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WO2009157033A2 - Électrocatalyseurs à base de nitrure de carbone mono/plurimétallique à noyau-enveloppe pour piles à combustible à basse température (pemfcs, dmfcs, afcs) et électrolyseurs - Google Patents

Électrocatalyseurs à base de nitrure de carbone mono/plurimétallique à noyau-enveloppe pour piles à combustible à basse température (pemfcs, dmfcs, afcs) et électrolyseurs Download PDF

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WO2009157033A2
WO2009157033A2 PCT/IT2009/000278 IT2009000278W WO2009157033A2 WO 2009157033 A2 WO2009157033 A2 WO 2009157033A2 IT 2009000278 W IT2009000278 W IT 2009000278W WO 2009157033 A2 WO2009157033 A2 WO 2009157033A2
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ptcl
pdcl
ircl
fuel cells
xylene
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WO2009157033A3 (fr
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Noto Vito Di
Enrico Negro
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Universita degli Studi di Padova
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • 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
    • H01M4/9075—Catalytic material 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/923—Compounds thereof with non-metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • 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

  • CORE-SHELL MONO/PLURIMETALLIC CARBON NITRIDE BASED ELECTROCATALYSTS FOR LOW-TEMPERATURE FUEL CELLS (PEMFCs, DMFCs, AFCs AND PAFCs) AND ELECTROLYSERS on behalf of: University of Padova
  • the invention concerns the anodic and cathodic electrocatalysts to be used in fuel cells operating at low temperatures such as PEMFCs, DMFCs, AFCs and PAFCs, and in H 2 electrolysers together with the methods used to prepare the materials constituting those electrocatalysts.
  • fuel cells operating at low temperatures such as PEMFCs, DMFCs, AFCs and PAFCs, and in H 2 electrolysers together with the methods used to prepare the materials constituting those electrocatalysts.
  • the fuel i.e., hydrogen, methanol, ethanol, glycerol, etc..
  • the oxidant air or oxygen
  • the protons produced at the anode migrate through the electrolyte to the cathode, where they are involved in the production of water and electric current.
  • the OH " ions produced at the cathode migrate through the electrolyte to the anode, where they are consumed in the production of water and electric current.
  • a supported Pt-Ru alloy electrocatalyst must be mounted at the anode of the cell so as to prevent the poisoning of the material by CO traces found in the fuel stream, while at the cathode the best performance is provided by an electrocatalyst characterized by supported Pt.
  • DMFCs provide an optimal performance with electrocatalysts having a metal content higher than about 40%. At the anode it is necessary to use a Pt-Ru alloy so as to efficiently oxidize the methanol fuel, while at the cathode the electrocatalyst is supported Pt.
  • cathodic electrocatalysts can be obtained by alloying the supported platinum with suitable first-row transition metals such as Fe, Co, Ni, Cr, Ti and Mn.
  • Palladium can also be used to prepare supported electrocatalysts, either by itself or alloyed with other metals such as Fe and Co.
  • these electrocatalysts are usually prepared by impregnating active carbons with salts of the desired metals followed by a subsequent reduction through a variety of methods (e.g., using chemical reagents such as NaBH 4 or formaldehyde, or under a H 2 current at a high temperature).
  • Catalysts for Io w- temperature fuel cells capable to operate without platinum-group metals (PGM) have been proposed, but they are still characterized by quite a poor performance and a very low durability. Thus, they are unsuitable for most applications.
  • PGM platinum-group metals
  • the only catalysts which can be used in practical low-temperature fuel cells are those based on PGM and for this reason they are very expensive; this is a major limiting factor to a widespread commercial application of this technology.
  • An important practical target is to obtain fuel cells capable to yield a high electrical power mounting as little weight of PGM as possible.
  • the procedure to prepare materials having a large surface area to be used as anodic and cathodic electrocatalysts consists of three steps.
  • the precursor is obtained through chemical reactions based on the following processes: a) sol-gel; b) gel-plastic; c) coagulation and/or flocculation and/or precipitation; d) metal-ligand complexation processes in organic solvent using as a ligand a molecule, a macromolecule or a macromolecular system.
