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WO2013018843A1 - Electrode de diffusion d'oxygène gazeux et son procédé de fabrication - Google Patents

Electrode de diffusion d'oxygène gazeux et son procédé de fabrication Download PDF

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Publication number
WO2013018843A1
WO2013018843A1 PCT/JP2012/069634 JP2012069634W WO2013018843A1 WO 2013018843 A1 WO2013018843 A1 WO 2013018843A1 JP 2012069634 W JP2012069634 W JP 2012069634W WO 2013018843 A1 WO2013018843 A1 WO 2013018843A1
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WO
WIPO (PCT)
Prior art keywords
electrode
gas diffusion
catalyst
carbon
silk
Prior art date
Application number
PCT/JP2012/069634
Other languages
English (en)
Inventor
Yoshio Takasu
Wataru Sugimoto
Ryojin OBINATA
Yoshinori Nishiki
Kazuhiro Hirao
Masaharu Uno
Takaaki NAKAI
Koji Nakano
Original Assignee
Shinshu University
Permelec Electrode Ltd.
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 Shinshu University, Permelec Electrode Ltd. filed Critical Shinshu University
Priority to JP2014502282A priority Critical patent/JP5960795B2/ja
Publication of WO2013018843A1 publication Critical patent/WO2013018843A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/083—Alkaline fuel cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • 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 gas diffusion electrodes for alkaline fuel cells, metal-air batteries and brine electrolysis; more in detail, relates to gas diffusion electrodes having corrosion resistant carbon-based catalyst, which achieves electrolysis performance corresponding to that by the conventional ones without using expensive platinum catalyst.
  • oxygen gas diffusion electrode is used at the cathode instead of hydrogen generation reaction, the reaction will be the equation (3), and the cell voltage will be reduced by 1.23 V theoretically, and by around 0.88 within the practical range of electric current density. The reduction of 700 kWh per ton of sodium hydroxide can be expected.
  • PTL 1 has disclosed the technology which lessens the resistance of a power supply part
  • PTL 2 has disclosed an optimum porosity in the oxygen gas diffusion electrode
  • PTL 3 has disclosed the gas diffusion electrode applying palladium and silver.
  • NPLs 1 and 2 report the recent development status of the gas diffusion electrode.
  • Fuel cells are clean power generation systems which can convert chemical energy into electrical energy at a high efficiency. By combining oxidation reaction of hydrogen or organic carbon materials with reduction reaction of oxygen in the air, electrical energy is obtained from the electromotive force and the commercialization of the process was highlighted as a battery for the space exploration in 1960s. Recently, the process has been focused, again, for fuel cell vehicles, a small portable power source, or a power source for load leveling of power storage for household and power station.
  • reaction of the equation (4) proceeds at the anode (fuel electrode) in an alkaline aqueous solution.
  • the alkaline fuel cells include the anode electrode comprising metals as a construction material of the porous electrode or carbon, the cathode electrode and an aqueous solution such as of potassium hydroxide as electrolyte which separates these electrodes.
  • the alkaline fuel cell as above-mentioned, if carbon dioxide enters the electrolyte, it reacts with the electrolyte to form carbonate ion, as shown by the equation (5). Further, if the carbonate ion concentrates, it, together with alkali metal in the electrolyte, forms carbonate and deposits on the electrode, impeding the electrode reaction.
  • the alkaline fuel cell has been regarded as having a potential problem of blocking of the cell member by absorbing carbon dioxide in case of air source material.
  • anion exchange membrane alkali of carbonate ion is consumed in the anode compartment as shown in the equation (5), and the carbonate ion, the pH of which has shifted on the acid side is again gasified and discharged outside the cell, proving that accumulation will not exceed a certain level.
  • KOH is applied as electrolyte
  • an anion membrane is chosen as diaphragm membrane, deposition of carbonate can be suppressed.
  • a new battery applying such metals as lithium, zinc, and aluminum as the anode and an air electrode as the cathode is being developed, and is attracting attentions not only as the fuel cells but also as the storages of renewable energy.
  • the metal-air battery which applies oxygen in air as active material of the cathode can reduce the weight and the volume.
  • the cathodic reaction in the discharge reaction of the lithium-air battery is as shown in the equation (3), and the anodic reaction is as per the equation (6).
  • the anodic discharge reaction of the zinc-air battery is as per the equation (7).
  • PTL 7 discloses lithium ion conductive material
  • PTL 8 discloses catalyst material
  • PTL 9 discloses the metal-air battery system
  • PTL 10 discloses non-aqueous electrolyte. The status quo of the present technology is reported in detail in NPL 3, giving comparisons of performance by different kinds of metal-air batteries.
