Oxygen evolution reaction catalyst

Abstract

The present invention provides an oxygen evolution reaction catalyst, the oxygen evolution reaction catalyst being an oxide material comprising iridium, tantalum, and ruthenium, the oxygen evolution reaction catalyst comprising a crystalline oxide phase having a rutile crystal structure, the crystalline oxide phase having a lattice constant a greater than 4.510 Å.

Description

[Technical field]

[0001] The present invention relates to oxygen evolution reaction catalysts, particularly, but not exclusively, to ternary oxide catalyst materials suitable for use in electrochemical fuel cells. [Background technology]

[0002] A fuel cell is an electrochemical cell that includes two electrodes separated by an electrolyte. A fuel, e.g., hydrogen, alcohols 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, converting the chemical energy of the fuel and oxidant into electrical energy and heat. Electrocatalysts are used to facilitate the electrochemical oxidation of the fuel at the anode and the electrochemical reduction of oxygen at the cathode.

[0003] Fuel cells are usually classified according to the nature of the electrolyte used. In most cases, the electrolyte is a solid polymer membrane that is electronically insulating but ionically conductive. In proton exchange membrane fuel cells, the membrane is proton conductive and protons generated at the anode are transported through the membrane to the cathode where they combine with oxygen to form water.

[0004] The main component of a proton exchange membrane fuel cell is a membrane electrode assembly, which is essentially composed of five layers. The central layer is a polymeric ion-conducting membrane. On either side of the ion-conducting membrane are electrocatalyst layers that contain electrocatalysts designed for a particular electrolysis reaction. Finally, adjacent to each electrocatalyst layer are gas diffusion layers. The gas diffusion layers must allow reactants to reach the electrocatalyst layers and must conduct the electrical current produced by the electrochemical reaction. Thus, the gas diffusion layers must be porous and electrically conductive. The membrane electrode assembly may be constructed by several methods. An electrocatalyst layer may be applied to a gas diffusion layer to form a gas diffusion electrode. Two gas diffusion electrodes may be placed on either side of an ion-conducting membrane and stacked together to form a five-layer membrane electrode assembly. Alternatively, an electrocatalyst layer may be applied to both sides of an ion-conducting membrane to form a catalyst-coated ion-conducting membrane. Subsequently, gas diffusion layers are applied to both sides of the catalyst-coated ion-conducting membrane. Finally, a membrane electrode assembly can be formed from an ion conducting membrane coated on one side with an electrocatalyst layer, a gas diffusion layer adjacent to the electrocatalyst layer, and a gas diffusion electrode on the opposite side of the ion conducting membrane.

[0005] Typically, tens or hundreds of membrane electrode assemblies are needed to provide enough power for most applications, so multiple membrane electrode assemblies are joined together to form a fuel cell stack. Field flow plates are used to separate the membrane electrode assemblies. The plates perform several functions: delivering reactants to the membrane electrode assemblies, removing products, providing electrical connections, and providing physical support.

[0006] It is known that there are many circumstances in which incorporating a water electrolysis catalyst into a fuel cell at either the anode or the cathode may prove beneficial. For example, WO 01 / 15247 describes how incorporating an additional or second catalyst composition in the anode for the purpose of electrolyzing water may improve the resistance of the fuel cell to cell voltage reversal. Cell voltage reversal may occur when the cell receives an insufficient fuel supply (e.g., as a result of fuel starvation). When this occurs, reactions other than fuel oxidation may take place in the fuel cell anode, including water electrolysis and oxidation of anode components. Oxidation of anode components is undesirable as it may result in significant degradation of the anode. Anode degradation may be reduced or avoided by incorporating a catalyst composition in the anode that promotes the oxygen evolution reaction, promoting water electrolysis over oxidation of anode components.

[0007] Another example of a situation where promoting water electrolysis may be beneficial is in the case of fuel cells where it is not practical or economical to purge hydrogen from the anode gas space with an inert gas such as nitrogen during shutdown or when the cell is restarted after being idle for some time. Both of these situations may result in a mixed composition of hydrogen and air on the anode while air is present on the cathode. Under these circumstances, as described by Tang et al. (Journal of Power Sources 158 (2006) 1306-1312), there may be an internal cell, which results in a high potential on the cathode. The high potential may cause oxidation of carbon, which is very damaging to the structure of the catalyst layer if it contains carbon. However, if the cathode layer can support oxygen evolution, the high potential may be used to drive water electrolysis rather than carbon corrosion.

[0008] Finally, in regenerative fuel cells, the electrodes are bifunctional, and both the anode and cathode must support two electrochemical reaction types at different times. When operating as a fuel cell, the cathode must reduce oxygen and the anode oxidizes hydrogen. When operating as an electrolyser, the cathode must generate hydrogen and the anode generates oxygen. It may therefore be beneficial to incorporate both conventional hydrogen oxidation and oxygen evolution reaction catalysts into the anode of such fuel cells, because in such an arrangement the anode can effectively carry out both the hydrogen oxidation and oxygen evolution reactions.

[0009] Various electrocatalysts for oxygen evolution reaction are known in the art. For example, WO 11 / 021034 discloses a catalyst layer comprising an electrocatalyst and an oxygen evolution reaction catalyst, the oxygen evolution reaction catalyst comprising iridium or iridium oxide and one or more metals M or oxides thereof, where M is selected from the group consisting of transition metals other than ruthenium and Sn.

