WO2020184664A1 - Matériau d'électrode de carbone, et batterie redox équipée de celui-ci - Google Patents

Matériau d'électrode de carbone, et batterie redox équipée de celui-ci Download PDF

Info

Publication number
WO2020184664A1
WO2020184664A1 PCT/JP2020/010823 JP2020010823W WO2020184664A1 WO 2020184664 A1 WO2020184664 A1 WO 2020184664A1 JP 2020010823 W JP2020010823 W JP 2020010823W WO 2020184664 A1 WO2020184664 A1 WO 2020184664A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbonaceous
electrode material
carbon
graphite particles
fiber
Prior art date
Application number
PCT/JP2020/010823
Other languages
English (en)
Japanese (ja)
Inventor
良平 岩原
小林　真申
貴弘 松村
佳奈 森本
Original Assignee
東洋紡株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to JP2020548830A priority Critical patent/JPWO2020184664A1/ja
Publication of WO2020184664A1 publication Critical patent/WO2020184664A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • 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
    • 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 carbon electrode material used in a redox battery, and more particularly to a carbon electrode material having excellent energy efficiency of the entire redox battery.
  • the redox battery is a battery that utilizes redox in an aqueous solution of redox ions, and is a large-capacity storage battery with extremely high safety because it has a mild reaction only in the liquid phase.
  • the main configuration of the redox battery is composed of external tanks 6 and 7 for storing electrolytic solutions (positive electrode electrolytic solution, negative electrode electrolytic solution) and an electrolytic cell EC.
  • electrolytic solution positive electrode electrolytic solution, negative electrode electrolytic solution
  • the ion exchange membrane 3 is arranged between the opposing current collector plates 1 and 1.
  • electrochemical energy conversion that is, charging is performed on the electrode 5 incorporated in the electrolytic cell EC.
  • Discharge is performed.
  • the material of the electrode 5 a carbon material having chemical resistance, conductivity, and liquid permeability is used.
  • an aqueous solution containing a metal ion whose valence changes due to redox is typically used as the electrolytic solution used in the redox battery.
  • the electrolytic solution has changed from a type in which an aqueous solution of iron hydrochloric acid is used for the positive electrode and an aqueous solution of chromium in hydrochloric acid for the negative electrode to a type in which a sulfuric acid aqueous solution of vanadium having a high electromotive force is used for both electrodes, and the energy density has been increased.
  • the electrolytic solution containing V 2+ is supplied to the liquid passage on the negative electrode side during discharge, and the positive electrode side is supplied.
  • An electrolytic solution containing V 5+ (actually an ion containing oxygen) is supplied to the liquid passage.
  • the liquid passageways of the negative electrode side, in the three-dimensional electrode V2 + is oxidized to V 3+ emit electrons.
  • the emitted electrons reduce V 5+ to V 4+ (actually oxygen-containing ions) in the three-dimensional electrode on the positive electrode side through an external circuit.
  • the electrode materials for redox batteries are particularly required to have the following performance.
  • Patent Document 1 discloses a carbonaceous material having a specific pseudographite microcrystal structure with high crystallinity as an electrode material of an Fe—Cr battery capable of increasing the total energy efficiency of the battery. Specifically, it has pseudographite microcrystals having an average ⁇ 002> plane spacing of 3.70 ⁇ or less and an average crystallite size of 9.0 ⁇ or more in the c-axis direction obtained by X-ray wide-angle analysis.
  • a carbonaceous material having a total acidic functional group amount of at least 0.01 meq / g is disclosed.
  • Patent Document 2 describes a carbonaceous fiber made from polyacrylonitrile fiber as an electrode for an electric field layer of an iron-chromium-based redox battery or the like that enhances the energy efficiency of the battery and improves the charge / discharge cycle life.
  • Patent Document 3 states that as a carbon electrode material for a vanadium-based redox battery, which has excellent energy efficiency in the entire battery system and whose performance does not change with long-term use, the ⁇ 002> plane spacing obtained from X-ray wide-angle analysis is 3. It has a pseudo-graphite crystal structure with a crystallite size of .43 to 3.60 ⁇ , a crystallite size of 15 to 33 ⁇ in the c-axis direction, and a crystallite size of 30 to 75 ⁇ in the a-axis direction.
  • An electrode is disclosed in which the determined amount of surface acidic functional groups is 0.2 to 1.0% of the total number of surface carbon atoms, and the number of surface-bonded nitrogen atoms is 3% or less of the total number of surface carbon atoms.
  • Patent Document 4 as a carbon electrode material that enhances the overall efficiency of the vanadium-based redox battery and lowers the cell resistance at the time of initial charging, the crystal structure on the carbonaceous fiber was obtained by X-ray wide-angle analysis ⁇ 002. > It is composed of a carbon composite material to which carbon fine particles having a surface spacing of 3.43 to 3.70 ⁇ and an average primary particle diameter of 30 nm or more and 5 ⁇ m or less are attached, and the crystal structure of the carbon composite material can be obtained by X-ray wide-angle analysis.
  • An electrode material having a surface spacing of 3.43 to 3.60 ⁇ , a crystallite size in the c-axis direction of 15 to 35 ⁇ , and a crystallite size in the a-axis direction of 30 to 75 ⁇ is disclosed. Has been done.
  • carbonaceous fibers and carbon fine particles are preferably adhered to each other in close proximity or by an adhesive such as phenol resin, and by using the adhesive, carbon which is an electrochemical reaction field is used. It is stated that only the originally contacted portion of the carbonaceous fiber can be fixed without excessively reducing the surface of the quality fiber.
  • the non-woven fabric is dipped in a solution containing 5% by weight (Example 1) of carbon fine particles (phenolic resin) or 5% by weight (Examples 2 to 4) of phenolic resin, and then carbonized.
  • a carbonized fiber non-woven fabric obtained by a dry oxidation treatment is disclosed.
  • Japanese Patent Publication Japanese Patent Laid-Open No. 60-232669
  • Japanese Patent Publication Japanese Patent Laid-Open No. 5-234612
  • Japanese Patent Publication Japanese Patent Laid-Open No. 2000-357520
  • Japanese Patent Publication Japanese Patent Laid-Open No. 2017-33758
