WO2012102715A1 - Ensemble électrode à membrane pour piles à combustible - Google Patents

Ensemble électrode à membrane pour piles à combustible Download PDF

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Publication number
WO2012102715A1
WO2012102715A1 PCT/US2011/022550 US2011022550W WO2012102715A1 WO 2012102715 A1 WO2012102715 A1 WO 2012102715A1 US 2011022550 W US2011022550 W US 2011022550W WO 2012102715 A1 WO2012102715 A1 WO 2012102715A1
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Prior art keywords
catalyst
npg
platinum
gold
pem
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English (en)
Inventor
Yi Ding
Rong Yue WANG
Shangling TIAN
Chaohao HOU
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Blue Nano Inc
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Blue Nano Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—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
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
    • 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
    • H01M4/9041—Metals or alloys
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • 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
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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 invention relates to the field of electrochemical technology, and more specifically relates to a catalyst with low precious metal loading for a fuel cell.
  • Liquid fuel cells especially direct formic acid fuel cells (DFAFC) and direct methanol fuel cells (DMFC) can effectively convert the chemical energy of liquid fuels into electricity. They have great potential application prospect in portable electronic devices and are expected to become the next generation power source due to their low operating temperature, compact structure, easily portable fuel. Compared with DMFC, DFAFC posses more advantage such as higher open circuit potential and less fuel crossover.
  • DFAFC direct formic acid fuel cells
  • DMFC direct methanol fuel cells
  • the high price of the catalyst is one of the key issues to inhibit the wide application of direct formic acid fuel cells.
  • the large amount of precious metals used as a catalyst is the primary cause of the fuel cell's high price.
  • formic acid is oxidized to protons (H + ), electrons, CO and CO 2 at the anode on a catalyst layer.
  • the protons cross through the proton exchange membrane to the cathode and the electrons are passed through an external circuit to the cathode.
  • the protons and electrons react with oxygen on the cathode catalyst to produce water.
  • Palladium and platinum are the major catalyst components at the direct formic acid fuel cell anode. Palladium catalysts display higher catalytic activity and the ability of anti-poisoning more readily than platinum. However, palladium's poor stability in an acidic environment severely limits its application. A platinum catalyst is easily poisoned because the carbon monoxide intermediate which is generated seriously hinders the formic acid's direct oxidation pathway.
  • the amount of platinum required for a catalyst must be reduced.
  • traditional method is to prepare the platinum catalyst as a nanoparticle.
  • Amorphous conductive carbon may also be used in the platinum nanoparticle catalysts as a means of support.
  • the method of preparing the platinum catalyst as nanoparticles improves the utilization of platinum and thus reduces its cost, there is still a need to improve: 1) platinum utilization; 2) stability (as the catalyst and support connect only by physical adsorption); 3) electron transport (in the conventional ink-process, Nafion should be added for proton transport which leads to decrease of electron transport).
  • a membrane electrode assembly (MEA) for a fuel cell comprising: an anode catalyst which includes a nanoporous gold having one or more coatings of one or more additional metals on its surface where the additional metals are selected from the group comprising: a group 10 element, preferably platinum, a group 15 element, preferably bismuth, or a combination thereof; the anode catalyst is secured to a first side of a proton exchange membrane having a first side and a second side and a cathode catalyst secured to the second side of the proton exchange membrane.
  • FIG.1 illustrates the current-voltage curve and the current-power polarization curve of a commercial Pt/C catalyst.
  • FIG.2 illustrates the current-voltage curve and the current-power polarization curve of two separate catalysts.
  • FIG.3 illustrates the current-voltage curve and the current-power polarization curve of two separate catalysts.
  • FIG.4 illustrates the full cyclic voltammetry(CV) curves of two separate samples.
  • FIG.5 illustrates the current-voltage curve and the current-power polarization curve of two separate samples.
  • FIG.6 illustrates the current-voltage curve and the current-power polarization curve of two separate samples.
  • FIG.7 illustrates the current-voltage curve and the current-power polarization curve of two separate samples.
  • FIG.8 illustrates the current-voltage curve and the current-power polarization curve of two separate samples.
  • FIG.9 illustrates the current-voltage curve and the current-power polarization curve of two separate samples.
  • FIG.10 illustrates the full cyclic voltammetry (CV) curves of a sample.
  • FIG.11 illustrates the voltage-time curves of two separate samples.
  • the present invention relates to a membrane electrode assembly for a fuel cell and a method of making the membrane electrode assembly for a fuel cell. More specifically, the present invention discloses a membrane electrode assembly which includes a catalyst with low precious metal loading for use within a direct formic acid fuel cell. The present invention also discloses a method for creating the membrane electrode assembly.
  • one solution is to alloy platinum with some other metal atoms like palladium or ruthenium, or to adsorption deposit some other metal atoms like bismuth or lead onto the surface of platinum.
  • the chemical or electrochemical corrosion method can be used to prepare the nanoporous metal from an alloy of appropriate composition and proportion in order to provide it with large surface area and a controllable, uniform structure.
  • the nanostructure materials can be used as catalysts, and especially as the electrocatalyst support, because of superior properties such as three dimensional nanostructure, continuous pore structure and pore wall, good electrical conductivity, high surface area, and strong poisoning resistance.
  • the inventors have developed a method of preparing the nanoporous gold supported platinum with surface alloy catalyst by surface modification onto the nanoporous gold supported platinum catalyst. This method can not only improve the platinum utilization greatly and decrease the usage of precious metal, but improve the poisoning resistance performance.
  • the nanoporous gold supported platinum surface alloy catalyst has the following advantages: 1) the nanoporous metal has a three dimensional, double continuous nanoporous structure which favors the conduction of electrons and the diffusion of reactants; 2) platinum is deposited onto the surface of nanoporous gold in the form of atomic layers which has low platinum loading and high utilization; 3) the platinum is combined with the nanoporous gold by metallic bond which has strong structural stability; 4) by other metal atoms modification onto the nanoporous surface, the formed surface alloy improve the poisoning resistance performance.