[0010] However, it would be desirable to provide improved oxygen evolution reaction catalysts, and in particular to provide catalysts that can improve the stability of membrane electrode assemblies during repeated reversal events. Furthermore, because iridium is rare and can be expensive, it would be desirable to provide catalytic materials that perform similarly to known catalysts but use less iridium.

[0011] The present invention has been devised in light of the above considerations. Summary of the Invention

[0012] The present inventors have discovered that ternary oxides can overcome one or more of the problems described above.

[0013] Accordingly, in a first aspect, the present invention provides an oxygen evolution reaction catalyst, the oxygen evolution reaction catalyst being an oxide material comprising iridium, tantalum, and ruthenium; the oxygen evolution catalyst comprises a crystalline oxide phase having a rutile crystal structure; An oxygen evolution reaction catalyst is provided in which the crystalline oxide phase has a lattice constant, a, greater than 4.510 Å.

[0014] Iridium may be present in an amount ranging from 50 to 80 atomic % based on the total atomic composition of iridium, tantalum, and ruthenium species in the oxygen generation reaction catalyst. Preferably, iridium is present in an amount of less than 70 atomic %, more preferably at most 65 atomic %, based on the total atomic composition of iridium, tantalum, and ruthenium species in the oxygen generation reaction catalyst.

[0015] Tantalum may be present in an amount ranging from 10 to 40 atomic %, based on the total atomic composition of the iridium, tantalum, and ruthenium species in the oxygen generation reaction catalyst. Preferably, tantalum is present in an amount of at least 15 atomic %, based on the total atomic percentage of the iridium, tantalum, and ruthenium species in the oxygen generation reaction catalyst. Preferably, tantalum is present in an amount of at most 35 atomic %, based on the total atomic composition of the iridium, tantalum, and ruthenium species in the oxygen generation reaction catalyst.

[0016] Ruthenium may be present in an amount ranging from 1 to 20 atomic %, based on the total atomic percentage of iridium, tantalum and ruthenium species in the oxygen generation reaction catalyst. Preferably, ruthenium is present in an amount of at least 5 atomic %, based on the total atomic percentage of iridium, tantalum and ruthenium species in the oxygen generation reaction catalyst. Preferably, ruthenium is present in an amount of up to 15 atomic %, based on the total atomic composition of iridium, tantalum and ruthenium species in the oxygen generation reaction catalyst.

[0017] The amounts of iridium, tantalum, and ruthenium are determined by the molar amounts of iridium, tantalum, and ruthenium included in the material preparation and may be confirmed using inductively coupled plasma mass spectrometry (ICPMS).

[0018] The present inventors have found that an oxygen evolution reaction catalyst having a composition as described above can provide increased stability and provide a membrane electrode assembly with suitable activity while conserving iridium compared to some known oxygen evolution reaction catalysts, particularly when compared to binary mixed metal oxide oxygen evolution reaction catalysts such as IrTa-based or RuIr-based materials.

[0019] The oxygen generation reaction catalyst may optionally contain metal species other than iridium, tantalum, and ruthenium, for example, in an amount of up to 5 atomic % based on the total atomic composition of the metal species in the oxygen generation reaction catalyst, preferably up to 1 atomic % based on the total atomic composition of the metal species in the oxygen generation reaction catalyst. Preferably, iridium, tantalum, and ruthenium constitute substantially all of the metal species present in the oxygen generation reaction catalyst. In other words, the metal species in the oxygen generation reaction catalyst essentially consists of, or preferably consists of, iridium, tantalum, and ruthenium. The ratio of the sum of iridium, tantalum, and ruthenium to oxygen is typically about 1:2. The oxygen generation reaction catalyst may optionally contain metal species in metallic form, for example, in an amount of up to 5 atomic % based on the total atomic composition of the metal species in the oxygen generation reaction catalyst, preferably up to 1 atomic % based on the total atomic composition of the metal species in the oxygen generation reaction catalyst. Such metal species in metallic form may include iridium and / or tantalum.

[0020] The crystalline oxide phase has a rutile MO2 (M is the metal species) structure. Phase identification is performed by comparing the X-ray diffraction pattern with reference to the PDF-4+ database (2021 release). The material contains a single crystalline oxide phase with reflection intensities consistent with the rutile MO2 phase, but reflection positions inconsistent with IrO2. In other words, the crystalline oxide phase may be a single oxide structure containing iridium, tantalum, and ruthenium. The crystalline oxide phase may be a single oxide structure containing Ir x Ta y Ru zO2 (wherein x+y+z=1). For example, x may be 0.50 to 0.70, y may be 0.20 to 0.40, and z may be 0.05 to 0.15. In particular, x may be 0.55 to 0.65, y may be 0.25 to 0.35, and z may be 0.08 to 0.12.