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an inexpensive carbon electrode material for a redox battery as well as to reduce cell resistance during initial charge / discharge to improve battery energy efficiency. It is in.
  • a carbon electrode material comprising a carbonaceous fiber (A), graphite particles (B), and a carbonaceous material (C) for binding the carbonaceous fibers (A), and satisfying the following requirements.
  • Lc (C) When the size of the crystallites in the c-axis direction obtained by X-ray diffraction in the carbonaceous material (C) is Lc (C), Lc (C) is less than 10 nm.
  • Lc (A) When the size of the crystallites in the c-axis direction obtained by X-ray diffraction in the carbonaceous fiber (A) is Lc (A), Lc (C) / Lc (A) is 1.0 or more.
  • the number of bound oxygen atoms on the surface of the carbon electrode material is less than 1.0% of the total number of carbon atoms on the surface of the carbon electrode material.
  • the BET specific surface area determined from the amount of nitrogen adsorbed is 0.5 m 2 / g or more. 2.
  • the mass content of the graphite particles (B) and the carbonaceous material (C) with respect to the total amount of the carbonaceous fiber (A), the graphite particles (B), and the carbonaceous material (C) is 20% or more, respectively.
  • the carbon electrode material according to 1, wherein the mass ratio of the carbonaceous material (C) to the graphite particles (B) is 0.2 to 4.0. 3. 3. 2.
  • Material. 4 The carbon according to any one of 1 to 3, wherein the graphite particles (B) have a scaly shape and the BET specific surface area determined from the amount of nitrogen adsorbed by the graphite particles (B) is more than 20 m 2 / g.
  • Electrode material A redox battery provided with the carbon electrode material according to any one of 4.1 to 3.
  • the carbon electrode material of the present invention is particularly useful as an electrode material for vanadium-based redox batteries because it has low resistance and can realize cost reduction by simplifying the manufacturing process.
  • FIG. 1 is a schematic view of a redox battery.
  • FIG. 2 is an exploded perspective view of a liquid flow type electrolytic cell having a three-dimensional electrode preferably used in the present invention.
  • the present inventors have been diligently studying in order to provide a carbon electrode material preferably used for vanadium-based redox batteries.
  • the conventional vanadium-based redox battery it is important not only to reduce the resistance but also to reduce the cost by simplifying the manufacturing process.
  • the introduction of an oxygen functional group is indispensable in order to improve the reaction activity, so that a dry or wet oxidation treatment step is required. Therefore, it has been found from the results of studies by the present inventors that further cost reduction cannot be expected when the conventional electrode material is used for a vanadium-based redox battery.
  • carbon blacks such as acetylene black (acetylene soot), oil black (furness black, oil soot), and gas black (gas soot) are used as particles showing reaction activity in redox batteries; Soot, carbon fiber powder, carbon nanotubes (CNT, carbon nanotube), carbon nanofibers, carbon aerogel, mesoporous carbon, glassy carbon powder, activated carbon, graphene, graphene oxide, N-doped CNT, boron-doped CNT, fullerene , Known carbon particles such as carbon particles such as petroleum coke, acetylene coke, and smokeless carbon coke.
  • carbon blacks having high reactivity and specific surface area and low crystallinity cannot be used because they are easily oxidized with respect to the charging liquid of the positive electrode.
  • these are rare and expensive, so they are not suitable as inexpensive electrode materials.
  • the inventors adopted graphite particles as the particles exhibiting reactivity.
  • the carbonaceous material (C) is a binding carbonaceous material that binds both carbonaceous fibers (A) and graphite particles (B), and meets the requirements of (1) and (2) below.
  • Lc (C) is less than 10 nm.
  • Lc (A) is 1.0 or more.
  • both the carbonic fiber (A) and the graphite particles (B) are bound” in other words, the carbonaceous material used in the present invention acts as a binder between the carbonic fiber and the graphite particles.
  • the carbonaceous material used in the present invention acts as a binder between the carbonic fiber and the graphite particles.
  • not in a film state means that the carbonaceous material (C) does not form a webbed state like a whole foot (boxoku) or a foot in the carbonaceous fibers (A). This is because when the film state is formed, the liquid permeability of the electrolytic solution deteriorates, and the reaction surface area of the graphite particles cannot be effectively used.
  • the carbonaceous material in the present invention is different from the carbonaceous material described in Patent Document 4 described above.
  • the carbonaceous material used exhibits an action as a partial adhesive based on the idea that only the portion where the carbonaceous fiber and the carbon fine particles originally contacted can be fixed (adhered). This is because there is only recognition that it should be done. Therefore, in the examples of Patent Document 4, the content of the carbonaceous material is at most 14.4% by mass.
  • the carbonaceous material strongly binds between carbonaceous fibers via graphite particles, so that an efficient conductive path can be formed, and the above-mentioned addition of graphite particles enables the formation of an efficient conductive path. It was found that the action was exerted more effectively and both low resistance and high oxidation resistance could be achieved.
  • the carbon positive electrode material of the present invention satisfies the following requirement (3).
  • (3) The number of bound oxygen atoms on the surface of the carbon positive electrode material is less than 1.0% of the total number of carbon atoms on the surface of the carbon positive electrode material.
  • the ratio of the number of bound oxygen atoms to the total number of carbon atoms may be abbreviated as O / C. According to the study results of the present inventors, it is clear that, unlike the conventional recognition, the vanadium-based redox battery can have a low resistance even if the O / C is reduced to less than 1.0%. It became.
  • oxygen atoms are introduced into parts other than the graphite particles involved in the electrode reaction, that is, parts of the carbonaceous fiber (A) and the carbonaceous material (B). Therefore, it is considered that it is not always necessary in the present invention in which graphite particles are supported.
