Catalytic modulation

Abstract

The present invention provides a method for preparing a catalytic material, the catalytic material comprising a support material and an electrocatalyst dispersed on the support material, the method comprising the steps of: i) providing a support material; then ii) depositing a silicon oxide precursor on the support material; then iii) performing a heat treatment step to convert the silicon oxide precursor to silicon oxide; then iv) depositing the electrocatalyst or a precursor to the electrocatalyst on the support material; and then v) removing at least a portion of the silicon oxide.

Description

[Technical Field]

[0001] The present invention relates to a method for preparing a catalytic material, which comprises adding silicon oxide to a support material prior to deposition of an electrocatalyst. [Background technology]

[0002] A fuel cell is an electrochemical cell containing two electrodes separated by an electrolyte. A fuel, e.g., hydrogen, an alcohol such as methanol or ethanol, or formic acid, is supplied to the anode, and an oxidant, e.g., oxygen or air, is supplied to the cathode. Electrochemical reactions occur at the electrodes, and the chemical energy of the fuel and oxidant is converted into electrical energy and heat. Electrocatalysts are used to promote the electrochemical oxidation of the fuel at the anode and the electrochemical reduction of oxygen at the cathode.

[0003] Fuel cells are typically classified according to the nature of the electrolyte used. In most cases, the electrolyte is a solid polymer membrane, which is electronically insulating but ionically conductive. In proton exchange membrane fuel cells (PEMFCs), the ion-conducting membrane conducts protons, and protons generated at the anode are transported across the ion-conducting membrane to the cathode, where they combine with oxygen to form water.

[0004] The main component of a PEMFC is a membrane electrode assembly, which essentially consists of five layers. The central layer is a polymeric ion-conducting membrane. On both sides of the ion-conducting membrane are electrocatalyst layers containing electrocatalysts designed for specific electrolysis reactions. Finally, adjacent to each electrocatalyst layer is a gas diffusion layer. The gas diffusion layers must allow reactants to reach the electrocatalyst layers and must conduct the electrical current generated by the electrochemical reactions. Therefore, the gas diffusion layers must be porous and electrically conductive.

[0005] The electrocatalyst layer also generally includes a proton-conducting material, such as a proton-conducting polymer, to aid in the transfer of protons from the anode electrocatalyst to the ion-conducting membrane and / or from the ion-conducting membrane to the cathode electrocatalyst.

[0006] Conventionally, membrane electrode assemblies can be constructed by a number of methods. Typically, this method involves applying one or both electrocatalyst layers to an ion-conducting membrane to form a catalyst-coated ion-conducting membrane. A gas diffusion layer is then applied to the electrocatalyst layer. Alternatively, an electrocatalyst layer is applied to a gas diffusion layer to form a gas diffusion electrode, which is then combined with the ion-conducting membrane. Membrane electrode assemblies can also be prepared by a combination of these methods, for example, applying one electrocatalyst layer to an ion-conducting membrane to form a catalyst-coated ion-conducting membrane and applying the other electrocatalyst layer as a gas diffusion electrode. The electrocatalyst layer is conventionally applied using an electrocatalyst ink containing the electrocatalyst material, the ion-conducting polymer, a solvent and / or diluent, and any agents desired to be included in the electrocatalyst layer.

[0007] The electrocatalyst layer generally comprises an electrocatalytic material comprising a metal or metal alloy suitable for fuel oxidation or oxygen reduction reactions, depending on whether the layer is used at the anode or cathode. Electrocatalysts for fuel oxidation and oxygen reduction are typically based on platinum or platinum alloyed with one or more other metals. Platinum or platinum alloy electrocatalysts can be in the form of unsupported nanometer-sized particles (e.g., metal black) or can be deposited as discrete ultra-high surface area nanoparticles, such as high surface area carbon materials, on an electrically conductive support material (supported electrocatalyst).

[0008] Suitable carbons typically include those from the carbon black family, such as oil furnace black, polar conductive black, acetylene black, and graphitized versions thereof. Exemplary carbons include Akzo Nobel Ketjen® EC300J and Cabot Vulcan® XC72R. Additionally, carbons specifically designed for fuel cell applications, such as those described in WO 2013 / 012894, can be used. Alternative materials for use as conductive supports include metal oxides or mixed oxides, particularly conductive mixed oxides such as niobia-doped titania, phosphorus-doped tin oxide, and mixed platinum group metal oxides or mixed metal oxides, such as those disclosed in WO 2012 / 080726.