  • the second step leads to the production of supported mono-plurimetallic carbon nitrides (S-MPM-CN) through suitable thermal treatments of the precursor in an inert atmosphere.
  • S-MPM-CN supported mono-plurimetallic carbon nitrides
  • the last step consists in the procedures to perform the chemical and electrochemical activations of the carbon nitride materials obtained in the second step.
  • Precursors are obtained as described below in a detailed way through: a) complexation reactions of transition metals with complexes such as cyanometallates or molecules such as acetonitrile acting as ligands to produce clusters; b) 3-D networking of the obtained clusters with suitable organic molecules and/or macromolecules and/or macromolecular systems over the chosen support.
  • Suitable supports include all the electron-conducting materials. Owing to the extremely large number of materials satisfying this criterion, the following list is reported only for illustrative and not for limitative purposes.
  • Typical examples of electron-conducting materials suitable as supports for this invention are graphite powders or platelets, powders of metals such as titanium, silver, gold, platinum, zirconium, manganese, tungsten, lead, scandium, vanadium, iron, cobalt, nickel, zinc, bismuth, copper, chromium, yttrium, niobium, molybdenum, ruthenium, rhodium, palladium, cadmium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, gallium, indium, thallium, silicon, germanium, tin, etc...
  • metals such as titanium
  • Procedure 1 is applied when all the networking and the coordinating agents are water-soluble molecules or macromolecules.
  • Procedure 2 is applied when at least one of the networking and coordinating agents are not soluble in water. It should be highlighted that it is possible to use more than one type of molecule, macromolecule or macromolecular systems at the same time as networking and coordinating agents for the metal clusters to obtain the precursor.
  • the molecules, macromolecules or macromolecular systems used for Procedure 1 must not contain sulphur atoms and must be very rich of oxygen atoms and hydroxyl groups.
  • Typical examples include polyethylene glycol, polyvinyl alcohol, glycerol, sucrose, glucose, fructose and in general all the water-soluble macromolecules such as carbohydrates, etc...
  • the molecules, macromolecules or macromolecular systems used for Procedure 2 must be soluble in organic solvents such as N-methyl-2-pyrrolidinone, dimethylformamide, dimethylacetamide, acetic acid, acetone, acetonitrile, benzene, 1-butanol, 2-butanol, 2-butanone, t-butyl alcohol, cyclohexane, diethyl ether, diethylene glycol, diglyme, dimethylether, dioxane, ethanol, ethyl acetate, ethylene glycol, heptane, hexane, methanol, methyl t-butyl ether, nitromethane, pentane, 1-propanol, 2- propanol, pyridine, tetrahydro
  • Typical molecules which can be used as networking agents for Procedure 2 include dianilines such as p-phenylenediamine; 4,4'-methylenedianilme; 1,4- diaminobutane; dianhydrides such as 1,2,4,5-benzenetetracarboxylic anhydride; 3,3',4,4'- benzophenonetetracarboxylic dianhydride; (+)-diacetyl-L-tartaric anhydride; diphosphines such as 1 ,2-bis(diphenylphosphino)ethane; (-)-2,3-0-isopropylidene-2,3-dihydroxy-l ,4- bis(diphenylphosphino)butane; (-)-l ,2-bis[(2R,5R)-2,5-diethylphospholano
  • Typical macromolecules which can be used as networking agents for Procedure 2 include polyimides such as Kapton, and Apical, polyamides such as Nylon 6 and Nylon 6,6, polyurethanes, polypyrrole, polyvinyl alcohol, polymethyl metacrylate, polyacrylonitrile, poly(tetramethylene ether) glycol, polyethylene glycol, etc...
  • Procedure 1 starts with the preparation of two solutions, A and B.
  • the first, solution A consists in a "soft" transition metal complex coordinated by good leaving groups and an aliquot of the selected networking agents dissolved in water.
