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WO1998018171A1 - Cathode inerte pour la reduction selective d'oxygene et procede permettant de la produire - Google Patents

Cathode inerte pour la reduction selective d'oxygene et procede permettant de la produire Download PDF

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Publication number
WO1998018171A1
WO1998018171A1 PCT/DE1997/002453 DE9702453W WO9818171A1 WO 1998018171 A1 WO1998018171 A1 WO 1998018171A1 DE 9702453 W DE9702453 W DE 9702453W WO 9818171 A1 WO9818171 A1 WO 9818171A1
Authority
WO
WIPO (PCT)
Prior art keywords
clusters
cathode
solvent
chalcogen
stabilizer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/DE1997/002453
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German (de)
English (en)
Inventor
Nicolas Alonso-Vante
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hahn Meitner Institut Berlin GmbH
Original Assignee
Hahn Meitner Institut Berlin GmbH
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 Hahn Meitner Institut Berlin GmbH filed Critical Hahn Meitner Institut Berlin GmbH
Priority to AU52216/98A priority Critical patent/AU5221698A/en
Priority to JP51883598A priority patent/JP4235986B2/ja
Priority to CA002269051A priority patent/CA2269051A1/fr
Priority to EP97947016A priority patent/EP0947016A1/fr
Publication of WO1998018171A1 publication Critical patent/WO1998018171A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • 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 invention relates to an inert cathode for the selective reduction of oxygen in an acidic medium by multi-electron transfer for electrochemical energy conversion in a methanol fuel cell with a thin surface coating of a selectively active catalyst material, based on semiconducting clusters of at least one transition metal and a chalcogen, and a method for their manufacture.
  • Fuel cells are electrochemical cells that continuously convert the chemical energy change of a fuel oxidation reaction into electrical energy.
  • the multi-electron transfer forms the physical basis for the energy conversion.
  • fuel molecules are oxidized with the release of electrons.
  • the ions formed on the anode and the cathode migrate to the electrodes in a closed circuit in the electrolyte and combine there to form water and carbon dioxide.
  • the use of an electrolytic acid provides natural protection against contaminating carbonate formation.
  • DE 38 02 236 A1 shows how a powder or a thin layer or film is produced from a mixture of substances to be reacted (metal carbonyl, chalcogen-containing compound and inert organic solvent) and for an inert electrode with catalytic activity in fuel cells can be used.
  • This metal chalcogenide is also polycrystalline and leads to a coarsely dispersed system in the solvent. It has coagulated clusters with a diameter in the ⁇ m range, which due to their size do not lead to a homogeneous distribution -
  • the method of spray pyrolytic deposition disclosed here which, however, uses a lot of material, it can lead to a surface coating on the electrode and can cause a locally different catalytic and selective effectiveness.
  • the layer thickness of the coating is limited downwards by the cluster size.
  • the thin surface coating has a degree of coverage from individual clusters in a colloidally disperse homogeneous distribution, which is generated by a small amount of material in the ng range per cm 2 of effective cathode area.
  • colloidal dispersion according to the invention ie. very finely divided arrangement of the individual clusters with a particle diameter in the nm range (for example 3 to 4 nm) in a homogeneous appearance effectively protects the cathode against catalyst poisoning and thus against a decrease in activity. Elaborate membranes are not required.
  • the cathode according to the invention with its thin surface coating, which only requires a layer thickness of, for example, 6 to 7 nm, has an advantage over a much thicker coating with a powder or a thin layer.
  • the extensive distribution of the individual clusters which leads to the low degree of coverage of the cathode surface, means that the material used is correspondingly low and in the ng range (for example 3.1 ng).
  • the catalyst material is very temperature stable, so that heat treatments can be carried out.
  • the basis of the catalyst material with a colloidally disperse cluster distribution is formed by semiconducting transition metals, in particular molybdenum (Mo), tungsten (W), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh) and iridium (Ir), as well as the chalcogens Sulfur (S), selenium (Se), especially red selenium, and tellurium (Te).
  • Mo molybdenum
  • W tungsten
  • Ru ruthenium
  • Os osmium
  • Co cobalt
  • Rh rhodium
  • Ir iridium
  • Binary clusters and ternary mixed clusters can be generated from these elements with the participation of oxygen (0).
  • the transition metal is ruthenium (Ru) and the chalcogen is sulfur (S) or selenium (Se) and the clusters have a molar ratio (x) of ruthenium (Ru) to the chalcogen (S, Se) in the range between 0.5 and 2.
  • Such clusters have a special resistance to electrolyte acids and, due to the 8-ring structure in the case of sulfur and red selenium, produce properties which are particularly favorable for the synthesis.
  • clusters with ruthenium (Ru) as transition metal and selenium (Se) as chalcogen are in the stoichiometric form (Ru) n Se, where (n) is between 1, 5 and 2, in particular at 1, 7 lies.
  • Clusters with this stoichiometric structure as a catalyst material meet the demands for high catalytic and selective activity to a particularly excellent degree.
  • the cathode according to the invention is effectively protected against chemical attacks by the thin surface coating made of the catalytically and selectively highly reactive material, so that no expensive cathode structures with platinum or similar noble metals or compounds are required. Therefore, according to a continuation of the invention, it is possible that the cathode has a porous and electrically conductive support. The porosity results in a high specific Cathode surface for the reactions.
  • the carriers can be inexpensive substrates, in particular made of carbon black or norit-type carbon, which are particularly suitable for use in a gas diffusion electrode in fuel cells. Gas diffusion electrodes are constructed in three phases with a hydrophobic and a hydrophilic layer and an intermediate reactive solid layer. The use of conventional substrates, such as, for example, glazed carbon or indium tin oxide (ITO) substrates, is also possible.
