Membrane electrode assembly and method for producing same, fuel cell, and electrolysis cell

Abstract

The invention relates to a membrane electrode assembly (1) having an anode (2), a cathode (3) and a hydrocarbon membrane (4) between the anode (2) and the cathode (3). The membrane electrode assembly (1) further comprises a protective layer (5) which is arranged between the anode (2) and the hydrocarbon membrane (4) and / or between the cathode (3) and the hydrocarbon membrane (4), wherein the protective layer (5) comprises at least one ceramic material (6) and a fluorine-containing ionomer (7), wherein the ceramic material (6) is dispersed in the fluorine-containing ionomer (7).

Description

[0001] Applicant:

[0002] Greenerity GmbH Industrial Area South E11 63755 Alzenau

[0003] Membrane electrode assembly and method for producing the same, fuel cell and electrolysis cell

[0004] Description

[0005] The invention relates to a membrane electrode assembly that can be used in particular for a proton exchange membrane fuel cell and a proton exchange membrane water electrolysis cell, as well as to a fuel cell and an electrolysis cell comprising this membrane electrode assembly. Furthermore, the invention also relates to methods for producing the membrane electrode assembly.

[0006] A fuel cell typically operates by supplying hydrogen to the anode and oxygen (air) to the cathode, producing water and electricity (and a certain amount of heat). On the cathode side of a catalyst-coated membrane (CCM), oxygen is reduced to produce water, while on the anode side, hydrogen is oxidized to protons, which migrate through the membrane to the cathode side to react with oxygen according to the following reaction equations:

[0007] (Cathode)

[0008] (Anode) H2A 2 H + + 2 e'

[0009] In water electrolysis, the reaction is reversed, i.e. water and electricity are fed into the cell to produce hydrogen and oxygen according to the following reaction equations:

[0010] (cathode) 2 H + + 2 e' A H2

[0011] (Anode) H2O A 1 / 2O2+ 2H + + 2 e"

[0012] The most common catalysts for each electrode and application are, for a fuel cell cathode, oxygen reduction reaction (ORR) catalysts such as platinum or platinum alloys supported on carbon; for a fuel cell anode, hydrogen oxidation reaction (HOR) catalysts such as platinum supported on carbon (Pt / C); for a water electrolysis cathode, hydrogen evolution reaction (HER) catalysts such as platinum supported on carbon; and for a water electrolysis anode, oxygen evolution reaction (OER) catalysts such as iridium oxide or iridium-ruthenium mixed oxide, unsupported or supported on another base metal oxide.

[0013] The catalyst metal types and supports listed above are selected based on optimal electrocatalytic activity and sufficient stability. Optimal electrocatalytic activity means the lowest possible overpotential to allow the reaction to proceed at an appropriate rate. Adequate stability means negligible corrosion or dissolution in the cell environment over the lifetime required by the application.

[0014] In the case of water electrolysis cells, hydrogen evolution on platinum is a simple reaction and occurs at very low overpotentials, meaning that the water electrolysis cell cathode potential remains close to zero during normal operation (vs. RHE - reversible hydrogen electrode). At this low potential, carbon is stable and can be used as a catalyst support.

[0015] Oxygen evolution at the anode occurs at potentials above the thermodynamic potential for water splitting, which is 1.23 V versus RHE. Typical anode potentials are well above this value due to reaction overpotentials, usually between 1.5 V and 2.0 V. In this voltage range, carbons are unstable and are oxidized over time; therefore, they are not used as catalyst supports on the anode side, nor in other parts of the cell on the anode side (e.g., transport layers or cell plates).

[0016] In a fuel cell, oxygen reduction occurs as a result of reaction overpotentials at voltages below the thermodynamic potential of the reaction between hydrogen and oxygen to form water, i.e., in contrast to water electrolysis, below 1.23 V vs. RHE. Therefore, typical cathode potentials are between 0.6 V and 1.0 V. At these potentials, carbon supports are stable and can be used to increase catalyst activity.

[0017] When a suitable catalyst is used on the anode side, such as a platinum-based catalyst dispersed on a high surface area carbon support, hydrogen oxidation is very efficient and proceeds readily at very low overpotentials, meaning that the anode voltage remains very close to zero versus RHE. This is true during normal operation. However, in a fuel cell stack, it can occasionally happen, e.g., during start-up, in cold and wet conditions, or during rapid transients, that one or more cells experience hydrogen starvation at the anode. This means that insufficient hydrogen is supplied to the anode to maintain the stack current and provide sufficient electrons. This situation drives the affected cells into voltage reversal.

