox, son procédé de fabrication, batterie redox et matériau en feuille conducteur pour électrode - Google Patents

Électrode pour batterie redox, son procédé de fabrication, batterie redox et matériau en feuille conducteur pour électrode Download PDF

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WO2020111084A1
WO2020111084A1 PCT/JP2019/046255 JP2019046255W WO2020111084A1 WO 2020111084 A1 WO2020111084 A1 WO 2020111084A1 JP 2019046255 W JP2019046255 W JP 2019046255W WO 2020111084 A1 WO2020111084 A1 WO 2020111084A1
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electrode
layer
nanocarbon
redox flow
flow battery
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PCT/JP2019/046255
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English (en)
Japanese (ja)
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丈智 西方
みゆき 冨田
ティンティン シュウ
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昭和電工株式会社
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an electrode for a redox flow battery in which an electrolyte is circulated for charging and discharging, a manufacturing method thereof, and a redox flow battery having the electrode and a conductive sheet material for the electrode.
  • redox flow batteries which are electrolyte flow batteries.
  • a redox flow battery supplies and circulates a positive electrode electrolytic solution and a negative electrode electrolytic solution to and from a battery cell having a positive electrode, a negative electrode, and a diaphragm interposed between both electrodes, and a power converter (for example, an AC/DC converter or the like).
  • a power converter for example, an AC/DC converter or the like.
  • an aqueous solution containing a metal ion (active material) whose valence changes by redox is usually used.
  • a redox flow battery for example, a vanadium redox flow battery using vanadium (V) as an active material of a positive electrode and a negative electrode is well known.
  • Carbon materials such as carbon nanotubes and carbon fibers are used as the material of the electrodes used in such a redox flow battery.
  • the present applicant discloses in Patent Document 1 that as an electrode material for a redox flow battery, a conductive sheet containing carbon nanotubes having an average fiber diameter of 1 ⁇ m or less and carbon fibers having an average fiber diameter of more than 1 ⁇ m, and an average fiber.
  • porous sheets made of carbon fibers having a diameter larger than 1 ⁇ m are laminated.
  • the redox flow battery described in Patent Document 1 has a large electric capacity, a low cell resistivity, and a small pressure loss when an electrolytic solution is passed through the electrodes. It cannot be said that the performance such as the rate is sufficient, and there is room for further improvement.
  • a laminated structure of an electrode of a redox flow battery when a laminated structure of an electrode of a redox flow battery is produced, a laminated structure is constituted by two layers of a conductive sheet containing carbon nanotubes and carbon fibers and a porous sheet made of carbon fibers. , The electrodes were made.
  • the conductive sheet tends to have low mechanical strength because it contains fine carbon nanotubes, and as a result, the mechanical strength as an electrode also tends to be low. Therefore, for a redox flow battery having sufficiently high mechanical strength. An electrode was sought.
  • An object of the present invention is to contribute to reduction of cell resistivity of a redox flow battery, and an electrode for a redox flow battery having sufficiently high mechanical strength, a method for producing the same, and a redox flow battery and a conductive sheet for an electrode. To provide the material.
  • the present inventors have arranged a first porous layer composed of carbon fibers on one surface of a composite conductive layer composed of both a nanocarbon material and carbon fibers for an electrode for a redox flow battery,
  • An integrated redox flow battery electrode with a nanocarbon layer composed of a nanocarbon material on the other side makes the mechanical strength of the electrode higher and damages less likely to occur, as well as redox flow.
  • the inventors have found that the cell resistivity is low when used in batteries, and have completed the present invention. More specifically, the present invention provides the following.
  • the present invention provides a composite conductive layer composed of both a nanocarbon material and a carbon fiber having an average fiber diameter of 1 ⁇ m or more, and one of the both surfaces of the composite conductive layer.
  • An electrode for a redox flow battery comprising: a first porous layer composed of and a nanocarbon layer located on the other surface of the composite conductive layer and composed of the nanocarbon material.
  • each of the nanocarbon layer and the composite conductive layer has a thickness of 0.01 mm to 0.20 mm, and the first porous layer has a thickness of 0.05 mm.
  • the electrode for a redox flow battery according to (1) which has a thickness of up to 0.30 mm.
  • the present invention further comprises a second porous layer which is located on a surface opposite to the composite conductive layer on both surfaces of the nanocarbon layer and which is composed of the carbon fiber.
  • a second porous layer which is located on a surface opposite to the composite conductive layer on both surfaces of the nanocarbon layer and which is composed of the carbon fiber.
  • it is the electrode for a redox flow battery according to (2).
  • the present invention is the electrode for a redox flow battery according to (3), wherein the thickness dimension of the second porous layer is 0.10 mm to 0.50 mm.
  • the present invention also provides the electrode for redox flow battery according to (3) or (4), wherein the thickness dimension of the first porous layer is smaller than the thickness dimension of the second porous layer. Is.
  • the present invention is the electrode for a redox flow battery according to any one of (1) to (5), wherein the nanocarbon material contains carbon nanotubes having an average fiber diameter of less than 1 ⁇ m.
  • the composite conductive layer contains 20 parts by mass to 90 parts by mass of the carbon fiber with respect to 100 parts by mass in total of the nanocarbon material and the carbon fiber, (1) to (6) ) It is an electrode for redox flow batteries as described in any one of the above.
  • the present invention is a redox flow battery having the electrode for redox flow battery according to any one of (1) to (7).
  • the present invention provides the redox flow battery electrode according to any one of (1) to (7) between the ion exchange membrane and the electrode plate, wherein the first porous layer is It is a redox flow battery provided so as to face an ion exchange membrane.
  • the present invention is a composite conductive layer composed of both a nanocarbon material and a carbon fiber having an average fiber diameter of 1 ⁇ m or more;
  • a conductive sheet material for an electrode comprising a first porous layer composed of carbon fibers and a nanocarbon layer located on the other surface of the composite conductive layer and composed of the nanocarbon material.
