WO2003054989A2 - Matiere de support en carbone pour une electrode et procede de fabrication de ladite matiere - Google Patents

Matiere de support en carbone pour une electrode et procede de fabrication de ladite matiere Download PDF

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Publication number
WO2003054989A2
WO2003054989A2 PCT/EP2002/014237 EP0214237W WO03054989A2 WO 2003054989 A2 WO2003054989 A2 WO 2003054989A2 EP 0214237 W EP0214237 W EP 0214237W WO 03054989 A2 WO03054989 A2 WO 03054989A2
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WO
WIPO (PCT)
Prior art keywords
carbon
extraction
electrode
carried out
diffusion
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PCT/EP2002/014237
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German (de)
English (en)
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WO2003054989A3 (fr
Inventor
Franziska Holzer
Stefan Müller
Hans Jürgen PAULING
Hans-Ulrich Reichardt
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Zoxy Energy Systems Ag
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Application filed by Zoxy Energy Systems Ag filed Critical Zoxy Energy Systems Ag
Priority to DE10296107T priority Critical patent/DE10296107D2/de
Priority to AU2002352248A priority patent/AU2002352248A1/en
Publication of WO2003054989A2 publication Critical patent/WO2003054989A2/fr
Publication of WO2003054989A3 publication Critical patent/WO2003054989A3/fr

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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
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • 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
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H01M4/8885—Sintering or firing
    • H01M4/8889—Cosintering or cofiring of a catalytic active layer with another type of layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous 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
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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