[0018] Under such a cell reversal (CR) condition, the anode voltage rises to values ​​that can be well above the cathode voltage, e.g., above 1.5 V vs. RHE, and the anode side of the cell can rapidly corrode and fail. Corrosion, i.e., the oxidation of the carbon, compensates for the aforementioned electron deficit. The anode component typically most exposed to corrosion is the carbon support of the catalyst.

[0019] Furthermore, increased potentials of up to over 1.5 V vs. RHE occur on the cathode side, particularly under start-stop operating conditions (SUSD). During start-up of the fuel cell, the anode is filled with air, and therefore also with oxygen, so that a so-called hydrogen-air front is created when hydrogen is admitted to the anode. At this hydrogen-air front, in addition to the oxidation of hydrogen, a reduction of oxygen occurs on the anode, which is accompanied by an oxidation reaction on the cathode side. The cathode component that is normally most exposed to oxidation or corrosion is the carbon support of the catalyst.

[0020] The carbon support on both the anode and cathode sides is oxidized according to the following reaction:

[0021] (Anode of a fuel cell under cell reversal, or cathode under SUSD)

[0022] C + 2 H2O -> CO2 + 4 H + + 4 e"

[0023] Fuel cell failure occurs when carbon corrosion has progressed to such an extent that the CCM's performance is significantly impaired under normal hydrogen supply conditions. In the absence of a suitable mitigation strategy, anode failure under cell reversal can occur very rapidly, typically within several tens of seconds to very few minutes.

[0024] To protect the carbon of the anode and / or cathode electrode from corrosion under cell inversion or SUSD conditions, a common technical solution is to add an oxygen evolution reaction (OER) catalyst to the electrode, which is usually homogeneously mixed with the hydrogen oxidation catalyst (anode) or the oxygen reduction catalyst (cathode). The presence of such catalysts, typically based on iridium oxide, enables the oxidation of water at the electrode at higher rates than carbon corrosion, thus favoring water oxidation over carbon oxidation, according to the following reaction:

[0025] (Anode under cell reversal, or cathode under SIISD) 2 H2O -> O2 + 4 H + + 4 e

[0026] In this way, the cell behaves like an electrolytic cell under cell reversal, where air (oxygen) is reduced at the cathode and water is oxidized to oxygen at the anode.

[0027] Therefore, cell current is maintained by water oxidation rather than carbon corrosion, allowing the anode to survive the cell reversal condition longer, and the cathode to survive starting and stopping cycles longer. The water oxidation reaction limits the rise in anode potential to values ​​of 1.6 to 2 V vs. RHE and therefore limits the carbon corrosion rate, meaning that carbon corrosion still occurs but at far lower rates than when the voltage is not regulated by the presence of the OER catalyst. Using such a protection strategy, the CCM can survive a cell reversal condition for periods of several tens of minutes and even up to many tens of hours.

[0028] The previous description shows that water electrolysis cell anodes normally operate under high potentials of 1.5 V to 2.0 V, but fuel cell anodes can also be exposed to similarly high potential values ​​over longer periods (cumulatively) due to hydrogen deficiency.

[0029] Furthermore, membranes are known for use in hydrocarbon-based fuel cells and water electrolysis cells, so-called hydrocarbon membranes. In this case, the structure of the ionomer (i.e., the proton-conducting polymer) contained in the membrane contains no fluorine, or only in limited amounts of a maximum of 5% by mass based on the mass of the ionomer used.

[0030] Compared to perfluorosulfonic acid (PFSA) membranes, hydrocarbon membranes offer several advantages. For example, they exhibit lower gas permeability through the membrane, allowing higher cell current yields to be achieved, even when using very thin membranes, which result in very low ionic resistance (and thus very good performance). Furthermore, they can operate for extended periods at high temperatures >100 °C with limited degradation, which is due to their low gas permeability (even at high temperatures) and the high glass transition temperature typical of hydrocarbon-based polymers. Operation at higher temperatures results in several system advantages: reduced cooling requirements, lower sensitivity to gas contaminants, and higher cell efficiency. Hydrocarbon membranes also emit lower amounts of aggressive degradation products, e.g.HF and superacidic sulfonic acid molecules released by PFSAs result in less damage to the metallic bipolar plates in the stack during operation, which in turn allows for longer lifetimes and / or the use of cheaper materials. Finally, hydrocarbon membranes have an improved environmental profile compared to perfluorinated ionomers because they do not contain perfluoroalkyl compounds and do not require perfluoroalkyl chemistry in their manufacturing.