  • the present inventors have found that when an electrode material having a small amount of oxygen atoms introduced and an O / C controlled to less than 1.0% is used for a vanadium-based redox battery, surprisingly low resistance can be achieved. I found it. The reason for this is unknown in detail, but the site where the electrode reaction occurs is the edge surface of the graphite particles with a small amount of oxygen atoms introduced, and the presence or absence of oxygen atoms does not contribute to the electrode reaction as long as the graphite particles are exposed. And so on. As a result, it is considered that the oxidation treatment step, which has been conventionally required, can be omitted, and a low-cost and low-resistance electrode material can be obtained.
  • the carbon positive electrode material of the present invention satisfies the following requirement (4).
  • the BET specific surface area determined from the amount of nitrogen adsorbed is 0.5 m 2 / g or more.
  • the BET specific surface area is also a requirement for low resistance.
  • oxygen atoms when oxygen atoms are introduced, the BET specific surface area of the electrode material also increases with defects in the carbon structure.
  • the O / C since the O / C is controlled to less than 1.0% from the viewpoint that only the graphite particles need to be exposed, the BET specific surface area in the absence of the graphite particles is very low. Therefore, when the BET surface area derived from the carried graphite particles is within the above range, the effect of adding the graphite particles is effectively exhibited and the desired effect can be obtained.
  • it is 1.0 m 2 / g or more.
  • the electrode material of the present invention is configured as described above, the reaction activity is enhanced by a simple process, and a low resistance and low cost electrode can be obtained.
  • the electrode material of the present invention is used as an electrode material for an electrolytic cell of a vanadium-based redox battery, it is possible to reduce the cell resistance at the time of initial charge / discharge and improve the battery energy efficiency.
  • FIG. 2 is an exploded perspective view of a liquid flow type electrolytic cell preferably used in the present invention.
  • an ion exchange membrane 3 is arranged between two opposing current collector plates 1, 1, and spacers 2 are provided on both sides of the ion exchange membrane 3 along the inner surfaces of the current collector plates 1, 1.
  • Passage passages 4a and 4b for the electrolytic solution are formed.
  • the electrode material 5 is arranged in at least one of the liquid passages 4a and 4b.
  • the current collector plate 1 is provided with a liquid inlet 10 and a liquid outlet 11 for the electrolytic solution. As shown in FIG.
  • the current collector plate 1 transports electrons. It is possible to improve the charge / discharge efficiency by using the entire surface of the pores of the electrode material 5 as an electrochemical reaction field while ensuring the above. As a result, the charging / discharging efficiency of the electrolytic cell is improved.
  • the electrode material 5 of the present invention is an electrode material in which the carbonaceous fiber (A) is used as a base material and the graphite particles (B) are carried by the carbonaceous material (C), and the above-mentioned (1) to (4). ) Satisfies the requirements.
  • the details of each requirement are as follows.
  • the carbonaceous fiber used in the present invention means a fiber obtained by heat-carbonizing a precursor of an organic fiber (details will be described later), and means a fiber in which 90% or more is composed of carbon in terms of mass ratio.
  • Precursors of organic fibers used as raw materials for carbonaceous fibers include acrylic fibers such as polyacrylonitrile; phenol fibers; PBO fibers such as polyparaphenylene benzobisoxazole (PBO); aromatic polyamide fibers; isotropic pitch and heterogeneity.
  • Pitch fibers such as sex pitch fibers and mesophase pitch; cellulose fibers; and the like can be used.
  • acrylic fiber acrylic fiber, phenol fiber, cellulose fiber, isotropic pitch fiber, and anisotropic pitch fiber are preferable as the precursor of the organic fiber from the viewpoint of excellent oxidation resistance, strength and elasticity, and acrylic.
  • Fiber is more preferred.
  • the acrylic fiber is not particularly limited as long as it contains acrylonitrile as a main component, but the content of acrylonitrile in the raw material monomer forming the acrylic fiber is preferably 95% by mass or more, preferably 98% by mass or more. Is more preferable.
  • the mass average molecular weight of the organic fiber is not particularly limited, but is preferably 10,000 or more and 100,000 or less, more preferably 15,000 or more and 80,000 or less, and further preferably 20,000 or more and 50,000 or less.
  • the mass average molecular weight can be measured by a method such as gel permeation chromatography (GPC) or solution viscosity.
  • the average fiber diameter of carbonaceous fibers is preferably 0.5 to 40 ⁇ m. If the average fiber diameter is smaller than 0.5 ⁇ m, the liquid permeability will deteriorate. On the other hand, if the average fiber diameter is larger than 40 ⁇ m, the reaction surface area of the fiber portion decreases and the cell resistance increases. Considering the balance between liquid permeability and reaction surface area, it is more preferably 3 to 20 ⁇ m.
  • the carbonaceous fiber structure as a base material, which improves the strength and facilitates handling and processability.
  • the structure is described in spun yarn, filament-focused yarn, non-woven fabric, knitted fabric, woven fabric, which is a sheet-like material made of carbon fiber, Japanese Patent Publication No. 63-200467, and the like.
  • Special knitted fabrics or paper made of carbon fiber can be mentioned.
  • non-woven fabrics made of carbon fibers, knitted fabrics, woven fabrics, special woven knitted fabrics, and paper made of carbon fibers are more preferable from the viewpoints of handling, processability, manufacturability, and the like.
  • the average fiber length is preferably 30 to 100 mm.
  • the average fiber length is preferably 5 to 30 mm.
  • the carbonaceous fiber is obtained by heat-carbonizing a precursor of an organic fiber, but the above-mentioned "heat carbonization treatment” includes at least a flame resistance step and a carbonization (calcination) step. Is preferable.
  • the carbonization step does not necessarily have to be performed after the flame resistance step as described above, and after the graphite particles and the carbonaceous material are attached to the flame resistant fibers as described in Examples described later.
  • a carbonization step may be performed, and in this case, the carbonization step after the flame resistance step can be omitted.
  • the flame-resistant step means a step of heating an organic fiber precursor preferably at a temperature of 180 ° C. or higher and 350 ° C. or lower in an air atmosphere to obtain a flame-resistant organic fiber.