  • a direct methanol fuel cell works at atmospheric or overpressure and working temperatures between 80 ° C and 100 ° C.
  • the high-energy methanol is cracked for hydrogen production without redirection via a reformer. Therefore, in a further embodiment of the invention, it is advantageous if the methanol fuel cell is designed as a direct fuel cell.
  • the process for producing the above-described inert cathode for selective oxygen reduction is characterized according to the invention in that, in order to produce thin surface coatings in the nm range, the porous support of the cathode is immersed in the catalyst material in the form of a colloid solution, then dried at room temperature and then at a temperature between 200 ° C and 300 ° C, in particular at 208 ° C, is annealed.
  • a process can be carried out without great expenditure in terms of equipment and costs and is achieved with a one-off Run best results.
  • the cathode surface is evenly coated with a liquid surface.
  • the solid constituents of the colloid are fixed on the carrier in a colloidally disperse, homogeneous distribution. Foreign substances that are still present can then simply be evaporated by the tempering process without damaging the catalyst material.
  • the colloid solution is advantageously designed such that the clusters float in an organic solvent with the appropriate addition of a long-chain stabilizer in a colloidally disperse homogeneous distribution, the boiling point (Tss) of the stabilizer being above the boiling point (T SL ) of the solvent .
  • Tss boiling point
  • T SL boiling point
  • the required cluster material can be made available in a tailored manner.
  • the solvent is the carrier.
  • the long-chain stabilizer prevents the clusters from sticking together to form a powder.
  • the amount to be used depends on the cluster occurrence in the solvent and can be determined via the molar ratio of the individual components.
  • the reaction takes place at the boiling point (T S L) of the solvent almost independent of the components used.
  • the position of the boiling point (Tss) of the stabilizer above the boiling point (T S L) of the solvent ensures that the solvent can be removed without affecting the stabilizer and thus the fine distribution of the clusters.
  • the stabilizer is only removed in the annealing process, so that only the colloidally dispersed, homogeneously distributed clusters are then on the cathode surface and form the solid coating.
  • the preparation of the colloidal solution can be carried out of the solvent by a wet-chemical-organic synthesis in continuation of the invention is particularly simple and inexpensive in the region of the boiling temperature (T S).
  • T S boiling temperature
  • This manufacturing process takes place in analogy to the manufacturing process of known catalyst materials in powder or thin film form. It is based on the combination of one or more metal carbonyls with a chalcogen in the solvent. In the invention there is also the stabilizer.
  • metal carbonyls M also as a combination of several metal carbonyls
  • 8-ring chalcogens e.g. red selenium and sulfur, due to their purity particularly good properties for synthesis.
  • Suitable organic solvents are:
  • long chain stabilizers are also extensive. The following are particularly suitable:
  • the solvent is xylene with a boiling temperature (T S ⁇ _) of 140 ° C and the stabilizer is 1-octadecanethiol with a boiling temperature (T S s) of 185 ° C.
  • T S ⁇ _ boiling temperature
  • T S s boiling temperature
  • the clusters with ruthenium (Ru) as transition metal and selenium (Se) as chalcogen are in the stoichiometric form (Ru) n Se, where (n) between 1, 5 and 2, in particular in 1, 7, and a tempering temperature of 208 ° C all components are given in order to obtain an optimal cathode with excellent catalytic and selective properties. Only about 3.1 ng of catalyst material per cm 2 of active electrode area are required due to its colloidal dispersion, which is extremely inexpensive.
  • the solvent xylene (100 ml) is purged with argon for 10 minutes to remove oxygen that would react with the components. Then powdered selenium (18 mg; 22.8 ⁇ M) is dissolved in the xylene by heating to 140 ° C. and the solution is then cooled again to room temperature.
  • the semiconducting transition metal carbonyl triruthenium dodeca-carbonyl (Ru 3 (CO) ⁇ 2 ; 72.9 mg; 11.4 ⁇ M) and the stabilizer 1-octadecanethiol (220 mg; 76.9 ⁇ M) are added.
  • the amount of stabilizer is approximately three times the amount of carbonyl at a molar ratio of 6.75.
  • the cluster formation then takes place after heating to the xylene boiling point (T S L) of 140 ⁇ C over a period of approximately 20 h. During the reaction, the colloid is constantly stirred and cooled by reflux.
  • the addition of a substrate for depositing a powder or a thin layer during cluster formation is not necessary in the production of the colloid.
  • the yield is 100%, ie all material brought in is also converted. There are no losses, for example due to deposits on the inside of the piston, as are known in the case of powder formation.
  • the clusters formed have a size of 3 nm to 4 nm.
  • the figure shows the negative profile of the electrochemical oxygen reduction currents depending on the electrode potential (NHE - normal hydrogen electrode, reference electrode) for several identical, tempered glass electrodes made of glazed carbon, each with a thin layer of 5 ⁇ l of colloidal solution of the catalytically active material Ru ⁇ ⁇ 7 They are covered, shown in 0.5 M sulfuric acid.
  • the vertical lines along the curve represent the small error bars for the multiple measurements. The course remains unchanged after the addition of 1 M methanol, which indicates the high selectivity of the inert cathode according to the invention.
  • the activation range lies in the lower straight line range of the curve and is better than that of platinum when using methanol, which proves the good catalytic property of the cathode according to the invention with its homogeneous surface coating, which was derived from a colloidally disperse colloid.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)
  • Catalysts (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