[0031] On the other hand, the inventors found that hydrocarbon membranes exhibit insufficient electrochemical stability at the high potentials typically used in water electrolysis anodes or those encountered in fuel cell anodes under cell reversal conditions, as well as fuel cell cathodes under SUSD, i.e., at voltages > 1.5 V. Under these high potentials, hydrocarbon membranes tend to oxidize and become damaged, leading to performance degradation and CCM failure.

[0032] There is therefore a need to improve the stability of CCMs (generally membrane electrode assemblies - MEA) containing hydrocarbon membranes for use conditions involving prolonged exposure of the anode or cathode to high potentials, either continuously or intermittently.

[0033] It is therefore an object of the invention to provide an MEA comprising a hydrocarbon membrane and being better protected against corrosion and thus oxidation, and consequently having a longer service life. Furthermore, it is an object of the present invention to provide a fuel cell or a water electrolysis cell which, due to the use of the membrane electrode assembly according to the invention, has an increased service life due to reduced corrosion and oxidation susceptibility. Furthermore, it is an object of the invention to provide a method for producing a membrane electrode assembly with reduced corrosion and oxidation susceptibility.

[0034] Membrane electrode arrangement must be specified.

[0035] These objects are achieved by the features of the independent claims. The dependent claims contain advantageous developments and refinements of the invention.

[0036] Accordingly, the object is achieved by a membrane electrode assembly (MEA) comprising an anode, a cathode and a hydrocarbon membrane located between the anode and the cathode and further comprising a protective layer arranged between the anode and the hydrocarbon membrane and / or the cathode and the hydrocarbon membrane.

[0037] The hydrocarbon membrane comprises at least one ionomer which is not fluorinated or whose fluorine content is not more than 5% by mass, based on the total mass of the ionomer.

[0038] The protective layer comprises at least one ceramic material and a fluorine-containing ionomer, wherein the ceramic material is distributed, i.e., dispersed, in the fluorine-containing ionomer. In other words, the protective layer can comprise a single ceramic material or a mixture of ceramic materials. The same applies to the fluorine-containing ionomer. In other words, the protective layer can comprise a single fluorine-containing ionomer or a mixture of two or more fluorine-containing ionomers. The fluorine-containing ionomer can be partially fluorinated or perfluorinated, or mixtures of partially fluorinated and / or perfluorinated ionomers can be used. Fluorinated ionomers are known to those skilled in the art, e.g., under the trade names Nation® (The Chemours Company), Forblue i-series (AGC Inc.), or Aquivion® (Solvay).The structure of the side chains can have a different number of CF2 groups or even branched structures and is not restricted in detail.

[0039] The ceramic material is not specifically limited and is advantageously characterized by electrically non-conductive properties and is dispersed, i.e., distributed, in the fluorine-containing ionomer(s). This can be achieved, for example, by preparing a protective layer dispersion during the production of the protective layer, in which the ceramic material and the fluorine-containing ionomer are sufficiently mixed before further processing into the protective layer. Electrically non-conductive properties are defined as materials with a specific conductivity of less than 10' 3 S / m. Conductivity is measured on powders at a compression of 50 MPa.

[0040] It has been found that the use of a protective layer comprising at least one ceramic material and at least one fluorine-containing ionomer between the hydrocarbon membrane and the anode and / or the cathode protects the MEA, and in particular the hydrocarbon membrane, from oxidation and thus also from corrosion, so that the MEA does not degrade even at sustained high potentials on the anode or cathode side. As a result, the MEA containing the hydrocarbon membrane with a protective layer does not lose its performance.

[0041] Oxidation of a hydrocarbon membrane in an MEA exposed to high anode or cathode potentials greater than 1.5 V and not containing a protective layer according to the present invention can be detected by the presence of a strong CO2 signal at the anode or cathode output of a cell. The inventors have found that this signal is suppressed in the presence of the protective layer, indicating that the hydrocarbon membrane is essentially not subject to oxidation. This demonstrates the effectiveness of the inventive approach to solving the above problem.

