WO2006003831A1 - 燃料電池用電極触媒及びその製造方法並びに該触媒を用いた燃料電池 - Google Patents
燃料電池用電極触媒及びその製造方法並びに該触媒を用いた燃料電池 Download PDFInfo
- Publication number
- WO2006003831A1 WO2006003831A1 PCT/JP2005/011512 JP2005011512W WO2006003831A1 WO 2006003831 A1 WO2006003831 A1 WO 2006003831A1 JP 2005011512 W JP2005011512 W JP 2005011512W WO 2006003831 A1 WO2006003831 A1 WO 2006003831A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon
- nitrogen
- boron
- fuel cell
- platinum
- Prior art date
Links
Classifications
-
- 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
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
- H01M4/881—Electrolytic membranes
-
- 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
- H01M4/923—Compounds thereof with non-metallic elements
-
- 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
- H01M4/926—Metals of platinum group 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to an electrode catalyst for a fuel cell having a small amount of platinum or a platinum alloy supported thereon, a production method thereof, and a fuel cell using the catalyst. More specifically, the present invention relates to an electrode catalyst for a polymer electrolyte fuel cell suitable for a force sword having a highly active oxygen reduction catalytic ability, a method for producing the same, and a fuel cell using the catalyst.
- the reaction occurs in the porous gas diffusion electrode.
- I AZ projected electrode area
- an electrode having a large specific surface area and conductive carbon black as a porous structure / catalyst support is generally used as the electrode.
- platinum (Pt) or platinum alloy-based catalysts are used as the catalyst, and these noble metal catalysts are supported in a highly dispersed state (particle size 2 to several tens of nm). It has been.
- the standard carrier materials for gold include (1) carbon black, such as Carbon Black, Bl Degussa-Huels (Frankfurt), and (2) furnace black, such as Vulcan XC-72 Cabot. (Massachusetts), (3) acetylene black, such as Shawinigan Black and Chevron Chemicals (Houston, Texas).
- Carbon black B1 as a standard support material for platinum
- Patent Document 1 describes Vulcan XC-72 and Shawi-Gan Black, for example, Patent Document 2.
- a group power consisting of B, N and P is used for a fuel cell in which a particle-like or fiber-like carbon support containing at least one selected element contains platinum particles or the like.
- a catalyst is disclosed.
- a compound containing at least one element selected from the group consisting of B, N, and P is converted into a gas state and introduced into a furnace containing a carbon support, where 600 to 900 ° C.
- At least one kind selected from the group consisting of B, N and P together with a carrier gas is generated by discharging in a vacuum chamber where a carbon carrier is installed and generating a plasma. It is produced by introducing a compound containing an element in a gas state and reacting for a certain time (for example, Patent Document 3).
- Patent Document 1 Japanese Patent Laid-Open No. 2001-85020 (Claim 1, [0041])
- Patent Document 2 US Pat. No. 5,759,944 (Example 1, Example 2)
- Patent Document 3 Japanese Patent Laid-Open No. 2004-79244 ([0010], [0025] to [0027])
- An object of the present invention is to control the crystal growth of a carbon substrate by a dopant and to perform an electronic state.
- the activity of platinum supported thereon can be further improved, and a fuel cell electrode catalyst capable of obtaining a high current density, a method for producing the same, and a fuel cell using the catalyst are provided. It is in.
- the invention according to claim 1 is an electrode catalyst for a fuel cell in which platinum or a platinum alloy is supported on a carbon base material, and the carbon base material is a carbon alloy fine particle doped with nitrogen atoms.
- This carbon substrate heat-reacts the nitrogen-containing compound and the thermosetting resin precursor, and superimposes, and the resulting nitrogen compound-containing thermosetting resin is heat treated and carbonized to carbonize.
- An electrode catalyst for a fuel cell which is a carbon alloy fine particle obtained by finely pulverizing a nitrogen compound-containing thermosetting resin.
- the invention according to claim 2 includes a polymerization step of obtaining a nitrogen compound-containing thermosetting resin by heating and polymerizing a nitrogen-containing compound and a thermosetting resin precursor.
- a carbonization step in which the nitrogen compound-containing thermosetting resin is carbonized by heat treatment, and the carbonized nitrogen compound-containing thermosetting resin is pulverized to obtain carbon-aromatic particles doped with nitrogen atoms.
- a method for producing an electrode catalyst for a fuel cell comprising a pulverization step and a step of obtaining a carbon substrate by supporting platinum on the carbon alloy fine particles.
- the invention according to claim 4 is an electrode catalyst for a fuel cell in which platinum or a platinum alloy is supported on a carbon base material, and the carbon base material is a carbon alloy fine particle doped with boron atoms.
- This carbon substrate was polymerized by heating and reacting a boron-containing compound and a precursor of thermosetting resin, and the resulting boron compound-containing thermosetting resin was heat treated and carbonized to be carbonized.
- An electrode catalyst for a fuel cell which is a carbon alloy fine particle obtained by finely pulverizing a boron compound-containing thermosetting resin.
- the invention according to claim 5 includes a polymerization step of obtaining a boron compound-containing thermosetting resin by heating and polymerizing a boron-containing compound and a thermosetting resin precursor.
- the A carbonization step in which the boron compound-containing thermosetting resin is carbonized by heat treatment, and the carbonized boron compound-containing thermosetting resin is pulverized to obtain carbon alloy particles doped with boron atoms. It is a method for producing an electrode catalyst for a fuel cell, comprising a powder frame step and a step of obtaining a carbon substrate by supporting platinum on the carbon alloy fine particles.
- the invention according to claim 7 is an electrode catalyst for a fuel cell in which platinum or a platinum alloy is supported on a carbon base material, wherein the carbon base material is doped with nitrogen atoms and boron atoms.
- the carbon substrate is polymerized by dissolving a nitrogen-containing compound and a boron-containing compound in a methanol solution of furfuryl alcohol or resol-type phenol resin, and performing a polymerization reaction under methanol subcritical or supercritical conditions.