Des cathodes inertes permettant la réduction d'oxygène, recouvertes d'une fine couche superficielle à action catalytique, conviennent à des piles à combustible. En présence de méthanol comme combustible, ce revêtement doit en outre présenter des propriétés sélectives que l'utilisation de matériaux en amas semi-conducteurs issus de chalcogénure de métal de transition, toutefois sous forme de poudre ou de fine couche, ne suffit pas à obtenir. La cathode inerte mise au point selon l'invention permet de parvenir aux propriétés catalytiques et sélectives voulues. Son revêtement superficiel mince comprend des amas du type susmentionné, répartis de manière homogène, comme une dispersion colloïdale, et sa production n'implique qu'une quantité minimale de matériau de l'ordre du nanogramme, pour un degré de couverture particulièrement faible avec un coefficient d'efficacité hautement sélectif et catalytique. Le revêtement s'obtient par immersion dans un colloïde qui contient le mélange en amas conjointement avec un stabilisant dans un solvant. Après application du colloïde, le solvant et le stabilisant sont éliminés par traitements thermiques.
PCT/DE1997/002453 1996-10-17 1997-10-16 Cathode inerte pour la reduction selective d'oxygene et procede permettant de la produire Ceased WO1998018171A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU52216/98A AU5221698A (en) 1996-10-17 1997-10-16 Inert cathode for selective reduction of oxygen and a method for the production thereof
JP51883598A JP4235986B2 (ja) 1996-10-17 1997-10-16 選択的酸素還元用の不活性陰極及びその製法
CA002269051A CA2269051A1 (fr) 1996-10-17 1997-10-16 Cathode inerte pour la reduction selective d'oxygene et procede permettant de la produire
EP97947016A EP0947016A1 (fr) 1996-10-17 1997-10-16 Cathode inerte pour la reduction selective d'oxygene et procede permettant de la produire