  • NPL 6 nanoshell structure, which has graphite component around metal particles, has been found (NPL 6) and it is reported that carbon material (carbon alloy) catalyst containing hetero elements or carbon-based catalyst having metal elements in nitrogen- containing polymer gives high performance. (NPLs 7 and 8)
  • Silk fibroin contains proteins comprising amino acids including glycine, alanine, and tyrosine, other than sericin.
  • the silk-derived activated carbon by the present invention can utilize all proteins obtained from cocoon as raw material.
  • the silk-derived activated carbon under the present invention is defined as the synthetic silk fibroin with sericin removed from raw silk subjected to carbonization in the inert gas flow, heat treatment and activation treatment. Activation treatment is not limited to steam activation, but can be conducted in gases containing carbon dioxide, alkali and ammonia.
  • NPLs 9, 10, 1 1, 12 and PTL 1 1 disclose that carbon-based electrode catalyst comprising silk-based activated carbon can be applied to acid fuel cells; and it is known that carbon- based electrode catalyst comprising silk-based activated carbon expresses superior performance in acidity by sulfuric acid.
  • PTL 1 1 and NPLs 9, 10, 1 1, 12 discloses suitability of carbon-based electrode catalyst comprising silk-based activated carbon when used in an alkaline solution. In other words, there has been no report as to what performance carbon-based electrode catalyst comprising silk-based activated carbon achieves in an alkaline solution, and the activity or stability of it remain unclear.
  • NPL 1 Soda and Chlorine, Vol.45, 85(1994)
  • NPL 2 J. Appl. Electrochem., 38, 1 177(2008)
  • NPL 3 Electrochemistry, Vol.78 529(2010)
  • NPL 4 Electrochemistry, Vol.78 970(2010)
  • NPL 5 Nature, 201, 1212 (1964)
  • NPL 7 J. Power Sources, 196, 1006 (201 1)
  • NPL 8 Nature, 443, 63 (2006)
  • NPL 10 J. Appl. Electrochem., 40, 675(2010)
  • NPL 1 1 Electrochemistry Communications, 1 1, 376(2009)
  • NPL 12 J. Power Sources, 195, 5840(2010) Summary of Invention
  • the present invention aims to solve the problems of the conventional technologies; to elucidate what performance the powder state carbon-based electrode catalyst comprising silk-derived activated carbon containing silk-derived nitrogen has in an alkaline solution; and to provide a gas diffusion electrode for alkaline fuel cells, metal-air batteries or brine electrolysis cells which, more in detail, can reduce consumption of expensive platinum catalyst and provide electrolysis performance almost equivalent to the conventional one, and is superior in durability as electrode in electrolysis in alkaline solution or at the time of emergency shut down and in stability in a long time operation.
  • the present invention provides an oxygen gas diffusion electrode for alkaline fuel cells, metal-air batteries or brine electrolysis cells used in an alkaline aqueous solution, characterized in that powder state carbon-based electrode catalyst comprising silk-derived activated carbon containing silk-derived nitrogen is supported on a porous conductive substrate.
  • the present invention provides an oxygen gas diffusion electrode, characterized in that the N/C (atomic ratio) in the carbon-based electrode catalyst is in a range of 0.004 - 0.07.
  • the present invention provides an oxygen gas diffusion electrode, characterized in that metal catalyst is contained in the carbon-based electrode catalyst.
  • the present invention provides an oxygen gas diffusion electrode, characterized in that the metal catalyst contained in the carbon-based electrode catalyst is precious metal comprising any one or more of Pt, Ir, Ru, Ag, and Pd.
  • the present invention provides an oxygen gas diffusion electrode, characterized in that metal oxides catalyst is contained in the carbon-based electrode catalyst.
  • the present invention provides an oxygen gas diffusion electrode, characterized in that the metal oxides catalyst contained in the carbon-based electrode catalyst comprises any one or more of titanium oxide, zirconium oxide, niobium oxide, tin oxide, tungsten oxide and tantalum oxide.
  • the present invention provides a manufacturing method for an oxygen gas diffusion electrode, characterized in that the powder state carbon-based electrode catalyst comprising silk-derived activated carbon containing silk-derived nitrogen is manufactured by baking silk fibroin at a temperature of 500 - 1500 degrees Celsius.
  • the oxygen gas diffusion electrode by the present invention applying silk-derived carbon-based electrode catalyst containing nitrogen is highly active in an alkaline aqueous solution for the use of alkaline fuel cells, metal-air batteries or brine electrolysis cells, and is durable and stable for a long time as electrode at charging and discharging of electrolysis and battery as well as at an emergency shutdown.