[0021] The lattice constant a of the crystalline oxide phase is preferably greater than 4.550 Å. The upper limit of the lattice constant a is not particularly limited, but a is typically less than 4.800 Å, preferably less than 4.750 Å, and more preferably less than 4.650 Å. For example, the lattice constant a may be about 4.567 Å. The lattice constant c of the crystalline oxide phase may be greater than 3.120 Å, preferably greater than 3.140 Å. The upper limit of the lattice constant c is not particularly limited, but c is typically less than 3.180 Å, and preferably less than 3.160 Å. For example, the lattice constant c may be about 3.158 Å. The values ​​provided for the lattice constants a and c are obtained at ambient temperature, i.e., about 25° C. Powder X-ray diffraction (PXRD) data are collected using a Bruker AXS D8 diffractometer with CuKα radiation (λ=1.5406+1.54439Å) in reflection geometry over the range 10<2θ<130° in 0.04° steps. To extract the lattice parameters, the reflection profile is modeled using the fundamental parameter approach [2] with reference data collected from NIST660 LaB6, and a Pawley refinement is performed using Topas [1]. The data are fitted to 20-77°2Θ using a Pawley model in P42 / mnm (same space group as IrO2) to extract the lattice parameters. For comparison, rutile crystal phase parameters have been described for IrO2 (a=0.4498nm) and RuO2 (a=0.4491nm).

[0022] The crystalline oxide phase may have a crystallite size calculated from the (011) hkl reflection in the range of 6.0 nm to 16.0 nm, suitably 8.0 nm to 14.0 nm, preferably 10.0 nm to 12.0 nm. Powder X-ray diffraction (PXRD) data were collected using a Bruker AXS D8 diffractometer using CuKα radiation (λ=1.5406+1.54439 Å) in reflection geometry over the range 10<2θ<130° in 0.04° steps. Peak phase refinement is performed using Topas [1], modeling the reflection profile using a fundamental parameter approach [2] with reference data collected from NIST660 LaB6. Reflections from the rutile phase were fitted using a series of peaks with independent sample broadening to obtain crystallite sizes along the crystallographic planes. Crystallite sizes are calculated using the volume-weighted column height LVol-IB method. [3]

[0023] The oxygen evolution reaction catalyst may include an amorphous phase, preferably an amorphous oxide phase, such as an oxide of tantalum, typically tantalum pentoxide Ta2O5. However, the oxide material is predominantly a crystalline oxide phase. Preferably, the crystallinity of the oxygen evolution reaction catalyst, i.e., the area ratio of the crystalline oxide phase to the amorphous phase, is at least 90%, preferably at least 95%. Powder X-ray diffraction (PXRD) data was collected in reflection geometry using a Bruker AXS D8 diffractometer, using CuKα radiation (λ=1.5406+1.54439Å) over the range 10<2θ<130° in 0.04° steps. For the determination of crystallinity, the X-ray scattering data from the crystalline oxide phase and the amorphous phase are fitted from 20 to 77°2Θ. The total area from the peaks that model the contributions from the crystalline phase and from the total X-ray scattering is used to calculate the scattering percentage. Most preferably, substantially all of the oxide material is a crystalline oxide phase.

[0024] The oxygen evolution reaction catalyst has a molecular weight of at least 30 ml, as determined based on the N2 adsorption isotherm at 77 K in accordance with ISO standard 9277:2010. 2 / g. Preferably, the BET surface area is at least 35 m 2 / g, more preferably at least 40m 2 / g. By providing an increased BET surface area, the catalytic performance of the material can be improved. The upper limit of the surface area is not particularly limited, but examples include 200 m 2 / g.

[0025] In a second aspect, the present invention provides a method for the synthesis of an oxygen evolution reaction catalyst according to the invention, comprising the steps of: Providing an aqueous solution of compounds of iridium, tantalum, and ruthenium; spray drying the solution to form a dry powder; and c) subjecting the powder to calcination, thereby forming an oxygen evolution reaction catalyst.

[0026] Providing an aqueous solution of iridium, tantalum, and ruthenium compounds includes providing an aqueous solution of a compound of iridium and a compound of ruthenium; and mixing the aqueous solution with an aqueous solution of a compound of tantalum.

[0027] The iridium compound, tantalum compound, and ruthenium compound may be provided in suitable amounts to provide a desired ratio of iridium to tantalum to ruthenium, for example, a molar ratio of Ir:Ta:Ru of about 6:3:1. In the preparation of the oxygen evolution reaction catalyst, a calcination step is used. The calcination step may be a single calcination step. Alternatively, a two-stage calcination process may be used, in which the powder is subjected to calcination for a first specific time, followed by further calcination for a second specific time. The first and second calcination steps may be performed at the same temperature or at different temperatures. The single calcination step and the specific calcination time may be carried out at a temperature of about 400°C to about 800°C, preferably about 500°C to about 700°C. The first and second times may be the same or different. The length of the single calcination step, the first specific time for calcination and the second specific time for calcination may suitably be 1 hour or more, typically 3 hours or more. The length of a single firing step, the first specific time for firing and the second specific time for firing may suitably be up to 10 hours.

[0028] Optionally, additional processing steps can be carried out between the first and second firing steps, for example the powder can be stirred or ground. This has the advantage that agglomerates can be broken down before the second firing step, allowing for a more uniform firing. However, the first and second firing steps can be carried out consecutively, with no further processing steps being carried out between the first and second firing steps.

[0029] Calcination can be carried out in a suitable gas atmosphere, such as air, N2, Ar, He, CO2, CO, O2, H2, and mixtures thereof. Preferably, calcination is carried out in an air atmosphere.

[0030] The oxygen evolution reaction catalysts of the present invention may find use in a variety of electrochemical applications, however one particularly preferred application is in electrochemical fuel cells.