  • the present invention further comprises a second porous layer which is located on a surface opposite to the composite conductive layer on both surfaces of the nanocarbon layer and which is composed of the carbon fiber.
  • the present invention is a method for producing an electrode for a redox flow battery, wherein a composite dispersion liquid containing a nanocarbon material and carbon fibers is applied to one surface of the first porous layer and dried to form a composite. And a step of forming a conductive layer, and applying a nanocarbon dispersion liquid containing the nanocarbon material to a surface of the composite conductive layer opposite to the first porous layer on both surfaces of the composite conductive layer, followed by drying to form a nanoparticle. And a step of forming a carbon layer, which is a method for manufacturing an electrode for a redox flow battery.
  • an electrode for a redox flow battery which can contribute to reduction of the cell resistivity of the redox flow battery and has sufficiently high mechanical strength, and a manufacturing method thereof.
  • FIG. 1 is a cross-sectional view showing an example of a redox flow battery electrode (hereinafter, may be simply referred to as “electrode”) according to the present embodiment.
  • the redox flow battery electrode 1 according to the present embodiment includes a composite conductive layer 11, a first porous layer 12 located on one surface of both surfaces of the composite conductive layer 11, and the other surface of the composite conductive layer 11. And the nanocarbon layer 13 located in the main structure. Further, it is preferable that the electrode 1 further has a second porous layer 15 located on the surface opposite to the composite conductive layer 11 on both surfaces of the nanocarbon layer 13.
  • the nanocarbon layer 13, the composite conductive layer 11, and the first porous layer 12 are sequentially provided on one surface of the second porous layer 15.
  • the first porous layer 12 is laminated so as to face the ion exchange membrane 60 described later.
  • the second porous layer 15 is provided such that the other surface thereof is adjacent to or opposite to the electrode plate 16 described later.
  • the redox flow battery electrode 1 has a laminated structure including at least three layers of the composite conductive layer 11, the first porous layer 12, and the nanocarbon layer 13, so that the mechanical structure of the electrode 1 is improved. Since the strength is increased, the overall thickness of the electrode 1 can be reduced, and the cell resistivity of the redox flow battery can be reduced accordingly.
  • the composite conductive layer 11 and the nanocarbon layer 13 containing the fine nanocarbon material are provided in the first porous layer 12 when the electrode laminated structure is produced. Since the layers can be laminated by a method such as sequentially coating on one side, the nanocarbon layer 13, the composite conductive layer 11, and the first porous layer 12 can be formed integrally. Therefore, even if the layer containing the nanocarbon material, particularly the nanocarbon layer 13 having a high concentration of the nanocarbon material, is provided, the first porous layer 12 has sufficient mechanical strength, and thus is formed of these layers. Since the electrode 1 also has sufficient mechanical strength as a whole, the electrode 1 can be less likely to be damaged and the electrode 1 can be manufactured more easily.
  • the nanocarbon layer 13 itself having a high concentration of the nanocarbon material has a property that mechanical strength is not sufficient and is easily damaged, it may be laminated and integrated with the composite conductive layer 11 and the first porous layer 12. Since the nanocarbon layer 13 is reinforced by at least the first porous layer 12 by being formed, it is possible to increase mechanical strength and prevent damage.
  • the nanocarbon layer 13 composed only of the nanocarbon material and the composite conductive layer 11 composed of both the nanocarbon material and the carbon fiber are integrated.
  • the nanocarbon material contained in the nanocarbon layer 13 is easily entangled and retained by the carbon fibers of the composite conductive layer 11, so that the nanocarbon material flows out (separates) from the nanocarbon layer 13. ) Is effectively suppressed, it is possible to prevent the deterioration of the electrode.
  • the composite conductive layer 11, the first porous layer 12, the nanocarbon layer 13, and the second porous layer 15 will be described in detail below.
  • the composite conductive layer 11 is configured to include both a nanocarbon material and carbon fibers having an average fiber diameter of 1 ⁇ m or more. As a result, the reactivity is enhanced by the nanocarbon material having a relatively large surface area, while the nanocarbon material is held by the carbon fibers, so that the nanocarbon material can be prevented from flowing out of the electrode 1.
  • the nanocarbon material may include a carbon material having a size of less than 1 ⁇ m in at least one of the three dimensions, and among them, from the viewpoint of acid resistance and oxidation resistance, the average fiber It preferably contains carbon nanotubes having a diameter of less than 1 ⁇ m.
  • the nanocarbon material in addition to carbon nanotubes, for example, carbon nanofibers and graphene can be cited.
  • the average fiber diameter of the carbon nanotubes is preferably 1 nm to 300 nm, more preferably 10 nm to 200 nm, and further preferably 15 nm to 150 nm.
  • the average fiber length of the carbon nanotubes is preferably 0.1 ⁇ m to 30 ⁇ m, more preferably 0.5 ⁇ m to 25 ⁇ m, still more preferably 0.5 ⁇ m to 20 ⁇ m. At this time, a plurality of types of carbon nanotubes having different average fiber diameters or average fiber lengths may be mixed.
  • the carbon fibers contained in the composite conductive layer 11 have a large average fiber diameter of 1 ⁇ m or more.
  • carbon fibers having an average fiber diameter of 1 ⁇ m or more it is possible to form a larger void inside the composite conductive layer 11 and reduce the pressure loss when the electrolytic solution is passed through the electrodes. .. Further, the effect of improving the conductivity and mechanical strength of the composite conductive layer 11 can be expected.
  • carbon fibers having an average fiber diameter of 200 ⁇ m or less the nanocarbon material is easily entangled and retained in the carbon fibers, so that the nanocarbon materials included in the composite conductive layer 11 and the adjacent nanocarbon layer 13 are The outflow to the electrolyte can be suppressed.
  • the average fiber diameter of the carbon fibers is preferably 1 ⁇ m to 200 ⁇ m, more preferably 2 ⁇ m to 100 ⁇ m, still more preferably 5 ⁇ m to 30 ⁇ m.