  • formation of hydrogen peroxide is suppressed by making precious metal catalyst or metal oxides catalyst coexist, which allows four-electron reduction only, leading to less deterioration of electrodes and electrochemical cells.
  • Fig. l shows XPS spectra and corresponding graphite-like structures with carbon- nitrogen materials of the silk-derived activated carbon by the present invention.
  • Fig.2 shows a schematic view of longitudinal section of the gas diffusion electrode by the present invention
  • Fig.3 shows a schematic view of longitudinal section of an alkaline fuel cell equipped with the gas diffusion electrode by the present invention
  • Fig.4 shows a schematic view of longitudinal section of a three-chamber electrolytic cell equipped with the gas diffusion electrode by the present invention
  • Fig.5 shows a schematic view of longitudinal section of a two-chamber electrolytic cell equipped with the gas diffusion electrode by the present invention
  • Fig.6 shows a schematic view of longitudinal section of a lithium-air battery equipped with the gas diffusion electrode by the present invention
  • Fig.7a shows a graph showing electric current-potential of oxygen reduction of the gas diffusion electrode by the present invention comprising the silk-derived activated carbon treated at 1200 degrees Celsius.
  • Fig.7b shows a graph showing the relation of the order of reaction of the gas diffusion electrode by the present invention comprising the silk-derived activated carbon treated at 1200 degrees Celsius.
  • Fig.8a shows a graph showing electric current-potential of oxygen reduction of the gas diffusion electrode by the present invention comprising the silk-derived activated carbon treated at 900 degrees Celsius.
  • Fig.8b shows a graph showing the relation of the order of reaction of the gas diffusion electrode by the present invention comprising the silk-derived activated carbon treated at 900 degrees Celsius.
  • Carbon-based electrode catalyst comprising silk-derived activated carbon
  • PTL 1 1 discloses the preparation method of the silk fibroin-derived carbon-based electrode catalyst.
  • the preparation method for the carbon-based electrode catalyst comprising silk-derived activated carbon by the present invention is almost equivalent to the method in PTL 1 1.
  • Raw material silk is baked in the atmosphere of inert gases including nitrogen for several hours at 500 degrees Celsius. After cooling down to room temperature, the baked raw material silk is pulverized by a ball mill.
  • the grain size is not necessarily specified, but that around ⁇ is suitable. Baking temperature below 500 degrees Celsius is not preferable, leading to an insufficient carbonization.
  • the powdered material is baked in an inert gas atmosphere for several hours at the baking temperature of 700-1500 degrees Celsius, most suitably at 1200 degrees Celsius. If the baking temperature is over 1500 degrees Celsius, nitrogen component will not remain in the powdered material, leading to an insufficient catalyst activity. (3) Activation treatment
  • the baked powder material is, then, subject to activation treatment.
  • Steam activation is performed in such a manner that the baked powder material is heated to, for instance, 850 degrees Celsius in an inert gas atmosphere and left for several hours with steam being supplied.
  • Activation treatment is not limited to steam activation, but can be performed in the gases including carbon dioxide, alkali, and ammonia.
  • the suitable temperature for the activation treatment will be 700 -1000 degrees Celsius.
  • Activation treatment increases the surface area of the powder material, especially the mesopore volume, which is effective to catalyst reaction, leading to an increase of catalyst activity.
  • the activated carbon contains nitrogen and oxygen in addition to carbon and with a rise of heat treatment temperature, N/C ratio (atomic ratio) decreases.
  • N/C ratio atomic ratio
  • Fig.l gives XPS (X-ray photoelectron spectroscopy) spectra and corresponding graphitelike structures with carbon-nitrogen materials of the silk-derived activated carbon by the present invention, showing (a) 700 degrees Celsius heat treatment, (b) 900 degrees Celsius heat treatment, (c) 1200 degrees Celsius heat treatment, (d) activated carbon (RP-20) and , (e) furnace black (Vulcan XC-72).
  • Fig.1 compares the XPS spectra related with the present invention, in which the vertical axis gives spectra intensity, and the horizontal axis gives the binding energy value. Different spectra are obtained depending of the binding energy of nitrogen atoms present in the carbon-nitrogen structure illustrated in the right figure.
  • pyridine-type nitrogen species (398.6eV) remains in the heating at 1200 degrees Celsius; pyrrole-type nitrogen species (400.5eV) and oxidation- type nitrogen species (402-405eV) remain in the heating at 900 degrees Celsius but disappear in the heating at 1200 degrees Celsius; and that graphite-type nitrogen species (401.3eV) shows stability.