  • MEA membrane electrode assembly
  • MEAs contain the electron collectors, the catalyst, and the proton exchange medium.
  • an MEA in its most basic form, is a proton exchange membrane (PEM) sandwiched between two electrodes.
  • the electrodes are the anode and the cathode which are electrically insulated from one another by the PEM.
  • the anode facilitates electrochemical oxidation of the fuel while the cathode promotes the electrochemical reduction of the oxidant.
  • an MEA may be comprised of an anode, an anode catalyst, a PEM, a cathode and a cathode catalyst.
  • an MEA may be comprised of an anode diffused layer, an anode catalyst, a PEM, a cathode diffused layer and a cathode catalyst.
  • PEM proto exchange membrane
  • the PEM is an electrolyte within an MEA and a fuel cell.
  • the semipermeable nature is a PEM's essential function as part of an MEA within a fuel cell where it acts to separate reactants and transport protons.
  • PEMs may be either pure polymer membranes, composite membranes, or any other type of membrane known in the art.
  • a PEM material may include a sulfonated tetrafluoroethylene based fluoropolymer-copolymer sold by the DuPont Corporation (Wilmington, DE) under the trade name Nafion®.
  • fuel cell refers to an electrochemical device that converts the chemical energy of a fuel, along with an oxidant, into electrical energy.
  • a fuel cell is different from a battery in that a fuel cell can continuously supply energy so long as fuel is supplied to the cell.
  • the fuel and the oxidant usually oxygen, are supplied continuously to a fuel cell from an external source.
  • the fuel and oxidant are contained within and when the reactants have been consumed, the battery must either be replaced or recharged.
  • MEAs membrane electrode assemblies
  • Anode a catalyst oxidizes the fuel which turns the fuel into a positively charged ion, a negatively charged electron, and carbon dioxide.
  • the PEM or electrolyte is a substance specifically designed so ions can pass through it, but the electrons cannot. The freed electrons travel through a wire creating the electric current. The ions travel through the electrolyte to the cathode.
  • fuel cells can be combined in series and/or parallel circuits. Series circuits yield higher voltage while parallel circuits allow a higher current to be supplied. These designs are called a fuel cell stack. The cell surface area can be increased, to allow stronger current from each cell.
  • the fuel cell is a proton exchange membrane fuel cell.
  • the fuel cell is a direct formic acid fuel cell.
  • a catalyst is a substance which modifies and/or increases the rate of a reaction without being consumed in the process. At present, it is necessary to greatly reduce the amount of group 10 elements and group 11 elements which are incorporated into a catalyst in order for fuel cells to achieve economic viability.
  • NPG nanoporous gold
  • a catalyst may refer to an anode catalyst. In another embodiment of the present invention, a catalyst may refer to a cathode catalyst or cathodic catalyst.
  • NPG refers to nanoporous gold, which are prepared according the present invention.
  • NPG refers to a nanoporous gold.
  • NPG refers to a plurality of particles containing nanostructure gold.
  • NPG-1 Pt refers to an NPG with one deposition cycle of platinum deposited onto its surface by electrochemical linear scanning from the open circuit potential to the negative potential.
  • platinum is deposited onto a NPG or catalyst from the open circuit potential to 0.3V (versus standard hydrogen electrode) by 50mV/s one time according to the present invention resulting in an NPG-1 Pt or catalyst.
  • NPG-1 Pt-Bi refers to an NPG-1 Pt catalyst with a layer of bismuth deposited onto its surface by under potential deposition.
  • bismuth is deposited onto the surface of an NPG-1 Pt catalyst at 0.2V (versus standard hydrogen electrode) for 400 seconds according to the present invention resulting in an NPG-1 Pt-Bi catalyst.
  • NPG-1 OPt refers to an NPG with ten deposition cycles of platinum deposited onto its surface by electrochemical linear scanning from the open circuit potential to the negative potential, which is repeated 10 times according to the process of the present invention.
  • a one deposition cycle of platinum is deposited onto the surface of an NPG catalyst from the open circuit potential to 0.3V (versus standard hydrogen electrode) by 50mV/s one time, and then this process is repeating 9 times according to the present invention resulting in an NPG-10Pt catalyst.
  • NPG-10Pt-Bi refers to an NPG-10Pt catalyst with a layer of bismuth deposited onto its surface by under potential deposition.
  • bismuth is deposited onto the surface of an NPG-10Pt catalyst at 0.2V (versus standard hydrogen electrode) for 400 seconds according to the present invention resulting in an NPG-10Pt-Bi catalyst.
  • NPG-Pt64 refers to a NPG onto which platinum has been deposited for 64 minutes through the use of the hydrazine vapor reduction method according to the present invention.
  • NPG-Pt64-Bi refers to an NPG-Pt64 catalyst with a layer of bismuth deposited onto its surface by under potential deposition.
  • bismuth is deposited onto the surface of an NPG-Pt64 catalyst at 0.3V (versus standard hydrogen electrode) for 400 seconds according to the present invention resulting in an NPG-Pt64-Bi catalyst.
  • NPG-Pt8 refers to a NPG onto which platinum has been deposited for 8 minutes through the use of the hydrazine vapor method according to the present invention.
  • NPG-Pt8-Bi refers to an NPG-Pt8 catalyst with a layer of bismuth deposited onto its surface by under potential deposition. In one embodiment of the present invention, bismuth is deposited onto the surface of an NPG-Pt8 catalyst at 0.2V (versus standard hydrogen electrode) for 400 seconds according to the present invention resulting in an NPG-Pt8-Bi catalyst.
  • NPG-Pt16 refers to a NPG onto which platinum has been deposited for 16 minutes through the use of the hydrazine vapor method according to the present invention.
  • NPG-Pt16-Bi refers to an NPG-Pt16 catalyst with a layer of bismuth deposited onto its surface by under potential deposition.