  • Typical examples of "soft" transition metal complexes used in the preparation of the solution A include, but are not limited to: HAuCl 4 , H 2 IrCl 6 , H 2 PtCl 6 , Li 2 PdCl 4 , (NH 4 ) 2 IrCl 6 , (NH 4 ) 2 OsCl 6 , (NH 4 )PdCl 4 , (NH 4 ) 2 PdCl 6 , (NH 4 ) 2 PtCl 4 , (NH 4 ) 3 RhCl 6 , (NH 4 ) 2 RuCl 6 , KAuCl 4 , KPt(NH 3 )Cl 3 , K 2 PdCl 4 , K 2 PtCl 4 , K 2 PtCl 4 , K
  • Solution B is obtained by dissolving in water a suitable amount of a metal complex, such as a cyanometallate, capable to act as a ligand for "soft" metals, together with an aliquot of the networking agents used in the preparation of the solution A.
  • a metal complex such as a cyanometallate
  • cyanometallates which can be used include, but are not limited to: KAg(CN) 2 , KAu(CN) 2 , K 2 Ni(CN) 4 K 2 Pd(CN) 4 , K 2 Pt(CN) 4 , K 3 Co(CN) 6 , K 3 Cr(CN) 6 K 3 Fe(CN) 6 , K 4 Fe(CN) 6 -H 2 O, K 3 Mn(CN) 6 , K 2 Pt(CN) 6 , K 4 Ru(CN) 6 .
  • Solutions A and B must be mixed together and stirred until they are completely transparent. Once the solution is well-mixed the resulting product must be let rest at room temperature. The chemical reaction is considered complete when one of the above-mentioned transitions (sol-gel and/or gel/plastic; coagulation and/or flocculation and/or precipitation; metal-ligand complexation process) is observed. It may be necessary to wait for a few days for these reactions to occur.
  • the selected support may be added in each of the steps outlined above.
  • Procedure 2 starts with the dissolution of the metal complexes in an organic solvent. This is usually accomplished by a two-step procedure. At first, the minimum amount of water is used to dissolve the desired amount of each water-soluble metal complex. Typical examples include, but are not limited to: HAuCl 4 , H 2 IrCl 6 , H 2 PtCl 6 , Li 2 PdCl 4 , (NH 4 ) 2 IrCl 6 , (NELO 2 OsCl 6 , (NH 4 )PdCl 4 , (NH 4 ) 2 PdCl 6 , (NH 4 ) 2 PtCl 4 , (NH 4 ) 2 PtCl 6 , (NH 4 ) 3 RhCl 6 , (NH 4 ) 2 RuCl 6 , KAuCl 4 , KPt(NH 3 )Cl 3 , K 2 PdCl 4 , K 2 PtCl 4 , K 2 PdCl 6 , K 2 PtCl 6
  • organic solvent Typical examples include, but are not limited to: N-methylpyrrolidone, dimethylformamide, dimethylacetamide, acetonitrile, etc...
  • a further coordinating agent may be dissolved into the organic solvent.
  • the molecules of the organic solvent may act as the coordinating agent themselves.
  • New metal coordination compounds soluble in the desired organic solvent and characterized by labile ligands are thus formed.
  • the desired networking agents are dissolved in a suitable organic solvent; typical examples include, but are not limited to: N-methylpyrrolidone, dimethylformamide, dimethylacetamide, acetonitrile, etc...
  • the solutions containing the metal complexes obtained previously are added, leading to the development of the 3D networking of the precursor.
  • the chemical reaction is considered complete when one of the above- mentioned transitions (sol-gel and/or gel/plastic; coagulation and/or flocculation and/or precipitation; metal-ligand complexation process) is observed. It may be necessary to wait for a few days for these reactions to occur.
  • the support may be added in each of the steps outlined above.
  • the organic solvent is removed from the product, for instance by evaporation, and the precursor can undergo the other steps of the preparation procedure.
  • the obtained precursor undergoes a thermal treatment as described below.