- An electrode catalyst for a fuel cell characterized in that it is a carbon alloy fine particle obtained by carbonizing a polymer fine particle obtained by heat treatment after obtaining the product fine particle.
- the invention according to claim 8 is a solution in which a nitrogen-containing compound and a boron-containing compound are dissolved in a methanol solution of furfuryl alcohol or resol type phenol resin, and polymerized under methanol subcritical or supercritical conditions.
- a polymerization step for obtaining polymer fine particles by carrying out a reaction a carbonization step for obtaining carbon alloy fine particles doped with nitrogen atoms and boron atoms by heat-treating the obtained polymer fine particles, and platinum on the carbon alloy fine particles
- a method for producing an electrode catalyst for a fuel cell comprising a step of obtaining a carbon base material by supporting a catalyst.
- the carbon base material contains an aqueous solution containing phenol, formaldehyde, and a base catalyst.
- An electrode catalyst for a fuel cell characterized in that it is carbon ultrafine particles obtained by carbonizing by heating high molecular ultrafine particles recovered from a solution that has been kept at a predetermined time and reacted and dried.
- the invention according to claim 11 includes a step of obtaining a reaction solution by holding an aqueous solution containing phenol, formaldehyde, and a base catalyst at a predetermined temperature for a predetermined time, and freeze-drying the reaction solution to obtain a polymer superpolymer.
- a method for producing an electrode catalyst for a fuel cell The invention's effect
- the carbon base material doped with nitrogen atoms or boron atoms is added with a function of oxygen reduction in addition to the function as a conductive material.
- the activation of is higher.
- the activity of the supported platinum is caused by the interaction between the electrically negative nitrogen atom and the electrically positive boron atom. Is further increased. As a result, a high current density can be obtained with a small amount of platinum.
- Patent Document 3 the surface of a carbon substrate that has already been prepared is modified with one or both of nitrogen and boron to achieve activation, whereas in the invention according to claim 1, 4 or 7, Since either or both of nitrogen and boron are added at the time of carbon preparation, the edge surface can be formed on the carbon surface by controlling the development of the carbon structure, and is expected in Patent Document 3. It also has an effect. For this reason, the present invention is more excellent in the activation of platinum than the invention of Patent Document 3.
- a carbon alloy doped with nitrogen atoms or boron atoms by carbonizing and pulverizing the nitrogen compound-containing thermosetting resin or boron compound-containing thermosetting resin. Fine particles are obtained.
- fine particles can be obtained by conducting a polymerization reaction of a furfuryl alcohol or a resol type phenol resin dissolved in nitrogen-containing compound and boron-containing compound under a subcritical or supercritical condition.
- a polymer can be obtained in the form of carbon alloy, and by carbonizing this polymer, carbon alloy fine particles doped with nitrogen and boron atoms can be obtained. Particles are obtained.
- the doping amount of nitrogen atoms or boron atoms can be easily adjusted.
- the carbon base material is ultrafine carbon particles, the ratio of the edge surface exposed by introducing defects on the carbon surface increases. This adds the function of oxygen reduction and further increases the activation of platinum carried by electronic and chemical interactions with such active surfaces.
- ultrafine polymer particles are obtained in the reaction solution by holding an aqueous solution containing phenol, formaldehyde, and a base catalyst at a predetermined temperature for a predetermined time.
- FIG. 1 is a graph showing the relationship between the X-ray incident angle and diffraction X-ray intensity of N, B-carbon alloy fine particles F to J of Examples 9 to 13 and carbon fine particles 1 of Comparative Example 1.
- FIG. 2 is a graph showing the relationship between the potential and current density of N-carbon alloy fine particles 1 and 2 of Examples 1 and 2 and carbon fine particles 1 of Comparative Example 1.
- FIG. 3 is a graph showing the relationship between the potential and current density of B-carbon alloy fine particles of Example 3 and carbon fine particles 1 of Comparative Example 1.
- FIG. 4 is a graph showing the relationship between the N and B-carbon alloy fine particles A, B and E of Examples 4, 5, and 8 and the carbon fine particle 1 of Comparative Example 1 and the current density.
- FIG. 5 (a) to (c) are the oxygen reduction initiation potentials of the N, B-carbon alloy fine particles A to E of Examples 4 to 8 and the carbon fine particles of Comparative Example 2, and the boron atoms and nitrogen atoms, respectively. It is a graph which shows the relationship with content.
- FIG. 6 is a graph showing NlsX-ray photoelectron spectra of N, B-carbon alloy fine particles A to E of Examples 4 to 8.
- FIG. 7 is a graph showing Bls X-ray photoelectron spectra of N, B-carbon alloy fine particles A to E in Examples 4 to 8.
- FIG. 8 is a photographic diagram of a field emission high resolution scanning electron microscope showing carbon ultrafine particles of Example 14.
- FIG. 9 Carbon base oxygen-reduced voltammo of Example 15 and Comparative Example 3 each carrying platinum. It is a figure which shows a gram.
- FIG. 10 is a diagram showing cyclic voltammograms of carbon substrates of Example 15 and Comparative Example 3 each carrying platinum.
- FIG. 11 is a schematic diagram of a three-pole rotating electrode cell.
- the first form of the carbon base material in the fuel cell electrode catalyst according to the present invention is carbon alloy fine particles.
- This carbon alloy fine particle is a carbon alloy fine particle in which one or both of a boron atom and a nitrogen atom located on both sides of a group 14 carbon atom and a carbon atom.
- the average particle size of the carbon alloy fine particles is 0.05 ⁇ m force or less than 45 ⁇ m. Preferably 0.05.0 .: m.
- the carbon material itself that has been used as a catalyst carrier for supporting platinum in a highly dispersed state has an oxygen reduction catalytic ability, and can be suitably used as an electrode catalyst for a fuel cell.
- the doping amount of nitrogen atom or boron atom when the doping amount of nitrogen atom or boron atom is 0.1 to 40 atom%, preferably 4 to 20 atom%, good electrode activity with respect to oxygen reduction. Indicates.