  • the average fiber length of the carbon fibers is preferably 0.01 mm to 20 mm, more preferably 0.05 mm to 10 mm, further preferably 0.1 mm to 8 mm.
  • the average fiber diameter and average fiber length of carbon nanotubes and carbon fibers, which are nanocarbon materials are randomly determined for each type of fibers (carbon nanotubes and carbon fibers) using a transmission electron microscope (TEM). It is possible to measure the diameters of 100 or more fibers and obtain the arithmetic mean value of the measured values.
  • TEM transmission electron microscope
  • the composite conductive layer 11 has a fine structure made of nanocarbon material and carbon fiber.
  • This fine structure is a structure in which a nanocarbon material is attached to the surface of carbon fiber.
  • the carbon nanotube which is a nanocarbon material, may have a structure that spans a plurality of carbon fibers.
  • the composite conductive layer 11 has a carbon fiber content of preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less based on 100 parts by mass of the total of the nanocarbon material and the carbon fiber. .. Further, the lower limit of the content of the carbon fiber is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 40 parts by mass or more based on 100 parts by mass of the total of the nanocarbon material and the carbon fiber. By setting the content of the carbon fibers in the composite conductive layer 11 within this range, it is possible to improve the reactivity in the composite conductive layer 11 and reduce the pressure loss when the electrolytic solution is passed through the electrodes. ..
  • the thickness (thickness dimension) of the composite conductive layer 11 in a dry state is preferably 0.01 mm to 0.20 mm, more preferably 0.01 mm to 0.15 mm, further preferably 0.02 mm to 0.15 mm, and further It is preferably 0.02 mm to 0.10 mm.
  • the thickness of the composite conductive layer 11 is preferably 0.01 mm or more, the reactivity in the composite conductive layer 11 is enhanced, and thus the charge/discharge efficiency of the redox flow battery can be enhanced.
  • the composite conductive layer 11 having a thickness of 0.01 mm or more integrally with the nanocarbon layer 13 as a layer constituting the laminated structure of the electrode 1 the nanocarbon material contained in the nanocarbon layer 13 is a composite material.
  • the nanocarbon layer 13 can be easily held by the electrode 1.
  • the thickness of the composite conductive layer 11 to 0.20 mm or less, when this electrode is used in a redox flow battery, the protons generated by charge and discharge move quickly to the ion exchange membrane, and The resistivity can be reduced.
  • the first porous layer 12 is provided on one surface of both surfaces of the composite conductive layer 11, and is composed of carbon fibers having an average fiber diameter of 1 ⁇ m or more.
  • the first porous layer 12 is a layer having a small pressure loss when the electrolytic solution is passed through the electrode, and has a high mechanical strength that can be easily handled alone.
  • the carbon fiber contained in the first porous layer 12 has a large average fiber diameter of 1 ⁇ m or more, similar to that contained in the composite conductive layer 11. Thereby, a larger void can be formed inside the first porous layer 12, so that the pressure loss when the electrolytic solution is passed through the electrode can be reduced.
  • the average fiber diameter of the carbon fibers contained in the first porous layer 12 is preferably 1 ⁇ m to 200 ⁇ m, more preferably 2 ⁇ m to 100 ⁇ m, still more preferably 5 ⁇ m to 30 ⁇ m.
  • the carbon fibers forming the first porous layer 12 include a woven fabric of relatively long fibers, a non-woven fabric (felt) woven without woven fibers, and a sheet of paper made by filtering relatively short fibers. Of these, any form may be used. At this time, as the average fiber length of the carbon fibers, it is preferable to adopt a length usually used in each form.
  • the thickness (thickness dimension) of the first porous layer 12 in a dry state is preferably 0.05 mm to 0.30 mm, more preferably 0.07 mm to 0.25 mm, further preferably 0.10 mm to 0.20 mm. Is. By setting the thickness of the first porous layer 12 in the above range, it is possible to sufficiently maintain the mechanical strength of the electrode for a redox flow battery and to suppress an increase in cell resistivity when used in a redox flow battery. ..
  • the composite conductive layer 11 and the first porous layer 12 may not be distinguished by a clear boundary, and the composite conductive layer 11 and the first porous layer 12 may be integrated.
  • the layer in which the composite conductive layer 11 and the first porous layer 12 are integrated has a region containing no nanocarbon material on one side in the thickness direction and a region containing nanocarbon material on the other side. May be configured to have. At this time, the region containing the nanocarbon material corresponds to the composite conductive layer 11, and the region not containing the nanocarbon material corresponds to the first porous layer 12.
  • the nanocarbon layer 13 is provided on the surface of the composite conductive layer 11 opposite to the first porous layer 12, and is made of a nanocarbon material. Since the nanocarbon layer 13 is an aggregate of nanocarbon materials having a nano size, it has a large surface area per unit volume and a large number of active points, as compared with other layers, and thus a layer where electrode reaction is actively performed. Is. On the other hand, since the nanocarbon layer 13 is inferior in mechanical strength to the other layers, in the present embodiment, the nanocarbon layer 13 is composed of the composite conductive layer 11 and the carbon fiber as the first porous layer. 12 and an integral laminated structure. Thereby, the insufficient strength of the nanocarbon layer 13 can be sufficiently compensated by the integration of the composite conductive layer 11 and the first porous layer 12 having high mechanical strength.
  • the nanocarbon material forming the nanocarbon layer 13 may include a carbon material having a size of less than 1 ⁇ m in at least one of the three dimensions. Among them, from the viewpoint of acid resistance and oxidation resistance, it is preferable to include carbon nanotubes having an average fiber diameter of less than 1 ⁇ m.
  • the average fiber diameter and average fiber length of the carbon nanotubes can be the same as those included in the composite conductive layer 11. At this time, a plurality of types of carbon nanotubes having different average fiber diameters or average fiber lengths may be mixed.