[0009] The method of depositing an electrocatalyst on a support material can affect the electrochemical performance of the supported electrocatalyst. Furthermore, it is important that the method for depositing the electrocatalyst on the support material be efficient and have a low environmental impact. Summary of the Invention

[0010] Accordingly, in a first aspect, the present invention provides a method of preparing a catalytic material, the catalytic material comprising a support material and an electrocatalyst dispersed on the support material, the method comprising: i) providing a support material; and then ii) depositing a silicon oxide precursor on a support material; and then iii) carrying out a heat treatment step to convert the silicon oxide precursor into silicon oxide, and then iv) depositing the electrocatalyst or a precursor of the electrocatalyst on a support material; and then v) removing at least a portion of the silicon oxide.

[0011] For the avoidance of doubt, steps i), ii), iii), iv) and v) must be performed in the order listed: i), ii), iii), iv), then v).

[0012] Surprisingly, the inventors have found that catalytic materials prepared by this method provide membrane electrode assemblies that perform better than similar catalytic materials prepared by conventional methods that do not involve the addition of silicon oxide prior to electrocatalyst deposition, followed by removal of at least a portion of the silicon oxide.

[0013] The present invention also provides, in a second aspect, a catalytic material obtainable by the method of the present invention.

[0014] In a third aspect, the present invention provides an electrocatalyst layer comprising a catalytic material according to the second aspect of the present invention and an ion-conducting polymer, wherein the weight ratio of ion-conducting polymer to support material is in the range of 1:3 to 6:5, inclusive. It is surprising and advantageous that the catalytic material of the present invention can be used in an electrocatalyst layer with reduced amounts of ion-conducting polymer compared to conventional electrocatalyst layers, while maintaining a desired level of electrochemical activity. Reducing the amount of ion-conducting polymer can subsequently result in higher porosity and higher rates of gas and water transport in the electrocatalyst, thereby increasing the performance of the electrocatalyst layer within a membrane electrode assembly. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a bar graph showing voltages at 0.2, 1.0, and 1.6 A / cm2 at low humidity for a membrane electrode assembly containing a cathode electrocatalyst layer comprising a catalyst material prepared by a method of the present invention and a membrane electrode assembly containing a cathode electrocatalyst layer comprising a comparative catalyst material. [Figure 2] 1 is a temperature sweep plot at 1.0 A / cm for a membrane electrode assembly containing a cathode electrocatalyst layer comprising a catalyst material prepared by a method of the present invention and a membrane electrode assembly containing a cathode electrocatalyst layer comprising a comparative catalyst material. [Figure 3]1 is an oxygen concentration sweep plot at high humidity for a membrane electrode assembly containing a cathode electrocatalyst layer comprising a catalyst material prepared by the method of the present invention and a membrane electrode assembly containing a cathode electrocatalyst layer comprising a comparative catalyst material. DETAILED DESCRIPTION OF THE INVENTION

[0016] Preferred and / or optional features of the invention will now be described. Any aspect of the invention may be combined with any other aspect of the invention unless the context requires otherwise. Any preferred or optional feature of any aspect may be combined with any aspect of the invention, singly or in any combination, unless the context requires otherwise.

[0017] The support material provided in step i) is preferably in powder form, and is preferably a conductive carbon support material. The support material does not comprise an electrocatalyst. The carbon support material can be carbon black or graphitized carbon black, such as commercially available carbon blacks from Cabot Corp. (Vulcan® XC72R) or Akzo Nobel (Ketjen® Black series), or graphitized versions of these carbon blacks, or other commercially available carbon blacks such as acetylene black (e.g., available from Chevron Phillips (Shawinigan Black® or Denka®)). The carbon support material can also be one specifically designed for use in fuel cells, such as those described in WO 2013 / 045894. The support material is not limited to carbon support materials, but can be any porous support material suitable for supporting an electrocatalyst. Thus, the support material can be a metal oxide or mixed oxide, in particular, niobia-doped titania, as disclosed in WO 2012 / 080726. titania), conductive mixed oxides such as phosphorus-doped tin oxide and mixed platinum-based metal oxides or mixed metal oxides, carbides (e.g. tungsten carbide, molybdenum carbide or titanium carbide, preferably tungsten carbide or titanium carbide), or nitrides, in particular conductive nitrides (e.g. titanium nitride or titanium aluminium nitride).

[0018] The catalytic material prepared by the method of the present invention comprises an electrocatalyst dispersed on a support material. Thus, the catalytic material is a supported electrocatalyst, and the term "supported" will be readily understood by those skilled in the art. For example, the term "supported" will be understood to include an electrocatalyst that is bound or immobilized to a support material by physical or chemical bonding. For example, the electrocatalyst may be bound or immobilized to the support material by ionic or covalent bonding, or by non-specific interactions such as van der Waals forces. The catalytic material comprises a support material and an electrocatalyst, preferably consists essentially of a support material and an electrocatalyst, and more preferably consists of a support material and an electrocatalyst.