  • Remaining amount of nitrogen component is not always restrictively specified, but it is confirmed that sufficient catalyst activity is kept in the range of 0.004-0.07 of N/C ratio.
  • the above-mentioned powder state activated carbon catalyst can obtain further improved activity as catalyst by supporting one or more of precious metal or its alloy from among Pt, Ir, Ru, Ag, and Pd. Since the above-mentioned powder state carbide intrinsically has catalytic activity, the amount of precious metal to be applied can be reduced.
  • the supporting of the catalyst metals can be carried out by an ordinary process. For instance, in case of Pt, the activated carbon is coated with Pt containing solution, or is immersed in Pt containing solution, followed by a heat treatment, reduction with hydrogen, etc. for platinum supporting.
  • the powder state activated carbon catalyst can obtain superior activity as catalyst through applying materials which support metal oxides as catalyst including titanium oxide, zirconium oxide, niobium oxide, tin oxide, tungsten oxide, tantalum oxide.
  • the supporting of catalyst metal is performed in an ordinary process, as above-mentioned.
  • the activated carbon is coated with Ti containing solution, or the activated carbon is immersed in Ti containing solution, followed by a heat treatment for supporting titanium oxide.
  • the powder state metal oxides is prepared in advance and mixed with the activated carbon for achieving a high activation.
  • high activation may be attributed to the porous construction of the electrode, which is the gap formed between the activated carbon and oxide particles.
  • porous conductive substrate such raw materials as cloth and fiber with baked powder comprising nickel, stainless steel and carbon are applicable.
  • the porous conductive substrate desirably has a suitable porosity together with sufficient conductivity for supply and removal of gas and solution. It is preferable to have 0.01-5 mm in thickness, 30-95 % in porosity, and a typical pore diameter of 0.001-1 mm.
  • the carbon cloth is a woven fabric of several hundreds of fine carbon fibers with a few ⁇ in diameter, which is superior in gas-liquid permeability and is preferable as a raw material of the substrate.
  • Another applicable raw material is the carbon paper, which is manufactured in such a manner that a thin membrane, as precursor, is prepared with a carbon material fiber by the paper making process, followed by baking. It should be noted that if power is directly supplied to the carbon-made conductive substrate, electric current locally concentrates for its insufficient conductivity, and such locally concentrated current flows also to the gas diffusion layer or the reaction layer, causing a poor electrolytic efficiency. However, if an additional conductive layer to be described is provided, electric current is supplied uniformly to the conductive substrate, which flows uniformly also to the gas diffusion layer and the reaction layer to achieve enhanced performance.
  • metal powder paste prepared with solvents including hydrophobic resin, water, naphtha, etc.
  • the hydrophobic resin fluororesin component
  • the metal powder for the brine electrolysis which is required to be stable in the alkaline solution at a high temperature and also inexpensive, silver or silver alloy (containing a small amount of copper, platinum, and palladium) is desirable.
  • dry processes such as vapor deposition and spattering are applicable.
  • the activated carbon and the catalyst metal/metal oxides particles are prepared to be a paste with solvents including hydrophobic resin, water, and naphtha and coated or fixed on the gas diffusion layer.
  • the hydrophobic resin fluororesin component
  • the viscosity is preferably controlled with such thickeners as carboxy methyl cellulose.
  • coating, drying and baking are most preferably repeated at several times.
  • Hydrophobic resin provides sufficient gas permeability and at the same time, prevents wetting by alkaline solution.
  • the powder state silk-derived activated carbon and the catalyst metal/metal oxides particles obtained in the above-mentioned manner are mixed with ion exchange resin solution (such as a solution of Nafion -registered trade name) to prepare paste and can be applied to the substrate by coating and drying.
  • ion exchange resin solution such as a solution of Nafion -registered trade name
  • the resin solution works as binder for the catalyst and simultaneously provides ion conductivity, contributing to the enhancement of performance.
  • heat treatment is conducted at a temperature of 60-140 degrees Celsius, considering the glass transition temperature and in an inert gas atmosphere, especially preferable at a high temperature treatment.
  • Suitable amount of the activated carbon is in a range of 10-1000 g/m 2 .
  • Fig.2 shows a schematic view of longitudinal section of the gas diffusion electrode by the present invention, illustrating the electrode substrate 16, the catalyst layer 17 and the conductive layer 18.
  • the present gas diffusion electrode is used under pressure in thickness direction and it is not desirable that the conductivity in thickness direction changes because of the pressure.
  • Press working is preferably performed to prepare a cathode with improved performance and a packing ratio of 20-50 %.
  • the press working is performed to enhance the conductivity through compressing the carbon material and also to stabilize the packing ratio and the conductivity when pressure is applied.