  • the dry thickness (thickness dimension) of the nanocarbon layer 13 is preferably 0.01 mm to 0.20 mm, more preferably 0.01 mm to 0.15 mm, and further preferably 0.01 mm to 0.10 mm. ..
  • the thickness of the nanocarbon layer 13 is preferably 0.01 mm to 0.20 mm, more preferably 0.01 mm to 0.15 mm, and further preferably 0.01 mm to 0.10 mm. ..
  • the thickness of the nanocarbon layer 13 is preferably 0.01 mm to 0.20 mm, more preferably 0.01 mm to 0.15 mm, and further preferably 0.01 mm to 0.10 mm. ..
  • the ratio (a/b) of the thickness dimension (a) of the composite conductive layer 11 to the thickness dimension (b) of the first porous layer 12 is preferably 0. 10 to 2.0, more preferably 0.20 to 1.5, still more preferably 0.20 to 1.0.
  • the ratio (c/b) of the thickness dimension (c) of the nanocarbon layer 13 to the thickness dimension (b) of the first porous layer 12 is preferably 0.05 to 2.0, more preferably 0.
  • the range is 0.05 to 1.0, and more preferably 0.2 to 1.0.
  • the nanocarbon layer 13 and the composite conductive layer 11 may not be distinguished by a clear boundary, and the nanocarbon layer 13 and the composite conductive layer 11 may be integrated. It is preferable that the layer in which the nanocarbon layer 13 and the composite conductive layer 11 are integrated has a region made of a nanocarbon material in at least a part of one side in the thickness direction. At this time, it is more preferable that the region made of the nanocarbon material has a layer having a constant thickness.
  • the boundary between them is unclear. May become integrated. Even in that case, since the integrated nanocarbon layer 13 and the composite conductive layer 11 are supported by the first porous layer 12, the mechanical strength of the redox flow battery electrode 1 can be increased.
  • the second porous layer 15 is a layer that is located on a surface opposite to the composite conductive layer 11 on both surfaces of the nanocarbon layer 13, and is composed of carbon fibers having an average fiber diameter of 1 ⁇ m or more. Can be provided.
  • the second porous layer 15 is a layer having a small pressure loss when the electrolytic solution is passed through the electrode, and has a high mechanical strength that can be easily handled by itself.
  • the electrolytic solution spreads inside the second porous layer 15, so that the nanocarbon layer of the second porous layer 15 is included.
  • the electrolytic solution can be spread over almost the entire surface adjacent to 13. As a result, the electrolytic solution flows more uniformly and vertically to the surface of the nanocarbon layer 13, so that the liquid permeability in the redox flow battery electrode 1 can be further enhanced.
  • the same carbon fiber contained in the first porous layer 12 can be used as the carbon fiber contained in the second porous layer 15 as the carbon fiber contained in the second porous layer 12.
  • the thickness (thickness dimension) of the second porous layer 15 in a dry state is preferably 0.10 mm to 0.50 mm, more preferably 0.15 mm to 0.40 mm, further preferably 0.20 mm to 0.40 mm. Is. By setting the thickness of the second porous layer 15 within the range of 0.10 mm to 0.50 mm, the electrolytic solution spreads uniformly inside the second porous layer 15, so that the liquid permeability of the electrode 1 is improved. You can
  • FIG. 2 is a schematic configuration diagram showing an example of the configuration of the redox flow battery according to the present embodiment, and shows an example in which a vanadium compound is used as an active material.
  • the redox flow battery 2 according to the present embodiment is used in a form called a battery cell stack in which the battery cell 6 is used as a minimum unit, or a single unit of the battery cell 6 is stacked, and an electrolytic solution is circulated in the battery cell 6. Charge and discharge.
  • the redox flow battery 2 includes a positive electrode cell 41 having a positive electrode 1a incorporated therein, a negative electrode cell 51 having a negative electrode 1b incorporated therein, and a positive electrode 1a and a negative electrode 1b interposed therebetween to separate the cells.
  • the battery cell 6 having the ion exchange membrane 60 that allows predetermined ions to permeate is the main component.
  • the redox flow battery 2 uses the above-mentioned redox flow battery electrode 1 for one or both of the positive electrode 1a and the negative electrode 1b.
  • the redox flow battery electrode 1 is disposed between the ion exchange membrane 60 and the electrode plate 16a.
  • the redox flow battery electrode 1 is used as the negative electrode 1b, the redox flow battery electrode 1 is disposed between the ion exchange membrane 60 and the electrode plate 16b.
  • the electrode 1 for redox flow battery is provided so that the surface of the first porous layer 12 opposite to the composite conductive layer 11 faces the ion exchange membrane 60.
  • the surface of the second porous layer 15 opposite to the nanocarbon layer 13 faces the electrode plates 16a and 16b.
  • the electrode 1 (the positive electrode 1a or the negative electrode 1b) is provided such that one surface of the second porous layer 15 faces the electrode plates 16a and 16b.
  • the surface opposite to the composite conductive layer 11 may be provided so as to face the electrode plates 16a and 16b.
  • the surface opposite to the nanocarbon layer faces the ion exchange membrane 60.
  • the electrode 1 for a redox flow battery described above as one or both of the positive electrode 1a and the negative electrode 1b, the charge/discharge efficiency of the electrolytic solution in the redox flow battery 2 is increased, and the redox flow battery 2 is used.
  • the cell resistivity of can be lowered.
  • the active material contained in the electrolytic solution on the positive electrode side and the negative electrode side of the redox flow battery 2 is, for example, one of a vanadium compound, a molybdenum compound, a tin compound, an iron compound, a chromium compound, a manganese compound, a titanium compound, and a zinc compound.
  • a vanadium compound as an active material in both the positive electrode side and negative electrode side electrolytic solutions, and also include a manganese compound in the positive electrode side electrolytic solution as an active material, and a titanium compound as an active material on the negative electrode side. It is also preferable to include it in the electrolytic solution.