  • the heat treatment temperature is more preferably 190 ° C. or higher, and even more preferably 200 ° C. or higher. Further, it is preferably 330 ° C. or lower, and more preferably 300 ° C. or lower.
  • the organic fibers may be thermally shrunk and the molecular orientation may be disrupted to reduce the conductivity of the carbonaceous fibers. Therefore, it is preferable to perform the flame resistance treatment of the organic fibers under tension or stretching. It is more preferable to carry out flameproofing treatment under tension.
  • the flame-resistant organic fibers obtained as described above are preferably heated at a temperature of 1000 ° C. or higher and 2000 ° C. or lower in an inert atmosphere (preferably in a nitrogen atmosphere) to obtain carbonic fibers.
  • the heating temperature is more preferably 1100 ° C. or higher, and even more preferably 1200 ° C. or higher. Further, it is more preferably 1900 ° C. or lower.
  • the heating temperature in the carbonization step can be selected according to the type of the organic fiber used as a raw material.
  • the heating temperature is preferably 800 ° C. or higher and 2000 ° C. or lower, and more preferably 1000 ° C. or higher and 1800 ° C. or lower.
  • the flame resistance step and carbonization step described above are preferably carried out continuously, and the rate of temperature rise when the temperature is raised from the flame resistance temperature to the carbonization temperature is preferably 20 ° C./min or less, more preferably. Is 15 ° C./min or less.
  • the rate of temperature rise is preferably 5 ° C./min or more in consideration of mechanical properties and the like.
  • the electrode material of the present invention is a carbonaceous fiber (A) and carbonaceous material (C) as defined in (2) above.
  • Lc (A) and Lc (C) are Lc (A) and Lc (C), respectively, Lc (C) / Lc (A) satisfies 1.0 or more. Therefore, in the present invention, Lc (A) in the carbonaceous fiber (A) is not particularly limited as long as the above (4) is satisfied, but it is preferably 1 to 15 nm.
  • Lc (A) is more preferably 2 to 10 nm. The method for measuring Lc (A) will be described in detail in the column of Examples described later.
  • Graphite particles (B) are necessary to increase the change in valence (reactivity) due to redox to obtain reaction activity and to increase conductivity.
  • graphite particles are useful for abundantly exposing the carbon edge surface, which is a reaction field, to realize low resistance. According to the results of the study by the present inventors, when the size of the crystallites in the c-axis direction obtained by X-ray diffraction is Lc (B) for the graphite particles, the value of Lc (B) is the value of the carbon edge surface.
  • Lc (B) is preferably 33 nm or less, more preferably 30 nm or less.
  • the lower limit of the above value is not particularly limited from the above viewpoint, but it is preferably about 15 nm or more in consideration of ensuring conductivity and oxidation resistance.
  • Graphite particles are generally roughly classified into natural graphite and artificial graphite.
  • natural graphite include scaly graphite, scaly graphite, earthy graphite, spheroidal graphite, flaky graphite and the like
  • artificial graphite include expanded graphite and graphite oxide.
  • graphite oxide, scaly graphite, scaly graphite, earthy graphite, flaky graphite, and expanded graphite are carbon edges as reaction fields. It is preferable because it has a surface.
  • scaly graphite, flaky graphite, and expanded graphite are more preferable because the carbon edge surface is very exposed and low resistance can be obtained, and the cost is low and the amount of resources is abundant.
  • These scaly graphite, flaky graphite, and expanded graphite may be added alone, or two or more of them may be mixed and used.
  • scaly graphite means that the appearance is leaf-like.
  • Scaly graphite is different from scaly graphite (which is lumpy in shape and is sometimes referred to as lump graphite).
  • the graphite particles used in the present invention preferably contain 20% or more in terms of mass ratio to the total amount of the carbonaceous fibers (A), the graphite particles (B), and the carbonaceous material (C) described later. , 25% or more is more preferable.
  • the upper limit is not particularly limited from the viewpoint of oxidation resistance and the like, but it is preferably about 60% or less in consideration of the balance between oxidation resistance and low resistance.
  • the content of the carbonaceous fiber (A) used for calculating the above content is the content of the structure when a structure such as a non-woven fabric is used as the base material.
  • the mass ratio of the carbonaceous material (C) described later to the graphite particles (B) is preferably 0.2 or more and 4.0 or less, and preferably 0.3 or more and 3.0 or less. More preferred. If the above ratio is less than 0.2, graphite particles will fall off more often, and the effect of reducing resistance due to the addition of graphite will not be effectively exhibited. On the other hand, if the above ratio exceeds 4.0, the carbon edge surface of the graphite particles, which is the reaction field, is covered, and the desired low resistance cannot be obtained.
  • BET specific surface area determined from nitrogen adsorption amount is preferably 20 m 2 / g greater, more preferably at least 30 m 2 / g.
  • the upper limit is not particularly limited from the above viewpoint, but it is preferably about 300 m 2 / g or less in consideration of oxidation resistance and binding property with a binder.
  • the carbonaceous material used in the present invention is added as a binder for strongly binding carbonaceous fibers and graphite particles, which cannot be bound originally, and is a carbonaceous material having poor oxidation resistance. It has the effect of protecting the fibers.
  • Lc (C) when the size of the crystallites in the c-axis direction obtained by X-ray diffraction in the carbonaceous material (C) as defined in (1) above is Lc (C), Lc (C) is When the size of the crystallites in the c-axis direction obtained by X-ray diffraction in the carbonaceous fiber (A) is Lc (A) as defined in (2) above and is less than 10 nm, Lc.
  • Lc (C) is preferably 8 nm or less, and more preferably 5 nm or less. If Lc (C) is less than 2 nm, the conductivity of the carbonaceous material (C) cannot be sufficiently exhibited and it becomes difficult to obtain the desired low resistance. Therefore, Lc (C) is preferably 2 nm or more, preferably 3 nm. The above is more preferable.
  • the ratio of Lc (C) / Lc (A) is 1.0 or more. That is, in the present invention, since Lc (C) is larger than Lc (A), the carbonaceous material (C) has high conductivity and becomes a lower resistance electrode material.