  • Carbon support material for an electrode and process for its manufacture Carbon support material for an electrode and process for its manufacture
  • the invention relates to a method for producing a carbon support material for an electrode, in particular for a rechargeable metal-oxygen battery, and to a carbon support material for an electrode according to the preamble of claim 10.
  • Such systems play an increasingly important role because of the flexibility and mobility that can be achieved through off-grid power supply systems such as fuel cells, accumulators or batteries.
  • off-grid power supply systems such as fuel cells, accumulators or batteries.
  • the service life expressed, for example, in operating hours or as the number of charging and discharging cycles, and the weight based on the total energy content, are further quality features.
  • metal-air-oxygen batteries which are also referred to as metal-air batteries
  • the metallic active material ie the active component for the negative electrode
  • Oxygen as a reactant on the positive electrode is removed from the surrounding air when discharged and released there when charged.
  • This allows a higher charge and energy density to be achieved with this type of rechargeable battery than with other electrochemical energy stores, which is a decisive criterion for numerous areas of application.
  • specific energy densities in the order of 100 to 150 Wh / kg are achieved with rechargeable zinc-air batteries.
  • the storage density of zinc-air batteries is thus about twice as large as that of a nickel-cadmium battery or about four times higher than that of a lead-acid battery.
  • This type of battery is also characterized by inexpensive battery components and good environmental compatibility.
  • a major difficulty in the implementation of electrically rechargeable metal-oxygen batteries is the development of the porous oxygen diffusion electrodes, which, depending on the specific area of application, have to meet a variety of requirements.
  • Oxygen is developed on these electrodes when the battery is charged and consumed when discharging.
  • the catalyst support which is usually formed by a carbon support material, plays an important role here.
  • Activated carbon is in terms of price, electrical conductivity and B. E.T. -Surface is an excellent substrate for catalysts. Their inadequate chemical and electrochemical stability has so far limited their use in bifunctional oxygen diffusion electrodes. Efforts have been made to improve the life of phosphoric acid fuel cells by a thermal activated carbon
  • the carbon carrier In the case of air electrodes for the classic hydrogen-air fuel cells, such as, for example, polymer electrolyte fuel cells, the carbon carrier is intended to offer the largest possible surface area for the catalyst particles, the size of which is in the range of a few nanometers. In the case of alkaline systems, greater demands are placed on the stability, in particular the corrosion stability, of the carbon carrier. In this context, methods for stabilizing the coal, such as thermal treatment with steam or acid or alkali washing, are known.
  • a method for producing a carbon support material for an electrode in which a by annealing carbon black in an inert atmosphere at temperatures of about 2500 to 3000 C for a period of 1 to 5 hours
  • carbon black is graphitized to stabilize against corrosion reactions or graphite is used as the starting material, that the graphitized carbon black or graphite is post-treated thermally in an oxidizing atmosphere to burn off part of the material and / or that the graphitized carbon black or the graphite is subjected to an extraction with a suitable gaseous or liquid extracting agent.
  • a first consideration of the invention can be seen in the fact that the graphitized carbon blacks or the graphite are thermally aftertreated in an oxidizing atmosphere by burning off part of the material.
  • a further key idea of the invention is that the graphitized carbon black or the graphite is subjected to an extraction with a suitable gaseous or liquid extraction agent.
  • a suitable gaseous or liquid extraction agent removes a proportion of amorphous soot or generally of combustion or other products from previous process steps.
  • a first essential advantage of the invention is the fact that the wetting properties of the carbon support material and thus the electrical properties of an electrode produced with the carbon support material can be significantly improved with the help of the thermal aftertreatment. Furthermore, the extraction, which can also be referred to as a cleaning step, provides an active carbon support material with which, in the case of oxygen reduction, i. during the discharge process, particularly high current densities can be achieved with the lowest possible potential.
  • the carbon black can be graphitized to increase the corrosion stability, for example, thermally in an inert atmosphere.
  • Detailed investigations, which led to the present invention, have surprisingly shown that the graphitic structure of the carbon material is not only of crucial importance for the stability of the carbon material.
  • the extraction can be carried out in a separating funnel or by mixing, in particular with the aid of a magnetic stirrer, followed by filtering off or simply by refluxing. Particularly good results are achieved, however, if the extraction is carried out as a Soxhlet extraction with chloroform as the extraction agent.
  • dichloromethane ethanol, ethyl acetate, hexane, isopropanol, toluene and / or water can also be used as the extraction fluid or extraction agent.
  • a drying step is preferably carried out after the extraction. This can be done, for example, in a drying cabinet at about 40 to 120 ° C., the temperature being able to be varied depending on the boiling point of the extracting agent used.
  • the carbon particles are physically comminuted, in particular to a grain size smaller than 250 ⁇ m.
  • the amount of burn-off in the material can be adjusted in a simple manner by varying the process parameters during the thermal aftertreatment.
  • the reproducibility of the results in the extraction step is also improved by this measure, which has an advantageous effect particularly in the industrial production of the coal carrier material according to the invention.
  • the carbon carrier material according to the invention can be used particularly advantageously in a method for producing an oxygen electrode, in particular for a rechargeable metal-oxygen battery.
  • Such a process has the following process steps:
  • the first and the second starting material become a rollable one Prepared diffusion or active material and then these materials are rolled into a diffusion or active layer of the desired thickness. Then the diffusion and active layers are again connected to the intermediate product by rolling.
  • the active material is rolled into a plastic tube, e.g. a sterile tube is inserted and rolled into an active layer of the desired thickness.
  • the sterile tube can be welded depending on the electrode size.
  • the kneadable and rollable active material filled into the sterile tube is, for example, gradually rolled down on a flat base from 1.5 mm to 0.35 mm thick. This can be done in a manner known per se with the help of marble or steel rollers and spacer plates. If the rolling is carried out by machine, it is advantageous if the distance between the rolling cylinders can be gradually reduced.