[0031] In a third aspect, the present invention provides a catalyst layer comprising an oxygen evolution reaction catalyst according to the present invention and a second electrocatalyst material, in which the oxygen evolution reaction catalyst of the present invention is the first electrocatalyst.

[0032] The second electrocatalyst material is preferably (i) the 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.

[0033] The second electrocatalyst material preferably does not include iridium or tantalum. Preferably, the second electrocatalyst material is an anode or cathode, preferably an anode, electrocatalyst material of a fuel cell. Typically, the second electrocatalyst material includes a platinum group metal other than iridium, or an alloy of a platinum group metal other than iridium, preferably a base metal, preferably a base metal as defined above. In particular, the second electrocatalyst material includes platinum, or an alloy of platinum with a base metal, preferably a base metal as defined above, more preferably titanium, vanadium, chromium, niobium, or tantalum. Alternatively, preferably, the second electrocatalyst material may include an alloy of platinum with another platinum group metal, preferably rhodium or ruthenium.

[0034] Preferably, the catalyst layer is an anode catalyst layer, preferably an anode catalyst layer for a proton exchange membrane fuel cell.

[0035] The loading of the primary metal, e.g., a platinum group metal as defined herein, of the second electrocatalyst material in the catalyst layer may be selected based on the intended use of the catalyst layer, in particular whether the catalyst layer is intended for use in an anode or a cathode. When used for an anode, preferably a proton exchange membrane fuel cell, the loading of the primary metal, e.g., a platinum group metal as defined herein, in the catalyst layer is suitably from 0.02 to 0.2 mg / cm. 2 , typically 0.02 to 0.15 mg / cm 2 , preferably 0.02 to 0.1 mg / cm 2 It could be.

[0036] The second electrocatalyst material is preferably in the form of particles, which may or may not be supported. The term "supported" will be readily understood by those skilled in the art. For example, the term "supported" is understood to mean that the electrocatalyst particles are dispersed on a support material and are bound or fixed to the support material by physical or chemical bonds. For example, the electrocatalyst may be bound or fixed to the support material by ionic or covalent bonds, or non-specific interactions such as van der Waals forces.

[0037] The oxygen evolution reaction catalyst of the present invention is preferably in the form of particles which may be supported or unsupported, preferably unsupported. The oxygen evolution reaction catalyst of the present invention is preferably in the form of particles dispersed in a catalyst layer.

[0038] When the particles are supported, the support material can be an electrically conductive carbon support material. Suitably, the support material is carbon powder, which can be, for example, carbon black or graphitized carbon black, such as commercially available carbon black (such as Cabot Corp. (Vulcan® XC72R) or Akzo Nobel (Ketjen® Black Series)). Another suitable carbon support material is acetylene black (such as that available from Chevron Phillips (Shawinigan Black®) or Denka). The support material can also be an electrically conductive carbon support material specifically designed for use in fuel cells, such as those described in WO 2013 / 045894. Alternatively, the support material can be a non-carbonaceous material. Examples of such support materials include titania, niobia, tantala, tungsten carbide, hafnium oxide, or tungsten oxide. Such oxides and carbides may also be doped with other metals to enhance their electrical conductivity, for example niobium doped titania.

[0039] The oxygen evolution reaction catalyst of the present invention and the second electrocatalyst material may be supported on the same support material or on different support materials.

[0040] The weight ratio of the oxygen evolution reaction catalyst of the present invention to the second electrode catalyst material in the catalyst layer may be 10:1 to 1:10. The weight ratio may be selected depending on whether the catalyst layer is intended for use in an anode or a cathode. In the case of an anode catalyst layer, preferably for a proton exchange membrane fuel cell, the weight ratio is preferably at least 0.5:1, preferably at least 0.75:1. The weight ratio is preferably at most 10:1, preferably at most 5:1, more preferably at most 2:1, even more preferably at most 1:1. In the case of a cathode catalyst layer, preferably for a proton exchange membrane fuel cell, the weight ratio is preferably 1:1 to 1:10, preferably 1:2 to 1:5.

[0041] The catalyst layer may include additional components in addition to the oxygen evolution reaction catalyst and the second electrode catalyst material according to the present invention. Such components may include, but are not limited to, ion-conducting polymers, such as proton-conducting polymers, included to improve ionic conductivity within the layer, hydrogen peroxide decomposition catalysts, hydrophobic additives (e.g., polymers such as polytetrafluoroethylene (PTFE) or inorganic solids, with or without surface treatment) or hydrophilic additives (e.g., polymers or inorganic solids such as oxides) to control reactant and water transport properties. The selection of additional components depends on whether the catalyst layer is used in the anode or cathode, and it is within the ability of a person skilled in the art to determine which additional components are appropriate.

[0042] To prepare the catalyst layer, the oxygen evolution reaction catalyst of the present invention, supported or unsupported, and the second electrode catalyst material, supported or unsupported, and any additional components may be dispersed in an aqueous and / or organic solvent to prepare the catalyst ink. If necessary, particle breakage may be performed by methods known in the art, such as high shear mixing, milling, ball milling, passing through a microfluidizer, and the like, or combinations thereof, to achieve a suitable particle size distribution. After preparation of the catalyst ink, the ink may be deposited on a substrate (e.g., a gas diffusion layer, an ion-conducting membrane, or a carrier / transfer substrate) to form the catalyst 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, gap coating techniques such as bar coating, pad coating, knife or doctor blade over roll, and application of a metering rod.