[0042] Without being bound by theory, it is believed that the hydrocarbon membrane in the MEA according to the present invention is not subject to oxidation because the protective layer reduces the potential at the membrane surface to values ​​lower than the anode or cathode potential. To maximize this effect, the ceramic material is preferably not electrically conductive. Furthermore, it is believed that avoiding contact between the membrane surface and the electrode catalyst material further protects the hydrocarbon membrane from oxidative degradation. The protective layer is very stable due to the stable materials it is made of and is therefore not degraded by the high potentials or by contact with a catalyst of the electrode layers, thus also protecting the hydrocarbon membrane from oxidation.

[0043] According to an advantageous further development, the protective layer is free of metal-containing catalysts, as this best supports the corrosion protection effect.

[0044] The hydrocarbon ionomers or hydrocarbon membranes made from them are not limited in detail.

[0045] Hydrocarbon ionomers, or hydrocarbon membranes made from them, are preferably of the sulfonated type. Sulfonated hydrocarbon ionomers are typically classified as sulfonated polystyrene copolymers (SPS), sulfonated polyimides (SPI), sulfonated polyphenylenes (SPP), sulfonated polyarylene-type polymers, or sulfonated polyphosphazenes (SPPh). The following exemplary hydrocarbon ionomer types can be mentioned within these classes:

[0046] Sulfonated polyaryl ethers (SPAE), sulfonated polyaryl ether ether nitriles (SPAEEN), sulfonated polyaryl ether ether ketones (SPAEK), sulfonated polyaryl ether nitriles (SPAEN), sulfonated polyaryl ether sulfones (SPAES), sulfonated polyaryl ether sulfone ketones (SPAESK), sulfonated polyether ether ketones (SPEEK), sulfonated polyether ketones (SPEK), sulfonated polyether sulfones (SPES), sulfonated polyimides (SPI), sulfonated polyketone ketones (SPKK), sulfonated polyphosphazenes (SPPh), sulfonated polyphenylene sulfones (SPPSf), sulfonated polyphenylene sulfide sulfones (SPPSSf), sulfonated Polyphenylene sulfide sulfonitriles (SPPSSfN), sulfonated polystyrenes (SPS), sulfonated polysulfones (SPSf), sulfonated polyphenylenes (sPP), sulfonated phenylated polyphenylenes (sPPP).Particularly stable hydrocarbon membranes are selected from sulfonated polyether ketones, sulfonated polyether ether ketones, sulfonated polyketone ketones, sulfonated polyphenylenes, sulfonated phenylated polyphenylenes and mixtures thereof.

[0047] Hydrocarbon ionomers can be linear polymers, cross-linked polymers, branched polymers, grafted polymers, and / or block polymers. They may optionally also contain heteroatoms such as F, N, S, and P. Block copolymers containing sulfonic acid-rich blocks alternating with sulfonic acid-poor or non-sulfonated blocks are particularly advantageous in terms of the combination of high proton conductivity, good mechanical properties, and high dimensional stability.

[0048] It has also been found that the presence of the ceramic material in the protective layer, in addition to providing high oxidation stability for the MEA, can also ensure very good adhesion between the protective layer and the hydrocarbon membrane, so that the hydrocarbon membrane, and thus the entire MEA, retains its integrity even under dynamic relative humidity conditions (alternating wet and dry) or conditions where the cell runs wet and warm, as in water electrolysis cells. To achieve such good adhesion, the total volume of the ceramic material in the protective layer, based on the total volume of the protective layer, is advantageously at least 17% by volume, and in particular at least 25% by volume, and in particular at least 30% by volume. The total volume of the protective layer is defined as the sum of the volumes of the individual components.The smaller the total volume of the ceramic material, the more the protective layer tends to detach from the hydrocarbon membrane due to the low compatibility between the (per)fluorinated ionomer and the hydrocarbon ionomer of the hydrocarbon membrane, and the MEA loses performance.

[0049] To provide excellent proton conductivity with good adhesion, which is achieved by a sufficiently high proportion of fluorinated ionomer, it is advantageous if the total volume of ceramic material in the protective layer is not too high. A particularly high proportion of ceramic material can also make the protective layer brittle and mechanically unstable. Therefore, the total volume of ceramic material in the protective layer, based on the total volume of the protective layer, is preferably less than 76% by volume, and in particular less than 65% by volume, and in particular less than 54% by volume.