  • the material is kept under dynamic vacuum at 10 "3 bar for 16-24 hours at 150-200°C, then a first step is performed stabilizing the material at a higher temperature (300-1200°C) for no longer than two hours. Lastly, a further thermal treatment under dynamic vacuum (10 "3 bar) is performed at high temperature (400-1200°C), lasting between one and six hours. The resulting material is finely ground and subsequently washed repeatedly with water so as to remove soluble reaction byproducts such as halides.
  • the washed material is activated with hydrogen peroxide, 10% vol., and is eventually dried.
  • the chemical reactions involved in the preparation of the precursor result in a compact and homogeneous material where the desired quantity of metallic centres is uniformly distributed.
  • the thermal treatment performed under vacuum removes most of the oxygen and hydrogen atoms of the organic binder from the material; furthermore, it provides the energy necessary to activate the nucleation and growth of the carbon nitride-based clusters of the desired metals.
  • the clusters are of nanometric size and have the programmed chemical composition.
  • the electron-conducting support provides a matrix featuring an extremely large surface area where the catalytic material based on mono-plurimetallic carbon nitrides is supported; furthermore, it guarantees to the material the electrical conductivity necessary for its operation.
  • the main aim of the prolonged washing with bidistilled water is the removal from the electro- active material of possible halide-based soluble derivatives: should they bind permanently on the active cluster sites, they would compromise the catalytic activity of the material.
  • the treatment with hydrogen peroxide is performed so as to "clean" the external surface of the clusters from impurities which could both poison the active catalytic sites and make the active metallic area of the material smaller.
  • This example reports the detailed description of the synthesis of a material of the type S-MPM- CN for the cathodic reduction of oxygen based on platinum and nickel.
  • 1067 mg of sucrose were dissolved in the minimum amount of milli-Q water ( ⁇ 2 ml), yielding a viscous, transparent solution.
  • 400 mg Of K 2 PtCl 4 and 332 mg Of K 2 Ni(CN) 4 with a hydration degree of 30% were each dissolved in the minimum amount of milli-Q water ( ⁇ 2 ml), yielding a deep red solution (A) and a clear yellow solution (B), respectively.
  • the transparent sucrose solution was equally divided among A and B.
  • the product was re-introduced into a quartz tube, where it underwent a further thermal treatment at 600°C under dynamic vacuum for two hours. Afterwards, the sample was removed from the tube, finely ground in a mortar and eventually washed four times with milli-Q water to remove the soluble byproducts and the chloride ions deriving from the chemical reactions involved in the preparation of the material. At the end of each washing step the mother waters were separated from the sample by centrifugation at 4500 rpm for 15 minutes.
  • the resulting wet slurry was then transferred to a Petri capsule and treated with about 20 ml of hydrogen peroxide, 10% vol. A significant evolution of bubbles was observed.
  • the Petri dish was placed under an IR lamp to remove the water yielding the final material.
  • This example includes the synthesis and characterization procedures of materials of the type S- MPM-CN for the cathodic reduction of oxygen based on platinum and nickel.
  • the preparation of the material is exactly the same as the one described in Example 1, with the only difference that the final thermal treatment, lasting two hours, was performed at 900°.
  • This example reports the detailed description of the synthesis of a material of the type S-MPM- CN for the cathodic reduction of oxygen based on platinum and iron.
  • sucrose 1067 mg were dissolved in the minimum amount of milli-Q water ( ⁇ 2 ml), yielding a viscous, transparent solution.
  • 400 mg of K 2 PtCl 4 and 814 mg of K 4 Fe(CN) 6 -SH 2 O were each dissolved in the minimum amount of milli-Q water ( ⁇ 2 ml), yielding a deep red solution (A) and a clear yellow solution (B), respectively.
  • the transparent sucrose solution was equally divided among
  • a and B 533 mg of XC-72R carbon black was added to each of A and B; the resulting black suspensions were diluted with about 5 ml of milli-Q water each to ensure a sufficiently low viscosity.
  • A was added dropwise into B; the final product was stirred for 2 hours and then allowed to rest overnight. The resulting black suspension was dried, treated and activated as described in
  • MPM-CN for the cathodic reduction of oxygen based on platinum and iron.