[0019] The electrocatalyst is preferably suitable for use in a fuel cell or electrolyzer, more preferably a proton exchange membrane fuel cell or electrolyzer. Accordingly, the catalytic material is preferably a fuel cell or electrolyzer catalytic material, more preferably a proton exchange membrane fuel cell or electrolyzer catalytic material. Accordingly, the catalytic material may be a proton exchange membrane fuel cell anode or cathode catalytic material. Accordingly, the electrocatalyst is preferably (i) platinum group metals (platinum, palladium, rhodium, ruthenium, iridium, and osmium); (ii) gold or silver; (iii) base metals; or an alloy or mixture containing one or more of these metals or their oxides. The base metal is tin or a transition metal that is not a noble metal. The noble metal is a platinum group metal (platinum, palladium, rhodium, ruthenium, iridium, or osmium) or gold. Preferred base metals are copper, cobalt, nickel, zinc, iron, titanium, molybdenum, vanadium, manganese, niobium, tantalum, chromium, and tin. Preferably, the electrocatalyst is not an alloy; i.e., preferably, the electrocatalyst is a reduced monometallic electrocatalyst selected from platinum group metals (platinum, palladium, rhodium, ruthenium, iridium, and osmium), preferably platinum. When the electrocatalyst is an alloy, it is preferably an alloy, preferably binary, of a platinum group metal, preferably platinum, with a base metal, preferably a preferred base metal defined above, more preferably nickel or cobalt, most preferably nickel. The atomic ratio of platinum group metal, preferably platinum, to alloying metal is typically within the range of 3:1 to 1:3, inclusive.

[0020] The silicon oxide precursor is any compound that can be converted to silicon oxide during the heat treatment step. The silicon oxide precursor can be a siloxane compound, i.e., a compound having an Si-O-Si bond. The siloxane can be formed by the reaction of one or more alkoxysilanes ((3-aminopropyl)triethoxysilane (APTE), 3-aminopropyl(diethoxy)methylsilane (APDME), tetraethylorthosilicate (TEOS), or methyltriethylorthosilicate (MTEOS)). Alternatively, the siloxane compound can be formed from a silazane, a chlorosilane, or a dimethylaminosilane. The heat treatment step allows the silicon oxide precursor to be converted to silicon oxide. The heat treatment step is preferably carried out in a reducing atmosphere, for example, under hydrogen or a mixture of hydrogen and an inert gas. Alternatively, the reducing atmosphere can be provided by carbothermal reduction. Preferably, the heat treatment step is carried out under a mixture of hydrogen and an inert gas. The heat treatment step is suitably carried out at a temperature in the range of 250°C to 500°C, preferably 290°C to 400°C, inclusive. Preferably, the heat treatment step is carried out as a single heat treatment step, i.e., not in two or more stages, and not with intermediate stages such as cooling stages, but in a single stage of heating at the required temperature (e.g., from room temperature to the required temperature, with a rise of 1 to 5°C / min). The silicon oxide present after step iii) is preferably present in an amount of 20 wt.% or less, preferably 15 wt.%, more preferably 12 wt.%, based on the weight of the support material. The silicon oxide present after step iii) is preferably present in an amount of at least 2 wt.%, more preferably at least 4 wt.%, based on the weight of the support material.

[0021] The electrocatalyst can be deposited in step iv) by any method known to those skilled in the art for depositing an electrocatalyst on a support material, and is compatible with the silicon oxide applied in step iii), i.e., the material produced in step iii) is not exposed to conditions that would remove the silicon oxide, e.g., conditions that are not sufficiently basic to dissolve the silicon oxide. For example, a method using a metal oxide sol and a reduction step, such as those described in WO 2005 / 123255, can be used. Alternatively, a method using an aqueous solution of a metal acid or salt and a reduction step, such as those described in WO 2013 / 045894, can be used. The alloy electrocatalyst can be deposited using any method known to those skilled in the art, such as the methods disclosed in WO 2014 / 184546 or WO 2017 / 203257. For the avoidance of doubt, the phrase "depositing the electrocatalyst or a precursor of the electrocatalyst on a support material" in step iv) refers to depositing on the silicon oxide-coated support material prepared in step iii). Preferably, all (e.g., 100%) of the electrocatalyst contained in the catalytic material is deposited in step iv) prior to step v). In this case, step v) provides the catalytic material. The alternative in which a precursor of the electrocatalyst is deposited in step iv) preferably applies to embodiments in which the electrocatalyst is an alloy electrocatalyst. In this alternative, the method includes an additional step vi) after step v) of forming the electrocatalyst to provide the catalytic material. The precursor may suitably be, for example, a constituent metal of the alloy electrocatalyst. In this case, step vi) includes depositing the remaining metals and forming an alloy to provide the catalytic material, for example, according to the methods disclosed in WO 2014 / 184546 or WO 2017 / 203257.