  • the above ratio is preferably 2 or more, and more preferably 3 or more.
  • the upper limit is preferably 5 or less.
  • the carbonaceous material (C) used in the present invention contains 20% or more of the above-mentioned carbonaceous fiber (A), graphite particles (B), and carbonaceous material (C) in terms of mass ratio to the total amount. Is preferable, and 30% or more is more preferable.
  • the upper limit is not particularly limited from the viewpoint of oxidation resistance and the like, but it is preferably about 60% or less in consideration of the liquid pressure loss and the like. More preferably, it is 50% or less.
  • the type of carbonaceous material (C) used in the present invention may be any as long as it can bind carbonaceous fibers (A) and graphite particles (B), and specifically, at the time of producing the electrode material of the present invention. It is not particularly limited as long as it exhibits binding property at the time of carbonization. Examples of such are pitches such as coal tar pitch and coal pitch; phenol resin, benzoxazine resin, epoxide resin, furan resin, vinyl ester resin, melanin-formaldehyde resin, urea-formaldehyde resin, resorcinol-formaldehyde.
  • pitches such as coal tar pitch and coal pitch
  • phenol resin benzoxazine resin, epoxide resin, furan resin, vinyl ester resin, melanin-formaldehyde resin, urea-formaldehyde resin, resorcinol-formaldehyde.
  • resins such as resins, cyanate ester resins, bismaleimide resins, polyurethane resins and polyacrylonitrile; furfuryl alcohols; rubbers such as acrylonitrile-butadiene rubber.
  • resins such as resins, cyanate ester resins, bismaleimide resins, polyurethane resins and polyacrylonitrile
  • furfuryl alcohols such as acrylonitrile-butadiene rubber.
  • rubbers such as acrylonitrile-butadiene rubber.
  • Commercially available products may be used for these.
  • pitches such as coal tar pitch and carboniferous pitch, which are particularly easily crystalline, are preferable because the desired carbonaceous material (C) can be obtained at a low firing temperature.
  • a polyacrylonitrile resin is also preferably used because the desired carbonaceous material (C) can be obtained at a low firing temperature. Pitches are particularly preferable.
  • the phenol resin since the phenol resin is not used, there are merits such as no harmful effects (formaldehyde generation at room temperature and formaldehyde odor) associated with the phenol resin, and no odor is generated at room temperature.
  • Patent Document 4 uses a phenol resin as an adhesive, in addition to the above-mentioned adverse effects, a separate facility for controlling the formaldehyde concentration in the work place to the control concentration or less is required, which is a cost aspect. , There are disadvantages in terms of work.
  • the pitches that are particularly preferably used will be described in detail.
  • the content of the mesophase phase liquid crystal phase
  • the content of the mesophase phase can be controlled by the temperature and time of the infusibilization treatment. If the content of the mesophase phase is low, one that melts at a relatively low temperature or is in a liquid state at room temperature can be obtained. On the other hand, if the content of the mesophase phase is high, it melts at a high temperature and a high carbonization yield can be obtained.
  • the content of the mesophase phase is preferably high (that is, the carbonization rate is high), for example, 30% or more is preferable, and 50% or more is more preferable.
  • the fluidity at the time of melting can be suppressed, and the carbonaceous fibers can be bound to each other through the graphite particles without excessively covering the surface of the graphite particles.
  • the upper limit is preferably 90% or less, for example, in consideration of the expression of binding property.
  • the melting point of the pitches is preferably 100 ° C. or higher, more preferably 200 ° C. or higher.
  • the upper limit is preferably 350 ° C. or lower, for example, in consideration of the development of binding property.
  • the electrode material of the present invention satisfies that the number of bound oxygen atoms on the surface of the carbon positive electrode material is less than 1.0% of the total number of carbon atoms on the surface of the carbon positive electrode material (O / C ⁇ 1.0%).
  • O / C can be measured by surface analysis such as X-ray photoelectron spectroscopy (XPS) and fluorescent X-ray analysis.
  • the electrode material of the present invention satisfies a BET specific surface area of 0.5 m 2 / g or more, which is determined from the amount of nitrogen adsorbed. If the BET specific surface area is less than 0.5 m 2 / g, the exposure of the edge surface of the graphite particles (B) is reduced, so that the desired low resistance cannot be obtained.
  • the basis weight of the electrode material of the present invention is 50 to 50 when the thickness of the spacer 2 sandwiched between the current collector plate 1 and the ion exchange membrane 3 (hereinafter referred to as "spacer thickness") is 0.3 to 3 mm. 500 g / m 2 is preferable, and 100 to 400 g / m 2 is more preferable.
  • spacer thickness the thickness of the ion exchange membrane 3 tends to be thin, and treatment and usage methods for reducing damage to the ion exchange membrane 3 are extremely important.
  • a non-woven fabric or paper having a flat surface processed on one side as a base material as the electrode material of the present invention.
  • Any known method can be applied to the flattening method, and examples thereof include a method of applying a slurry to one side of a carbonaceous fiber and drying it; a method of impregnation and drying on a smooth film such as PET.
  • the thickness of the electrode material of the present invention is preferably at least larger than the spacer thickness.
  • the spacer thickness is 1.5 to 1.5 to. 6.0 times is preferable.
  • the ion exchange membrane 3 may be pierced by the compressive stress of the sheet-like material. Therefore, it is recommended to use the electrode material of the present invention having a compressive stress of 9.8 N / cm 2 or less. preferable.
  • the electrode material of the present invention in order to adjust the compressive stress and the like according to the basis weight and thickness of the electrode material of the present invention, it is also possible to use the electrode material of the present invention in a laminated manner such as two layers or three layers. Alternatively, it can be combined with another form of electrode material.