- nitrogen and boron atoms are doped at the same time, higher electrode activity is exhibited due to the interaction between the two.
- the atomic ratio (BZN) when both nitrogen (N) and boron (B) atoms are doped, the atomic ratio (BZN) is from 0.06 to L5, preferably from 0.2 to 0.4.
- the atomic ratio ((B + N) ZC) is preferably 0.03-0.4. Within the range of these atomic ratios, both atoms interact well, and highly active force-bonded particles can be obtained.
- (a) Method for producing carbon alloy fine particles doped with nitrogen atoms In order to produce carbon alloy fine particles doped with nitrogen atoms, first, nitrogen sources such as phthalocyanine, acrylonitrile, EDTA (ethylene diamine tetraacetic acid), melamine and the like, as well as furan coconut resin and phenol resin. A precursor of thermosetting resin is mixed and reacted by heating to obtain a nitrogen compound-containing thermosetting resin. For example, when phthalocyanine is used as the nitrogen-containing compound and furfuryl alcohol is used as the precursor of the thermosetting resin, an acid such as hydrochloric acid is added to the mixture, preferably 80 to 200 ° C.
- nitrogen sources such as phthalocyanine, acrylonitrile, EDTA (ethylene diamine tetraacetic acid), melamine and the like
- furan coconut resin and phenol resin A precursor of thermosetting resin is mixed and reacted by heating to obtain a nitrogen compound-containing thermosetting resin.
- an acid such as hydrochloric
- a phthalocyanine-containing furan resin can be obtained by heating at a temperature within the range of 1 to cause a polymerization reaction.
- the compounding ratio of furfuryl alcohol and melamine or phthalocyanine is 1: (0.07-3), preferably C: N.
- ⁇ MA 1 Set to (0. 1 to 0.5).
- the obtained phthalocyanine-containing furan resin is carbonized by heat treatment at a predetermined temperature in an inert atmosphere such as nitrogen or helium.
- the heat treatment temperature is not particularly limited as long as it is a carbonizable temperature, but a preferable temperature is 400 to 1500 ° C, and a more preferable temperature is 500 to 1200 ° C.
- the average particle diameter doped with nitrogen atoms is preferably 0.05 ⁇ m or less, preferably 45 ⁇ m or less, preferably from 0.05 ⁇ m to 0.1 by finely pulverizing with a ball mill such as a planetary ball mill. Carbon alloy fine particles of ⁇ m or less can be obtained.
- the fine particles obtained as described above are loaded with 0.5 to 60% by weight, preferably 10 to 50% by weight, more preferably 20 to 50% by weight of platinum or a platinum alloy, whereby the fuel cell of the present invention is supported.
- An electrode catalyst is obtained.
- the platinum alloy include Pt—Fe, Pt—Cr, Pt—Ru, Pt—Ni, and Pt—Cu.
- the method for supporting platinum is not particularly limited, and a known method can be employed. For example, there is a method in which carbon alloy fine particles are dispersed in a platinum colloid solution, platinum is reduced, and then solid-liquid separation and drying are performed. According to this method, the amount of platinum supported can be easily adjusted by changing the amount of carbon alloy fine particles dispersed in the colloidal gold solution.
- boron-containing compounds such as BF methanol complex or BF tetrahydrofuran (THF) complex as a boron source.
- a thermosetting resin precursor such as furan resin and phenol resin are mixed and reacted by heating to obtain a boron compound-containing thermosetting resin.
- boron-containing compounds such as BF methanol complex or BF tetrahydrofuran (THF) complex
- THF BF tetrahydrofuran
- thermosetting resin When using a methanol complex and using furfuryl alcohol as a precursor of thermosetting resin, it is preferably heated at a temperature in the range of 80 to 200 ° C. to cause a polymerization reaction, thereby producing a BF-containing furan. A rosin can be obtained.
- the boron atom doping amount described above is 0.1 to
- the compounding ratio of furfuryl alcohol and BF should be C: B.
- the average particle diameter doped with boron atoms is preferably 0.05 ⁇ m or less, preferably not more than 45 ⁇ m, preferably 0.05 ⁇ m to 0.1 ⁇ m, by pulverizing with a ball mill such as a planetary ball mill.
- the following carbon alloy fine particles can be obtained.
- the fine particles thus obtained are loaded with 0.5 to 60% by weight of platinum or a platinum alloy, preferably 10 to 50% by weight, more preferably 20 to 50% by weight.
- a battery electrode catalyst is obtained.
- examples of the platinum alloy include Pt—Fe, Pt—Cr, Pt—Ru, Pt—Ni, and Pt Cu.
- the method for supporting platinum is not limited to the force generally used in the method described in (a) above.
- thermosetting resin such as furan resin and phenol resin.
- the body is mixed and reacted by heating to obtain a boron nitrogen compound-containing thermosetting resin.
- a boron nitrogen compound-containing thermosetting resin for example, BF methanol complex as boron-containing compound, nitrogen-containing
- thermosetting resin When melamine is used as a compound and furfuryl alcohol is used as a precursor of thermosetting resin, it is preferably heated at a temperature in the range of 80 to 200 ° C. to cause a polymerization reaction. A BF-containing furan resin can be obtained. Nitrogen atoms and boron mentioned above
- the atomic ratio of C: N: B is 1: (0. 04-2): (0.02-: 0, preferably 1: (0.3-0.7): (0. 4 ⁇ 1.5).
- the obtained polymer fine particles are carbonized at a predetermined temperature described in the above (a) under an inert atmosphere such as nitrogen or helium, thereby obtaining carbon alloy fine particles doped with nitrogen atoms and boron atoms. be able to.
- the fine particles thus obtained are supported by 0.5 to 60% by weight, preferably 10 to 50% by weight, more preferably 20 to 40% by weight of platinum or platinum alloy.
- a battery electrode catalyst is obtained.