[0022] Although essentially all of the silicon oxide is removed in step (v), it is preferred that a small amount of silicon oxide is not harmful. Therefore, step (v) removes most, preferably essentially all, of the silicon oxide from the support material. The silicon oxide can be removed using a fluorination process or a hydrolysis process, preferably using a hydroxide solution, particularly a basic solution such as tetraethylammonium hydroxide. Up to 5 wt.%, preferably 4 wt.% or less, more preferably up to 2 wt.%, and even more preferably up to 1 wt.%, of silicon oxide, based on the weight of the support material, can remain on the catalyst material after removal. Removing essentially all of the silicon oxide means that the silicon oxide can be removed so that ≧0 wt.% and less than 1 wt.%, preferably less than 0.5 wt.%, preferably less than 0.01 wt.%, of silicon oxide, based on the weight of the support material, remains on the catalyst material.

[0023] The electrocatalyst loading in the catalytic material may be expressed in terms of the weight percent of active metal, e.g., platinum group metal, relative to the total weight of the catalytic material, which can be determined using inductively coupled plasma mass spectrometry (ICPMS). The loading may suitably be at least 10 wt.% active metal, e.g., platinum group metal. The electrocatalyst loading may suitably be 90 wt.% or less active metal, e.g., platinum group metal, typically 60 wt.% or less active metal, e.g., platinum group metal, for example, 50 wt.% or less active metal, e.g., platinum group metal, relative to the total weight of the catalytic material. This is controlled in the method of the present invention by controlling the weight ratio of active metal, e.g., platinum group metal, to the support material in step iv) of the method.

[0024] The electrocatalyst layer of the present invention comprises an ion-conducting polymer, such as a proton-conducting polymer. Thus, the ion-conducting polymer may comprise an ionomer, such as a perfluorosulfonic acid material (e.g., perfluorosulfonic acid ionomer materials from Nafion® (Chemours Company), Aciplex® (Asahi Kasei), Aquivion® (Solvay Specialty Polymer), Flemion® (Asahi Glass Co.), and 3M®), or an ionomer based on a partially fluorinated or non-fluorinated hydrocarbon that is a sulfonated or phosphonated polymer, such as those available from FuMA-Tech GmbH as the fumapem® P, E, or K series of products, or from JSR Corporation, Toyobo Corporation, etc. Preferably, the ionomer is a perfluorosulfonic acid ionomer, particularly the Nafion® series available from Chemours, particularly Nafion® 1100EW, the Aquivion® series available from Solvay, particularly Solvay® 830EW, and 3M 825EW perfluorosulfonic acid ionomer. It is surprising and advantageous that the catalyst material of the present invention can be used in an electrocatalyst layer with a reduced amount of ion-conducting polymer compared to conventional electrocatalyst layers, while maintaining or even improving electrochemical activity. Reducing the amount of ion-conducting polymer can increase the performance of the electrocatalyst layer in a membrane electrode assembly by resulting in higher porosity and higher rates of gas and water transport in the electrocatalyst layer. Therefore, the weight ratio of ion-conducting polymer to support material is preferably within the range of 1:3 to 6:5, preferably 1:1 to 4:5, alternatively preferably 1:2 to 4:5, more preferably 2:3 to 4:5 (including the upper and lower limits thereof).

[0025] The electrocatalyst loading in the electrocatalyst layer will depend on the intended application. In this context, the electrocatalyst loading is defined as mg / cm2 For example, in a fuel cell cathode, the loading is typically at least 0.05 mg / cm. 2 and 1.0 mg / cm 2 For fuel cell anodes, the loading is typically at least 0.02 mg / cm 2 and 1.0 mg / cm 2 For example, when the electrocatalyst in the fuel cell cathode is a platinum alloy, the electrocatalyst loading is mgPt / cm 2 For example, in a fuel cell cathode containing a platinum-containing electrocatalyst, the electrocatalyst loading is preferably at least 0.05 mg Pt / cm 2 , typically 1.0 mgPt / cm 2 Preferably, 0.75 mgPt / cm or less 2 Below, for example, 0.5 mgPt / cm 2 or less than 0.3 mgPt / cm 2 For fuel cell anodes, the electrocatalyst loading is preferably at least 0.02 mg Pt / cm 2 , typically 1.0 mgPt / cm 2 Preferably, 0.75 mgPt / cm or less 2 Below, for example, 0.5 mgPt / cm 2 or less, or 0.2 mg / Ptcm 2 The following is the result.