  • bismuth is deposited onto the surface of an NPG-Pt16 catalyst at 0.2V (versus standard hydrogen electrode) for 400 seconds according to the present invention resulting in an NPG-Pt16-Bi catalyst.
  • 3*NPG-Pt64 refers to a trinal NPG-Pt64 which results when an NPG-Pt64 catalyst is crushed and dispersed in an ethanol solution containing a sulfonated tetrafluoroethylene based fluoropolymer-copolymer (i.e., National®) according to the present invention.
  • 3*NPG-Pt64-Bi refers to a 3*NPG-Pt64 catalyst with a layer of bismuth deposited onto its surface by under potential deposition.
  • bismuth is deposited onto the surface of an 3 * NPG-Pt64 catalyst at 0.2V (versus standard hydrogen electrode) for 400 seconds according to the present invention resulting in a 3 * NPG-Pt64-Bi catalyst.
  • Group 10 elements includes nickel, palladium and platinum.
  • Group 11 elements as used herein, includes copper, silver and gold.
  • Group 15 elements includes nitrogen, phosphorus, arsenic, antimony and bismuth.
  • organic dispersion solution refers to a solution comprising ethanol, isopropyl alcohol, acetone or combinations thereof.
  • a 0.05 -50 atomic layer platinum has thickness of 0.01-500nm. Additionally, different atomic layers of platinum have corresponding platinum loading. In one embodiment of the present invention, a 0.05 -50 atomic layer platinum has thickness of 0.25-1 Onm, because platinum has a certain atomic radius, a 0.05 atomic layer of platinum still has a thickness of the atomic radius. In another embodiment of the present invention, the loading does not reach one atomic layer, that is to say, platinum does not cover with the NPG completely. In still another embodiment of the present invention, a 0.05 -20 atomic layer platinum has thickness of 0.25-4nm. In yet another embodiment of the present invention, a 0.05 -5 atomic layer platinum has thickness of 0.25-1 nm.
  • a coverage of 0.01-0.99 refers to a surface coverage of one material (e.g. NPG or Pt) by another material (e.g. Bi) of between 1 % and 99%.
  • the coverage may be between 0.05 and 0.80.
  • the coverage may be between 0.1 and 0.65.
  • the coverage may be between 0.20 and 0.50.
  • a 0.01-0.99 atomic layer bismuth has thickness of about 0.0025-0.5 nm. Additionally, different atomic layers of bismuth have corresponding bismuth loading.
  • a 0.01-0.99 atomic layer bismuth has thickness of about 0.25nm, because bismuth have a certain atomic radius, a 0.05 atomic layer of bismuth still has a thickness of each atomic radius respectively.
  • the loading of bismuth does not reach one atomic layer, that is to say, bismuth dose not cover the NPG-Pt completely.
  • the bismuth dose does not cover the NPG-Pt completely.
  • the present invention discloses a membrane electrode assembly (MEA) for a fuel cell comprising: an anode catalyst which includes a nanoporous gold having one or more coatings of one or more additional metals selected from the group comprising: a group 10 element, a group 15 element, or a combination thereof on its surface; the anode catalyst is secured to a first side of a proton exchange membrane having a first side and a second side and a cathode catalyst is secured to the second side of the proton exchange membrane.
  • the Group 10 elements include platinum and the Group 15 elements include bismuth.
  • the membrane electrode assembly includes an anode catalyst comprised of a nanoporous gold, one or more layers of platinum bonded to the surface of the nanoporous gold and less than one layer of bismuth bonded to the surface of the platinum.
  • the MEA described above may possess the following characteristics: a thickness of 0.05-50pm; a width of
  • the membrane electrode assembly as described above may be for use in a direct formic acid fuel cell.
  • the present invention also discloses a membrane electrode assembly (MEA) for a fuel cell comprising: an anode catalyst which includes a nanoporous gold having one or more coatings of one or more additional metals selected from the group comprising: a group 10 element, a group 11 element, a group 15 element, or a combination thereof on its surface; the anode catalyst is secured to a first side of a proton exchange membrane having a first side and a second side and a cathode catalyst is secured to the second side of the proton exchange membrane.
  • the Group 10 elements include platinum
  • the Group 11 elements include silver and gold
  • the Group 15 elements include bismuth.
  • the membrane electrode assembly includes an anode catalyst comprised of a
  • nanoporous gold one or more layers of platinum bonded to the surface of the
  • the MEA described above may possess the following characteristics: a thickness of 0.05-50 m; a width of 0.1 -100cm; a length of 0.2-1000cm; and a three dimensional nanoporous gold structure having an atomic layer of platinum with a uniform thickness of 0.05-50 bonded to its surface and a layer of bismuth atoms having a coverage of 0.01-0.99 bonded to the layer of platinum.
  • the membrane electrode assembly as described above may be for use in a direct formic acid fuel cell.
  • the anode catalyst described above may possess the following characteristics: a thickness of 0.05-50 ⁇ ; a width of 0.1 -100cm; a length of 0.2-1000cm; and a three dimensional nanoporous gold structure having an atomic layer of platinum with a uniform thickness of 0.05-50 bonded to its surface and a layer of 0.01-0.99 atoms bismuth bonded to the layer of platinum.
  • an MEA may be comprised of an anode catalyst which is an NPG-Pt-Bi catalyst, a proton exchange membrane (PEM) and a cathode catalyst.
  • the gold-silver alloy article may be in the range of 0.2-1000 cm long, 0.1-100 cm wide, 0.05-50 urn thick, and 10-60% gold (wt.%).
  • the gold-silver alloy article has a thickness of IOOnm- ⁇ ⁇ , a width of 1- 0cm, and a length of 2-15cm, and comprising 20-50% gold (wt.%).
  • a layer of platinum having a thickness of 0.01 -500nm may be deposited onto the surface of the NPG.
