Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/90—Selection of catalytic material
  • H01M4/9008—Organic or organo-metallic compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/42—Silicides
• • 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
  • H01M4/8807—Gas diffusion layers
• • 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
  • H01M4/8867—Vapour deposition
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M2008/1095—Fuel cells with polymeric electrolytes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells

Definitions

• the present invention relates to the field of supported catalyst layers. More particularly, it relates to the use of organometallic complexes of platinum (Pt) for the chemical vapor deposition of PtSi on the surface of a support.
• Pt platinum
• the platinum-based catalytic layers have applications in many fields, for example air catalysis (treatment of pollutants: volatile organic compounds (VOCs), nitrogen oxides (NOx)), the generation of hydrogen by reforming of hydrocarbons, biofuels or the storage of hydrogen by adsorption, filtration of water, etc.
• air catalysis treatment of pollutants: volatile organic compounds (VOCs), nitrogen oxides (NOx)
• VOCs volatile organic compounds
• NOx nitrogen oxides
• the catalytic layer is an essential element in the membrane-electrode assembly.
• the fuel cell electrodes are the seat of electrochemical reactions (oxidation of hydrogen at the anode and reduction of oxygen at the cathode), said reactions being possible only in the presence of a catalyst.
• such electrodes comprise a support for mechanical resistance comprising at least one electronically conductive microporous layer, also called diffusion layer, coated with a catalytic layer and in contact with a proton conductor (generally a motherboard).
• the catalyst generally used is platinum implemented in the form of spherical particles whose diameter is of the order of a few nanometers. These catalyst particles are deposited on carbon particles whose diameter is of the order of a few tens of nanometers (20 to 80 nm inclusive) which may be in the form of agglomerates.
• the set is usually called "platinum carbon” or "Pt / C”.
• the active layers are produced in two different ways: the ionomer and the platinum carbon are suspended in solvents. This suspension, called ink, is then deposited on the membrane or on the diffusion layer to form the active layers after evaporation of the solvents; or the ionomer is impregnated (for example by spraying) onto a previously manufactured porous layer containing the platinum carbon and a non-conductive protonic polymer binder.
• the best active layers of Pt nanoparticles made by conventional techniques, have an electro-active surface of about 250 cm 2 of Pt per 1 cm 2 of geometric area (in other words a roughness factor of 250) and contain about 0 , 4 mg Pt / cm 2 , ie an electro-active mass area of the order of 65 m 2 / g of Pt.
• unsupported catalysts mention may be made of the production by Choi et al. [5] electrodes with unsupported catalyst using platinum nanowires electrodes.
• the idea is to use elongated rather than spherical catalyst structures to increase the electro-active mass area.
• this method leads to a mass electro-active surface area of Pt of 2 m 2 / g, unsatisfactory with respect to the values obtained with conventional catalytic layers.
• the present invention aims to propose the preparation of a new catalytic layer having an increased electro-active surface for a given Pt loading.
• the present invention thus relates, according to a first of its aspects, to the use, as a precursor for the chemical vapor deposition of PtSi at the surface of a support, of at least one organometallic complex of Pt comprising at least:
• the R units are chosen, independently of one another, from (C 1 -C 4) alkoxy groups;
• R 'units being chosen, independently of one another, from (C 1 -C 4 ) alkyl and (C 3 -C 4 ) cycloalkyl groups;
• It also relates, in another of its aspects, to a process for forming a PtSi-based catalytic layer on the surface of a support, comprising at least one step of chemical vapor deposition of PtSi at the surface of said support, from one or more organometallic compounds of Pt as defined above.
• Chemical vapor deposition (known by the abbreviation CVD or "Chemical Vapor Deposition” in English), especially from organometallic compounds (MOCVD or "Metalo-Organic Chemical Vapor Deposition” in English) is a good technique. known for obtaining controlled deposits of good quality. This technique is particularly preferred for liquid-phase impregnation which requires a large amount of deposited material, is likely to induce a deposit inhomogeneity due to the flow of liquid and requires a heat treatment step (drying and calcination).
• the MOCVD consists in vaporizing a volatile precursor of the metal, namely an organometallic complex, which will thermally decompose on the substrate to form a metal layer.
• the CVD deposition of a film or Pt particles on a support from Pt organometallic complexes is described in FR 2 940 980.
• the present invention further aims, according to another of its aspects, a support having a catalytic layer based on PtSi, characterized in that at least 20% by weight, preferably at least 40% by weight of the Pt forming the electrostatic surface. -active said layer, therein present in a form coordinated with silicon.
• the present invention relates to a support having a catalytic layer based on PtSi obtained according to the method described above.
• the catalytic layer based on PtSi according to the invention has a mass electro-active surface greater than or equal to 500 cm 2 / mg, preferably greater than or equal to 800 cm 2 / mg.