[0026] The electrocatalyst layer may contain additional components. For example, a proton exchange membrane fuel cell electrocatalyst layer of the present invention may contain an oxygen evolution reaction catalyst along with a hydrogen oxidation reaction (anode) or oxygen reduction reaction (cathode) electrocatalyst. Such additional components may also include, but are not limited to, a hydrogen peroxide decomposition catalyst, a hydrophobic additive (e.g., a polymer such as polytetrafluoroethylene (PTFE) or an inorganic solid, with or without a surface treatment) or a hydrophilic additive (e.g., a polymer or inorganic solid, such as an oxide) to control reactant and water transport properties. The selection of additional components is within the ability of one skilled in the art and is determined depending on the application of the electrocatalyst layer.

[0027] To prepare the electrocatalyst layer, the catalyst material of the present invention and any additional components are dispersed in an aqueous and / or organic solvent to form a catalyst ink. If necessary, particle disruption is performed by methods known in the art, such as high-shear mixing, milling, ball milling, passage through a microfluidizer, or the like, or a combination thereof, to achieve a suitable particle size distribution. After preparing the catalyst ink, the ink is deposited on a substrate (e.g., a gas diffusion layer, an ion-conducting membrane, or a support material / transfer substrate) to form the electrocatalyst layer. The ink may be deposited by any suitable technique known in the art, including, but not limited to, gravure coating, slot die (slot, extrusion) coating, screen printing, rotary screen printing, inkjet printing, spraying, painting, bar coating, pad coating, gap coating techniques such as knife or doctor blade over roll, and metering rod application.

[0028] The electrocatalyst layer may be deposited on a gas diffusion layer to form the gas diffusion electrode of the present invention. The gas diffusion layer comprises a gas diffusion substrate and, preferably, a microporous layer. When the microporous layer is present, the electrocatalyst layer is deposited on the microporous layer. Typical gas diffusion substrates include nonwoven papers or webs comprising a carbon fiber network and a thermosetting resin binder (e.g., TGP-H series of carbon fiber papers available from Toray Industries Inc. (Japan), H2315 available from Freudenberg FCCT KG (Germany), Sigracet® series available from SGL Technologies GmbH (Germany), or Ballard Power Systems Examples of suitable carbon substrates include the AvCarb® series manufactured by Epson Corporation, or woven carbon cloth. Carbon paper, web, or cloth can be pretreated prior to electrode fabrication and incorporated into membrane electrode assemblies to make it either more wettable (hydrophilic) or more resistant to wettability (hydrophobic). The nature of any optional treatment depends on the type of fuel cell and the operating conditions used. The substrate can be made more wettable by incorporating materials such as amorphous carbon black via impregnation from a liquid suspension, or made more hydrophobic by impregnating the substrate's pore structure with a colloidal suspension of a polymer such as PTFE or polyfluoroethylenepropylene (FEP), followed by drying and heating above the softening point of the polymer. A typical microporous layer comprises a mixture of carbon black and a polymer such as polytetrafluoroethylene (PTFE).

[0029] In the catalyst-coated ion-conducting membrane of the present invention, an electrocatalyst layer is deposited on the ion-conducting membrane by coating a catalyst ink directly onto the membrane or indirectly by transfer from a decal transfer substrate to form the catalyst-coated ion-conducting membrane. The catalyst-coated ion-conducting membrane of the present invention may include a second electrocatalyst layer on its opposite surface, which may or may not be in accordance with the present invention. The ion-conducting membrane is preferably any membrane suitable for use in proton exchange membrane fuel cells; for example, the membrane may be based on perfluorinated sulfonic acid materials such as Nafion™ (Chemours Company), Aquivion® (Solvay Specialty Polymers), Flemion® (Asahi Glass Group), and Aciplex™ (Asahi Kasei Chemicals Corp.), as well as perfluorosulfonic acid ionomer materials manufactured by 3M®. Alternatively, the membrane may be based on a sulfonated hydrocarbon membrane, such as those available from FuMA-Tech GmbH as the fumapem® P, E, or K series of products, or those available from JSR Corporation, Toyobo Corporation, and others.

[0030] The thickness of the ion-conductive membrane is not particularly limited and depends on the intended use of the ion-conductive membrane. For example, a typical fuel cell ion-conductive membrane has a thickness of at least 5 μm, preferably at least 8 μm, and more preferably at least 10 μm. A typical fuel cell ion-conductive membrane has a thickness of 50 μm or less, preferably 30 μm or less, and more preferably 20 μm or less. Thus, a typical fuel cell ion-conductive membrane has a thickness within the range of 5 to 50 μm, preferably 8 to 30 μm, and more preferably 10 to 20 μm (including the upper and lower limits).