[0043] When a catalyst layer is deposited on a carrier / transfer substrate by coating the catalyst ink on the carrier / transfer substrate, a catalyst carrier / transfer substrate is formed. The carrier / transfer substrate is intended to be removed from the layer in a subsequent step. For example, a catalyst layer may be transferred to a gas diffusion layer or ion conductive membrane by decal transfer, and the carrier / transfer substrate is removed immediately after the transfer process or at some point thereafter.

[0044] Prior to removing the carrier / transfer substrate, additional layers may be deposited on the exposed surface of the catalyst layer, for example, an ion-conducting ionomer layer may be applied from an ionomer dispersion using any suitable deposition technique known as described above for depositing the catalyst layer. Further additional layers may be added as required, for example, as described in International Application No. GB2015 / 050864. The carrier / transfer substrate is removed from the catalyst layer at the appropriate time. The carrier / transfer substrate may be formed from any suitable material that allows the catalyst layer to be removed without damaging it. 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).

[0045] The properties of the catalyst layer, such as thickness, electrocatalyst loading, porosity, pore size distribution, average pore size, and hydrophobicity, vary depending on whether it is used in the anode or cathode. The thickness of the catalyst layer may be preferably at least 1 μm, typically at least 5 μm. The thickness of the catalyst layer may be preferably 15 μm or less, typically 10 μm or less.

[0046] In a fourth aspect, the present invention provides a gas diffusion electrode comprising a gas diffusion layer according to the third aspect and a catalyst layer.

[0047] Preferably, the catalyst layer is directly adjacent to the gas diffusion layer. This can be achieved, for example, by depositing the catalyst layer directly on the gas diffusion layer. The gas diffusion layer can be based on or include a conventional gas diffusion substrate. Typical substrates include nonwoven papers or webs containing a network of carbon fibers and a thermosetting resin binder (e.g., TGP-H series of carbon fiber papers available from Toray Industries Inc., Japan, or H2315 series available from Freudenberg FCCT KG, Germany, or Sigracet series available from SGL Technologies GmbH, Germany, or AvCarb series from Ballard Power Systems Inc.), or woven carbon cloth. Carbon papers, webs, or cloths can be pretreated prior to fabrication of the electrode and incorporated into the membrane electrode assembly to make it either more wettable (hydrophilic) or more resistant to wettability (hydrophobic). The nature of any 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 by impregnation from a liquid suspension, or made more hydrophobic by impregnating the pore structure of the substrate with a colloidal suspension of a polymer such as PTFE or polyfluoroethylenepropylene (FEP), followed by drying and heating above the melting point of the polymer. For applications such as proton exchange membrane fuel cells, a microporous layer can also be applied to the gas diffusion substrate on the side that contacts the catalyst layer. The microporous layer typically comprises a mixture of carbon black and a polymer such as polytetrafluoroethylene (PTFE).

[0048] In a fifth aspect, the present invention provides a catalytic membrane comprising an ion-conducting membrane according to the third aspect and a catalytic layer.

[0049] Here, a catalyst layer is deposited on the ion-conducting membrane by direct coating of a catalyst ink onto the membrane or by indirect transfer from a carrier or transfer substrate to form a catalyst-coated membrane. The ion-conducting membrane can be any membrane suitable for use in proton exchange membrane fuel cells, for example, the membrane can 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.). Alternatively, the membrane can be based on sulfonated hydrocarbon membranes such as those available as fumapem® P, E, or K series products from FuMA-Tech GmbH, JSR, Toyobo, and other companies. Alternatively, the membrane can be based on polybenzimidazole doped with phosphoric acid operating in the range of 120°C to 180°C.

[0050] The ion-conducting membrane component may include one or more materials that impart mechanical strength to the ion-conducting membrane component. For example, the ion-conducting membrane component may include a porous reinforcing material such as an expanded PTFE material or a nanofiber network, e.g., an electrospun fiber network.

[0051] The ion-conducting membrane may include one or more hydrogen peroxide decomposition catalysts, either as a layer on one or both sides of the membrane, or as a layer embedded within the membrane, uniformly dispersed throughout or within the layer. Examples of hydrogen peroxide decomposition catalysts suitable for use are known to those skilled in the art and include metal oxides such as cerium oxide, manganese oxide, titanium oxide, beryllium oxide, bismuth oxide, tantalum oxide, niobium oxide, hafnium oxide, vanadium oxide, and lanthanum oxide, suitably cerium oxide, manganese oxide or titanium oxide, preferably cerium dioxide (ceria).

[0052] The ionically conductive membrane component may optionally include a recombination catalyst, in particular a catalyst for the recombination of unreacted H2 and O2 that may diffuse into the membrane from the anode and cathode, respectively, to produce water. Suitable recombination catalysts include metals (e.g., platinum) on high surface area oxide support materials (silica, titania, zirconia, etc.). Further examples of recombination catalysts are disclosed in EP 0631337 and WO 00 / 24074.

[0053] In a sixth aspect, the present invention provides a membrane electrode assembly comprising a catalyst layer according to the third aspect, a gas diffusion electrode according to the fourth aspect, or a catalyst membrane according to the fifth aspect.