- the kind of platinum alloy and the method for supporting platinum are the same as the supporting method in the method for producing carbon alloy fine particles doped with nitrogen atoms described in (a) above.
- Another method for producing carbon alloy fine particles doped with nitrogen and boron atoms is the following subcritical method.
- this method first, in a methanol solution of furfuryl alcohol or resole phenol resin, a nitrogen-containing compound similar to the above and a boron-containing compound such as BF methanol complex or BF tetrahydrofuran (THF) complex as a boron source.
- a nitrogen-containing compound similar to the above and a boron-containing compound such as BF methanol complex or BF tetrahydrofuran (THF) complex
- the compound is dissolved and a polymerization reaction is performed.
- a polymerization reaction for example, furfuryl alcohol in methanol
- the polymerization reaction of furfuryl alcohol is carried out under methanol subcritical or supercritical conditions at 200 to 350 ° C.
- the compounding ratio of the nor complex is 1: (0.2 to 0.8): (0.1 to 0.4), preferably 1: (0.3 to 0.7) in terms of the C: N: B atomic ratio. ): Set to (0.15 to 0.4).
- the obtained polymer fine particles are carbonized at a predetermined temperature described in the above (a) under an inert atmosphere such as nitrogen or helium to obtain carbon alloy fine particles doped with nitrogen atoms and boron atoms. be able to. Carbon alloy fine particles doped with nitrogen atoms and boron atoms can be obtained.
- the fine particles thus obtained are supported by 0.5 to 60% by weight, preferably 10 to 50% by weight, more preferably 20 to 40% by weight of platinum or platinum alloy.
- a battery electrode catalyst is obtained.
- the type of platinum alloy and the method for supporting platinum are described in the above (a). This is the same as the loading method in the child manufacturing method.
- the second form of the carbon substrate in the fuel cell electrode catalyst according to the present invention is ultrafine carbon particles produced by a sol-gel method.
- the average particle size of ultrafine carbon particles produced by this method is 10 to 1 OOnm.
- the carbon ultrafine particles are produced as follows. First, an aqueous solution containing a base catalyst such as phenol, formaldehyde, and sodium carbonate is prepared. By holding this aqueous solution at a predetermined temperature for a predetermined time, phenol and formaldehyde are reacted. Polymer ultrafine particles are generated in the reaction solution.
- the predetermined temperature is preferably 60 to 90 ° C, more preferably 80 to 90 ° C.
- the predetermined time is preferably 1-20 hours, more preferably 8-18 hours.
- the reaction solution is cooled to liquid nitrogen temperature, frozen and dried to collect ultrafine polymer particles. Further, the collected ultrafine polymer particles are then heat-cured at 100 to 250 ° C.
- the mixing weight ratio of phenol, formaldehyde and sodium carbonate is 1: (1-2): (0. 05-0.2), preferably 1: (1. 4 to 1.6): Set to (0. 05 to 0.1).
- the ultrafine particles thus obtained are loaded with 0.5 to 60% by weight, preferably 10 to 50% by weight, more preferably 20 to 40% by weight of platinum or a platinum alloy.
- a fuel cell electrode catalyst is obtained.
- the kind of platinum alloy and the method for supporting platinum are the same as the method for supporting the carbon alloy fine particles doped with nitrogen atoms described in (a) above.
- the solid fuel cell according to the present invention is manufactured using the fuel cell electrode catalyst described in [1] and [2] above.
- a solid polymer fuel cell is composed of an anode (fuel electrode) and a force sword (acid additive electrode), which are arranged so that cells built in a battery module are sandwiched between sheet-like solid polymer electrolyte membranes. They are organized.
- a fluorine-based ion exchange typified by a perfluorosulfonic acid rosin membrane (for example, a naphthoion membrane manufactured by DuPont).
- a replaceable oil membrane is used.
- an electrode reaction layer containing the fuel cell electrode catalyst described in [1] and [2] above is formed in layers.
- the anode and the force sword are configured to include the electrode reaction layer including the electrode catalyst for fuel cells described in [1] and [2] above and the electrode substrate. Both electrodes are bonded together as a MEA (Membrane Electrode Assembly) by hot-pressing them to the main surfaces of the polymer electrolyte membrane on the electrode reaction layer side.
- MEA Membrane Electrode Assembly
- the electrode base material supports a catalyst layer and supplies and discharges reaction gases (fuel gas and oxidant gas), and also has a porous sheet (for example, carbon base) that also functions as a current collector. 1 par) is used.
- a reactive gas is supplied to each of the electrodes, a gas phase (reactive gas), a liquid phase is formed at the boundary between the catalyst layer supporting the platinum-based noble metal provided on both electrodes and the solid polymer electrolyte membrane.
- a three-phase interface (solid polymer electrolyte membrane) and solid phase (catalyst possessed by both electrodes) is formed, and direct current power is generated by causing an electrochemical reaction.
- H + ions generated on the anode side move toward the cathode side in the polymer electrolyte membrane, and e "(electrons) move to the force sword side through an external load.
- oxygen contained in the oxidant gas reacts with H + ions and e- that have moved from the anode side to produce water. Will generate direct current power from hydrogen and oxygen to produce water.
- phthalocyanine 13 lg
- furfuryl alcohol furfuryl alcohol
- hydrochloric acid an appropriate amount of hydrochloric acid
- N-carbon alloy fine particles 1 This carbonized product was pulverized with a planetary ball mill to obtain carbon alloy fine particles (hereinafter referred to as “N-carbon alloy fine particles 1” t) having an average particle diameter of 0.1 doped with 13.4 atomic% of nitrogen atoms. .
- This platinum colloid solution was dropped into 0.2 g of the above N-force single Bonalloy fine particles, and the N-carbon alloy fine particles were uniformly dispersed in the platinum colloidal solution by ultrasonic irradiation for 20 minutes.
- the reducing agent was added dropwise to the dispersion over 20 minutes, followed by stirring for 12 hours. Thereafter, the obtained liquid was filtered through a membrane filter made of hydrophilic polytetrafluoroethylene (PTFE) having an opening diameter of 1.0 ⁇ m and separated into solid and liquid.