  • a known cation exchange membrane can be used as the ion exchange membrane 60 used in the redox flow battery 2.
  • a perfluorocarbon polymer having a sulfonic acid group a hydrocarbon-based polymer compound having a sulfonic acid group, a polymer compound doped with an inorganic acid such as phosphoric acid, a part of which is a proton-conductive functional group.
  • perfluorocarbon polymers having a sulfonic acid group are preferable, and Nafion (registered trademark) is more preferable.
  • a conductive material containing carbon can be used. More specifically, a conductive resin composed of graphite and an organic polymer compound, or a conductive resin in which a part of graphite is replaced with one or both of carbon black and diamond-like carbon, and carbon and the resin are kneaded.
  • An example of the molded material is a molded material. Of these, it is preferable to use a molding material obtained by kneading and molding carbon and resin.
  • the electrode plates 16a and 16b may be provided with a flow path of an electrolytic solution which communicates with the outside of the redox flow battery electrode 1. More specifically, it is preferable that a groove portion including a groove or a recess for improving the liquid permeability of the electrolytic solution is formed on the electrode side. Only one groove or recess may be formed in the electrode plates 16a and 16b as in the groove portion 161 shown in FIG. 1, and a plurality of grooves or recesses may be formed on the surface facing the redox flow battery electrode 1. May be. Further, the size of the groove or the dent is not particularly limited. Further, the electrode plates 16a and 16b may exchange electricity via a current collector plate (not shown).
  • the redox flow battery 2 includes a positive electrode electrolytic solution tank 42 that stores a positive electrode electrolytic solution that is circulated and supplied to the positive electrode cell 41, a positive electrode forward pipe 43 that sends the positive electrode electrolytic solution from the positive electrode electrolytic solution tank 42 to the positive electrode cell 41, and a positive electrode electrolytic solution. And a positive electrode return pipe 44 for returning from the positive electrode cell 41 to the positive electrode electrolyte tank 42.
  • a pump 45 for circulating the positive electrode electrolytic solution is arranged in the positive electrode outward piping 43.
  • the redox flow battery 2 includes a negative electrode electrolytic solution tank 52 that stores a negative electrode electrolytic solution that is circulated and supplied to the negative electrode cell 51, and a negative electrode outward piping 53 that sends the negative electrode electrolytic solution from the negative electrode electrolytic solution tank 52 to the negative electrode cell 51. And a negative electrode return pipe 54 for returning the negative electrode electrolytic solution from the negative electrode cell 51 to the negative electrode electrolytic solution tank 52.
  • a pump 55 for circulating the negative electrode electrolytic solution is arranged in the negative electrode outward piping 53.
  • the electrolytic solution in the positive electrode electrolytic solution tank 42 is sent to the battery cell 6 (more strictly, the positive electrode cell 41) through the positive electrode outward piping 43 by operating the pump 45. ..
  • the positive electrode electrolytic solution sent to the battery cell 6 is discharged upward through the inside of the battery cell 6 and returned to the positive electrode electrolytic solution tank 42 through the positive electrode return pipe 44, whereby the positive electrode electrolytic solution is directed in the direction of arrow A in the figure. Circulate.
  • the electrolytic solution in the negative electrode electrolytic solution tank 52 is sent to the battery cell 6 (more strictly, the negative electrode cell 51) through the negative electrode outward pipe 53 by operating the pump 55.
  • the electrolytic solution sent to the battery cell 6 is circulated in the direction of arrow B in the figure by being discharged upward through the inside of the battery cell 6 and returned to the negative electrode electrolytic solution tank 52 through the negative electrode return pipe 54.
  • the battery cell 6 of the redox flow battery 2 has been described as a single cell, but it may be configured in a form called a cell stack in which a plurality of single cells are stacked (not shown).
  • the polar plates 16a and 16b of the adjacent battery cells 6 in the stacked cell stacks may be formed by one bipolar plate, and the stacked structure of the electrode 1 may be provided on each of both surfaces thereof.
  • the conductive sheet material for electrodes is a conductive sheet material used for electrodes, particularly for the above-described redox flow battery electrode 1.
  • This conductive sheet material is a composite conductive layer 11 composed of both a nanocarbon material and carbon fibers, and a first porous layer composed of carbon fibers and located on one surface of both surfaces of the composite conductive layer 11. 12 and a nanocarbon layer 13 located on the other surface of the composite conductive layer and made of a nanocarbon material.
  • the conductive sheet material for electrodes By forming the conductive sheet material for electrodes into the above layer structure, it is possible to obtain a structure in which the first porous layer is arranged on one surface of the composite conductive layer and the nanocarbon layer is arranged on the other surface. At the same time, the first porous layer ensures the mechanical strength that can withstand the production of the laminated structure, so that the conductive sheet material for electrodes is less likely to be damaged and the production of electrodes is facilitated. Therefore, it is possible to contribute to the reduction of the cell resistivity of the redox flow battery, and it is possible to more easily obtain an electrode having high mechanical strength.
  • a dispersion containing a nanocarbon material and carbon fibers is applied to one surface of the first porous layer 12 and dried to form the composite conductive layer 11.
  • a step of forming a nanocarbon layer 13 by applying a dispersion liquid containing only a nanocarbon material to one of both surfaces of the composite conductive layer 11 opposite to the first porous layer 12 and then drying it.
  • the composite conductive layer 11 is integrated with the first porous layer 12 by forming a composite conductive layer 11 by applying a dispersion liquid containing a nanocarbon material and carbon fibers on one surface of the first porous layer 12. It becomes possible to change. Further, the nanocarbon layer 13 is formed by applying the dispersion liquid containing only the nanocarbon material to the surface opposite to the first porous layer 12 of both surfaces of the composite conductive layer 11 to form the nanocarbon layer 13. Can be integrated with the composite conductive layer 11 and the first porous layer 12. Accordingly, when the composite conductive layer 11 or the nanocarbon layer 13 that is a thin layer containing carbon nanotubes is integrally provided on the first porous layer 12, damage to these layers is unlikely to occur, and thus the redox flow is prevented. The production of the battery electrode can be made easier.