  • a layer of platinum having a thickness of 0.25-1 Onm may be deposited onto the surface of the NPG.
  • the PEM used in the MEA is between 0.2 and 10 cm larger than either the NPG-Pt-Bi catalyst or the anode catalyst.
  • the PEM used in the MEA is between 0.5 and 2 cm larger than either the NPG-Pt-Bi catalyst or the anode catalyst.
  • the anode catalyst may be a catalyst ranging from a NPG-Pt1-Bi to a NPG-Pt1000-Bi. In another embodiment, the anode catalyst may be a catalyst ranging from a NPG-Pt1-Bi to a NPG-Pt500-Bi. In still another embodiment, the anode catalyst may be a catalyst ranging from a NPG-Pt 5-Bi to a NPG-Pt100-Bi. In yet another embodiment, the anode catalyst may be a catalyst ranging from a NPG-Pt10-Bi to a NPG-Pt50-Bi. In another embodiment, the anode catalyst may be a NPG-Pt64-Bi catalyst. In still another embodiment, the anode catalyst may be a NPG-Pt16-Bi catalyst. In yet another embodiment, the anode catalyst may be a
  • the anode catalyst may be a catalyst ranging from a NPG-1 Pt-Bi catalyst to a NPG-100 Pt-Bi catalyst. In yet another embodiment, the anode catalyst may be a catalyst ranging from a NPG-3Pt-Bi catalyst to a NPG-8Pt-Bi catalyst. In still another embodiment, the anode catalyst may be a
  • the anode catalyst may be a
  • the anode catalyst may be a
  • the present invention also discloses a method of preparing a membrane electrode assembly (MEA) comprising the steps of: immersing or placing a gold-silver alloy article in a concentrated nitric acid solution to selectively remove silver from the gold-silver alloy article in order to form a nanoporous gold (NPG); rinsing the NPG in deionized water followed by depositing one or more layers of platinum onto the surface of the NPG wherein the layers of platinum ranging in thickness from sub-monoatomic to a plurality of monoatomic or atomic layers in order to form an NPG-Pt article; and depositing bismuth onto the surface of the NPG-Pt article resulting in an NPG-Pt-Bi catalyst followed by forming the MEA by either:
  • the present invention includes the preparation methods of making various nanoporous gold supported platinum catalysts by de-alloying gold and silver alloys to obtain a nanoporous gold, which is then modified by methods which include: (i) surface ion adsorption and electrochemical reduction, (ii) under potential deposition (UPD) combined with in-situ replacement, (iii) using a chloroplatinic ion and hydrazine vapor reduction method to deposit the platinum onto the surface of the nanoporous gold, or a combination thereof.
  • the nanoporous gold supported platinum catalyst is then immersed in a perchloric acid solution containing bismuth oxide to form the Bi-modified nonporous gold catalyst supported platinum catalyst.
  • a gold-silver alloy article is used.
  • the method described above includes a gold-silver alloy article which is 0.2-1000 cm long, 0.1-100 cm wide, 0.05-50 urn thick, and 10-60% gold (wt.%).
  • the gold-silver alloy article may have a thickness of 100 ⁇ -1 ⁇ , a width of 1- 0cm, and a length of 2-15cm, and comprising 50% gold (wt.%).
  • a concentrated nitric acid solution is used.
  • the method described above includes a gold-silver alloy article being immersed in concentrated nitric acid for a time period ranging from 0.1 to 1000 minutes at a temperature in the range of 0 to 60°C.
  • the method described above includes a gold-silver alloy article being immersed in concentrated nitric acid for a time period ranging from 15 to 60 minutes at a temperature in the range of 20-40X.
  • a layer of platinum may be deposited onto the NPG using a method selected from the group comprising: (1 ) a surface ion adsorption and electrochemical reduction method; (2) an under potential deposition method combined with in-situ replacement; (3) a chloroplatinic ion solution and hydrazine vapor method; or (4) a combination thereof.
  • thicknesses of NPG wherein a layer of platinum is deposited ranging in thickness from sub-monoatomic to a plurality of atomic layers, and for large platinum loading, the NPG can be adsorbed in a chloroplatinic ion or chloroplatinous ion solution; or for option (2) the under potential deposition method combined with in-situ replacement may be utilized to deposit a layer of platinum having a thickness of 50-500nm onto the surface of NPG; or for option (3) the chloroplatinic ion and hydrazine vapor method may be utilized to deposit a layer of platinum having a thickness of less than 10Onm onto the surface of NPG.
  • the concentration of chloroplatinic ion or chloroplatinous ion in option (1) is preferably 0.001-10000mM
  • the NPG is placed into the chloroplatinic ion or chloroplatinous ion solution for a soaking time period in the range of 1 second to 10 hours and a cleaning step to rinse the chloroplatinic ion or chloroplatinous ion solution from the NPG is completed between land 10 times.
  • the chloroplatinic ion solution in option (3) has a concentration in the range of 0.1 - 10g/L, has an pH value of between 8-11 and the NPG is exposed to the hydrazine vapor for a period of time ranging from 1-1000 minutes.
  • chloroplatinous ion in option (1 ) is preferably 0.5-1 OmM
  • the NPG is placed into the chloroplatinic ion or chloroplatinous ion solution for a soaking time period in the range of 3-30 minutes and a cleaning step to rinse the chloroplatinic ion or chloroplatinous ion solution from the NPG is completed between 3 and 6 times.
  • the concentration of the chloropiatinic ion solution in option (3) is 1g/L
  • the pH value of the chloropiatinic ion solution is 10
  • the period of time the NPG is exposed to the hydrazine vapor is in the range of 5-60 minutes.
  • the method described above includes the process of depositing bismuth onto the surface of a NPG-Pt article.
  • This deposition may be accomplished by any methods known in the art.