- PTFE hydrophilic polytetrafluoroethylene
- the carbonized product is pulverized with a planetary ball mill to obtain carbon alloy fine particles (hereinafter referred to as “carbon alloy fine particles 2”) having an average particle diameter of 0.1 ⁇ m doped with 13.4 atomic% of nitrogen atoms. It was.
- carbon alloy fine particles 2 carbon alloy fine particles having an average particle diameter of 0.1 ⁇ m doped with 13.4 atomic% of nitrogen atoms. It was.
- 10% by weight of platinum was supported on the soot-carbon alloy fine particles 2.
- B-carbon alloy fine particles carbon alloy fine particles having an average particle diameter of 0.1 doped with 14.4 atomic% of boron atoms.
- 10% by weight of platinum was supported on the B-carbon alloy fine particles.
- Comparative carbon fine particles 1 made of furan rosin were obtained in the same manner as in Example 1 except that phthalocyanine as a nitrogen source was not added.
- the comparative carbon fine particles 1 were loaded with 10% by weight of platinum in the same manner as in Example 1.
- the obtained contents were filtered on a hydrophilic PTFE membrane filter having an opening diameter of 1.0 m, and the solvent was distilled off from the passing material to obtain a membrane filter having an opening diameter of 0.45 m.
- Fine particles were obtained by washing on top.
- the obtained polymer fine particles were heated from a room temperature at a rate of 10 ° C. Z under a nitrogen atmosphere and kept at a temperature of 1000 ° C. for 1 hour for heat treatment.
- polymer fine particles are carbonized, and carbon alloy fine particles (hereinafter referred to as “N, B-carbon alloy fine particles A”) having a submicron particle diameter doped with 4 atomic% nitrogen atoms and 1.2 atomic% boron atoms, respectively. )
- N, B-carbon alloy fine particles A carbon alloy fine particles having a submicron particle diameter doped with 4 atomic% nitrogen atoms and 1.2 atomic% boron atoms, respectively.
- 10% by weight of platinum was supported on the N, B-carbon alloy fine particles A
- Example 5 Example 4 except that 2.3 g of melamine as a nitrogen source and 36 g of BF methanol complex as a boron source were dissolved in 150 ml of a methanol solution in which 6 g of furfuryl alcohol was dissolved.
- N, B-carbon alloy fine particles B having a particle size of submicron doped with 4 atom% nitrogen atoms and 1.7 atom% boron atoms were obtained.
- This N, B-carbon alloy fine particle B was loaded with 10% by weight of platinum in the same manner as in Example 1.
- Example 4 The same as Example 4 except that 3 g of melamine as a nitrogen source and 48 g of BF methanol complex as a boron source were dissolved in 150 ml of a methanol solution containing 6 g of furfuryl alcohol.
- N, B-carbon alloy fine particles C having a particle size of submicron doped with 5 atom% nitrogen atoms and 1.4 atom% boron atoms were obtained.
- the N, B-carbon alloy fine particles C were loaded with 10% by weight of platinum in the same manner as in Example 1.
- Example 4 is the same as Example 4 except that 4.5 g of melamine as a nitrogen source and 72 g of BF methanol complex as a boron source were dissolved in 150 ml of a methanol solution in which 6 g of furfuryl alcohol was dissolved.
- N, B-carbon alloy fine particles D having a particle size of submicron doped with 5.4 atomic% nitrogen atoms and 1.4 atomic% boron atoms were obtained.
- 10% by weight of platinum was supported on the N, B-carbon alloy fine particles D.
- Example 4 except that 7.5 g of melamine as a nitrogen source and 121 g of BF methanol complex as a boron source were dissolved in 150 ml of a methanol solution in which 6 g of furfuryl alcohol was dissolved.
- N, B-carbon alloy fine particles E having a particle size of submicron doped with 12.8 atomic% nitrogen atoms and 2.6 atomic% boron atoms were obtained.
- 10% by weight of platinum was supported on this N, B-force single Bonalloy fine particle E.
- comparative carbon fine particles 2 made of furan rosin were obtained in the same manner as in Example 4 except that an appropriate amount of hydrochloric acid was added.
- the comparative carbon fine particles 2 were loaded with 10% by weight of platinum in the same manner as in Example 1.
- This carbonized product is pulverized with a planetary ball mill, and carbon alloy fine particles with an average particle size of 0 (hereinafter referred to as “B, N-carbon alloy” doped with 2.7 atomic% of nitrogen atoms and 0.2 atomic% of boron atoms). Fine particles F ”).
- This N, B-carbon alloy fine particle F was loaded with 10% by weight of platinum in the same manner as in Example 1.
- Example 9 except that melamine 2.lg as a nitrogen source and 34g of BF methanol complex as a boron source were dissolved in 100ml of a methanol solution in which 10g of furfuryl alcohol was dissolved.
- B-carbon alloy fine particles G having an average particle size of 0.1111 doped with 3 atom% nitrogen atoms and 0.6 atom% boron atoms were obtained.
- 10% by weight of platinum was supported on the N, B-carbon alloy fine particles G.
- Example 9 except that 4.7 g of melamine as a nitrogen source and 76 g of BF methanol complex as a boron source were dissolved in 100 ml of a methanol solution in which 10 g of furfuryl alcohol was dissolved.
- the average particle diameter of 0.1 111 is doped with 3.2 atomic% of nitrogen atoms and 0.5 atomic% of boron atoms, respectively.
- ⁇ B—carbon alloy fine particles H were obtained.
- 10% by weight of platinum was supported on the N, B-carbon alloy fine particles H.
- Example 9 9.4 atomic percent nitrogen and 7.4 atomic percent boron Average particle size of 0.1 1 111? ⁇ B—carbon alloy fine particles I were obtained.
- the N, B-carbon alloy fine particles I were loaded with 10% by weight of platinum in the same manner as in Example 1.