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19644628A DE19644628C2 (de) 1996-10-17 1996-10-17 Verfahren zur Herstellung einer inerten Kathode für die selektive Sauerstoffreduktion und Anwendung der hergestellten Kathode
DE19644628.7 1996-10-17

Publications (1)

Publication Number Publication Date
WO1998018171A1 true WO1998018171A1 (fr) 1998-04-30

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PCT/DE1997/002453 Ceased WO1998018171A1 (fr) 1996-10-17 1997-10-16 Cathode inerte pour la reduction selective d'oxygene et procede permettant de la produire

Country Status (6)

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EP (1) EP0947016A1 (fr)
JP (1) JP4235986B2 (fr)
AU (1) AU5221698A (fr)
CA (1) CA2269051A1 (fr)
DE (1) DE19644628C2 (fr)
WO (1) WO1998018171A1 (fr)

Cited By (3)

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US8383287B2 (en) 2007-07-12 2013-02-26 Toyota Jidosha Kabushiki Kaisha Fuel cell electrode catalyst and polymer electrolyte fuel cell using the same
US9193604B2 (en) 2007-09-14 2015-11-24 Toyota Jidosha Kabushiki Kaisha Fine particle composite, method for producing the same, catalyst used for solid polymer fuel cell, and solid polymer fuel cell
US10050283B2 (en) 2012-06-22 2018-08-14 Centre National De La Recherche Scientifique (C.N.R.S) Process for preparing nanoparticles of a catalyst for cathodic reduction of dioxygen in the presence of methanol