[0031] The ion-conducting membrane may contain additional components, such as a peroxide decomposition catalyst and / or a radical decomposition catalyst, and / or a recombination catalyst. The recombination catalyst catalyzes the recombination of unreacted H and O, which can diffuse from the anode and cathode of the fuel cell, respectively, into the ion-conducting membrane to produce water. The ion-conducting membrane may also contain a reinforcing material, such as a planar porous material (e.g., expanded polytetrafluoroethylene (ePTFE) as described in USRE 37307), embedded within the thickness of the ion-conducting membrane to provide improved ion-conducting membrane strength, such as increased tear resistance and reduced dimensional change upon hydration and dehydration, thus further increasing the durability of the membrane electrode assembly and the lifespan of fuel cells incorporating the catalytic ion-conducting membranes of the present invention. Other approaches to forming reinforced ion-conducting membranes include those disclosed in U.S. Patent Nos. 7,807,063 and 7,867,669, where the reinforcement is a rigid polymer film, such as a polyimide, into which multiple pores are formed and then filled with a PFSA ionomer. The selection of additional components is within the ability of one skilled in the art to determine depending on the application of the electrocatalyst layer.

[0032] Any reinforcement present may extend across the entire thickness of the ion conductive membrane, or may extend through only a portion of the thickness of the ion conductive membrane. It will be understood that the thickness of the ion conductive membrane extends perpendicular to the plane of the ion conductive membrane, e.g., it is in the z-direction of the penetration plane. It may be further advantageous to reinforce the periphery of the first and second surfaces of the ion conductive membrane to a greater extent than the central plane of the first and second surfaces of the ion conductive membrane. Conversely, it may be desirable to reinforce the center of the first or second surface of the ion conductive membrane to a greater extent than the periphery of the first or second surface of the ion conductive membrane.

[0033] The catalyst ink is coated onto the decal transfer substrate to deposit the electrocatalyst layer on the decal transfer substrate, forming a catalyst decal transfer substrate. Prior to removal of the decal transfer substrate, additional layers may be deposited on the exposed surface of the electrocatalyst layer; for example, an ion-conducting ionomer layer may be applied from an ionomer dispersion using any suitable known deposition technique, as described above with respect to the deposition of the electrocatalyst layer. Additional layers may be added as needed, for example, as described in PCT Patent Application No. GB2015 / 050864. The decal transfer substrate is then removed from the electrocatalyst layer at an appropriate time. The decal transfer substrate may be formed from any suitable material that can be removed without damaging the electrocatalyst layer. Examples of suitable materials include fluoropolymers such as polytetrafluoroethylene (PTFE), ethylene tetrafluoroethylene (ETFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene propylene (FEP - a copolymer of hexafluoropropylene and tetrafluoroethylene), and polyolefins such as biaxially oriented polypropylene (BOPP).

[0034] As will be understood by those skilled in the art, the membrane electrode assembly of the present invention can be constructed in several ways, provided that it includes at least one electrocatalyst layer of the present invention. For example, the membrane electrode assembly can include a catalyst-coated ion-conductive membrane of the present invention including two electrocatalyst layers, at least one of which is an electrocatalyst layer of the present invention, with a gas diffusion layer applied to each electrocatalyst layer. Alternatively, the membrane electrode assembly can include an ion-conductive membrane sandwiched between two gas diffusion electrodes, with at least one of the two gas diffusion electrodes being a gas diffusion electrode of the present invention. The membrane electrode assembly can also include a catalyst-coated ion-conductive membrane having one electrocatalyst layer and a gas diffusion electrode on the opposite side of the ion-conductive membrane, with either or both of the electrocatalyst layer and the gas diffusion electrode being of the present invention. [Example]

[0035] Preparation of catalytic materials A catalytic material consisting of 50 wt. % Pt / C was prepared by the following method according to the present invention. 10 g of carbon black was slurried in 1 L of demineralized water, and 150 ml of 35% ammonia solution was added with stirring. The mixture was heated to 60°C before adding 7.64 g of tetraethylorthosilicate (TEOS). After stirring for 2 hours, the mixture was allowed to cool to ambient temperature, then filtered and washed with demineralized water. The resulting solid was dried overnight at 105°C, then heated to 350°C at a rate of 2°C / min under 5% H2 / N2 and held for 3 hours to convert the SiO2 precursor to SiO2. After cooling to ambient temperature, the fired, SiO2-coated carbon intermediate was then dispersed in 1 L of demineralized water, and 10 g of Pt was added according to the procedure disclosed in WO 2005 / 123255. The sample was collected by filtration, washed with demineralized water, and then redispersed in 1 L of demineralized water. 210 ml of a 35 wt. % tetraethylammonium hydroxide solution was added with stirring, and the mixture was stirred overnight at ambient temperature. The product was then collected by filtration, washed with demineralized water, and dried overnight at 105°C.

[0036] The comparative catalyst material used was 50% Pt / C, where the carbon support is carbon specifically designed for use in fuel cells as described in WO 2013 / 045894, prepared by a conventional deposition process without the use of silicon oxide.