  • the preparation of the material is exactly the same as the one described in Example 3, with the only difference that the final thermal treatment, lasting two hours, was performed at 900°.
  • sucrose 1280 mg were dissolved in the minimum amount of milli-Q water ( ⁇ 2 ml), yielding a viscous, transparent solution.
  • 595 mg of K 3 Co(CN) 6 were then dissolved in B, yielding a clear yellow solution.
  • the transparent sucrose solution was equally divided among A and B.
  • This example includes the synthesis and characterization procedures of materials of the type S- MPM-CN for the cathodic reduction of oxygen based on palladium, cobalt and nickel.
  • the preparation of the material is exactly the same as the one described in Example 5, with the only difference that the final thermal treatment, lasting two hours, was performed at 500°, 700° and 900° for the PdCoNi-CNi 500/G, PdCoNi-CNi 700/G, PdCoNi-CNi 900/G materials, respectively.
  • MPM-CN for the cathodic reduction of oxygen based on palladium, cobalt and nickel.
  • MPM-CN for the cathodic reduction of oxygen based on palladium, cobalt and nickel.
  • the preparation of the material is exactly the same as the one described in Example 9, with the only difference that the final thermal treatment, lasting two hours, was performed at 500°, 700° and 900° for the PdCoNi-CN h 500/G, PdCoNi-CN h 700/G, PdCoNi-CN h 900/G materials, respectively.
  • the cathode catalytic layer of a membrane-electrode assembly was prepared using a commercial EC-20 electrocatalyst provided by ElectroChem Inc. using a Pt loading of about 0.4 mgp t /cm 2 .
  • the gas diffusion layers applied to the anodic and cathodic sides of each MEA were P50 and P50T carbon paper provided by Ballard Power Systems.
  • the active layer of each MEA was characterized by an area of about 4
  • Nafion 117 membranes provided by Ion Power were used for all the MEAs as polymer electrolytes.
  • a commercial MEA provided by ElectroChem Inc. was used as the reference; it was assembled on a Nafion 117 membrane with the EC-20 electrocatalyst on both the anode and the cathode side.
  • Each electrode featured an area of 1 cm 2 and was characterized by a platinum loading of 1 mgp t /cm 2 .
  • the polarization curves of all the MEAs were collected in the same conditions: temperature of the anode/cell/cathode: 85/85/85°C; hydrogen flow rate: 800 seem; air flow rate: 1.7 slpm; oxygen flow rate: 1 slpm; relative humidity of the reactants: 100%; back pressure of the reactants: 65 psig.
  • Each MEA was allowed to operate for a few hours before collecting the final polarization curves reported in this patent.
  • the current and power values were normalized on the mass of noble metals effectively located on each cathode. This operation was performed since in fuel cells fed with pure hydrogen the loading of precious metals at the anode can be as low as 1/8 with respect to the cathode without any significant degradation in the performance of the overall
  • Oxidant Air Oxidant: Pure Oxygen
  • Target DOE 2010 0.3 It is observed that the supported platinum-based materials (i.e., PtNi-CNi 600/G, PtNi-CNi 900/G, PtFe-CNi 600/G, PtFe-CNi 900/G) provide very good performances, much better than those obtained with the reference MEA. In particular, the performance always falls between the DOE status of 2006 and the target set for 2010, almost reaching it in the case of PtNi-CNi 600/G, PtNi-CNi 900/G and PtFe-CNi 600/G materials mounted at the cathode of MEAs fed with pure oxygen. However, it should be highlighted that even if the MEAs are fed with air very good performances are achieved, much better than those obtained with the reference MEA and surpassing the DOE status of 2006.
  • the palladium-based materials i.e., PdCoNi-CNi 500/G, PdCoNi-CNi 600/G, PdCoNi-CN, 700/G, PdCoNi-CNi 900/G, PdCoNi-CN 1 , 500/G, PdCoNi-CN h 600/G, PdCoNi- CN h 700/G, PdCoNi-CN h 900/G
  • Procedure 1 i.e., PdCoNi-CNi 500/G, PdCoNi-CNi 600/G, PdCoNi-CNi 700/G, PdCoNi-CNi 900/G
  • the materials prepared starting from precursors obtained following Procedure 2 provide results comparable with those of the reference MEAs when they are applied to MEAs fed with pure oxygen.