  • the nanocarbon dispersion liquid containing the nanocarbon material used in the manufacturing method according to the present embodiment can be obtained by dispersing the nanocarbon material in the dispersion medium.
  • the nanocarbon material can include a carbon material having a size of less than 1 ⁇ m in at least one of the three dimensions. Among them, from the viewpoint of acid resistance and oxidation resistance, it is preferable to include carbon nanotubes having an average fiber diameter of less than 1 ⁇ m.
  • the dispersion medium is not particularly limited, and water can be used, for example.
  • a dispersant When dispersing the nanocarbon material in the dispersion medium, it is preferable to add a dispersant to the dispersion medium, which can facilitate uniform dispersion of the nanocarbon material.
  • a dispersant a known dispersant can be used, and for example, a water-soluble conductive polymer can be used.
  • the method for preparing the nanocarbon dispersion by dispersing the nanocarbon material is not particularly limited, and examples thereof include a method using a ball mill, a paint shaker, ultrasonic waves, a jet mill, and the like. Among them, the method using ultrasonic waves or a wet jet mill is preferable in that the nanocarbon material can be uniformly dispersed while suppressing damage to the nanocarbon material.
  • the composite dispersion liquid containing a nanocarbon material and carbon fibers used in the manufacturing method according to the present embodiment can be obtained, for example, by further dispersing carbon fibers in the above-mentioned nanocarbon dispersion liquid. Further, a composite dispersion liquid may be obtained by simultaneously dispersing the nanocarbon material and the carbon fiber in the dispersion medium.
  • carbon fibers having an average fiber diameter of 1 ⁇ m or more can be used.
  • the method of dispersing the carbon fiber in the nanocarbon dispersion is not particularly limited, and examples thereof include a method using ultrasonic waves, a ball mill, and a magnetic stirrer.
  • the first porous layer 12 the one made of carbon fibers having an average fiber diameter of 1 ⁇ m or more as described above is used.
  • a woven fabric, felt, paper or the like made of carbon fiber having an average fiber diameter of 1 ⁇ m or more and processed into a predetermined size can be used.
  • the composite dispersion liquid As a means for applying the composite dispersion liquid to the first porous layer 12, for example, a roll coater method or a spray method can be used. Then, after applying the composite dispersion liquid to the first porous layer 12, the dispersion medium is distilled off to form the composite conductive layer 11 on one surface of the first porous layer 12.
  • a nanocarbon layer 13 is formed by applying a nanocarbon dispersion liquid to the surface of the composite conductive layer 11 located on the opposite side of the first porous layer 12 from both surfaces. To do.
  • the nanocarbon layer 13 can be formed on the composite conductive layer 11 by applying the nanocarbon dispersion liquid to the composite conductive layer 11 and then distilling the dispersion medium. In this way, a laminate having the three layers of the first porous layer 12, the composite conductive layer 11 and the nanocarbon layer 13 can be obtained.
  • the obtained laminated body is processed into a predetermined size if necessary, and then, as shown in FIG. 3(C), on a surface of the nanocarbon layer 13 opposite to the composite conductive layer 11, the surface is located. It is preferable to stack the second porous layer 15.
  • the second porous layer 15 may be held by the electrode plate 16 as shown in FIG. In this case, for the redox flow battery, by stacking a laminate having the nanocarbon layer 13, the composite conductive layer 11 and the first porous layer 12 in this order on the second porous layer 15 held by the electrode plate 16. The electrode 1 can be obtained.
  • the second porous layer 15 as with the first porous layer 12, a layer made of carbon fiber having an average fiber diameter of 1 ⁇ m or more is used.
  • the second porous layer 15 is disposed so as to face the nanocarbon layer 13 of the laminated body having the first porous layer 12, the composite conductive layer 11 and the nanocarbon layer 13, and is press-formed while being heated if necessary. Thereby, it can be integrated with the laminated body having the first porous layer 12, the composite conductive layer 11, and the nanocarbon layer 13.
  • the press pressure and heating temperature during press molding can be determined by preliminary experiments.
  • the redox flow battery electrode 1 can be manufactured by heating at a temperature of 50° C. to 250° C. under a pressure of 10 MPa to 20 MPa.
  • the nanocarbon layer 13 may be laminated with the second porous layer 15 not held by the electrode plate 16.
  • the conductive sheet material for electrodes is obtained by laminating the second porous layer 15.
  • You can The redox flow battery electrode 1 can be obtained by processing the obtained electrode conductive sheet material into a predetermined size and then attaching the electrode plate 16 to the second porous layer 15 if necessary.
  • the redox flow battery electrode 1 thus produced can be incorporated into the redox flow battery 2 shown in FIG. 2 by a conventional method.
  • the redox flow battery electrode 1 is used as the positive electrode 1a
  • the redox flow battery electrode 1 is provided between the ion exchange membrane 60 and the positive electrode plate 16a.
  • the redox flow battery electrode 1 is used as the negative electrode 1b
  • the redox flow battery electrode 1 is provided between the ion exchange membrane 60 and the negative electrode plate 16b.
  • Example 1 Preparation of Dispersion Liquid Containing Nanocarbon Material A solution was prepared by dissolving 0.3 mg of polyisothionaphthenesulfonic acid, which is a water-soluble conductive polymer, as a dispersant in 30 mL of pure water. To this solution, 0.4 g of VGCF (registered trademark)-H (average fiber diameter: 150 nm, average fiber length: 15 ⁇ m) manufactured by Showa Denko Co., Ltd. as a carbon nanotube, which is a nanocarbon material, was added, and the mixture was ultrasonically cleaned for 30 minutes. By performing the dispersion treatment, a dispersion liquid (dispersion liquid A) of the nanocarbon material was obtained.