  • bismuth is deposited onto the surface of a NPG-Pt article by placing the NPG-Pt article into a perchloric acid solution containing bismuth and adding a 0-0.5V potential (versus standard hydrogen electrode) to the NPG-Pt article for a deposition time period of 1-1000 minutes to obtain an
  • NPG-Pt-Bi catalyst In another embodiment of the present invention, bismuth is deposited onto the surface of a NPG-Pt article by placing the NPG-Pt article into a perchloric acid solution containing bismuth and soaking the NPG-Pt article for a soaking time period of 1-1000 minutes to obtain an NPG-Pt-Bi catalyst.
  • the concentration of the perchloric acid solution containing Bi is 3-5mM
  • the deposition potential is 0.2-0.4V (versus standard hydrogen electrode)
  • the deposition time period is 5-10 minutes or the soaking time period is 5-10 minutes.
  • the sulfonated tetrafluoroethylene based fluoropolymer-copolymer solution has a wt.% of 1-70%.
  • the sulfonated tetrafluoroethylene based fluoropolymer-copolymer solution has a wt.% of 20-40%.
  • the PEM is 0.2 to 10 cm larger than either the cathodic catalyst or the anode catalyst.
  • the PEM is 0.2 to 10 cm larger than either the NPG-Pt-Bi catalyst or the anode catalyst.
  • the NPG-Pt-Bi catalyst, the PEM and the cathodic catalyst are hot pressed together to form the MEA using a pressure of 0.1 -1 MPa cm "2 at 20-150°C for 10-1000 seconds.
  • the anode catalyst, the PEM and the cathodic catalyst are hot pressed together to form the MEA using a pressure of 0.1-1 MPa cm "2 at 20-150°C for 10-1000 seconds.
  • the PEM is 0.5 to 2 cm larger than either the NPG-Pt-Bi catalyst or the anode catalyst and the NPG-Pt-Bi catalyst.
  • the PEM and the cathodic catalyst are hot pressed together to form the MEA using a pressure of 0.2-0.6 MPa cm "2 at 50-140°C for 60-600 seconds; or the anode catalyst, the PEM and the cathodic catalyst are hot pressed together to form the MEA using a pressure of 0.2-0.6 MPa cm "2 at 50-140°C for 60-600 seconds.
  • the present invention can control the catalyst support's surface area by adjusting the thickness and pore size of the nanoporous gold.
  • the present invention can control a catalyst's catalytic activity by adjusting the platinum loading by methods which include: i) regulating the time of adsorption deposition, ii) regulating the time of UPD combined with in-situ replacement, or iii) regulating the time of reduction in hydrazine vapor.
  • the present invention can also control a catalyst's catalytic activity by controlling the amount of platinum deposited onto the NPG and by adjusting the bismuth loading by regulating the deposition potential and deposition time period (or soaking time period). It also can control the fuel cell capability by adjusting the combination of structures in the MEA which are regulated by the hot-press pressure, the hot-press temperature and the hot-press time.
  • the membrane electrode assembly (MEA) with low precious metal loading for direct formic acid fuel cell prepared by the methods of the present invention may possess the following characteristics: at least one side of the MEA contains a Bi-modified nanoporous gold supported platinum catalyst, and the Bi-modified nanoporous gold supported platinum catalyst has thickness of about 0.05-50pm, width of 0.1-100cm, length of 0.2-1000cm, morphology of three-dimensional nanoporous gold structure which is covered with a uniform thickness of 0.05-50 atomic layer of platinum covered with a layer of bismuth atoms bonded to the nanoporous gold and/or layer of platinum; said layer of bismuth or ruthenium having a coverage of 0.01-0.99 (i.e. covering between 1 % and 99% of the platinum).
  • the MEA with low precious metal loading for direct formic acid fuel cell prepared by the method described in the present invention has the following advantages:
  • NPG has superior electron transfer ability and superior chemical and electrochemical corrosion resistance than the traditional fuel cell catalyst support (like carbon).
  • the controllable platinum deposition method can control the deposition of platinum in atomic scale, improve the utilization of platinum, and reduce the precious platinum loading by orders of magnitude.
  • the surface modification can make the adsorption deposited platinum catalyst with good catalytic activity originally improve further, and can make the catalyst with bad catalytic activity originally improve greatly.
  • the Bi-modified nanoporous gold supported platinum catalyst can not only be brushed (or sprayed, painted) onto the diffusion layer after crushing which it is compatible with the traditional technology, but also it can be directly attached to the proton exchange membrane(PEM) which make the preparing method more simple.
  • the Bi-modified nanoporous gold supported platinum catalyst prepared by the rational design can decrease the precious metal loading about an order of magnitude. And it can improve the fuel cell apparent power nearly two times under the condition of decreasing the platinum loading about two orders of magnitude.
  • a 12K gold-silver alloy sample (1.2 cm long, 1 cm wide, 500 nm thick) was placed in concentrated nitric acid for 120 minutes to selectively dissolve silver from the alloy and to form a nanoporous gold (NPG) which was then rinsed and cleaned in deionized water.
  • NPG nanoporous gold
  • NPG-1 Pt catalyst was placed in 0.1 M HCI0 4 solution containing 3mM bismuth in order to deposit bismuth onto the surface of the NPG-1 Pt catalyst by adding 0.2V potential (versus standard hydrogen electrode) for 400 seconds to form an
  • NPG-1 Pt-Bi catalyst with a diffusion layer of 1*1 cm 2 was placed on one side of a proton exchange membrane (PEM) which was 3cm long and 2.8cm wide.
  • a cathodic catalyst was then placed on the other side of the PEM and all three components were then hot-pressed under a pressure of 0.5MPa for 195 seconds at 70°C to form a membrane electrode assembly (MEA).
  • MEA membrane electrode assembly
  • FIG.1 illustrates the current-voltage curve and the current-power polarization curve of a commercial Pt/C catalyst with 2.2mg/cm 2 of platinum loading both in the anode and in the cathode which was operated at 40°C in a direct formic acid fuel cell.