[0054] As will be understood by those skilled in the art, the membrane electrode assembly can be constructed by several methods, provided that it contains at least one catalyst layer. For example, the membrane electrode assembly can include a catalyst-coated ion-conducting membrane that includes two catalyst layers, at least one of which is the catalyst layer of the present invention, and a gas diffusion layer is applied to each catalyst layer. Alternatively, the membrane electrode assembly can include an ion-conducting membrane sandwiched between two gas diffusion electrodes, at least one of which is the gas diffusion electrode of the present invention. The membrane electrode assembly can also include a catalyst-coated ion-conducting membrane with one catalyst layer and a gas diffusion electrode on the opposite side of the ion-conducting membrane, and either or both of the catalyst layer and the gas diffusion electrode are of the present invention.

[0055] The electrochemical device in which the catalyst layer, gas diffusion electrode, catalyst membrane and membrane electrode assembly of the present invention can be used includes a fuel cell, in particular a proton exchange membrane.Accordingly, in a seventh aspect, the present invention provides a fuel cell comprising the catalyst layer according to the third aspect, the gas diffusion electrode according to the fourth aspect, the catalyst membrane according to the fifth aspect, or the membrane electrode assembly according to the sixth aspect.The fuel cell of the present invention is preferably a proton exchange membrane fuel cell.

[0056] Proton exchange membrane fuel cells can operate with hydrogen or hydrogen-rich fuels at the anode, or can be fueled with hydrocarbon fuels such as methanol. The catalyst layers, gas diffusion electrodes, catalyst membranes, and membrane electrode assemblies of the present invention can also be used in fuel cells where the membrane uses charge carriers other than protons, for example OH-2, such as those available from Solvay Solexis SpA, FuMA-Tech GmbH. - A conductive membrane is included.

[0057] The catalyst layers and gas diffusion electrodes of the present invention may also be used in other low temperature fuel cells that use liquid ionically conducting electrolytes such as aqueous acid and alkaline solutions or concentrated phosphoric acid. Another electrochemical device in which the catalyst layers, gas diffusion electrodes, catalyst membranes and membrane electrode assemblies of the present invention may be used is as the anode electrode of a regenerative fuel cell in which both hydrogen oxidation and oxygen evolution reactions are carried out.

[0058] The oxygen evolution reaction catalyst of the present invention may also be used in the anode of a proton exchange membrane electrolyzer. Thus, in an eighth aspect, the present invention provides an anode catalyst layer for a proton exchange membrane electrolyzer, the anode catalyst layer comprising the oxygen evolution reaction catalyst of the present invention. In a ninth aspect, the present invention provides a proton exchange membrane electrolyzer comprising the anode catalyst layer of the eighth aspect of the present invention. Those skilled in the art will appreciate that there are similarities between such a catalyst layer and the catalyst layer of the third aspect of the present invention, and that any aspect discussed above with respect to the catalyst layer of the third aspect of the present invention that is compatible with the anode of a proton exchange membrane electrolyzer is intended to apply to the catalyst layer of the eighth aspect of the present invention.

[0059] The present invention includes combinations of the described aspects and preferred features, except where such combinations are clearly essential or explicitly avoided. In particular, any aspect of the present invention may be combined with any other aspect of the present invention, unless the context otherwise requires. Any of the preferred or optional features of any aspect may be combined, singly or in any combination, with any aspect of the present invention, unless the context otherwise requires. [Brief description of the drawings]

[0060] BRIEF DESCRIPTION OF THE DRAWINGS Embodiments and experiments illustrating the principles of the present invention are now discussed with reference to the accompanying drawings. [Figure 1] 1 shows an X-ray diffraction pattern of an oxygen evolution reaction catalyst according to the present invention. [Diagram 2] 1 shows a plot of current versus cycle number in a wet cell for test buttons containing the oxygen evolution reaction catalyst of the present invention and a comparative oxygen evolution reaction catalyst. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0061] Aspects and embodiments of the present invention will now be discussed with reference to the accompanying figures and examples. Further aspects and embodiments will be apparent to those skilled in the art. All documents mentioned in this specification are incorporated herein by reference.

[0062] Two different materials were prepared and characterized. The first of these ("Example 1") is an oxygen evolution reaction catalyst according to the present invention. The second material ("Comparative Example 1") is an iridium tantalum mixed oxide oxygen evolution reaction catalyst as disclosed in WO 11 / 021034.

[0063] As shown and discussed below, oxygen evolution reaction catalysts according to the present invention have been found to exhibit slightly higher activity during wet cell testing than comparative materials, while providing iridium saving benefits (due to lower iridium content) and improved stability.

[0064] Example 1: Synthesis of ternary mixed oxide materials The synthesis method of the ternary mixed oxide according to this embodiment can be divided into three main steps: 1) providing an aqueous solution of compounds of iridium, ruthenium, and tantalum; 2) spray drying the resulting mixture; and 3) Calcining the product to form the oxygen evolution reaction catalyst.