  • Improved bonding effect of catalyst to the substrate also contributes to enhancement of the conductivity.
  • compression of the substrate and the reaction layer and improved bonding effect of the catalyst and the substrate lead to an increase in supply capacity of raw material oxygen gas.
  • Preferable press conditions include a temperature range from room temperature-360 degrees Celsius, and a pressure range of 0.1-5 MPa. According to these methods, a gas diffusion electrode with high conductivity and high catalytic activity is manufactured.
  • Fig.3 shows a schematic view of longitudinal section of an alkaline fuel cell equipped with the gas diffusion electrode by the present invention.
  • the figure shows the ion exchange membrane 1 (anion-selectively exchangeable) working as solid polymer electrolyte, the oxygen electrode plate (cathode) 2 and the hydrogen electrode plate (anode) 3, which are both the gas diffusion electrode adhering respectively to the ion exchange membrane 1 with each reaction layer positioned inside, constituting membrane-electrode assembly (MEA) with the ion exchange membrane 1 tightly sandwiched by the both electrodes.
  • MEA membrane-electrode assembly
  • the oxygen electrode 2 and the hydrogen electrode 3 are prepared in such a manner that the silk-derived activated carbon and the catalyst particles comprising metal or metal oxides are coated and baked, together with a binder of hydrophobic resin, on the electrode substrate of the carbon paper, etc.
  • the frame-shaped gasket for oxygen electrode 4 and the frame-shaped gasket for hydrogen electrode 5 are tightly adhered.
  • the porous current collector for oxygen electrode 6 and the porous current collector for hydrogen electrode 7 are provided at the internal edges of the gasket for oxygen electrode 4 and the gasket for hydrogen electrode 5, respectively so as to contact the oxygen electrode 2 and the hydrogen electrode 3.
  • the gasket for oxygen electrode 4 is in contact with the periphery of the oxygen electrode frame 8 having a multiple number of concaves on the side of the ion exchange membrane, constituting the oxygen electrode compartment 9 between the oxygen electrode frame 8 and the oxygen electrode 2.
  • the gasket for hydrogen electrode 5 is in contact with the periphery of the hydrogen electrode frame 10 having a multiple number of concaves on the side of the ion exchange membrane, constituting the hydrogen electrode compartment 1 1 between the hydrogen electrode frame 10 and the hydrogen electrode 3.
  • the oxygen gas inlet 12 opens laterally at the upper part of the oxygen electrode frame 8
  • the unreacting oxygen gas and produced water outlet 13 opens laterally at the lower part of the oxygen electrode frame 8
  • the hydrogen gas inlet 14 opens laterally at the upper part of the hydrogen electrode frame 10
  • the unreacting hydrogen gas outlet 15 opens laterally at the lower part of the hydrogen electrode frame 10.
  • Aqueous solutions such as of potassium hydroxide are supplied to each compartment as required.
  • Oxygen-containing gas and hydrogen as fuel are supplied to the oxygen electrode 2 and the hydrogen electrode 3, respectively, of the fuel cell having the above-mentioned construction.
  • the supply amount of hydrogen should be 1-2 times the theoretical one.
  • Hydrogen gas, as raw material can be procured from natural gas or hydrogen gas generated by the petroleum reforming, but the mix rate of CO should be as low as possible, with an allowable level of below 10 ppm.
  • Supply gases are subject to moisturizing treatment as required.
  • the supply amount of oxygen also should be 1 -2 times the theoretical one. In general, the larger the oxygen concentration, the larger electric density is applicable.
  • the hydroxide ion permeates the membrane to the anode, where it reacts with hydrogen to dissociate into water and electron.
  • This electron is supplied to the external load from the anode terminal, transfers energy, reaches via the cathode terminal to the cathode, and is utilized for the reaction at the cathode.
  • Fig.4 shows a schematic view of longitudinal section of a three-chamber electrolytic cell equipped with the gas diffusion electrode by the present invention
  • the three-chamber electrolytic cell 21 is separated into the anode compartment 23 and the cathode compartment 24 by the cation exchange membrane 22 of perfluorosulfonic acid group.
  • a porous DSE (Registered trademark of Permelec Electrode Ltd.) anode 25 for chlorine generation is closely attached to the cation exchange membrane 22 on the side of the anode compartment 23; the gas diffusion electrode (cathode ) 26 is positioned on the side of the cathode compartment of the cation exchange membrane 22 with a gap; and by the gas diffusion electrode 26, the cathode compartment 24 is separated into the catholyte compartment 27 on the side of the cation exchange membrane 22 and the cathode gas compartment 28 on the opposite side.