[0037] Preparation of membrane electrode assembly The catalyst material prepared by the method of the present invention and the comparative catalyst material were used in the cathode electrocatalyst layer. Cathode electrocatalyst layer ink (cathode ink) was prepared by wetting the catalyst material with a PFSA ionomer (Nafion® 1100EW) dispersed in a 20% water / 80% propan-1-ol mixture. The mixture was mechanically stirred using an overhead stirrer until all the catalyst was wetted and dispersed in the liquid. The ink was then processed by ball milling to form a well-dispersed ink. Three such inks were prepared: EL1: Contains a catalyst prepared according to the present invention and 70% by weight of ionomer of the support material. EL2: Comparative catalyst material and support material containing 70% ionomer by weight. EL3: Comparative catalyst material and support material containing 90% ionomer by weight.

[0038] The anode electrocatalyst layer ink (anode ink) was prepared by wetting the anode catalyst material with a PFSA ionomer (Nafion® 1100EW) dispersed in an 83% water / 17% propan-1-ol mixture. The anode electrocatalyst material was 20% Pt / XC72R. This mixture was mechanically stirred using an overhead stirrer until all the catalyst was wetted and dispersed in the liquid. The ink was then processed through an Eiger ball mill to form a well-dispersed ink.

[0039] The anode ink and cathode inks EL1, EL2, and EL3 were deposited onto a PTFE sheet to form an electrocatalyst layer, and a 50 cm thick electrode was fabricated by transferring the appropriate layer to either side of a PFSA-reinforced membrane (20 μm thick) at a temperature of 150°C to 200°C. 2 The catalyst loading of the cathode electrocatalyst was 0.2 mg Pt / cm. 2 The amount of the anode electrocatalyst supported was 0.1 mg Pt / cm 2 It was.

[0040] Gas diffusion layers were applied to each side of each catalyst-coated ion-conductive membrane to form complete membrane electrode assemblies MEA1, MEA2, and MEA3. The gas diffusion layers used were carbon fiber paper with a carbon-containing hydrophobic microporous layer and PTFE applied to the side in contact with the catalyst-coated ion-conductive membrane. MEA1 included a cathode electrocatalyst layer formed from EL1, MEA2 included a cathode electrocatalyst layer formed from EL2, and MEA3 included a cathode electrocatalyst layer formed from EL3.

[0041] Membrane electrode assembly performance test Pure oxygen, air or synthetic air was used as the cathode reactant and pure H2 as the anode reactant (all gases 99.9% pure).

[0042] The stoichiometric flow rates of the anode (s = 2 for H) and cathode (s = 9.5 for O and s = 2 for air) reactants are such that the current density is >0.2 A cm -2 It is used at a constant flow rate (0.2Acm -2 (corresponding to a stoichiometric flow rate) but with a current density <0.2 A cm -2 The cell was used in a 1000-kJ / s ...

[0043] The MEA was operated at 500 mAcm under H2 / air at 100 kPa gauge, 100% RH, and 80°C. -2The cathode catalyst layer was then conditioned by applying a constant current density of 500 mA cm. The cell voltage was monitored until a stable value was observed. Unless otherwise stated, the conditioning step lasted for 2 hours. The cathode catalyst layer was then exposed to a series of cathode starvation steps followed by a current density of 500 mA cm until a stable voltage was observed. -2 The cathode was held at 50 cm for 2 hours. The cathode starvation step (purging the cathode compartment with pure nitrogen) reduces the cathode voltage to below 0.1 V and is intended to provide an electrochemical cleaning step for the cathode catalyst before measuring its activity under H / O. 2 Polarization curves for the single cells were performed in H2 / (O2 and air) at an inlet pressure of 100 kPa gauge, 80°C, and a relative humidity at the cell inlet of 100% RH or 30% RH. The cell current density was held at each point for 10 minutes, and the cell voltage was averaged over the last minute of this hold. The cell voltages under H2 / air shown in the figure were recorded in the descending voltage direction, from low to high currents. The polarization curves under H2 / (O2, air) were not corrected for internal (ohmic) resistance.

[0044] Temperature sweeps were performed under H2 / air at 50 cm 2 The experiments were carried out on a single cell. The anode and cathode stoichiometry was set at 2, and the anode and cathode pressure was controlled at 100 kPa gauge at the cell inlet. The dew point of the anode and cathode humidifiers was controlled at 53°C, while the cell temperature was varied from 35 to 90°C. This has the effect of very high humidity at low temperatures and very low humidity at high temperatures. Temperature sweeps were recorded from low to high temperatures at the specified 53°C dew point, and the cell voltage was not corrected for internal resistance. The current density was 1000 mA / cm for 10 minutes at each temperature. 2 The voltage was held at 100 Hz and the voltage was averaged from the data recorded during the last minute of the hold.