[0065] TaCl5 (Alfa Aesar) was received in sealed ampoules of approximately 100 gms each. These were scored and the TaCl5 powder was poured into a glass bottle. The mass of TaCl5 was measured to an accuracy of + / - 0.01 g. 200 ml of concentrated HCl was measured and poured into a separate glass bottle. The TaCl5 was slowly dissolved in concentrated HCl under constant stirring. Using the measured mass of TaCl5, IrCl3 was weighed out to get a final Ir:Ta ratio of 6:3. It was then dissolved in a beaker containing 1400 ml of demineralized H2O under constant stirring. Similarly, RuCl3 was weighed out to get a final Ru:Ta of 1:3. It was then dissolved in the solution in the beaker. This process was repeated four more times to yield five separate bottles containing approximately 100 g of TaCl in 200 ml of concentrated HCl and five corresponding beakers containing IrCl and RuCl dissolved in HO with a molar ratio of Ir:Ta:Ru (6:3:1).

[0066] Prior to spray drying, TaCl5 (in concentrated HCl) was mixed and stirred with its corresponding IrCl3 and RuCl3 (in demineralized H2O) solutions. The mixture was fed through a 5 mm diameter silicone feed tube and a 1.0 ml nozzle and spray dried (GEA-Niro A / S mobile unit spray dryer) at an inlet temperature of 290°C, an atomizer pressure of 2 bar, and a flow rate of 9 kg / h ± 0.5 kg / h. The resulting powder was collected in a powder bottle and the process was repeated for each TaCl5 / IrCl3 and RuCl3 pair.

[0067] Each powder bottle containing the dried Ir / Ta / Ru chlorides was placed in a separate crucible and heated to a temperature of 500°C (10°C / min -1 The powder was then ground at 14000 RPM using a sieve mesh size of 0.08 cm to break down agglomerates. The ground powder was then heated at 500°C (10°C / min -1 The mixture was then further fired at a ramp rate of 100° C. for an additional 6 hours. This process was repeated for each crucible and each of the final products was blended on a roller.

[0068] Comparative Example 1: Synthesis of Binary Mixed Oxide Materials For comparison, an IrTa mixed oxide oxygen evolution reaction catalyst was prepared using a conventional method as disclosed in WO 2011 / 021034. Calcination was carried out at a temperature of 500° C., and the atomic percentages of iridium and tantalum were 70 and 30, respectively.

[0069] X-ray diffraction analysis FIG. 1 shows the X-ray diffraction pattern of the material produced according to Example 1.

[0070] X-ray Data Collection Powder X-ray diffraction (PXRD) data were collected using a Bruker AXS D8 diffractometer with CuKα radiation (λ=1.5406+1.54439Å) in reflection geometry over the range 10<2θ<130° in 0.04° steps. Phase identification was performed using Bruker AXS Diffrac Eva V4.2 (2014) with reference to the PDF-4+ database (2021 release). This showed that the material contains a single crystalline oxide phase with reflection intensities consistent with a rutile MO2 phase, but reflection positions inconsistent with IrO2.

[0071] Sample fit Pawley refinement and peak phase refinement were performed using Topas [1], modeling the reflection profile using a fundamental parameter approach [2] with reference data collected from NIST660 LaB6. The data were fitted from 20 to 77°2θ using the Pawley model in P42 / mnm (same space group as IrO2) to extract the lattice parameters. For the rutile phase, the data were fitted separately using a set of peaks with independent sample-dependent broadening to obtain crystallite sizes along a selection of crystallographic planes. Any amorphous material may be fitted using a separate set of peaks to allow for calculation of crystallinity. All crystallite sizes are calculated using the volume-weighted column height LVol-IB method. [3]

[0072] Table 1 provides the lattice constants a and c obtained from the data collected in Example 1.

[0073] [Table 1]

[0074] Table 2 provides the crystallite sizes obtained from the (011) hkl reflections.

[0075] [Table 2]

[0076] Preparation of buttons for wet cell testing An ink for each catalyst was made by mixing 100 mg of catalyst with 12 wt% Nafion 1100 water-based ionomer and 20 wt% IPA. The ink was then diluted with 4 g of ultrapure water and sprayed directly onto a sheet of Toray carbon paper Teflon-coated with 6% PTFE. The target catalyst loading was 20 μgIr / cm as measured using a Fischerscop XDV XRF. 2 A 20 mm circular punch was used to cut disks from the coated electrodes. The circular electrodes were immersed in a solution of 1 M H2SO4 and placed in a vacuum chamber, where the pressure was reduced to 400 mbar for 45 minutes to impregnate the electrodes with acid.

[0077] Wet battery iridium dissolution test The electrode was introduced into a standard three electrode electrochemical cell as the working electrode via a gold wire connector. The electrochemical cell had a Pd / C reference electrode, a Pt mesh counter electrode, and a volume of 100 ml was heated to 60 °C using a heating jacket supplied by a heated water bath. Oxygen was removed from the electrolyte by bubbling nitrogen gas through the electrolyte for at least 20 min. The potential of the working electrode was controlled using a potentiostat. First, the BOL activity of the electrode towards the oxygen evolution reaction (OER) was determined as a cyclic voltammogram, recorded by cycling the potential of the working electrode from 0 V to 1.35 V to 0 V vs. RHE at a scan rate of 50 mV / s. The potential of the electrode was then cycled 1000 times between 0.6 V to 1.35 V vs. RHE using a triangular waveform at 100 mV / s. Finally, the EOL activity of the electrode towards OER was determined as a cyclic voltammogram, recorded by cycling the potential of the working electrode from 0 V–1.35 V–0 V vs. RHE at a scan rate of 50 mV / s. A 1 ml sample of the electrolyte was taken after the BOL CV and before the EOL CV, and the Ir concentration in the electrolyte was measured by ICPMS.