[0050] Particularly suitable volume ranges of ceramic material are from 17 to 76 volume%, from 25 to 65 volume% and especially from 30 to 54 volume%. The optimal volume fraction of the ceramic material in the protective layer can be determined with regard to the above requirements through optimization by starting the amount of ceramic material at low values ​​and increasing it, for example, in 5 volume% steps until the minimum amount Cc_min is found that provides good adhesion. The amount of ceramic material can then be further increased up to the point Cc_max at which the MEA ionic resistance through the protective layer begins to measurably increase, for example by more than 5% above the value at which good adhesion was initially determined. The optimal amount of ceramic material Cc_ opt then lies between the two values ​​Cc_min and Cc_max. In general, the optimal volume fraction of ceramic material can depend on factors such as the chemical nature of the ceramic material, its specific surface area (e.g., determined by BET, i.e., using nitrogen adsorption according to DIN ISO 9277:2003-05 "Determination of specific surface area of ​​solids by gas adsorption using the BET method"), the method used to mix the ceramic material with the fluorinated ionomer, etc.

[0051] Good adhesion between the hydrocarbon membrane and the protective layer, and generally between the different layers of the MEA, can be determined by immersing the MEA in boiling water for an extended period of time, e.g., 4 hours, and visually observing the MEA. If the adhesion is good, the MEA maintains its integrity, meaning the different layers do not separate from each other, and no other small particles detach from the MEA.

[0052] According to an advantageous further development, the specific surface area of ​​the ceramic material, measured according to BET (according to DIN ISO 9277:2003-05 “Determination of the specific surface area of ​​solids by gas adsorption according to the BET method”), is 5 to 800 m 2 / g and especially 20 to 500 m 2 / g. Ceramic materials with a specific surface area in the specified range can be easily dispersed in fluorinated ionomers.

[0053] The ceramic material is advantageously one that is stable in hydrogen at low potentials. In other words, the ceramic material in the protective layer is preferably reduction-stable at low potentials (close to zero) in the presence of hydrogen. Indeed, especially in the case of a fuel cell application, the anode side will be exposed to low potentials in a hydrogen environment most of the time (normal operation). However, even in a water electrolysis cell, the anode may be exposed to low potentials during stops, with hydrogen transferring from the cathode side to the anode side. Therefore, if the ceramic material is not stable to hydrogen at low potentials, the metal will be reduced and gradually dissolved, and the function of the protective layer will be lost over time.In water electrolysis cell applications, this requirement is less stringent, as the anode is exposed to low potentials less frequently; in addition, stopping strategies can be developed that prevent such a condition from occurring at the anode altogether (e.g., drawing very small currents from the stack). In view of very good reduction stability, it is therefore advantageous if the ceramic material exhibits a weight loss of less than 2 mass% when exposed to a 3.3 vol% hydrogen flow in argon for 12 hours at a temperature of 80 °C.

[0054] Furthermore, the ceramic material is advantageously selected from at least one of oxides, nitrides, carbides, silicides, borides, and mixtures thereof. The oxides, nitrides, carbides, silicides, and borides are not specifically restricted. However, they are advantageously oxides, nitrides, carbides, silicides, and borides of at least one of the following metals: silicon, tantalum, niobium, zinc, titanium, zirconium, cerium, tungsten, antimony, or mixtures thereof. Due to the very good reduction stability, the ceramic material is particularly selected from Nb2Ü5, Ta2Ü5, SiÜ2, WO3, ZrÜ2, and mixtures thereof.

[0055] Further advantageously, in light of minimal additional proton resistance due to the MEA, the equivalent weight of the proton-conductive polymer of the protective layer can be less than 1050 g / mol, preferably less than 950 g / mol, and more preferably less than 850 g / mol. The equivalent weight indicates the weight of the ionomer per mole of functional groups, in particular sulfonic acid groups.

[0056] The layer thickness of the protective layer can further advantageously be adjusted or selected in light of minimal additional proton resistance by the MEA. The lower limit of the layer thickness is not particularly restricted, as long as a layer with a controlled layer thickness without defects has been produced. Preferably, the protective layer has a layer thickness of greater than or equal to 0.1 μm, more preferably greater than or equal to 0.15 μm, and even more preferably greater than or equal to 0.2 μm. It is essential that the layer is continuous, in other words, closed, i.e., that it has no cracks or defects. The layer thickness can be determined using scanning electron microscopy.