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DE19914681C2 (de) * 1999-03-31 2002-07-18 Joerg Mueller Polymer-Elektrolyt-Membran Brennstoffzellensystem in Mikrosystemtechnik
DE19914680C2 (de) * 1999-03-31 2003-02-20 Joerg Mueller Polymer-Elektrolyt-Membran mit integrierter Katalysatormetall-dotierter poröser Graphit-Kontaktschicht
DE19914661C2 (de) * 1999-03-31 2002-11-14 Joerg Mueller Verfahren zur Herstellung einer intergriert verschalteten Polymer-Elektrolyt-Membran-Brennstoffzelle
DE10052189B4 (de) * 2000-10-21 2007-09-06 Daimlerchrysler Ag Mehrschichtige Gasdiffusionselektrode einer Polymerelektrolytmembran-Brennstoffzelle, Membranelektrodenanordnung, Verfahren zur Herstellung einer Gasdiffusionselektrode und einer Membranelektrodenanordnung sowie Verwendung der Membranelektrodenanordnung
US7879753B2 (en) * 2003-05-27 2011-02-01 Industrie De Nora S.P.A. Catalyst for oxygen reduction
JP2005317288A (ja) * 2004-04-27 2005-11-10 Japan Science & Technology Agency 白金フリー硫化物系燃料電池触媒とその製造方法
KR100684767B1 (ko) * 2005-07-29 2007-02-20 삼성에스디아이 주식회사 연료 전지 캐소드용 촉매, 이를 포함하는 막-전극 어셈블리및 연료 전지 시스템
EP1772916A3 (fr) * 2005-08-31 2009-01-28 Samsung SDI Co., Ltd. Catalyseur catodique pour pile à combustble et ensemble membrane-électrode
KR101223630B1 (ko) 2005-11-11 2013-01-17 삼성에스디아이 주식회사 연료 전지의 캐소드 전극용 촉매, 이의 제조 방법, 이를포함하는 연료 전지용 막-전극 어셈블리 및 이를 포함하는연료 전지 시스템
US9012107B2 (en) 2005-11-11 2015-04-21 Samsung Sdi Co., Ltd. Cathode catalyst for fuel cell, method of preparing same, and membrane-electrode assembly comprising same
KR100684853B1 (ko) * 2005-11-30 2007-02-20 삼성에스디아이 주식회사 연료 전지용 캐소드 촉매, 이를 포함하는 연료 전지용막-전극 어셈블리 및 연료 전지 시스템
KR100766977B1 (ko) * 2006-03-31 2007-10-12 삼성에스디아이 주식회사 연료 전지용 캐소드 촉매, 및 이를 포함하는 연료전지용연료 전지용 막-전극 어셈블리 및 연료 전지 시스템
EP1811595B1 (fr) 2006-01-18 2010-07-28 Samsung SDI Co., Ltd. Catalyseur à cathode, assemblage membrane-électrode et système de pile à combustible
KR100766976B1 (ko) 2006-04-28 2007-10-12 삼성에스디아이 주식회사 연료 전지용 캐소드 촉매, 이의 제조방법, 이를 포함하는연료 전지용 막-전극 어셈블리 및 연료전지 시스템
KR100728182B1 (ko) 2006-05-12 2007-06-13 삼성에스디아이 주식회사 연료 전지용 캐소드 촉매, 이를 포함하는 연료 전지용막-전극 어셈블리, 및 이를 포함하는 연료 전지 시스템
KR100728188B1 (ko) * 2006-05-16 2007-06-13 삼성에스디아이 주식회사 연료 전지용 캐소드 촉매, 이를 포함하는 연료 전지용막-전극 어셈블리 및 연료 전지 시스템
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JP5056236B2 (ja) * 2007-07-24 2012-10-24 トヨタ自動車株式会社 燃料電池用電極触媒、酸素還元型触媒の性能評価方法、及びそれを用いた固体高分子型燃料電池
JP5056257B2 (ja) * 2007-08-09 2012-10-24 トヨタ自動車株式会社 燃料電池用電極触媒、酸素還元型触媒の性能評価方法、及びそれを用いた固体高分子型燃料電池
JP5056258B2 (ja) * 2007-08-09 2012-10-24 トヨタ自動車株式会社 燃料電池用電極触媒、酸素還元型触媒の性能評価方法、及びそれを用いた固体高分子型燃料電池
JP5056256B2 (ja) * 2007-08-09 2012-10-24 トヨタ自動車株式会社 燃料電池用電極触媒、酸素還元型触媒の性能評価方法、及びそれを用いた固体高分子型燃料電池
JP5678499B2 (ja) * 2010-07-15 2015-03-04 トヨタ自動車株式会社 リチウム空気電池

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DE3802236A1 (de) * 1988-01-22 1989-08-03 Hahn Meitner Kernforsch Mischung von stoffen zur erzeugung eines metallchalkogenids und verwendung einer solchen mischung
WO1990005798A1 (fr) * 1988-11-17 1990-05-31 Physical Sciences Inc. Electrocatalyseur, ses procedes de preparation, electrodes preparees selon lesdits procedes et leurs modes d'utilisation
EP0621234A1 (fr) * 1993-04-20 1994-10-26 Institute of Gas Technology Procédé de préparation de poudres céramiques submicroniques de l'ordre du nanomètre à partir de précurseurs incorporés dans une mousse polymérique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8383287B2 (en) 2007-07-12 2013-02-26 Toyota Jidosha Kabushiki Kaisha Fuel cell electrode catalyst and polymer electrolyte fuel cell using the same
US9193604B2 (en) 2007-09-14 2015-11-24 Toyota Jidosha Kabushiki Kaisha Fine particle composite, method for producing the same, catalyst used for solid polymer fuel cell, and solid polymer fuel cell
US10050283B2 (en) 2012-06-22 2018-08-14 Centre National De La Recherche Scientifique (C.N.R.S) Process for preparing nanoparticles of a catalyst for cathodic reduction of dioxygen in the presence of methanol

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AU5221698A (en) 1998-05-15
JP4235986B2 (ja) 2009-03-11
DE19644628A1 (de) 1998-04-23
CA2269051A1 (fr) 1998-04-30
EP0947016A1 (fr) 1999-10-06
JP2001502467A (ja) 2001-02-20
DE19644628C2 (de) 2001-05-23

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