[0078] 2 shows a plot of A / mg of iridium versus cycle number in wet cells for test buttons containing the oxygen evolution reaction catalyst of Example 1 of the present invention and the comparative oxygen evolution reaction catalyst of Comparative Example 1. The cycle data for both Example 1 and Comparative Example 1 show an initial decay of oxidation current in the first 50-100 cycles, followed by a constant current for the remaining cycles. This suggests that after the initial catalyst decay, materials with very stable activity are formed in both cases.

[0079] Wet cell activity test The electrode was introduced into a standard three electrode electrochemical cell as the working electrode via a gold wire connector. The electrochemical cell had a Pd / C reference electrode, a Pt mesh counter electrode, and a volume of 100 ml was heated to 60 °C using a heating jacket supplied by a heated water bath. The electrolyte was deoxygenated by bubbling nitrogen gas through it for at least 20 min. The potential of the working electrode was controlled using a potentiostat. The activity of the electrode towards the OER was determined as a linear sweep voltammogram, recorded by sweeping the potential of the working electrode from 1 V to 1.55 V to 0 V vs. RHE at 1 mV / s.

[0080] Chart 1 shows the oxygen generation reaction overvoltage of the oxygen generation reaction catalyst of Example 1 of the present invention and the comparative oxygen generation reaction catalyst of Comparative Example 1. The overvoltages are similar, indicating that the oxygen generation reaction catalyst of the present invention is as active as Comparative Example 1 and can conserve iridium while maintaining stable activity.

[0081] [Table 3]

[0082] BET surface area analysis The BET surface area of ​​the oxide material produced in Example 1 was 40.3 m 2 The BET surface area was determined based on the N2 adsorption isotherm at 77 K according to ISO standard 9277:2010(en).

[0083] References 1. Topas v4.2 / v5.0:General Profile and Structure Analysis Software for Powder Diffraction Data,Bruker AXS,Karlsruhe,Germany,(2003-2015). 2. RW Cheary and A. Coelho, J. Appl. Cryst. (1992), 25, 109-121 3. F.Bertaut and P.Blum(1949)C.R.Acad.Sci.Paris 229,666

Claims

1. An oxygen generation reaction catalyst, wherein the oxygen generation reaction catalyst is an oxide material containing iridium, tantalum, and ruthenium, the oxygen generation catalyst contains a crystalline oxide phase having a rutile crystal structure, the crystalline oxide phase has a lattice constant a greater than 4.510 Å, an oxygen generation reaction catalyst.

2. The oxygen generation reaction according to claim 1, wherein ruthenium is present in an amount in the range of 1 to 15 atomic percent based on the total atomic percentage of iridium species, tantalum species, and ruthenium species in the oxygen generation reaction catalyst.

3. The oxygen generation reaction catalyst has a BET surface area of at least 30 m ２ / g, and is the oxygen generation reaction catalyst according to claim 1.

4. A method for synthesizing the oxygen generation reaction catalyst according to claim 1, providing an aqueous solution of a compound of iridium, tantalum, and ruthenium, spray-drying the solution to form a dry powder, subjecting the powder to firing to thereby form the oxygen generation reaction catalyst, a method comprising.

5. The step of providing an aqueous solution of a compound of iridium, tantalum, and ruthenium, comprises a sub-step of providing an aqueous solution of a compound of iridium and a compound of ruthenium, and a sub-step of mixing the aqueous solution with an aqueous solution of a compound of tantalum, the method according to claim 4.

6. The method according to claim 4, wherein the aqueous solution of the compound of iridium, tantalum, and ruthenium has an Ir:Ta:Ru molar ratio of 5 to 7:2 to 4:0.5 to 1.

5.

7. The method according to claim 4, wherein the firing is carried out at a temperature in the range of 400 °C to 800 °C.

8. A catalyst layer comprising the oxygen generation reaction catalyst according to claim 1 and a second electrode catalyst material.

9. The catalyst layer according to claim 8, wherein the cathode layer is an anode catalyst layer, optionally an anode catalyst layer for a proton exchange membrane fuel cell.

10. The second electrode catalyst material, platinum group metals (platinum, palladium, rhodium, ruthenium, iridium, and osmium), gold or silver, base metals, or selected from alloys or mixtures containing one or more of these metals or their oxides, the catalyst layer according to claim 8.

11. The catalyst layer according to claim 8, wherein the weight ratio of the oxygen generation reaction catalyst to the second electrode catalyst material in the catalyst layer is 10:1 to 1:

10.

12. A gas diffusion electrode comprising a gas diffusion layer and the catalyst layer according to claim 8.

13. A catalyst membrane comprising an ion conductive membrane and the catalyst layer according to claim 8.

14. A membrane electrode assembly comprising the catalyst layer according to claim 8, the gas diffusion electrode according to claim 12, or the catalyst film according to claim 13.

15. A fuel cell comprising the catalyst layer according to claim 8, the gas diffusion electrode according to claim 12, or the catalyst film according to claim 13.

16. A fuel cell comprising the membrane electrode assembly according to claim 14.

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