  • the electrode material of the present invention can be produced by adhering graphite particles and a precursor of a carbonaceous material (before carbonization) to a carbonaceous fiber (base material), and then undergoing a carbonization step and a graphitization step. .. In each step, a known method can be arbitrarily applied. In the present invention, in order to control the O / C to less than 1.0%, the oxidation treatment step (dry air oxidation) usually performed after the graphitization step is not performed.
  • Step of adhering graphite particles and precursors of carbonaceous material to carbonaceous fibers First, graphite particles and precursors of carbonaceous material are attached to carbonaceous fibers.
  • a known method can be arbitrarily adopted for adhering the graphite particles and the precursor of the carbonaceous material to the carbonaceous fiber. For example, a method of heating and melting the above-mentioned carbonaceous material precursor, dispersing graphite particles in the obtained melt, immersing carbonaceous fibers in the melt dispersion, and then cooling to room temperature can be mentioned.
  • the above carbonaceous material precursor and graphite particles are mixed with a solvent such as water or alcohol to which a binder (temporary adhesive) that disappears during carbonization such as polyvinyl alcohol is added.
  • a method can be used in which the carbonaceous fibers are dispersed, the carbonaceous fibers are immersed in the dispersion, and then heated and dried.
  • the excess liquid among the melt dispersion liquid and the dispersion liquid in which the carbonaceous fiber is immersed can be passed through a nip roller provided with a predetermined clearance to squeeze the excess dispersion liquid when immersed in the dispersion liquid.
  • the surface of the excess dispersion liquid when immersed in the dispersion liquid with a doctor blade or the like can be removed by scraping the surface.
  • the carbonization step is performed to calcin the product after the attachment obtained in the above step. As a result, carbonaceous fibers are bound to each other via graphite particles.
  • the heating temperature is more preferably 1000 ° C. or higher, further preferably 1200 ° C. or higher, even more preferably 1300 ° C. or higher, still more preferably 1500 ° C. or lower, still more preferably 1400 ° C. or lower.
  • the treatment corresponding to the carbonization step may be performed even after the fiber is made flame resistant, but the carbonization treatment performed after the fiber is made flame resistant may be omitted. That is, the method for producing the electrode material of the present invention is roughly classified into the following method 1 and method 2.
  • Method 1 Flame resistance of fiber ⁇ Carbonization of fiber ⁇ Adhesion of graphite particles and carbonaceous material ⁇ Carbonization ⁇ Graphite formation
  • Method 2 Flame resistance of fiber ⁇ Adhesion of graphite particles and carbonaceous material ⁇ Carbonization ⁇ Graphite According to the above method 1, the processing cost increases because carbonization is performed twice, but the sheet used as the electrode material is not easily affected by the difference in volume shrinkage ratio, so that the obtained sheet is deformed (warpage occurs). It has the advantage of being difficult to do.
  • the processing cost can be reduced because the carbonization step may be performed once, but the sheet obtained by the difference in the volume shrinkage ratio at the time of carbonization of each material is easily deformed. Which of the above methods 1 and 2 should be adopted may be appropriately determined in consideration of these.
  • the graphitization step is a step performed in order to sufficiently enhance the crystallinity of the carbonaceous material, improve the electron conductivity, and improve the oxidation resistance to the sulfuric acid solution in the electrolytic solution.
  • After the carbonization step it is preferably heated at a temperature of 1200 ° C. or higher in an inert atmosphere (preferably in a nitrogen atmosphere), more preferably 1300 ° C. or higher.
  • the upper limit is preferably 2000 ° C. or lower in consideration of the affinity of the carbonaceous material for the electrolytic solution.
  • the oxidation treatment since the O / C is controlled to less than 1.0%, the oxidation treatment usually performed after the graphitization step is not performed.
  • the oxidation treatment is carried out to introduce an oxygen functional group such as a hydroxyl group, a carbonyl group, a quinone group, a lactone group or a free radical oxide to the surface of the electrode material, and the O / C is carried out by the oxidation treatment. This is because is increased to 1.0% or more.
  • Lc (A) of carbonaceous fiber, Lc (B) of graphite particles, and Lc (C) of carbonaceous material. ) was measured as follows. Each of the carbonaceous fibers, graphite particles, and carbonaceous material (single substance) used in this example was sequentially subjected to the same heat treatment as in Example 2, and the measurement was performed using the final treated sample. Basically, carbon crystallinity is dominated by the influence of thermal energy given to the sample, and it is thought that the thermal history of the highest temperature given to the sample determines the crystallinity of Lc, but it depends on the degree of subsequent oxidation treatment. It is considered that the graphene laminated structure formed during the graphitization step is disturbed, and the crystallinity may be lowered due to the generation of defective structures. Therefore, the final processed sample was used.
  • the carbonaceous fibers (A) and graphite particles (B) used for the electrode material of the present invention, and the carbonaceous material (C) for binding them are peak-separated from the chart obtained by the above wide-angle X-ray measurement. Therefore, each Lc value was calculated. Specifically, the peak where the apex is seen in the range of 26.4 ° to 26.6 °, which is twice the diffraction angle ⁇ (2 ⁇ ), is the graphite particle (B), and the range of 25.7 ° to 26.2 °. The peak in which the apex is seen was defined as the carbonaceous material (C).
  • each Lc was calculated by the following method.
  • the following simple method was used without correcting the so-called Lorentz factor, polarization factor, absorption factor, atomic scattering factor, etc. That is, the real intensity from the baseline of the peak corresponding to the ⁇ 002> diffraction was re-plotted to obtain the ⁇ 002> corrected intensity curve. From the length of the line segment (half-value width ⁇ ) where the line parallel to the angle axis drawn to the height of 1/2 of the peak height intersects the correction intensity curve, the size of the crystallite in the c-axis direction is calculated by the following equation. I asked for Lc.