  • VGCF registered trademark
  • Dispersion Liquid Containing Nanocarbon Material and Carbon Fiber A solution was prepared by dissolving 0.3 mg of polyisothionaphthenesulfonic acid, which is a water-soluble conductive polymer, as a dispersant in 30 mL of pure water. In this solution, 0.3 g of VGCF (registered trademark)-H (average fiber diameter 150 nm, average fiber length 15 ⁇ m) manufactured by Showa Denko KK as carbon nanotubes, which is a nanocarbon material, and carbon fiber donacarb made by Osaka Gas Chemicals, Inc.
  • VGCF registered trademark
  • H average fiber diameter 150 nm, average fiber length 15 ⁇ m
  • the content of carbon fiber in this dispersion B is 40 parts by mass when the total content of the nanocarbon material and the carbon fiber is 100 parts by mass.
  • a carbon paper having a size of 100 mm ⁇ 100 mm and a thickness of 0.19 mm (manufactured by SGL Carbon Co., model number GDL-29AA) is arranged, and the nanocarbon material and the carbon fiber described above are arranged.
  • the dispersion liquid B containing was applied by using a spray as a coating means. Then, it dried and formed the composite conductive layer in the 1st porous layer.
  • the thickness obtained by subtracting the thickness b of the first porous layer from the total thickness of the first porous layer on which the composite conductive layer is formed was determined as the thickness a of the composite conductive layer.
  • the content of carbon fibers in the composite conductive layer is the content of carbon fibers contained in dispersion B when the total content of the nanocarbon material and carbon fibers contained in dispersion B is 100 parts by mass ( Mass part).
  • the composite conductive layer formed on the first porous layer was coated with the above-mentioned dispersion liquid of the nanocarbon material using a spray as a coating means. Then, it was dried to form a nanocarbon layer on the composite conductive layer, thereby obtaining a conductive sheet material for electrodes.
  • the thickness obtained by subtracting the thickness of the first porous layer and the composite conductive layer from the thickness of the electrode conductive sheet material was determined as the thickness c of the nanocarbon layer.
  • the electrode plate is made of a flat-plate molding material obtained by kneading and molding carbon and plastic, and has a concave portion on its main surface, and the concave portion is surrounded by a peripheral wall.
  • the size of the recess is 49 mm ⁇ 49 mm ⁇ depth 0.37 mm (that is, the height of the peripheral wall surrounding the recess is 0.37 mm), and the width of the peripheral wall surrounding the recess is 1 mm.
  • the size of the recess is such that the second porous layer described below fits into the recess without any gap.
  • a plurality of grooves are formed in parallel with each other on the surface of the electrode plate facing the electrode.
  • the width of each groove formed in the electrode plate is 0.5 mm
  • the depth of each groove is 1.0 mm
  • the interval between the grooves is 0.5 mm.
  • the second porous layer carbon paper having a size of 49 mm ⁇ 49 mm (manufactured by Toray Industries, Inc., model number TGP-H-120, thickness 0.37 mm) was used, and this second porous layer was used as a concave portion of the electrode plate. Mated.
  • the conductive sheet material for electrodes is cut into a size of 50 mm ⁇ 50 mm, and the conductive sheet material for electrodes is arranged on the electrode plate so that the nanocarbon layer of the conductive sheet material for electrodes faces the second porous layer.
  • the electrodes thus prepared were used as a positive electrode and a negative electrode, respectively, and these electrodes were arranged such that the first porous layer side of the electrodes faced the ion exchange membrane.
  • Nafion (registered trademark) 212 model number
  • a gold-plated brass plate was placed as a current collector plate on the outside of the two electrode plates to form a single cell of a redox flow battery.
  • the obtained redox flow batteries were evaluated for charge/discharge characteristics and durability.
  • An aqueous solution containing vanadium ions (IV valence) and sulfuric acid was introduced into the positive electrode side, and an aqueous solution containing vanadium ions (III valence) and sulfuric acid was introduced into the negative electrode side as electrolyte solutions, and 25 mL of each electrolyte solution was circulated by a tube pump.
  • the flow rate of the electrolytic solution was set to 64 mL/min.
  • the current during charge/discharge was 2.5 A (100 mA/cm 2 ), the charge stop voltage was 1.75 V, and the discharge stop voltage was 1.00 V.
  • the cell resistivity was a value obtained by calculating the charge average voltage and the discharge average voltage at the fifth charge/discharge cycle and using the following formula.
  • Cell resistivity [ ⁇ cm 2 ] (charge average voltage [V] ⁇ discharge average voltage [V]) ⁇ electrode area [cm 2 ] ⁇ (2 ⁇ charge current [A])
  • the charge/discharge efficiency was measured at the fifth charge/discharge cycle.
  • the redox flow battery was disassembled, the second porous layer and the electrode plate were removed from the electrodes, and the presence or absence of cracks in the nanocarbon layer and the composite conductive layer was visually checked. Confirmed by.
  • those in which cracks are not observed in both the nanocarbon layer and the composite conductive layer are " ⁇ "
  • one of the nanocarbon layer and the composite conductive layer or Those having cracks on both sides were marked with "x”.
  • Example 2 In "2. Preparation of dispersion containing nanocarbon material and carbon fiber", a single cell of a redox flow battery was constructed in the same manner as in Example 1 except that the amount of carbon fiber added was 0.4 g. At this time, the content of the carbon fibers in the dispersion B is 57 parts by mass when the total content of the nanocarbon material and the carbon fibers is 100 parts by mass. Charge/discharge characteristics and durability of the obtained redox flow battery were evaluated in the same manner.
  • Example 3 In “3. Formation of composite conductive layer", carbon paper having a size of 100 mm x 100 mm and a thickness of 0.11 mm (manufactured by Toray Industries, Inc., model number TGP-H-30) was used as the first porous layer, except that A single cell of a redox flow battery was constructed in the same manner as in Example 2. Charge/discharge characteristics and durability of the obtained redox flow battery were evaluated in the same manner.