  • 3M HCOOH was pumped into the fuel cell at the anode, and air was pumped in at the cathode as an oxidant.
  • the apparent area of the cell is 1cm 2 .
  • the curves show the commercial Pt/C discharge of 44mW at 40°C.
  • FIG.2 illustrates the current-voltage curve and the current-power polarization curve of a sample having a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and an NPG-1 Pt-Bi catalyst (made by 1 time platinum adsorption-deposition and bismuth under potential deposition) with 0.5mg/cm 2 gold + 0.0025mg/cm 2 platinum loading as an anode and operated at 40°C within a direct formic acid fuel cell.
  • a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and an NPG-1 Pt-Bi catalyst (made by 1 time platinum adsorption-deposition and bismuth under potential deposition) with 0.5mg/cm 2 gold + 0.0025mg/cm 2 platinum loading as an anode and operated at 40°C within a direct formic acid fuel cell.
  • a 12K gold-silver alloy sample (1.2 cm long, 1 cm wide, 500 nm thick) was placed in concentrated nitric acid for 120 minutes to selectively dissolve silver from the alloy and to form a nanoporous gold (NPG) which was then rinsed and cleaned in deionized water;
  • NPG was then placed in the mixed solution of 0.1 M HCI0 4 and 1mM H 2 PtCl 6 where it soaked for 5 minutes accompanied by electrochemical linear scanning from the open circuit potential to negative potential ended at 0.3V (versus standard hydrogen electrode) by 50mV/s in a three electrode system. This process step is repeated 10 times in order to form an NPG-10Pt catalyst;
  • NPG-10Pt catalyst was placed in 0.1 M HCI0 4 solution containing 3mM bismuth in order to deposit bismuth onto the surface of the NPG-10Pt catalyst by adding 0.2V potential (versus standard hydrogen electrode) for 400 seconds to form a
  • NPG-10Pt-Bi catalyst with a diffusion layer of 1 * 1 cm 2 was placed on one side of a proton exchange membrane PEM which was 3cm long and 2.5cm wide).
  • a cathodic catalyst was then placed on the other side of the PEM and all three components were then hot-pressed under a pressure of 0.5MPa for 95 seconds at 70°C to form a membrane electrode assembly (MEA).
  • MEA membrane electrode assembly
  • FIG.3 illustrates the current-voltage curve and the current-power polarization curve of a sample having a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and an NPG-10Pt-Bi catalyst (made by 10 times platinum adsorption-deposition and bismuth under potential deposition) with 0.5mg/cm 2 gold + 0.025mg/cm 2 platinum loading as an anode, operated at 40°C within a direct formic fuel cell.
  • a Membrane Electrode Assembly was hot-pressed at 70°C and 0.5Mpa for 195 seconds. 3M HCOOH was pumped into the fuel cell at the anode, and air was pumped in at the cathode as oxidant.
  • the apparent area of the cell is 1cm 2 .
  • the curves show that the NPG-10Pt-Bi catalyst has a discharge 71mW. This discharge capacity is 1.6 times the discharge capacity of the commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading. Surprisingly, even when each catalyst is normalized to the platinum mass specific power densities, the NPG-10Pt-Bi catalyst's discharge capacity is 142 times that of the Pt/C catalyst. Even more surprisingly, when normalized to the precious metal mass specific power densities, the NPG-10Pt-Bi catalyst's discharge capacity is 6.8 times that of the Pt/C catalyst.
  • FIG.4 illustrates the full cyclic voltammery(CV) curves of a sample having a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and an
  • NPG-10Pt-Bi catalyst made by 10 times platinum adsorption-deposition and bismuth under potential deposition
  • 0.5mg/cm 2 gold + 0.025mg/cm 2 platinum loading as an anode in 0.1 M HCI0 4 .
  • the curves show the bismuth oxidation peak is at 0.9V.
  • a 12K gold-silver alloy sample (1.2 cm long, 1 cm wide, 100 nm thick) was placed in concentrated nitric acid for 15 minutes to selectively dissolve silver from the alloy and to form a nanoporous gold (NPG) which was then rinsed and cleaned in deionized water.
  • NPG nanoporous gold
  • NPG-Pt64 catalyst was placed in 0.1 M HCIO 4 solution containing 3mM bismuth in order to deposit bismuth onto the surface of the NPG-Pt64 catalyst by adding 0.3V potential (versus standard hydrogen electrode) for 400 seconds to form an
  • NPG-Pt64-Bi catalyst with a diffusion layer of 1 * 1 cm 2 NPG-Pt64-Bi catalyst with a diffusion layer of 1 * 1 cm 2 .
  • the NPG-Pt64-Bi catalyst with a diffusion layer of 1*1 cm 2 was placed on one side of a proton exchange membrane PEM which was 3cm long and 2.8cm wide. A cathodic catalyst was then placed on the other side of the PEM and all three components were then hot-pressed under a pressure of 0.5MPa for 195s at 110°C to form a membrane electrode assembly (MEA).
  • MEA membrane electrode assembly
  • FIG.5 illustrates the current-voltage curve and the current-power polarization curve of a sample having a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and an NPG-Pt64 catalyst (0.1mg/cm 2 gold + 0.03mg/cm 2 platinum loading) as an anode , operated at 40°C within a direct formic acid fuel cell.
  • a Membrane Electrode Assembly was hot-pressed at 110°C and 0.5Mpa for 195 seconds. 3M HCOOH was pumped into the fuel cell at the anode, and air was pumped in at the cathode as an oxidant. The apparent area of the cell is 1cm 2 .
  • the curves show the NPG-Pt64 catalyst discharges 17mW which decreases a lot although it had lower platinum loading compared to the Pt/C catalyst.
  • FIG.6 illustrates the current-voltage curve and the current-power polarization curve of a sample having a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and an NPG-Pt64-Bi catalyst (0.1 mg/cm 2 gold + 0.03mg/cm 2 platinum loading) as an anode, operated at 40°C within a direct formic acid fuel cell.