  • the gas diffusion electrode 26 is prepared in such a manner that the silk-derived activated carbon and the catalyst particles comprising metal or metal oxides are coated and baked, together with a binder of hydrophobic resin, on the electrode substrate of the carbon paper, etc.
  • Fig.5 shows a schematic view of longitudinal section of a two-chamber (zero gap type) electrolytic cell equipped with the gas diffusion electrode by the present invention.
  • the two-chamber electrolytic cell 31 is divided into the anode compartment 33 and the cathode gas compartment 34 by the cation exchange membrane 32 of peril uorosulfonic acid group.
  • the DSE anode 35 for chlorine generation is closely adhered and on the cathode gas compartment 34 of the cation exchange membrane 32, the gas diffusion cathode 36 with the same structure as in Fig.4 is installed in tight contact. If electric power is supplied to the both electrodes, while brine is supplied to the anode compartment 33 and wet oxygen-containing gas is supplied to the cathode gas
  • compartment 34 of the two-chamber electrolytic cell 31, respectively, sodium ion formed at the anode compartment 33 permeates through the cation exchange membrane 32 to the gas diffusion cathode 36 in the cathode gas compartment 34.
  • oxygen in the oxygen-containing gas supplied to the cathode gas compartment 34 is reduced to hydroxide ion by the help of catalyst in the electrode catalyst layer of the gas diffusion cathode 36, bonds with the sodium ion to form sodium hydroxide, and dissolves in moisture supplied together with oxygen-containing gas to form sodium hydroxide aqueous solution.
  • a hydrophilic layer may be disposed between the cation exchange membrane 32 and the gas diffusion electrode 36.
  • Fig.6 shows a schematic view of longitudinal section of a lithium-air battery equipped with the gas diffusion electrode by the present invention, as an example.
  • the lithium air battery cell 41 is divided into the anode compartment (hydrogen electrode compartment) 43 and the cathode compartment (oxygen electrode compartment) 44 by the solid electrolyte 42 having Li ion-selective permeability.
  • the solid electrolyte 42 On the side of the anode compartment of the solid electrolyte 42, the lithium anode 45 and the non-aqueous organic electrolyte solvent 47 are filled, and on the side of the cathode compartment, the alkaline electrolyte 48 and the gas diffusion electrode (oxygen electrode) 46 are provided.
  • the gas diffusion electrode 46 is prepared in such a manner that silk-derived activated carbon and catalyst particles of metal or metal oxides are coated together with the binder of
  • hydrophobic resin, etc. on the electrode substrate of carbon paper, etc., followed by baking.
  • Li ion formed at the hydrogen electrode compartment 43 permeates through the solid electrolyte 42 to the oxygen electrode compartment 44.
  • oxygen in the oxygen-containing gas supplied to the oxygen electrode compartment 44 diffuses in the gas diffusion electrode 46, reacts with water to be reduced to hydroxide ion by the help of catalyst particles in the electrode catalyst layer, moves to the oxygen electrode compartment 44 and bonds with the Li ion to form lithium hydroxide.
  • Spongiform silk material was baked at 500 degrees Celsius in nitrogen atmosphere for 6 hours for carbonization and crushed by a ball mill to approx. ⁇ in grain diameter.
  • the crushed silk powder was baked at 1200 degrees Celsius in nitrogen atmosphere for 7 hours. Then, it was treated at 850 degrees Celsius for 3 hours for steam activation to prepare silk- derived activated carbon catalyst.
  • prepared silk-derived activated carbon catalyst was fixed with National resin liquid on a glassy carbon substrate (6 mm ⁇ ) as an electrode.
  • the electrode was installed on a rotary electrode apparatus with a glassy carbon plate as counter electrode. The relation of voltage vs.
  • Fig.7a and Fig.7b show the relation of electric current-potential of oxygen reduction and the relation of the order of reaction, respectively, of the carbon-based electrode catalyst comprising silk- derived activated carbon, prepared by the heat treatment at 1200 degrees Celsius.
  • oxygen reduction current was confirmed from around 0.8V, proving the possession of reducibility to oxygen.
  • Equation (3) The reduction of oxygen is not only 4-electron reduction by Equation (3), but also is known by Equation (8).
  • the electrode was manufactured in the same manner as with Example 1 , except that the heat treatment was 900 degrees Celsius.
  • Fig.8a and Fig.8b show a 1 graph showing electric current-potential of oxygen reduction and the relation of the order of reaction, respectively, of the carbon-based electrode catalyst comprising silk-derived activated carbon, prepared by the heat treatment at 900 degrees Celsius.
  • oxygen reduction current was confirmed from around 0.8 V, proving the possession of reducibility to oxygen.