  • Example 4 In “1. Preparation of dispersion containing nanocarbon material”, addition of VGCF (registered trademark)-H (average fiber diameter 150 nm, average fiber length 15 ⁇ m) manufactured by Showa Denko KK, which is a nanocarbon material (carbon nanotube) The amount was 0.5 g. Moreover, in “2. Preparation of dispersion containing nanocarbon material and carbon fiber”, VGCF (registered trademark)-H (average fiber diameter 150 nm, average, manufactured by Showa Denko KK, which is a nanocarbon material (carbon nanotube), is used. The amount of the fiber length (15 ⁇ m) added was 0.4 g.
  • the content of the carbon fiber in the dispersion B is 50 parts by mass when the total content of the nanocarbon material and the carbon fiber is 100 parts by mass. Except for these, a single cell of a redox flow battery was constructed in the same manner as in Example 3. Charge/discharge characteristics and durability of the obtained redox flow battery were evaluated in the same manner.
  • Example 5 In “1. Preparation of Dispersion Liquid Containing Nanocarbon Material” and “2. Preparation of Dispersion Liquid Containing Nanocarbon Material and Carbon Fiber”, instead of VGCF-H, graphene (xGnP-C- manufactured by XG Science Co., Ltd. A single cell of a redox flow battery was constructed in the same manner as in Example 1 except that 300) was used. Charge/discharge characteristics and durability of the obtained redox flow battery were evaluated in the same manner.
  • Example 1 A single cell of a redox flow battery was constructed by using the same conductive sheet as in Example 13 of WO 2016/104613.
  • the conductive sheet described in Example 13 of WO2016/104613 when the total content of the nanocarbon material and the carbon fiber is 100 parts by mass, VGCF-H of 45 is used as the carbon nanotube. 5 parts by mass of VGCF (registered trademark)-X (average fiber diameter 15 nm, average fiber length 3 ⁇ m, manufactured by Showa Denko KK), and 50 parts by mass of Dona Carbo Chop SG-249 as carbon fiber. Contains.
  • This conductive sheet was cut into a size of 50 mm ⁇ 50 mm, and the conductive sheet was placed on the electrode plate so that one surface of the conductive sheet faced the second porous layer. Then, the first porous layer was cut into a size of 50 mm ⁇ 50 mm, and the first porous layer was arranged so as to overlap with the other surface of the conductive sheet.
  • a single cell of a redox flow battery was constructed in the same manner as in Example 1 except for the above. That is, the single cell of the redox flow battery configured in Comparative Example 1 does not have the nanocarbon layer. Charge/discharge characteristics and durability of the obtained redox flow battery were evaluated in the same manner.
  • Comparative example 2 A single cell of a redox flow battery was constructed in the same manner as in Comparative Example 1 except that carbon paper having a size of 50 mm ⁇ 50 mm (Toray Industries, Inc., model number TGP-H-30) was used as the first porous layer. did. That is, the single cell of the redox flow battery configured in Comparative Example 2 also does not have the nanocarbon layer as in Comparative Example 1. Charge/discharge characteristics and durability of the obtained redox flow battery were evaluated in the same manner.
  • Table 1 shows various conditions in Examples 1 to 5 and Comparative Examples 1 to 2, cell resistivity, charge/discharge efficiency (Coulomb efficiency), and durability.
  • the electrodes of Examples 1 to 5 were located on one of both surfaces of the composite conductive layer and a composite conductive layer composed of both a nanocarbon material and carbon fibers having an average fiber diameter of 1 ⁇ m or more.
  • Comparative Example 1 that does not have a nanocarbon layer by including the first porous layer that is configured and the nanocarbon layer that is located on the other surface of both surfaces of the composite conductive layer and that is formed of a nanocarbon material It was found that the cell resistivity of the redox flow battery was reduced as compared with the No. 2 electrode. Further, the total thickness of the composite conductive layer and the nanocarbon layer forming the electrodes of Examples 1 to 5 should be smaller than the thickness of the composite conductive layer forming the electrodes of Comparative Examples 1 and 2 having no nanocarbon layer. Nonetheless, since the electrode material was not damaged, it was found that the electrode material having such a laminated structure is less likely to be damaged, and as a result, the electrode is easily manufactured. ..
  • the electrodes of Examples 1 to 5 do not cause cracks after charge and discharge, so that the mechanical strength of the electrodes can be increased. confirmed.

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Abstract

L'invention concerne : une électrode destinée à une batterie redox qui peut contribuer à la réduction de la résistance d'élément de la batterie redox et qui présente une résistance mécanique suffisamment élevée ; son procédé de fabrication ; une batterie redox ; et un matériau en feuille conducteur destiné à une électrode. Une électrode (1) destinée à une batterie redox comprend : une couche conductrice composite (11) formée à la fois par un matériau de nanocarbone et des fibres de carbone ayant un diamètre de fibre moyen de 1 µm ou plus ; une première couche poreuse (12) positionnée sur une surface parmi les deux surfaces de la couche conductrice composite (11) et formée par des fibres de carbone ; et une couche de nanocarbone (13) positionnée sur l'autre surface de la couche conductrice composite (11) et formée par un matériau de nanocarbone.
PCT/JP2019/046255 2018-11-26 2019-11-26 Électrode pour batterie redox, son procédé de fabrication, batterie redox et matériau en feuille conducteur pour électrode WO2020111084A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016104613A1 (fr) * 2014-12-26 2016-06-30 昭和電工株式会社 Électrode pour batteries à flux redox, et batterie à flux redox
WO2018062356A1 (fr) * 2016-09-30 2018-04-05 昭和電工株式会社 Batterie à flux redox

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016104613A1 (fr) * 2014-12-26 2016-06-30 昭和電工株式会社 Électrode pour batteries à flux redox, et batterie à flux redox
WO2018062356A1 (fr) * 2016-09-30 2018-04-05 昭和電工株式会社 Batterie à flux redox

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