  • a Membrane Electrode Assembly was hot-pressed at 110°C and 0.5Mpa for 195 seconds. 3M HCOOH was pumped into the fuel cell at the anode, and air was pumped in at the cathode as an oxidant. The apparent area of the cell is 1cm 2 .
  • NPG-Pt64-Bi discharge capacity is 55 times that of Pt/C.
  • NPG-Pt64-Bi catalyst's discharge capacity is 12.7 times that of the Pt/C catalyst.
  • a 12K gold-silver alloy sample (1.5 cm long, 1 cm wide, 100 nm thick) was placed in concentrated nitric acid for 15 minutes to selectively dissolve silver from the alloy to form a nanoporous gold (NPG) which is then rinsed and cleaned in deionized water.
  • NPG nanoporous gold
  • NPG-Pt8 catalyst was then placed in a solution of 0.1 M HCI0 4 containing 5mM bismuth in order to deposit bismuth onto the surface of the NPG-Pt8 catalyst by adding 0.2V potential (versus standard hydrogen electrode) for 400 seconds to form an NPG-Pt8-Bi catalyst with a diffusion layer of 1 * 1 cm 2 .
  • FIG.7 illustrates the current-voltage curve and the current-power polarization curve of a sample having a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and an NPG-Pt8-Bi catalyst (0.1mg/cm 2 gold + 0.006mg/cm 2 platinum loading) as an anode, operated at 40°C within a direct formic acid fuel cell.
  • the NPG-Pt8-Bi catalyst was prepared by de-alloying a 12K Ag-Au alloy with 68%(wt.%) and a thickness of 100nm in nitric acid for 15 minutes at 30°C to create an NPG, followed by depositing platinum onto the surface of the NPG for 8 minutes to create an NPG-Pt catalyst, followed by modifying bismuth onto the NPG-Pt catalyst at 0.2V (versus standard hydrogen electrode) for 400 seconds resulting in an NPG-Pt8-Bi catalyst.
  • a membrane electrode assembly was hot-pressed at 110°Cand 0.5Mpa for 195 seconds. 3M HCOOH was pumped into the fuel cell at the anode, and air was pumped in at the cathode as an oxidant.
  • the apparent area of the cell is 1cm 2 .
  • the curves show that the NPG-Pt8-Bi catalyst discharged 60mW which demonstrates a higher discharge capacity ( .4 times) than of the Pt/C with 2.2mg/cm 2 platinum loading. Normalized to the platinum mass specific power densities, the NPG-Pt8-Bi catalyst's discharge capacity is 500 times that of the Pt/C catalyst. Surprisingly, even when each catalyst is normalized to the precious metal mass specific power densities, the NPG-Pt8-Bi catalyst's discharge capacity is 28 times that of the Pt/C catalyst.
  • a 12K gold-silver alloy sample (1.5 cm long, 1 cm wide and 100 nm thick) was placed in concentrated nitric acid for 15 minutes to form a nanoporous gold NPG which is then cleaned and rinsed in deionized water;
  • NPG-Pt16 catalyst was then placed in solution of 0.1 M HCI0 4 containing 5mM bismuth in order to deposit bismuth onto the surface of the NPG-Pt16 catalyst by adding 0.2V potential (versus standard hydrogen electrode) for 400 seconds to form an NPG-Pt16-Bi catalyst with a diffusion layer of 1 * 1 cm 2 ;
  • the NPG-Pt16-Bi catalyst with a diffusion layer of 1 * 1 cm 2 was placed on one side of a proton exchange membrane (PEM) which was 3cm long and 2.8cm wide.
  • a cathodic catalyst was then placed on the other side of the PEM and all three components were then hot-pressed under a pressure of 0.5MPa for 195 seconds at 110°C to form a membrane electrode assembly (MEA).
  • MEA membrane electrode assembly
  • FIG.8 illustrates the current-voltage curve and the current-power polarization curve of a sample having a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and an NPG-Pt16-Bi catalyst (0.1 mg/cm 2 gold + 0.01 mg/cm 2 platinum loading) as an anode, operated at 40°C within a direct formic acid fuel cell.
  • the NPG-Pt16-Bi catalyst was prepared by de-alloying a 12K Ag-Au alloy with 68%(wt.%) nitric acid and a thickness of 100nm in nitric acid for 15 minutes at 30°C to create an NPG, followed by depositing platinum onto the surface of the NPG for 16 minutes to create an NPG-Pt catalyst, followed by modifying bismuth onto the NPG-Pt16 catalyst at 0.2V (versus standard hydrogen electrode) 400seconds resulting in an NPG-Pt16-Bi catalyst.
  • a membrane electrode assembly was hot-pressed at 110°Cand O.SMpa for 195 seconds.
  • 3M HCOOH was pumped into the fuel cell at the anode, and air was pumped in at the cathode as an oxidant.
  • the apparent area of the cell is 1cm 2 .
  • the curves show that the NPG-Pt16-Bi catalyst discharged 80mW which demonstrates a higher discharge capacity ( .8 times) than that of the Pt/C catalyst with 2.2mg/cm 2 platinum loading. Normalized to the platinum mass specific power densities, the NPG-Pt16-Bi catalyst's discharge capacity is 400 times that of the Pt/C catalyst. Surprisingly, even when each catalyst is normalized to the precious metal mass specific power densities, the NPG-Pt 6-Bi catalyst's discharge capacity is 36 times that of the Pt/C catalyst.
  • a 12K gold-silver alloy sample (1 cm long, 1 cm wide, 100 nm thick) was placed in concentrated nitric acid for 15 minutes to form a nanoporous gold (NPG) which is then cleaned and rinsed in deionized water.
  • NPG nanoporous gold
  • NPG-Pt64 catalyst was placed in 0.1 M solution of HCI0 containing 5mM bismuth in order to deposit bismuth onto the surface of the NPG-Pt64 catalyst by adding 0.2V potential (versus standard hydrogen electrode) for 400 seconds to make NPG-Pt64-Bi catalyst.