- Example 9 except that 29 g of melamine as a nitrogen source and 460 g of BF methanol complex as a boron source were dissolved in 100 ml of a methanol solution in which 10 g of furfuryl alcohol was dissolved.
- the average particle size of 0.1 111 is doped with 7.7 atomic% of nitrogen atoms and 10.6 atomic% of boron atoms, respectively.
- ⁇ B—carbon alloy fine particles J were obtained.
- 10% by weight of platinum was supported on the N, B-force single Bonalloy fine particles J.
- N-carbon alloy particles 1 of Example 1 before carrying platinum N-carbon alloy particles 2 of Example 2, B-carbon alloy particles of Example 3, N, B-carbon alloy particles A to 4 of Examples 4 to 13, respectively.
- Elemental ratio and carbonization yield of J, Comparative Carbon Fine Particle 1 of Comparative Example 1 and Comparative Carbon Fine Particle 2 of Comparative Example 2 were determined by X-ray photoelectron spectroscopy (XPS) method. The results are shown in Table 1. The charged atomic ratio indicates the amount of N and B dopants at the time of preparation.
- Example 1 N-force-horn Py 3 ⁇ 4 ⁇ 1) 13: 2: 0- ⁇ 0.16
- Example 2 ⁇ -force-hona 2) 16: 2: 0 ⁇ 0 0.16
- Example 3 ⁇ -force-honah ⁇ i difficulty) 2.7: 0: 1 ⁇ ⁇ ⁇
- Example 4 ( ⁇ , ⁇ -kar-honalloy 3 ⁇ 4 particle ⁇ ) 5.2: 2 : 1 48 0.32 0.060
- Example 5 ( ⁇ , ⁇ -Carton Honalloy Fine Particles ⁇ ) 9.3: 2: 1 41 0.42 0.066
- Example 6 ( ⁇ , ⁇ -Force-Hon Nyung Lung C) 6.5: 2: 1 39 0.28 0.076
- Example ⁇ ⁇ , ⁇ -Car-Ho-Han Nya D fine particle) 3.8: 2: 1 39 0.26 0.081
- Example 8 ( ⁇ , ⁇ -Car-Ha-Hon han ⁇ ⁇ ) 2.7: 2: 1 8 0.20 0.220
- the N, B-carbon alloy fine particles obtained in Examples 4 to 13 were fixed at V: 2 and the atomic ratio of nitrogen and boron in the raw material was fixed at 2: 1.
- the total dope amount of these N, B carbon alloy fine particles (B + N) ZC varied depending on the charged atomic ratio.
- the BZN ratio at this time varied depending on the charging ratio. This Thus, it was found that the doping level in the prepared carbon alloy fine particles can be changed by changing the charged atomic ratio.
- an electrode activity test was conducted on these electrode catalysts in order to investigate the redox function.
- the electrode activity related to this oxygen reduction was measured using a tripolar rotating electrode cell 1 schematically shown in FIG.
- the working electrode (rotating electrode) 2 in the central part has a polymer insulator around it and an electrode part made of glassy carbon at the central part.
- a catalyst ink prepared as follows was applied to each of the electrode parts to obtain a working electrode.
- Reference numeral 3 is a reference electrode (AgZAgCl), and reference numeral 4 is a counter electrode (Pt).
- the obtained catalyst ink was sucked with a small amount of pipette, applied to the glassy carbon part (diameter 5 mm) of the rotating electrode device, and dried to prepare a working electrode.
- Fig. 5 shows the element ratio and oxygen reduction obtained from XPS for N, B-carbon alloy fine particles A to E of Examples 4 to 8 and Comparative carbon fine particle 2 of Comparative Example 2 after carrying platinum, respectively. The relationship with the starting potential is shown.
- the N, B-carbon alloy fine particles of Examples 4 to 8 have higher oxygen reduction activity than the comparative carbon fine particles of Comparative Example 2 in which nitrogen atoms and boron atoms are not doped.
- the oxygen reduction activity tends to increase as the doping amount of nitrogen atoms and boron atoms (B + N) ZC increases.
- NZC and BZC it was examined which of nitrogen atom and boron atom is involved in oxygen reduction. As shown in Fig. 5 (b) and (c), both elements were compared. The same tendency was observed, and it was found that nitrogen and boron interacted to bring about activity.
- N 1 sX-ray photoelectron spectra and B 1 sX-ray photoelectron spectra of N, B-carbon alloy fine particles A to G of Examples 4 to 10 after carrying platinum are shown in Figs. 6 and 7, respectively. Show. From Fig. 6, each N and B carbon alloy fine particle has two states. When the doping amount of boron and nitrogen atoms is small, the peak on the high bond energy side is dominant, but as the doping amount increases, Nls It was found that the low energy peak of became dominant. In contrast, Fig. 7 shows that all N and B carbon alloy fine particles show a single spectrum, and the binding energy tends to shift to higher side as the doping amount of boron atom and nitrogen atom increases.
- an active carbon material is given by generating an electrically negative nitrogen atom and an electrically positive boron atom by interaction of a nitrogen atom and a boron atom in an elementary atom.
- the polymer ultrafine particles recovered were cured by heating at 200 ° C for 5 hours.
- the cured ultrafine polymer particles were heated from room temperature at a rate of 10 ° CZ in a nitrogen atmosphere, and carbonized by holding at 1000 ° C for 1 hour to obtain ultrafine carbon particles having an average particle size of 30 nm.
- Figure 8 shows a field emission high-resolution scanning electron microscope (FE—SEM) image of these ultrafine carbon particles.
- FE—SEM field emission high-resolution scanning electron microscope
- Comparative Example 3 was a commercially available platinum-supported catalyst (trade name ETC-10) purchased from ElectroChem, USA. This catalyst is a furnace black made of Vulcan XC-72 Cabot with a carbon substrate carrying 10% by weight of platinum.
- FIG. 9 shows the oxygen reduction voltammogram and Fig. 10 shows the cyclic voltammogram.