  • BET specific surface area measurement Approximately 100 mg of a sample was collected, vacuum dried at 120 ° C. for 12 hours, weighed 90 g, and the BET specific surface area was measured using a specific surface area / pore distribution measuring device Gemini2375 (manufactured by Micromeritics). It was measured. Specifically, the amount of nitrogen gas adsorbed at the boiling point (-195.8 ° C.) of liquid nitrogen was measured in a relative pressure range of 0.02 to 0.95, and an adsorption isotherm of the sample was prepared. Based on the results in the range of relative pressure 0.02 to 0.15, the BET specific surface area per weight (unit: m 2 / g) was determined by the BET method.
  • Electrode material obtained by the method described later was cut into an electrode area of 16 cm 2 having an electrode area of 10 cm in the vertical direction (liquid flow direction) and 1.6 cm in the width direction, and the cell shown in FIG. 1 was assembled.
  • a Nafion 212 membrane was used as the ion exchange membrane.
  • the electrode material one each for the felt base material (No. 1 to 4 and No. 7 to 9) described later and two each for the spunlace base material (No. 5 to 6) are arranged on the positive and negative electrodes, and the cell is arranged.
  • the spacer thickness was adjusted so that the filling rate of the electrode material inside was 0.1 to 0.2 g / cc for the felt base material and 0.3 to 0.4 g / cc for the spunlace base material.
  • the reason why the filling rate in the cell was changed for each base material used in this way is that since the base material thickness of spunlace is thin and it is easy to be highly filled, the contact with the current collector plate is insufficient with the same filling rate as felt. This is because the contact resistance between the electrode material and the current collector plate increases.
  • the specific spacer thickness was 2.5 mm for the felt base materials (No. 1 to 4 and No. 7 to 9) described later, and 0.8 mm for the spunlace base material (No. 5 to 6).
  • the total cell resistance was calculated by the following formula from the voltage curve after 10 cycles with a voltage range of 1.70 to 1.00 V at 100 mA / cm 2 .
  • a 2.5 moL / L sulfuric acid aqueous solution of 2.0 moL / L vanadium oxysulfate was used as the positive electrode electrolytic solution, and a 2.5 moL / L sulfuric acid aqueous solution of 2.0 moL / L vanadium sulfate was used as the negative electrode electrolytic solution. ..
  • the amount of electrolyte was too large for the cell and piping.
  • the liquid flow rate was 10 mL per minute, and the measurement was performed at 30 ° C.
  • VC50 charge voltage obtained from the electrode curve with respect to the amount of electricity when the charge rate is 50%.
  • V D50 discharge voltage obtained from the electrode curve with respect to the amount of electricity when the charge rate is 50%.
  • I current density (mA / cm 2 )
  • Example 1 In this example, using the scaly graphite particles A to D shown in Table 1, an electrode material was prepared as follows and various items were measured. Of these, A, B, and D are commercially available products, and the particle sizes shown in Table 1 are the values listed in the catalog. In C, scaly graphite particles having a particle size of 5 ⁇ m were pulverized by a bead mill for 6 hours with a Labostar mini machine manufactured by Ashizawa Finetech Co., Ltd., and the particle size was measured by a laser diffraction method. Note that D is an example in which Lc is large.
  • Example 2 using some of the carbon particles in Table 1, an electrode material was prepared as follows and various items were measured. ⁇ Manufacturing of non-woven fabric made of carbonaceous fiber> Polyacrylonitrile fibers with an average fiber diameter of 16 ⁇ m are heated at 300 ° C. in an air atmosphere to make them flame resistant, and felt needle SB # 40 (Foster Needle) and punching density are used using the short fibers (length 80 mm) of the flame resistant fibers. A flame-resistant non-woven fabric having a grain size of 300 g / m 2 and a thickness of 4.3 mm was produced by felting at 250 fibers / cm 2 . Next, it is heated at 300 ° C.
  • Kao's Leodor TW-L120 nonionic surfactant
  • polyvinyl alcohol temporary adhesive
  • JFE Chemical's MCP250 carbonaceous material
  • the felt After immersing the felt produced above in the dispersion liquid thus obtained, the felt was passed through a nip roller to remove excess dispersion liquid. Next, it was dried at 150 ° C. for 20 minutes in an air atmosphere, carbonized (calcined) at 1000 ° C. for 1 hour in a nitrogen atmosphere, and then graphitized at 1500 ° C. for 1 hour.
  • an electrode material No. 1 having a thickness of 3.8 mm and a basis weight of 298.0 g / m 2 was obtained.
  • No. 7 denotes a comparative example simulating Patent Document 3 described above, in which carbonaceous fibers were treated as follows without using graphite particles and carbonaceous material to obtain an electrode material.
  • a felt made of flame-resistant polyacrylonitrile fiber (thickness 4.3 mm, grain size 150 g / m 2 , fiber diameter 10 ⁇ m, mean curvature 32 R) was carbonized (calcined) at 1000 ° C. for 1 hour in a nitrogen atmosphere, and then 1500. Graphitized at ° C. for 1 hour and oxidized at 700 ° C. for 15 minutes.
  • An electrode material (comparative example) of 7 was produced.
  • the rate of temperature rise when raising the temperature from the flame resistance temperature to the carbonization temperature is No. Same as 1.
  • Table 2A and Table 2B show the above No. The measurement results of various items in 1 to 9 are shown.
  • No. Nos. 1 to 6 are electrode materials satisfying the requirements of the present invention, and low-resistance electrode materials were obtained without any oxidation treatment.
  • No. No. 7 is an example in which no graphite particles or carbonaceous material was used and only carbonaceous fibers were used, and an oxygen functional group was introduced, but no reduction in resistance was observed.
  • No. No. 8 is an example in which a carbonaceous fiber and a carbonaceous material are used without using graphite particles and an oxygen functional group is introduced, but no reduction in resistance is also observed.
  • Lc (C) / Lc (A) was less than 1, and this requirement was not satisfied, so that the cell resistance increased. It is considered that this is because the graphite particles cannot be effectively used because the conductivity of the carbonaceous material (C) is insufficient.
  • the cell resistance at the time of initial charge / discharge can be reduced, and a carbon electrode material having excellent battery energy efficiency can be provided. Therefore, it is useful as an electrode material for a redox battery using, for example, a vanadium-based electrolytic solution.
  • the carbon electrode material of the present invention is suitably used for flow type and non-flow type redox flow batteries, redox batteries combined with lithium, capacitor, and fuel cell systems.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)