  • the NPG-Pt64-Bi catalyst was crushed and dispersed in an ethanol solution followed by the addition of a National ® solution and then brushed onto carbon paper to form a 3*NPG-Pt64-Bi catalyst with a diffusion layer of 1 * 1cm 2 .
  • FIG.9 illustrates the current-voltage curve and the current-power polarization curve of a sample having a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and a 3 * NPG-Pt64-Bi catalyst (0.3mg/cm 2 gold + 0.09mg/cm 2 platinum loading) as an anode, operated at 40°C within a direct formic acid fuel cell.
  • the 3 * NPG-Pt64-Bi catalyst was prepared by crushing and dispersing a NPG-Pt64-Bi catalyst into an ethanol solution with a 30% Nafion ® solution and then brushing onto a diffusion layer.
  • a Membrane Electrode Assembly was hot-pressed at 110°C and 0.5Mpa for 195 seconds.
  • 3M HCOOH was pumped into the fuel cell at the anode, and air was pumped in at the cathode as an oxidant.
  • the apparent area of the cell is 1cm 2 .
  • the curves show that the 3 * NPG-Pt64-Bi catalyst discharged 78mW which demonstrates a higher discharge capacity (1.7 times) than that of the Pt/C catalyst with 2.2mg/cm 2 platinum loading. Normalized to the platinum mass specific power densities, the 3*NPG-Pt64-Bi catalyst's discharge capacity is 43 times that of the Pt/C catalyst.
  • FIG.10 illustrates the full cyclic voltammery (CV) curves of a sample having a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and a 3 * NPG-Pt64-Bi catalyst (0.3mg/cm 2 gold + 0.09mg/cm 2 platinum loading) as an anode in 0.1 M HCI0 4 .
  • the curves show a bismuth oxidation peak is at 0.9V.
  • FIG. 11 illustrates the voltage-time curves at a constant current density
  • the sample is a commercial Pt/C catalyst with 2.2mg/cm 2 platinum loading as a cathode and a
  • 3 HCOOH was pumped into the fuel cell at the anode.
  • the 3 * NPG-Pt64-Bi catalyst was prepared by brushing the crushed trinal NPG-Pt64-Bi catalyst with a 30% Nafion ® solution onto the diffusion layer.
  • a Membrane Electrode Assembly was hot-pressed at 110°C and 0.5Mpa for 195 seconds.
  • 3M HCOOH was pumped into the fuel cell at the anode, and air was pumped in at the cathode as an oxidant.
  • the apparent area of the cell is 1cm 2 .
  • the curves show that, at the constant current density of 200mA/cm 2 , the cell potential had good stability and remained stable at 330mV after preliminary activation.

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Abstract

L'invention concerne un ensemble électrode à membrane (MEA) pour piles à combustible qui comprend: un catalyseur d'anode qui comprend de l'or nanoporeux possédant un ou plusieurs revêtements sur sa surface, les métaux supplémentaires étant sélectionnés dans le groupe comprenant: un élément du groupe (10), de préférence du platine, un élément du groupe (15), de préférence, du bismuth, ou une combinaison de ceux-ci; le catalyseur d'anode est fixé à un premier côté d'une membrane échangeuse de protons possédant un premier et un second côté et un catalyseur de cathode est fixé à un second côté de la membrane échangeuse de protons.
PCT/US2011/022550 2011-01-26 2011-01-26 Ensemble électrode à membrane pour piles à combustible Ceased WO2012102715A1 (fr)

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WO2018215413A1 (fr) * 2017-05-24 2018-11-29 Centre National De La Recherche Scientifique Procede de preparation d'une membrane conductrice, transparente et flexible
CN114079071A (zh) * 2021-10-12 2022-02-22 江苏大学 一种自支撑膜电极的制备方法及其应用
CN114433082A (zh) * 2022-03-04 2022-05-06 昆明理工大学 一种增强孔隙型Pt基合金膜催化剂及其制备方法
CN114525511A (zh) * 2022-03-01 2022-05-24 天津理工大学 一种纳米多孔金属电极材料的制备方法

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US7632779B1 (en) * 2008-12-09 2009-12-15 Filigree Nanotech, Inc. Method of preparing a catalyst for direct formic acid fuel cells
US20100316931A1 (en) * 2009-06-10 2010-12-16 Friedrich Wilhelm Wieland Electrocatalyst, Fuel Cell Cathode and Fuel Cell

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US20050112432A1 (en) * 2002-08-27 2005-05-26 Jonah Erlebacher Method of plating metal leafs and metal membranes
US20040229077A1 (en) * 2003-05-14 2004-11-18 Akihito Mori Plated material and method of manufacturing the same, terminal member for connector, and connector
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018215413A1 (fr) * 2017-05-24 2018-11-29 Centre National De La Recherche Scientifique Procede de preparation d'une membrane conductrice, transparente et flexible
FR3066768A1 (fr) * 2017-05-24 2018-11-30 Centre National De La Recherche Scientifique Procede de preparation d’une membrane conductrice, transparente et flexible.
US11279998B2 (en) 2017-05-24 2022-03-22 Centre National De La Recherche Scientifique Method for preparing a conductive, transparent and flexible membrane
US12247279B2 (en) 2017-05-24 2025-03-11 Centre National De La Recherche Scientifique Method for preparing a conductive, transparent and flexible membrane
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CN114079071B (zh) * 2021-10-12 2022-12-16 江苏大学 一种自支撑膜电极的制备方法及其应用
CN114525511A (zh) * 2022-03-01 2022-05-24 天津理工大学 一种纳米多孔金属电极材料的制备方法
CN114433082A (zh) * 2022-03-04 2022-05-06 昆明理工大学 一种增强孔隙型Pt基合金膜催化剂及其制备方法

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