  • the preparation of the first starting material into the mouldable diffusion material and / or the second starting material into the mouldable active material can be carried out by boiling in petroleum.
  • the starting materials can be heated in petroleum with slow stirring, and when a temperature of about 150 ° C. is reached, an elastic, formable and rollable carbon-PTFE mass is formed after a few minutes.
  • the petroleum is then poured off and any remaining petroleum is pressed out of the active or the diffusion material removed.
  • up to 1.5 to 4 times the dry weight mass is pressed out for the active material and up to 2 to 6 times for the diffusion material.
  • a temperature profile is set during the sintering in such a way that liquid portions remaining in the intermediate product, in particular petroleum, are evaporated before the sintering temperature is reached.
  • connection of the current collector to the diffusion layer of the intermediate product can be carried out in a particularly simple manner in that the current collector is placed on the diffusion layer of the intermediate product, that at least one layer of an absorbent material is applied to the current collector and to the active layer of the intermediate product, and that Intermediate product is pressed with the current collector and the layers of absorbent material.
  • the layers of the absorbent material which can be, for example, a suitable absorbent, optionally multi-layer paper, in particular normal copy or household paper, recycled paper and / or fine tissue paper, removed beforehand become.
  • spinels, metal oxides, in particular transition metal oxides, silver and / or transition metal complexes, in particular with nitrogen-containing macrocycles can be used as catalyst materials.
  • perovskites in particular La Ca CoO.
  • Silver and transition x 1-x 3 transition metal complexes essentially make the cathodic
  • Perovskites of the general formula ABO are characterized by good mobility of the oxide ions, which makes them interesting catalysts for electrode materials. Furthermore, by partially substituting the A or B cation with a cation A 'or B ? electronic and ionic defects are induced in the perovskite with a different value. In this way, it is possible to influence the catalytic activity of the perovskite essentially caused by the transition metal component B.
  • “Furnace black” carbon blacks are preferably used as the carbon black component, but in principle other carbon blacks, for example acetylene black, can also be used.
  • oxygen electrode with the carbon carrier material according to the invention can be found wherever oxygen or air cathodes play a role, for example in fuel cells and in principle also with so-called super capacitors.
  • the oxygen electrode described above can be used particularly advantageously in the case of rechargeable metal-oxygen batteries, for example metal-air batteries and in particular in zinc-air batteries.
  • At least one separator is preferably provided to prevent dendrite formation during charging and thus to prevent internal short circuits.
  • Fig. 1 current / voltage curves of two different bifunctional oxygen electrodes
  • Fig. 3 is a diagram with life measurements on various bifunctional oxygen electrodes.
  • Material A is an industrially available graphite material with a surface area of approximately 100 m / g. This material was used without further treatment and serves as a reference.
  • Material B is a carbon carrier material produced from material A in the extraction step according to the invention.
  • the starting substance for the materials C, D and E was an industrially available carbon black material, which in the case of the material C was only subjected to a graphitization step in accordance with the preamble of claim 1. Material C thus also serves as a reference.
  • Material D emerged from material C after carrying out the extraction step according to the invention.
  • Material E was produced by graphitizing the starting carbon black material with the aid of a graphitization process that is different from that of materials C and D and by subsequent thermal activation in accordance with the first characterizing feature of claim 1. Extraction was not carried out for material E.
  • the carbon material was crushed after the graphitization and sieved through a 250 ⁇ m sieve.
  • the thermal activation was carried out in an oven at about 600 C with purging with compressed air. This thermal activation was preferably carried out in such a way that a burn-off of about 10 to 12% of the material was obtained.
  • the activation time is then on the order of approximately 200 minutes.
  • the thermal activation increases the BET surface area from 70 to 100 m / g.
  • the carbon black starting material for the material E is graphitized in an inert atmosphere at about 2700 C for one hour, the crystallinity of the increases
  • the activation of the surface properties (e.g. the wetting behavior) of the graphitized carbon black is significantly worse than that of the untreated material. Since the carbon carrier material in the oxygen electrode is essentially responsible for the oxygen reduction, the absolute size of the wettable surface of the carbon carrier material has a direct effect on the absolute activity of the oxygen electrode. Due to the thermal o activation at 600 C in air, the surface of the
  • Coal carrier material increased to about 100 m / g and the activity of the coal carrier material can thus be significantly improved.
  • the crystallinity of the graphitized material for materials C and D is significantly greater than for material E and overall comparable to the situation for materials A and B.
  • the XRD measurements also showed that the graphitic Crystal growth begins at temperatures from 1000 C and that there is a significant increase in crystallites from 2700 C.
  • the BE T. Surface of the graphitized carbon black starting material for materials C and D was approximately 40 m / g.
  • the only graphitized carbon black starting material ie a material in which neither a thermal aftertreatment nor an extraction was carried out, Despite the small BET surface area and the high crystallinity, the oxygen electrode was less stable.
  • the commercially available graphite material A has a very large B.E. at around 100 m / g. T. surface on. This material is very well wettable and can be used without further pretreatment
  • La Ca CoO can be used. 0.6 0.4 3
  • Oxygen electrodes which were produced by the method according to the invention starting from material A, show current densities of up to in terms of oxygen reduction
  • FIG. 1 and 2 each show current / voltage curves of bifunctional oxygen electrodes which were produced using materials A to E as a carbon carrier material.
  • a 45% KOH lye was used as the electrolyte.
  • the reduction was measured with oxygen and a mercury / mercury oxide electrode was used as the reference electrode.
  • the oxygen reduction potentials are in both cases with the extracted material, ie better with material B and material D.
  • the effect of the method according to the invention can be seen particularly clearly in FIG. 1 when comparing material A and B in the oxygen reduction, ie in the lower left part of the diagram.