Abstract

Le matériau d'électrode de carbone de l'invention est constitué de fibres carbonées (A), de particules de graphite (B) et d'une matière carbonée (C) liant ceux-ci, et satisfait les conditions suivantes. (1) Dans la matière carbonée (C), lorsque la taille de cristallite dans une direction axiale (c) obtenue par diffraction des rayons X est représentée par Ｌｃ（Ｃ）, alors Ｌｃ（Ｃ）est inférieure à 10nm ; (2) dans les fibres carbonées (A), lorsque la taille de cristallite dans une direction axiale (c) obtenue par diffraction des rayons X est représentée par Ｌｃ（A）, alors Ｌｃ（Ｃ）／Ｌｃ（Ａ） est supérieur ou égal à 1,0 ; (3) le nombre d'atomes d'oxygène liés à la surface du matériau d'électrode de carbone, est inférieur à 1,0% du nombre d'atomes de carbone total à la surface du matériau d'électrode de carbone ; enfin, (4) la surface spécifique BET obtenue à partir de la quantité d'adsorption d'azote, est supérieure ou égale à ０,５ｍ2／ｇ.
PCT/JP2020/010823 2019-03-13 2020-03-12 Matériau d'électrode de carbone, et batterie redox équipée de celui-ci WO2020184664A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020548830A JPWO2020184664A1 (fr) 2019-03-13 2020-03-12

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-046210 2019-03-13
JP2019046210 2019-03-13

Publications (1)

Publication Number Publication Date
WO2020184664A1 true WO2020184664A1 (fr) 2020-09-17

Family

ID=72426633

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/010823 WO2020184664A1 (fr) 2019-03-13 2020-03-12 Matériau d'électrode de carbone, et batterie redox équipée de celui-ci

Country Status (2)

Country Link
JP (1) JPWO2020184664A1 (fr)
WO (1) WO2020184664A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59101776A (ja) * 1982-11-30 1984-06-12 Toyobo Co Ltd 電極材
JPS63222080A (ja) * 1987-03-10 1988-09-14 東レ株式会社 炭素繊維多孔体の製造方法
WO2003034519A1 (fr) * 2001-10-16 2003-04-24 Toray Industries, Inc. Textile tisse en fibres de carbone pour pile a combustible, element electrode, pile a combustible, unite mobile et procede de production dudit textile
JP2013016476A (ja) * 2011-06-09 2013-01-24 Toray Ind Inc ガス拡散電極基材およびその製造方法
JP2017033758A (ja) * 2015-07-31 2017-02-09 東洋紡株式会社 レドックス電池用炭素電極材
WO2019049756A1 (fr) * 2017-09-07 2019-03-14 東洋紡株式会社 Matériau d'électrode de carbone pour batterie redox et procédé de fabrication associé
WO2019049755A1 (fr) * 2017-09-07 2019-03-14 東洋紡株式会社 Matériau d'électrode de carbone pour batterie redox et procédé de fabrication associé
WO2019049934A1 (fr) * 2017-09-07 2019-03-14 東洋紡株式会社 Matériau de base de couche de diffusion de gaz pour piles à combustible, couche de diffusion de gaz pour piles à combustible et pile à combustible

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59101776A (ja) * 1982-11-30 1984-06-12 Toyobo Co Ltd 電極材
JPS63222080A (ja) * 1987-03-10 1988-09-14 東レ株式会社 炭素繊維多孔体の製造方法
WO2003034519A1 (fr) * 2001-10-16 2003-04-24 Toray Industries, Inc. Textile tisse en fibres de carbone pour pile a combustible, element electrode, pile a combustible, unite mobile et procede de production dudit textile
JP2013016476A (ja) * 2011-06-09 2013-01-24 Toray Ind Inc ガス拡散電極基材およびその製造方法
JP2017033758A (ja) * 2015-07-31 2017-02-09 東洋紡株式会社 レドックス電池用炭素電極材
WO2019049756A1 (fr) * 2017-09-07 2019-03-14 東洋紡株式会社 Matériau d'électrode de carbone pour batterie redox et procédé de fabrication associé
WO2019049755A1 (fr) * 2017-09-07 2019-03-14 東洋紡株式会社 Matériau d'électrode de carbone pour batterie redox et procédé de fabrication associé
WO2019049934A1 (fr) * 2017-09-07 2019-03-14 東洋紡株式会社 Matériau de base de couche de diffusion de gaz pour piles à combustible, couche de diffusion de gaz pour piles à combustible et pile à combustible

Also Published As

Publication number Publication date
JPWO2020184664A1 (fr) 2020-09-17

Similar Documents

Publication Publication Date Title
JP7049350B2 (ja) レドックスフロー電池用炭素電極材およびその製造方法
JP7088197B2 (ja) レドックスフロー電池用炭素電極材およびその製造方法
JP6617464B2 (ja) レドックス電池用炭素電極材
JP6786776B2 (ja) レドックス電池用電極材の製造方法
JP6973075B2 (ja) レドックス電池用炭素電極材
JP2017027918A (ja) レドックスフロー電池用電極材
JP2023154069A (ja) 炭素電極材及びレドックス電池
WO2020184663A1 (fr) Matériau d'électrode de carbone, et batterie redox équipée de celui-ci
WO2020184451A1 (fr) Matériau d'électrode de carbone pour batterie redox à base de manganèse et titane
JP6809257B2 (ja) 炭素質材料およびこれを用いた電池
WO2021225106A1 (fr) Matériau d'électrode de carbone pour batterie redox et batterie redox pourvue dudit matériau d'électrode de carbone
WO2020184664A1 (fr) Matériau d'électrode de carbone, et batterie redox équipée de celui-ci
WO2020184450A1 (fr) Matériau d'électrode positive de carbone pour batterie redox à base de manganèse et titane, et batterie équipée de celui-ci
WO2020184449A1 (fr) Matériau d'électrode de carbone pour batterie redox, et batterie redox équipée de celui-ci
WO2021225105A1 (fr) Matériau d'électrode de carbone pour batterie redox et batterie redox pourvue dudit matériau d'électrode de carbone
WO2023080236A1 (fr) Matériau d'électrode pour batteries à flux redox et batterie à flux redox le comprenant
WO2021225107A1 (fr) Matériau d'électrode de carbone pour batterie à flux redox à base de manganèse/titane

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2020548830

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20769946

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20769946

Country of ref document: EP

Kind code of ref document: A1