- the voltammogram of FIG. 9 was obtained by measuring the carbon substrate carrying platinum of Example 15 and Comparative Example 3 in the same manner as in Comparative Evaluation No. 2. From FIG. 9, the tendency is more pronounced as the oxygen reduction current density increases as a whole, especially as the potential decreases, compared to that in Comparative Example 3 where the carbon substrate carrying the white metal of Example 15 is a commercially available catalyst. There was something to do
- the cyclic voltammogram of Fig. 10 is obtained by applying the carbon substrate carrying platinum of Example 15 and Comparative Example 3 onto a glassy carbon electrode in the same manner as in Comparative Evaluation No. 2, and acting this.
- the electrode was obtained by measurement under the following conditions.
- the electrode was immersed in 1M sulfuric acid from which dissolved oxygen had been removed by publishing nitrogen in advance, and a potential scan of 0.2 to 1.3V vs AgZAgCl was performed at a sweep rate of 50mVZs without rotation.
- the current-potential relationship is plotted. From FIG. 10, it was found that the carbon base material carrying platinum of Example 15 did not show a clear H2 desorption wave than that of Comparative Example 3. That is, it was presumed that Example 15 had a different platinum loading state than that of Comparative Example 3, which caused a difference in the activity of the white metal.
- Example 1 of carbon alloy particles doped with nitrogen atoms and 10% by weight of platinum loaded Example 1 of carbon alloy particles doped with nitrogen atoms and boron atoms and loaded with 10% by weight of platinum
- Example 12 of platinum alloy particles with platinum loaded Force by 10% by weight supported sol-gel method Comparative Example 1 of carbon substrate supporting 10% by weight of platinum not doped with nitrogen atoms of Example 14 and Example 1 of ultra-one-bonn fine particles, and 10% of platinum A commercial force loaded on a weight percent, and the current density at a potential of 0.6 V vs. AgZAgCl were measured for Comparative Example 3 of one bon black. The results are shown in Table 2.
- Example 12 the current density per unit surface area of Example 1, Example 12 and Example 14 was higher than that of Comparative Examples 1 and 3.
- the current density of Example 12 doped with both nitrogen and boron atoms was about twice as high as that of Example 1 doped with only nitrogen atoms.
- platinum was supported on the ultrafine carbon particles by the sol-gel method of Example 14, a higher current density was obtained.
- the polymer electrolyte fuel cell electrode catalyst of the present invention has a highly active oxygen reduction catalytic ability and is used on the power sword side of a fuel cell.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004197481A JP2007311026A (ja) | 2004-07-05 | 2004-07-05 | 燃料電池用電極触媒及びその製造方法並びに該触媒を用いた燃料電池 |
JP2004-197481 | 2004-07-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006003831A1 true WO2006003831A1 (ja) | 2006-01-12 |
Family
ID=35782642
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/011512 WO2006003831A1 (ja) | 2004-07-05 | 2005-06-23 | 燃料電池用電極触媒及びその製造方法並びに該触媒を用いた燃料電池 |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP2007311026A (ja) |
WO (1) | WO2006003831A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008282725A (ja) * | 2007-05-11 | 2008-11-20 | Gunma Univ | 炭素系燃料電池用電極触媒の製造方法 |
EP2716362A4 (en) * | 2011-05-23 | 2014-11-19 | Teijin Ltd | PARTICULATE CARBON CATALYST AND METHOD OF MANUFACTURING THEREOF |
CN106000438A (zh) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | 一种氮磷共掺杂孔状碳材料的制备方法及其应用 |
WO2021132475A1 (ja) | 2019-12-27 | 2021-07-01 | Agc株式会社 | 触媒層、触媒層形成用液および膜電極接合体 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5320579B2 (ja) * | 2008-06-05 | 2013-10-23 | 清蔵 宮田 | ガス拡散電極及びその製造方法、膜電極接合体及びその製造方法、燃料電池部材及びその製造方法、燃料電池、蓄電装置及び電極材 |
JP4964292B2 (ja) | 2009-12-07 | 2012-06-27 | 日清紡ホールディングス株式会社 | 電極及び電池 |
JP5608595B2 (ja) | 2010-03-30 | 2014-10-15 | 富士フイルム株式会社 | 含窒素カーボンアロイ、その製造方法及びそれを用いた炭素触媒 |
CN103299464B (zh) | 2011-01-14 | 2016-02-24 | 昭和电工株式会社 | 燃料电池用电极催化剂的制造方法、燃料电池用电极催化剂和其用途 |
JP5638433B2 (ja) | 2011-03-24 | 2014-12-10 | 株式会社東芝 | 電解装置および冷蔵庫 |
JP5893305B2 (ja) * | 2011-09-09 | 2016-03-23 | 国立大学法人東京工業大学 | 固体高分子形燃料電池用電極触媒およびその製造方法 |
JP2014188496A (ja) * | 2013-03-28 | 2014-10-06 | Panasonic Corp | 触媒 |
WO2017154359A1 (ja) | 2016-03-11 | 2017-09-14 | 日産自動車株式会社 | 燃料電池用炭素粉末ならびに当該燃料電池用炭素粉末を用いる触媒、電極触媒層、膜電極接合体および燃料電池 |
JP6800608B2 (ja) * | 2016-05-17 | 2020-12-16 | 日清紡ホールディングス株式会社 | 電池電極、電池電極触媒層用組成物及び電池 |