• a PtSi-based catalytic layer according to the invention is more particularly applicable in proton exchange membrane fuel cells.
• the present invention relates to a proton exchange membrane fuel cell comprising a support having a catalytic layer as defined above.
• the support more particularly forms all or part of one or more electrodes of said cell, in particular the anode.
• the invention thus makes it possible to obtain electrodes for PEMFC cells with high electrocatalytic reactivity and having a reduced platinum loading, thus making it possible to reduce costs.
• a PEMFC stack incorporating a catalytic layer according to the invention may have a platinum loading rate of less than or equal to 0.05 g Pt / A, preferably less than or equal to 0.02 g Pt / A.
• the CVD deposition from the organometallic complexes of the invention can be achieved at temperatures lower than those usually employed in MOCVD techniques. More particularly, for the CVD deposit, the substrate to be treated can be brought to a temperature ranging from 150 to 380 ° C. Such a reduced temperature makes it possible to envisage the use of substrates of various natures, in particular of more fragile substrates. Other characteristics, variants and advantages of the formation of a catalytic layer based on PtSi according to the invention will emerge more clearly on reading the description, examples and figures which will follow, given by way of illustration and not limitation.
• organometallic complexes of Pt comprising at least:
• R units being chosen, independently of each other, from (C 1 -C 4) alkoxy groups, in particular being tributoxy groups;
• R 'units being chosen, independently of one another, from (C 1 -C 4) alkyl and (C 3 -C 4) cycloalkyl groups; in particular from (C 1 -C 4) alkyl groups and more particularly being methyl groups; and
• (C 1 -C 4) alkoxy group is meant a -O- (C 1 -C 4) alkyl group.
• (C 1 -C 4) alkyl group is meant a saturated, linear or branched aliphatic group comprising from 1 to 4 carbon atoms.
• (C3-C4) cycloalkyl group is meant a cyclic alkyl group comprising 3 or 4 carbon atoms.
• the organometallic complex may be of formula (I) below:
• R 1 and R 2 are a ligand selected from:
• R units are chosen, independently of one another, from (C 1 -C 4) alkoxy groups
• R 'units being chosen, independently of each other, from (C 1 -C 4) alkyl and (C 3 -C 4 ) cycloalkyl groups; in particular from (C 1 -C 4 ) alkyl groups; and
• the organometallic complex used according to the invention comprises two ligands chosen from O-Si (R) 3 and N- (Si (R ') 3 ) 2 , R and R' being as defined above.
• the two ligands are of the same nature.
• the ligand may be selected from O-Si (OtBu) 3 and N- (TMS) 2 , with TMS representing trimethylsiloxane.
• An organometallic complex according to the invention may comprise a ligand other than the above-mentioned O-Si (R) 3 and N- (Si (R ') 3 ) 2 ligands. It may be in particular a halogen-type ligand such as a chlorine atom.
• the organometallic complex is the (cod) Pt (OSi (OtBu) 3 ) 2 .
• the organometallic complex is (cod) Pt (Cl) (N (TMS) 2 ).
• organometallic complexes can be synthesized synthetic methods known to those skilled in the art, and more particularly developed in Example 1.
• the complex (cod) Pt (OSi (OtBu) 3 ) 2 can be synthesized by reaction of (tBuO) 3 SiONa with the (cod) PtCl 2 , according to a method similar to that described in the publication Ruddy et al. [6].
• the organometallic complexes according to the invention are capable of decomposing at a temperature below 200 ° C., in particular below 150 ° C., in particular around 130 ° C. .
• Such a decomposition temperature makes it possible to envisage the CVD deposition by heating the substrate to be treated at temperatures lower than those usually used for the CVD deposits, as developed hereinafter.
• the support on which is formed the catalytic layer according to the invention depends of course on the intended application.
• It may be in particular a ceramic, a heat-resistant polymer, a glass, a perovskite such as LaA10 3 , Si, SiC, a textile having a microporous carbonaceous surface layer.
• the support may be a carbon support, in particular porous.
• the porous support may more particularly be a filter support for catalysis such as a foam or honeycomb. It can have a porosity of 2 to 600 cpsi (channels per square inch) and / or 2 to 60 ppi (pores per square inch).
• the support may also be a diffusion layer type support (known in English as “gas diffusion layer” (GDL)), usually implemented for fuel cells.
• GDL gas diffusion layer
• GDL generally consists of a fibrous structure treated with a hydrophobic material, a slice of silica (better known under the name of "wafer” in English), layers of glass, or a structure of honeycomb type.
• the support used according to the invention may comprise one or more intermediate layers, in particular chosen from: metal films, an organic layer, diffusion layers for example consisting of at least one material selected from carbon, graphite, nanotubes.