  • material B an approximately twice as large current density with the same potential with respect to the reference electrode as for material A. This applies to high
  • material E in the oxygen evolution reaction i.e. during the charging process, which is shown in FIG. 2 in the upper right area, shows the best voltage values.
  • the electrochemical reaction takes place on the catalyst.
  • the electrons must come from the catalyst grain, i.e. from the semiconductor to which coal is transferred to reach the current collector.
  • the electrical resistance between the catalyst and carbon grain can have a decisive influence on the ohmic part of the total overvoltage.
  • oxygen reduction i.e. when unloading, the reaction takes place primarily on the coal itself, so that contact resistance should be less relevant.
  • the cleaning process which in the present case was carried out as a Soxhlet extraction with chloroform, can provide an active carbon carrier with a very high current load for the oxygen reduction.
  • Lifetime measurements were also carried out with the oxygen electrodes, which were produced using the materials C to E. Results of these measurements are shown in FIG. 3.
  • the bifunctional oxygen electrodes were operated at +/- 6 mA / cm each during a cycle. Each cycle lasted 6.4 hours in the following sequence: 3 hours reduction, 12 minutes break, 3 hours oxidizing and 12 minutes break.
  • the lifetime measurement was carried out in 15% KOH lye as an electrolyte with a 1.5 molar KF solution and a saturated ZnO solution. This electrolyte is preferably used in the zinc-air battery, since the structural changes on the zinc electrode can be kept to a minimum.
  • the active material contains only half of the weight of PTFE.
  • This low PTFE content changes the consistency of the PTFE-carbon mixture in such a way that filtering off the PTFE-catalyst-carbon mixture is extremely time-consuming and is often impossible due to filter closures.
  • the following procedure has overcome this problem:
  • the active material and the diffusion material must be boiled separately in high-boiling petroleum. 20 ml of "special" petroleum are used per 1 g of diffusion or active material.
  • Mass of the dry weight (applies to acetylene black).
  • the Aktvi material is easy to knead and process. Smaller areas can be created between suitable, non-sticky paper.
  • a plastic tube for example a sterile tube, is used, which is welded depending on the electrode size.
  • the sterile tube with contents is rolled down in stages on a flat surface from 1.5 mm to 0.35 mm. The gradual rolling down takes place according to the following rolling mode:
  • the spacer plates With a starting distance of 1.5 mm, the spacer plates are parallel to the sterile hose. The contents of the sterile tube are slowly rolled with a marble or steel roller. Subsequently, a change is made to thinner spacer plates, with steps of between 1.4 mm and 0.4 mm in 0.1 mm steps and between 0.4 mm and 0.35 mm in 0.05 mm steps.
  • the final thickness of 0.35 mm proved to be optimal for the materials C, D and E.
  • the rolled material can be stored in the foil for a long time.
  • the diffusion material is very tough and kneading makes it even tougher and therefore difficult to machine. For this reason, the elastic material is carefully brought into a flat, film-like shape by hand and then rolled down to the desired final thickness of 0.8 to 0.9 mm with a heatable roller (60 C).
  • a PTFE film is used as a base for the dough and baking paper as a cover.
  • 1.5 mm is carried out in 0.1 mm steps and between 1.5 mm and 0.9 mm (final thickness) in 0.05 mm steps.
  • the diffusion layer is placed on a flat surface, on which a 1 mm thick cardboard and baking paper are already arranged.
  • the sterile film of the active layer is then cut open in the middle of one side.
  • the film is opened and the active layer is placed on the diffusion layer.
  • the film still lying on the surface of the active layer is removed.
  • the active layer (0.35 mm thick) and the diffusion layer (0.85 mm thick) are rolled together using the following procedure:
  • a sheet of recycled paper is placed on the active layer. With 1.2 mm spacers, the electrode is rolled, turned 90 and rolled again.
  • fine tissue paper, a sheet of recycled paper and a flat steel plate are placed on the active layer in the following order. Then the stack with the cardboard on the back removed from the steel plate and turned over so that the cardboard now lies on the top. Cardboard and baking release paper are removed and the current collector (expanded Ni) is attached to the exposed diffusion layer. The Ni expanded metal previously cleaned with acetone is only placed on the diffusion layer. Then four layers of household paper and a flat steel plate are placed in the following order.
  • Diffusion layer penetrates and adheres, is a pressure of 20
  • the household paper absorbs the petroleum removed from the electrode during pressing.
  • the pressing time is 10 minutes.
  • the stack is removed from the press and the sheets soaked in petroleum are removed.
  • the electrode is now ready for sintering.
  • Two sheets of Al foil are placed on top of one another on an Al plate.
  • the electrode is then placed with the pantograph down.
  • Two sheets of Al foil and finally the second Al plate are placed on the electrode.
  • the stack is lightly compressed in the press.
  • the press is then opened a small gap, which prevents the press from jamming during heating.
  • the temperature controller is set to 340 C for heating.
  • the temperature is tracked with the help of thermal sensors placed sideways in the AI plates.
  • the remaining petroleum ether evaporates, which is suctioned off through the fume cupboard.
  • 250 C the temperature is maintained until no petroleum vapors are visible.
  • continue to heat until o when 300 C is reached (with thermocouple on the aluminum
  • the sintering pressure of 40 kg / cm is set. After 20 minutes, the heating is switched off and the press is depressurized. The hot stack is removed from the press by means of a lifting device and the electrode can be removed from the stack using spatulas and tongs.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Procédé de fabrication d'une matière de support en carbone pour une électrode, en particulier pour une batterie rechargeable zinc-oxygène, selon lequel la suie est graphitisée en vue de sa stabilisation. Cette suie graphitisée est soumise à un double post-traitement. Une matière de support en carbone de ce type permet d'obtenir des propriétés électrochimiques considérablement améliorées.
PCT/EP2002/014237 2001-12-21 2002-12-13 Matiere de support en carbone pour une electrode et procede de fabrication de ladite matiere WO2003054989A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE10296107T DE10296107D2 (de) 2001-12-21 2002-12-13 Kohleträgermaterial für eine Elektrode und Verfahren zu dessen Herstellung
AU2002352248A AU2002352248A1 (en) 2001-12-21 2002-12-13 Carbon support material for an electrode and method for producing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10163388.2 2001-12-21
DE10163388A DE10163388B4 (de) 2001-12-21 2001-12-21 Verfahren zur Herstellung einer Sauerstoff-Elektrode und Verwendung einer nach dem Verfahren hergestellten Sauerstoff-Elektrode