  • the cost of palladium on the open market is much lower with respect to platinum (between three and four times less). While palladium-based systems provide a worse performance with respect to those based on platinum, the former are nevertheless interesting as they lead to the possibility to prepare fuel cells capable to produce electric power at a lower unit cost.
  • Fig. 1 Performance curves of the materials indicated in the graph mounted on the cathode of MEAs prepared as described in the text, a) Polarization curves normalized on both the electrode surface are and the PGM mass mounted on the cathode, b) Polarization curves normalized only on the PGM mass mounted on the cathode, c) Power curves normalized on the PGM mass mounted at the cathode. Test conditions: temperature of the anode/cell/cathode: 85/85/85°C; hydrogen flow rate: 800 seem; air flow rate: 1.7 slpm; relative humidity of the reactants: 100%; back pressure of the reactants: 65 psig.
  • Fig. 6 Performance curves of the materials indicated in the graph mounted on the cathode of MEAs prepared as described in the text. Data were normalized as reported in the description of Fig. 1. Tests were performed as reported in the description of Fig. 2.

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  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Ceramic Engineering (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Fuel Cell (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne la préparation d'électrocatalyseurs destinés à être montés sur l'anode ou la cathode de piles à combustible ou d'électrolyseurs à H2. Les matériaux décrits dans l'invention sont particulièrement appropriés pour une application dans des piles à combustibles à membrane électrolytique polymère (PEMFCs), des piles à combustible à méthanol direct (DMFCs), des piles à combustible alcalines (AFCs) et des piles à combustible à acide phosphorique (PAFCs). L'objet de l'invention est la préparation d'électrocatalyseurs à noyau-enveloppe dans lesquels des sites métalliques actifs supportés sur des nanoagrégats de nitrure de carbone (enveloppe) sont supportés sur des matériaux conducteurs d'électrons (noyau) appropriés tels que des charbons actifs ou des nanopoudres métalliques. Les matériaux préparés présentent une composition métallique bien contrôlée et comprennent également la quantité d'azote souhaitée. Le protocole de préparation comprend trois étapes. Dans la première, le précurseur est obtenu par réactions du type: a) sol-gel; b) gel-plastique; c) coagulation-floculation-précipitation; d) des procédés de complexage métal-ligand dans un solvant organique utilisant, en tant que ligand, une molécule, une macromolécule ou un système macromoléculaire. La seconde étape consiste en un procédé de pyrolyse du précurseur dans une atmosphère inerte conduisant à la production des matériaux de nitrure de carbone supportés. Dans la dernière étape, l'activation chimique et électrochimique de l'électrocatalyseur est mise en oeuvre. Les précurseurs sont obtenus par l'intermédiaire de réactions conduisant: a) au complexage d'un métal de transition avec une autre molécule ou complexe de coordination se comportant comme un ligand pour obtenir des agrégats; b) à la liaison en réseau 3D des agrégats obtenus par l'intermédiaire de molécules organiques appropriées et/ou de macromolécules et/ou de systèmes macromoléculaires sur le support.
PCT/IT2009/000278 2008-06-26 2009-06-22 Électrocatalyseurs à base de nitrure de carbone mono/plurimétallique à noyau-enveloppe pour piles à combustible à basse température (pemfcs, dmfcs, afcs) et électrolyseurs Ceased WO2009157033A2 (fr)

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ITPD2008A000188 2008-06-26
IT000188A ITPD20080188A1 (it) 2008-06-26 2008-06-26 Elettrocatalizzatori "nocciolo-guscio" a base di carbonitruri mono/plurimetallici per celle a combustibile a bassa temperatura (pemfc, dmfc, afc e pafc) ed elettrolizzatori

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