ES2966033T3 (es) | 2019-11-04 | 2024-04-18 | Heraeus Precious Metals Gmbh | Catalizador de alta estabilidad para una celda electroquímica |
KR102549883B1 (ko) * | 2021-03-30 | 2023-07-03 | 부산대학교 산학협력단 | 금속-유기 골격체 기반의 촉매 및 이를 이용한 산소 검출용 전극 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60189168A (ja) * | 1984-03-06 | 1985-09-26 | Toshiba Corp | 燃料電池電極用多孔質板 |
JPH10223226A (ja) * | 1997-02-06 | 1998-08-21 | Kureha Chem Ind Co Ltd | 二次電池電極用炭素質材料 |
JP2004119398A (ja) * | 2001-01-16 | 2004-04-15 | Showa Denko Kk | 電池用触媒組成物、ガス拡散層及びこれらを備えた燃料電池 |
-
2004
- 2004-07-05 JP JP2004197481A patent/JP2007311026A/ja active Pending
-
2005
- 2005-06-23 WO PCT/JP2005/011512 patent/WO2006003831A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60189168A (ja) * | 1984-03-06 | 1985-09-26 | Toshiba Corp | 燃料電池電極用多孔質板 |
JPH10223226A (ja) * | 1997-02-06 | 1998-08-21 | Kureha Chem Ind Co Ltd | 二次電池電極用炭素質材料 |
JP2004119398A (ja) * | 2001-01-16 | 2004-04-15 | Showa Denko Kk | 電池用触媒組成物、ガス拡散層及びこれらを備えた燃料電池 |
Non-Patent Citations (1)
Title |
---|
ANAHARA T. ET AL: "Arinkai oyobi Chorinkai Alcohol o Mochiiru Carbon Alloy Biryushi no Gosei. (Synthesis of carbon alloy particles using sub/supercritical alcohols)", DAI 29 KAI THE CARBON SOCIETY OF JAPAN NENKAI YOSHISHU, 4 December 2002 (2002-12-04), pages 56 - 57, XP002998935 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008282725A (ja) * | 2007-05-11 | 2008-11-20 | Gunma Univ | 炭素系燃料電池用電極触媒の製造方法 |
EP2716362A4 (en) * | 2011-05-23 | 2014-11-19 | Teijin Ltd | PARTICULATE CARBON CATALYST AND METHOD OF MANUFACTURING THEREOF |
US9692060B2 (en) | 2011-05-23 | 2017-06-27 | Teijin Limited | Particulate carbon catalyst including nitrogen and metal and method for producing the same |
CN106000438A (zh) * | 2016-06-03 | 2016-10-12 | 兰州交通大学 | 一种氮磷共掺杂孔状碳材料的制备方法及其应用 |
WO2021132475A1 (ja) | 2019-12-27 | 2021-07-01 | Agc株式会社 | 触媒層、触媒層形成用液および膜電極接合体 |
Also Published As
Publication number | Publication date |
---|---|
JP2007311026A (ja) | 2007-11-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2006003831A1 (ja) | 燃料電池用電極触媒及びその製造方法並びに該触媒を用いた燃料電池 | |
Wang et al. | Bifunctional catalytic activity guided by rich crystal defects in Ti3C2 MXene quantum dot clusters for Li–O2 batteries | |
JP4452889B2 (ja) | 燃料電池用電極触媒及びその製造方法並びに該触媒を用いた燃料電池 | |
JP4452887B2 (ja) | 燃料電池用電極触媒の製造方法及びその方法で製造された電極触媒並びにその電極触媒を用いた燃料電池 | |
Vinayan et al. | Synthesis and investigation of mechanism of platinum–graphene electrocatalysts by novel co-reduction techniques for proton exchange membrane fuel cell applications | |
Kim et al. | Three-dimensional entangled and twisted structures of nitrogen doped poly-(1, 4-diethynylbenzene) chain combined with cobalt single atom as a highly efficient bifunctional electrocatalyst | |
JP5348658B2 (ja) | 燃料電池電極素材用白金系合金触媒の製造方法 | |
KR101679809B1 (ko) | 질소(N)가 도핑된 탄소에 담지된 백금(Pt)촉매의 제조방법 및 이의 이용하여 제조된 질소(N)가 도핑된 탄소에 담지된 백금(Pt)촉매 | |
Bao et al. | Formic acid electro-oxidation catalyzed by PdNi/graphene aerogel | |
CN1801514A (zh) | 用于燃料电池的Pt/Ru合金催化剂 | |
JP4041429B2 (ja) | 燃料電池用電極およびその製造方法 | |
WO2012114108A1 (en) | Oxygen reduction reaction catalyst | |
Liu et al. | Pt/graphene with intercalated carbon nanotube spacers introduced by electrostatic self-assembly for fuel cells | |
Wang et al. | Nanoscale graphite-supported Pt catalysts for oxygen reduction reactions in fuel cells | |
JP2014207220A (ja) | 炭素触媒及びその製造方法、及び該炭素触媒を用いた触媒インキ並びに燃料電池 | |
Shiva Kumar et al. | Palladium supported on phosphorus–nitrogen dual-doped carbon nanoparticles as cathode for hydrogen evolution in PEM water electrolyser | |
JP6757933B2 (ja) | 白金担持体とそれを用いた酸素還元触媒およびその製造方法ならびに燃料電池、金属空気電池 | |
WO2013035191A1 (ja) | 燃料電池用触媒層及びその用途 | |
Ozdemir | A novel method to produce few layers of graphene as support materials for platinum catalyst | |
CN111729680B (zh) | 一种具有异质结构的高效双功能氧电催化剂及其制备和应用 | |
Zhu et al. | Titanium dioxide encapsulated in nitrogen-doped carbon enhances the activity and durability of platinum catalyst for Methanol electro-oxidation reaction | |
JP6727263B2 (ja) | 燃料電池用アノード触媒層及びそれを用いた燃料電池 | |
Cao et al. | Pt/XC-72 catalysts coated with nitrogen-doped carbon (Pt/XC-72@ C–N) for methanol electro-oxidation | |
Zhao et al. | Poly (bis-2, 6-diaminopyridinesulfoxide) as an active and stable electrocatalyst for oxygen reduction reaction | |
Yang et al. | Synthesis of high-performance low-Pt (1 1 1)-loading catalysts for ORR by interaction between solution and nonthermal plasma |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: DE |
|
122 | Ep: pct application non-entry in european phase | ||
NENP | Non-entry into the national phase |
Ref country code: JP |