  • the order of reaction n of the product is approx. 3.8 and the generation efficiency of hydrogen peroxide was approx. 10%.
  • the electrode was manufactured in the same manner as with Example 1 , except that the particles of silk-derived activated carbon of Example 2 and Zr0 2 were mixed so as to be 1 : 1 in apparent volume ratio. The same evaluation was conducted as with Example 1. As a result, equivalent amount of oxygen reduction current to Example 1 was observed, proving the possession of reducibility to oxygen. The order of reaction n of the product is approx. 4 and the generation of hydrogen peroxide was suppressed.
  • the amount of catalyst was controlled to 100 g/m 2 .
  • a hydrogen anode as counter electrode a commercially available gas diffusion electrode with Pt/C catalyst was applied.
  • An anion exchange membrane was interleaved between two porous electrodes and treated with hot-press at 130 degrees Celsius for 5 minutes to unify them.
  • Nickel foams were provided on the back side of the electrodes as a respective current collector and pinched by the graphite-made current distributers with a groove processed.
  • the cells were assembled and 2M KOH was filled in the cathode compartment.
  • Silk raw material was baked at 500 degrees Celsius in nitrogen atmosphere for 6 hours for carbonization and crushed by a ball mill to approx. ⁇ in grain diameter.
  • the crushed silk powder was baked at 900 degrees Celsius in nitrogen atmosphere for 7 hours. Then, it was treated at 850 degrees Celsius for 3 hours for steam activation to prepare silk- derived activated carbon catalyst.
  • Prepared carbon-based catalyst was mixed with PTFE aqueous suspension (31JR manufactured by Du Pont-Mitsui Fluorochemicals Company, Ltd.) and sufficiently stirred in the water with triton, corresponding to 20 wt% and carboxy methyl cellulose, corresponding to 1.5 wt%.
  • the mixed suspension was coated on the 0.4mm thick carbon cloth so that the weight of activated carbon per projected area becomes 100 g/m 2 , followed by drying at 60 degrees Celsius.
  • the conductive layer was prepared as follows.
  • Silver particles (AgC-H manufactured by Fukuda Metal Foil & Powder Co., LTD.) and PTFE aqueous suspension (31 JR manufactured by Du Pont-Mitsui Fluorochemicals Company, Ltd.) were mixed and sufficiently stirred in the water with triton, corresponding to 20 wt% and carboxy methyl cellulose, corresponding to 1.5 wt%.
  • the mixed suspension was coated on the rear face of the gas diffusion layer so that the weight of silver particle per projected area becomes 100g/m 2 , followed by drying at 60 degrees Celsius, baking at 305 degrees Celsius for 15 minutes in the electric furnace, and press working at 0.6MPa so that the packing ratio of gas diffusion cathode becomes 40%.
  • An electrolysis cell was constructed in the following manner.
  • DSE anode for chlorine generation (manufactured by Permelec Electrode Co., Ltd.) with ruthenium oxide as chief element was applied and, as ion exchange membrane, Flemion F8020 (manufactured by Asahi Glass Co., Ltd.) was applied.
  • Hydrophilic layer which was carbon cloth of 0.4mm in thickness with hydrophilic treatment was interleaved between the gas diffusion cathode and the ion exchange membrane. The anode and the gas diffusion cathode are pressed, facing inward and respective members were tightly adhered so that the ion exchange membrane positions in vertical direction.
  • Brine concentration in the anode compartment was controlled so that the concentration of the sodium hydroxide in the cathode compartment becomes 32 wt% and electrolysis operation was conducted at a current density of 60A/dm 2 at 90 degrees Celsius supplying oxygen gas to the cathode at approx. 1.2 times the theoretical amount.
  • the initial cell voltage was 2.13 V.
  • the cell voltage was as low as 2.15 V and the electric current efficiency was maintained at approx. 95 %.
  • Example 2 The same electrode was prepared as with Example 1 , except that the particles of silk- derived activated carbon and Zr0 2 were mixed to be 1 : 1 as the apparent volume ratio, and the activated carbon amount was 80 g/m .
  • the electrolytic cell similar to that of Example 1 was constructed for the routine test. The initial cell voltage was 2.14 V and the same value was given in the electrolytic operation in 150 days. The voltage increase after the short- circuiting test was 0 mV.
  • Silk-derived activated carbon catalyst was prepared as with Example 1.
  • the electrolytic cell similar to that of Example 1 was constructed for the routine test.
  • the initial cell voltage was 2.17 V and the same value was given in the electrolytic operation in 150 days.
  • the voltage increase after the short-circuiting test was 0 mV.