• Chemical vapor deposition can be carried out by any method known to those skilled in the art.
• the chemical vapor deposition comprises at least two steps: a first step of vaporizing the precursor under conditions that do not affect its stability, and a second step of decomposing the precursor on a support.
• the CVD deposition is carried out by a method of chemical vapor deposition with liquid injection of organometallic precursors (also known under the name “Direct Liquid Injection Metal Organic Chemical Vapor Deposition” ( DLI-MOCVD)).
• organometallic precursors also known under the name “Direct Liquid Injection Metal Organic Chemical Vapor Deposition” ( DLI-MOCVD)
• the principle of DLI-MOCVD comes from classical CVD systems. This principle is for example described in WO 2007/088292.
• the organometallic complexes are supplied in liquid form and injected at high pressure by injectors.
• the organometallic complexes are thus introduced into the deposition chamber, in which the support to be treated is located.
• the complexes are then subjected to a decomposition which causes the formation of the deposit on said support.
• This method advantageously makes it possible to control the morphology of the particles as a function of the CVD parameters (mass of product injected, injection frequency, duration of the deposition) and allows an easy implementation on an industrial scale.
• Figure 1 schematically shows a standard device for the deposition by DLI-MOCVD.
• Such a device is more particularly formed of a reservoir for storing the precursor solution (1), an injector (2) connected to the liquid reservoir via a feed line, a carrier gas supply line, for example N 2 , an evaporator (7), a gas distribution system (4).
• the deposition chamber (5) which contains the support to be treated (6), comprises a heating system, a gas supply (3) and means for pumping and pressure regulation.
• the said organometallic complex (s) may be dissolved beforehand in a solvent adapted to the process, in particular which does not react with the precursor or with the support.
• a solvent adapted to the process in particular which does not react with the precursor or with the support.
• it may be toluene.
• DLI-MOCVD it is up to those skilled in the art to adjust the conditions of deposition by DLI-MOCVD, such as, for example, the concentration of organometallic complexes in the solution, the pressure and temperature conditions, the nature of the reactive gas, in particular in view of the nature of the substrate, the surface to be treated, the thickness of the desired catalytic layer, etc.
• the vaporization is done under pressure and temperature conditions to obtain a precursor vapor pressure sufficient for the deposit, while remaining in its stability range.
• the substrate in turn, is heated beyond this stability range, which allows the decomposition of the organometallic complex and the formation of the catalytic layer.
• the enclosure can be placed:
• a neutral atmosphere in particular using a gas chosen for example from N 2 , Ar, He, or
• oxygen having the advantage of promoting the combustion of organic materials, or
• the chemical vapor deposition is carried out in a chamber under atmosphere O 2 + N 2 , for example formed of 20% by weight of N 2 and 80% by weight of O 2 .
• the chemical vapor deposition is carried out at a pressure ranging from 1 mbar to 150 mbar, in particular from 1 to 5 mbar.
• the temperature at which the substrate to be treated is carried is always greater than or equal to the decomposition temperature of the precursor.
• the substrate for the CVD deposition from the organometallic complexes according to the invention can be heated at a temperature ranging from 150 ° C. to 380 ° C., in particular at a temperature of less than or equal to 300 ° C., especially a temperature of less than or equal to 270 ° C.
• the substrate (6) can be heated to a temperature of approximately 270 ° C., the evaporator (7) to approximately 100 ° C. and the distribution system gases (4) at about 130 ° C.
• Different conditions may make it possible to promote the deposition on the substrate, in particular with respect to a deposit on the walls of the enclosure.
• a reactive gas may be injected into the deposition chamber to promote the decomposition of the precursor (ALD process "atomic layer deposition” or deposit of atomic layers).
• the support may be subjected to at least one activation of its surface to be treated, to create hydroxyl bonds for modulating the intensities of the inking sites on the surface.
• This activation can more particularly consist of a thermal activation, a laser activation (LCVD), a UV activation, a plasma activation (PECVD), an ion beam activation or an electron beam activation (EBCVD). . Such activation is more particularly carried out simultaneously with the deposit.
• the CVD treatment from one or more organometallic complexes according to the invention makes it possible to obtain a catalytic layer based on PtSi.
• the catalytic layer formed has a homogeneous thickness and structure.
• the thickness of the catalytic layer formed on the support depends on the conditions used for the CVD deposition, in particular for DLI-MOCVD deposition, the precursor concentration used, the vaporization time, respective temperatures in the reactor and the support.
• the catalytic layer obtained may have a thickness ranging from 2 to 25 nm, in particular from 2 to 20 nm.
• the platinum of the catalytic layer formed is in the form of particles of nanometric size coordinated with nano-sized particles of Si, dispersed at the surface of the substrate.