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WO2003054989A2 true WO2003054989A2 (fr) 2003-07-03
WO2003054989A3 WO2003054989A3 (fr) 2004-06-03

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DE (2) DE10163388B4 (fr)
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ATE329511T1 (de) 2002-01-25 2006-07-15 Krinner Innovation Gmbh Ständer zum aufspannen von stabförmigen teilen
JP5276203B2 (ja) 2011-09-07 2013-08-28 本田技研工業株式会社 金属酸素電池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1547162A (en) * 1975-07-22 1979-06-06 Shell Int Research Supported catalysts for fuel cells
US5648307A (en) * 1994-12-05 1997-07-15 Agency Of Industrial Science And Technology, Ministry Of International Trade And Industry Method for production of gas diffusion electrode
DE19722487A1 (de) * 1996-05-29 1997-12-18 Ucar Carbon Tech Chemisch modifizierter Graphit für elektrochemische Elemente
EP0955684A1 (fr) * 1998-04-21 1999-11-10 Sony Corporation Poudre de graphite utilisable comme materiau d'électrode d'une batterie secondaire au lithium
WO2000003445A2 (fr) * 1998-07-09 2000-01-20 Ucar Carbon Technology Corporation Electrode faite d'un composite souple a base de graphite

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1547162A (en) * 1975-07-22 1979-06-06 Shell Int Research Supported catalysts for fuel cells
US5648307A (en) * 1994-12-05 1997-07-15 Agency Of Industrial Science And Technology, Ministry Of International Trade And Industry Method for production of gas diffusion electrode
DE19722487A1 (de) * 1996-05-29 1997-12-18 Ucar Carbon Tech Chemisch modifizierter Graphit für elektrochemische Elemente
EP0955684A1 (fr) * 1998-04-21 1999-11-10 Sony Corporation Poudre de graphite utilisable comme materiau d'électrode d'une batterie secondaire au lithium
WO2000003445A2 (fr) * 1998-07-09 2000-01-20 Ucar Carbon Technology Corporation Electrode faite d'un composite souple a base de graphite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHU X ET AL: "Surface modification of carbons for enhanced electrochemical activity" MATERIALS SCIENCE AND ENGINEERING B, ELSEVIER SEQUOIA, LAUSANNE, CH, Bd. 49, Nr. 1, 5. September 1997 (1997-09-05), Seiten 53-60, XP004113742 ISSN: 0921-5107 *

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Publication number Publication date
DE10163388B4 (de) 2009-09-17
DE10296107D2 (de) 2006-10-26
DE10163388A1 (de) 2003-07-10
AU2002352248A8 (en) 2003-07-09
AU2002352248A1 (en) 2003-07-09
ZA200204011B (en) 2002-07-23
WO2003054989A3 (fr) 2004-06-03

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