[0045] Oxygen concentration sweep was performed at 50 cm 2 The current density was 1000 mA / cm. 2The oxygen concentration was fixed at 0.05°C, while the oxygen concentration was varied from 100% O2 to 75, 50, 30, 21, and 10% using N2 as the diluent gas. Cell humidity was controlled at 100% RH, and cell temperature was maintained at 80°C. The anode and cathode stoichiometries were set at 2 and 10, respectively. The current density was held at each oxygen concentration for 10 minutes, and the voltage was averaged from the data recorded during the last minute of the hold. The oxygen concentration sweep was not corrected for internal resistance.

[0046] Experimental results Figure 1 shows the current density at 0.2, 1.0, and 1.6 A / cm under hot, dry conditions (80°C and 30% RH at 50 kPa-gauge inlet). 2 The performance of MEA1 is compared to that of MEA2 and MEA3 at 1000 kJ / s. It can be seen that at all current densities, MEA1, which uses the catalyst material prepared by the method of the present invention, performs significantly better than MEA2, a comparable MEA using catalyst material prepared by a conventional method. A conventional method for improving performance under hot dry conditions is to add a higher percentage of ionomer to the cathode catalyst layer. This was done for MEA3, which contains the comparative catalyst material on the cathode side. As expected, performance increased compared to MEA2, but was still lower than MEA1 at all current densities. This demonstrates that the process of the present invention allows for the use of less ionomer while simultaneously achieving better performance across a range of current densities than MEAs made with the comparative catalyst material.

[0047] Figure 2 shows the current at 1.0 A / cm 2This shows that at moderate current densities, MEA 1, containing a cathode electrocatalyst layer comprising a catalyst material prepared by the process of the present invention, performs better (has higher voltage) than MEAs containing electrocatalyst layers comprising conventional catalyst materials, i.e., MEA 3, over a range of hot, dry conditions (65-90°C with a dew point of 53°C). It is particularly surprising that MEA 1, whose cathode electrocatalyst layer contains only 70% ionomer by weight relative to the carbon support material, performs better than MEA 3, whose cathode electrocatalyst layer contains 90% ionomer by weight relative to the carbon support material. Typically, MEAs with higher ionomer levels in the cathode are expected to perform better under hot, dry conditions. Therefore, with catalyst materials prepared by the process of the present invention, less ionomer can be used, which means higher porosity in the electrocatalyst layer and higher rates of gas and water transport.

[0048] As shown in Figure 3, under lower oxygen concentrations (i.e., closer to real-world operating conditions), MEA 1 performs better than MEA 3. This demonstrates the advantages in electrochemical performance associated with using the methods of the present invention to prepare catalytic materials.

Claims

1. 1. A method of preparing a catalytic material, the catalytic material comprising a support material and an electrocatalyst dispersed on the support material, the method comprising: i) providing a support material; and then ii) depositing a silicon oxide precursor on said support material; and then iii) carrying out a heat treatment step to convert said silicon oxide precursor into silicon oxide; and then iv) depositing the electrocatalyst or a precursor of the electrocatalyst onto the support material; and then v) removing at least a portion of said silicon oxide.

2. 2. The method of claim 1, wherein in step v), after at least a portion of the silicon oxide is removed, up to 5 wt. % of the silicon oxide remains in the catalyst material.

3. The method according to claim 1 or 2, wherein the heat treatment step is carried out at a temperature in the range of 250°C to 500°C, inclusive.

4. The method of claim 1 or 2, wherein the support material is a conductive carbon material.

5. The method of claim 3 wherein the support material is a conductive carbon material.

6. 3. The method of claim 1 or 2, wherein the electrocatalyst is a reduced monometallic electrocatalyst.

7. The method of claim 3 , wherein the electrocatalyst is a reduced monometallic electrocatalyst.

8. 5. The method of claim 4, wherein the electrocatalyst is a reduced monometallic electrocatalyst.

9. 6. The method of claim 5, wherein the electrocatalyst is a reduced monometallic electrocatalyst.

10. A method for preparing an electrocatalyst layer comprising a catalyst material comprising a support material and an electrocatalyst dispersed on the support material, and an ion-conducting polymer, comprising: the weight ratio of ion-conducting polymer to support material is in the range of 1:3 to 6:5, inclusive; The method comprises: i) providing a support material; and then ii) depositing a silicon oxide precursor on said support material; and then iii) carrying out a heat treatment step to convert said silicon oxide precursor into silicon oxide; and then iv) depositing the electrocatalyst or a precursor of the electrocatalyst onto the support material; and then v) removing at least a portion of said silicon oxide to provide said catalytic material; and then vi) dispersing the catalyst material and the ion-conducting polymer in an aqueous solvent and / or an organic solvent to prepare a catalyst ink; and then vii) depositing said catalyst ink onto a substrate to form said electrocatalyst layer.

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