• the nanoparticles of Pt and Si may more particularly have a size ranging from 1 to 100 nm in diameter, in particular from 1 to 10 nm, more particularly from 4 to 8 nm.
• the PtSi-based layer formed according to the invention has excellent catalytic properties.
• the catalytic layer formed according to the invention may have an electro-active surface ranging from 500 to 800 cm 2 Pt / cm 2 of surface of the treated support.
• the platinum loading can be between 2 and 7 ⁇ g Pt / cm 2 of the surface of the treated support.
• the catalytic layer according to the invention can thus have a mass electro-active surface greater than or equal to 500 cm 2 / mg of Pt.
• the mass electro-active surface of said catalytic layer obtained according to the process of the invention is greater than or equal to 600 cm 2 / mg Pt, in particular greater than or equal to 700 cm 2 / mg, and more preferably higher or equal to 800 cm 2 / mg of Pt.
• a catalytic layer based on PtSi according to the invention is more particularly applicable in the field of manufacturing proton exchange membrane fuel cells (PEMFC).
• the support having a catalytic layer according to the invention may more particularly form a part of one or more electrodes of said cell, in particular the anode.
• the platinum loading rate for the electrode may advantageously be less than or equal to 0.05 g Pt / A, preferably less than or equal to 0.04 g Pt / A, in particular less than or equal to 0.03 g Pt And more preferably less than or equal to 0.02 g Pt / A.
• a catalytic layer according to the invention is not limited to an application for fuel cells PEMFC type, but can be used for any other application of the catalyst layers, for example for devices catalyzing air, generating hydrogen by reforming hydrocarbons, or biofuels, storing hydrogen by adsorption or filtering water.
• Figure 1 schematic representation of the device for depositing by DLI-
• Figure 2 thermogravimetric analysis of the precursor (cod) Pt (OSi (OtBu) 3) 2 under N 2 (30 mL / min), heating at 10 ° C / min.
• Figure 3 TEM image of a catalytic layer according to the invention (Figure 3a) and size distribution diagram established from the TEM analysis ( Figure 3b).
• the complex (cod) Pt (OSi (OtBu) 3) 2 is synthesized according to a protocol similar to that described in reference [6], with the difference that the sodium salt (tBuO 2 SiONa is used in place of the sodium salt. potassium (tBuO ⁇ SiOK.
• This complex is formed by reaction of (tBuO) SiONa with (cod) PtCl 2 .
• the compound (tBuO) SiONa is synthesized from (tBuO) 3 SiOH and sodium in pentane.
• This complex is synthesized according to a protocol similar to that described by Wendt et al. [7], by reaction between LiN (TMS) 2 and CodPtCl 2 .
• the complex (cod) Pt (OSi (OtBu) 3) 2 prepared according to Example 1 was deposited according to a method of chemical vapor deposition with liquid injection of organometallic precursors (DLI-MOCVD), using a device as shown schematically in Figure 1 and according to the protocol detailed below.
• DLI-MOCVD liquid injection of organometallic precursors
• GDL gas diffusion layer type
• PTFE polytetrafluoroethylene
• the deposition by DLI-MOCVD is carried out according to the following protocol:
• the temperature setpoints are 100 ° C for the evaporator, 130 ° C for the gas distributor and 270 ° C for the sample holder.
• TEM Transmission Electron Microscopy
• Figure 3a shows the image obtained by TEM (120 keV)
• Figure 3b the size distribution diagram established from the TEM analysis.
• This analysis shows the formation of nanoparticles of Pt and Si, of average nanometric size ranging from 4 to 6 nm.
• EDX Energy dispersive analysis
• the catalytic layers formed on GDLs as described in Example 2 are tested in a membrane electrode assembly (MEA).
• MEA membrane electrode assembly
• the MEA is composed of two layers: the proton conductive membrane (ionomer perf uorosulfoné sold under the Nafion ® reference) and the gas diffusion layer comprising the catalyst.
• the LDGs as prepared in Example 2 were impregnated with a solution of Nafion ® (0.5% by weight in water / isopropanol 1: 1) using an airbrush (Nafion loading of about 100 ⁇ g.cm-2).
• Nafion ® 0.5% by weight in water / isopropanol 1: 1
• airbrush Nafion loading of about 100 ⁇ g.cm-2.
• the working electrode incorporating the MEA assembly active surface of 0.5 cm 2
• a reference electrode Hg / HgSO
• a counter electrode platinum
• the total number of reactive surface sites can be determined by measuring the absorption of hydrogen, followed by oxidation. This method is based on the measurement of the charge required to remove the monolayer absorbed from H, according to the reactions:
• the electroactive surface S can be obtained by the following equation:

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• 2012
  • 2012-01-17 FR FR1250458A patent/FR2985740A1/fr not_active Withdrawn
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