  • Example 2 The same electrode was prepared as with Example 1 , except that the particles of silk- derived activated carbon and Ag were mixed to be 1 :1 as the apparent volume ratio, and the activated carbon amount was 80 g/m .
  • the electrolytic cell similar to that of Example 1 was constructed for the routine test. The initial cell voltage was 2.14 V and the same value was given in the electrolytic operation in 150 days. The voltage increase after the short- circuiting test was 0 mV.
  • the oxygen gas diffusion cathode was prepared in such a manner that furnace black particle was applied as catalyst particle, silver particle and PTFE aqueous suspension was mixed to be 1 : 1 of the apparent volume ratio between the particle and the resin, and the suspension was coated on the 0.4 mm carbon cloth and dried at 60 degrees Celsius and baked for 15 minutes at 305 degrees Celsius in an electric furnace, followed by the press working at 0.2 MPa. Electrolysis test as with Example 1 was conducted and it was found that the cell voltage increased from the initial voltage at 2.16 V to 2.20 V in 150 days operation. After the short-circuiting test, the voltage increased by 70 mV, showing dysfunction as an electrode.
  • the present invention relates to the gas diffusion electrode applying the silk-derived carbon-based electrode catalyst containing nitrogen, which is highly active in an alkaline aqueous solution for the use of alkaline fuel cells, metal-air batteries or brine electrolysis cells and durable as electrode at charging and discharging of electrolysis and battery with long time stability.
  • Such electrode is widely applied in the above fields of gas diffusion electrode in various industries.

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Abstract

La présente invention vise à produire une électrode de diffusion de gaz et son procédé de fabrication pour piles à combustible alcalines, batteries métal-air ou piles à électrolyse de saumure permettant plus précisément d'obtenir des performances d'électrolyse pratiquement équivalentes au système classique sans avoir à utiliser un catalyseur de platine coûteux, et ayant une durabilité supérieure en tant qu'électrode d'électrolyse dans une solution alcaline ou lors d'une interruption d'urgence et ayant une meilleure stabilité lors d'un fonctionnement prolongé. La présente invention vise à produire une électrode de diffusion d'oxygène gazeux pour piles à combustible alcalines, batteries métal-air ou piles à électrolyse de saumure utilisées dans une solution aqueuse alcaline, caractérisée en ce qu'un catalyseur d'électrode à base de carbone à l'état de poudre, comprenant du charbon actif dérivé de la soie et contenant de l'azote dérivé de la soie est appliqué à la surface d'un substrat conducteur poreux.
PCT/JP2012/069634 2011-07-29 2012-07-24 Electrode de diffusion d'oxygène gazeux et son procédé de fabrication WO2013018843A1 (fr)

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WO2015018670A1 (fr) * 2013-08-07 2015-02-12 Sytoch Gmbh Dispositif de stockage de l'énergie électrique à partir de la soie
JP2015028932A (ja) * 2013-07-05 2015-02-12 東洋インキＳｃホールディングス株式会社 燃料電池用水性触媒ペースト組成物、及び燃料電池
WO2015038965A1 (fr) * 2013-09-13 2015-03-19 Meadwestvaco Corporation Structures catalytiques au charbon actif et leurs procédés d'utilisation et de fabrication
JP2015220037A (ja) * 2014-05-15 2015-12-07 国立大学法人 名古屋工業大学 含窒素天然有機物を用いた空気極の製造方法
US11075382B2 (en) 2014-05-30 2021-07-27 Duracell U.S. Operations, Inc. Cathode for an electrochemical cell including at least one cathode additive
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JP2015028932A (ja) * 2013-07-05 2015-02-12 東洋インキＳｃホールディングス株式会社 燃料電池用水性触媒ペースト組成物、及び燃料電池
WO2015018670A1 (fr) * 2013-08-07 2015-02-12 Sytoch Gmbh Dispositif de stockage de l'énergie électrique à partir de la soie
CN105556704A (zh) * 2013-08-07 2016-05-04 嘉华投资有限公司 基于丝的电能存储装置
WO2015038965A1 (fr) * 2013-09-13 2015-03-19 Meadwestvaco Corporation Structures catalytiques au charbon actif et leurs procédés d'utilisation et de fabrication
US11090606B2 (en) 2013-12-05 2021-08-17 Dionex Corporation Gas-less electrolytic device and method
JP2015220037A (ja) * 2014-05-15 2015-12-07 国立大学法人 名古屋工業大学 含窒素天然有機物を用いた空気極の製造方法
US11075382B2 (en) 2014-05-30 2021-07-27 Duracell U.S. Operations, Inc. Cathode for an electrochemical cell including at least one cathode additive

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