[0057] In the context of a lightweight construction of the MEA and a minimal additional proton resistance, it is also advantageous if the layer thickness of the protective layer is not too large and thus in particular less than 10 pm, in particular less than 5 pm and in particular less than 3 pm.

[0058] Particularly advantageously, the thickness of the protective layer is in a range from 0.1 to 10 pm, in particular from 0.2 to 5 pm and in particular in a range from 0.5 to 3 pm. The cathode comprises at least one catalyst catalyzing the cathode reaction. Advantageously, the cathode comprises at least one platinum-containing catalyst, wherein a loading of the cathode with catalyst, expressed in platinum weight per unit area of ​​the cathode, in particular from 0.02 to 1 mgPt / cm 2 , especially from 0.05 to 0.6 mgPt / cm 2 and in particular from 0.1 to 0.4 mgPt / cm 2The platinum-containing catalyst can be platinum or a platinum alloy.

[0059] Particularly advantageous in order to improve the efficiency of the cathode reaction, the platinum-containing catalyst of the cathode is supported, wherein the support of the platinum-containing catalyst preferably comprises carbon.

[0060] In order to ensure the efficiency of the MEA in the case of water electrolysis or to improve the long-term stability in the case of the fuel cell, the anode comprises at least one oxygen evolution catalyst (OER catalyst).

[0061] Due to its excellent catalytic activity and stability against dissolution during operation, the OER catalyst comprises, in particular, iridium oxide or an iridium-ruthenium mixed oxide. Alternatively or additionally, the OER catalyst can be supported, in particular on a base metal oxide, which is preferably a titanium oxide or a niobium oxide. For the purposes of the present invention, base metals are understood to be metals with a standard potential vs. RHE of less than 0.7 V.

[0062] A further advantageous development, in the light of the increase in efficiency of the MEA, provides that the anode further comprises a hydrogen oxidation reaction catalyst (HOR catalyst), in particular a platinum-containing HOR catalyst, wherein the loading of the anode with platinum-containing HOR catalyst, expressed in platinum weight per unit area of ​​the anode, in particular from 0.01 to 0.2 mgPt / cm 2 and in particular from 0.03 to 0.1 mgPt / cm 2The HOR catalyst is particularly advantageously supported on a carbon-containing carrier.

[0063] The membrane electrode assembly is advantageously designed either as a fuel cell membrane electrode assembly or as

[0064] Water electrolysis cell membrane electrode assembly formed.

[0065] If the MEA is designed as a water electrolysis cell membrane electrode assembly, the loading of the anode with catalyst, expressed in iridium weight per unit area of ​​the anode, is advantageously from 0.05 to 2 mglr / cm 2 , especially from 0.1 to 1.5 mglr / cm 2 and in particular from 0.2 to 1 mglr / cm 2 .

[0066] If the MEA is designed as a fuel cell membrane electrode assembly, the loading of the anode with catalyst, expressed in iridium weight per unit area of ​​the anode, is advantageously from 0.005 to 0.05 mglr / cm 2, especially from 0.006 to 0.03 mglr / cm 2 .

[0067] If the MEA is designed as a water electrolysis cell membrane electrode assembly, a layer thickness of the hydrocarbon membrane is preferably 150 pm or less.

[0068] The hydrocarbon membrane can have mechanical reinforcement, for example in the form of fibers or reinforcing structures. A reinforcing structure can, for example, be introduced during the manufacturing process of the hydrocarbon membrane from an ionomer dispersion or ionomer solution. In this case, a previously formed reinforcing structure, such as ceramic materials or polymeric materials such as (bi-)axially stretched PTFE (ePTFE) or woven structures such as fabrics made of polyketone (PK) fibers, polyetherketone (PEK) fibers, polyetheretherketone (PEEK) fibers, perfluoroalkoxyalkane (PFA) fibers, or polyphenylene sulfide (PPS) fibers, is impregnated with a corresponding ionomer dispersion and subsequently dried so that the pores of the reinforcing structure are filled with ionomer.In this case, where the hydrocarbon membrane has a mechanical reinforcement, the layer thickness of the hydrocarbon membrane is advantageously from 20 to 120 pm, in particular from 30 to 100 pm.

[0069] If the MEA is designed as a fuel cell membrane electrode assembly, a layer thickness of the hydrocarbon membrane is preferably 20 pm or less.

[0070] The hydrocarbon membrane can have mechanical reinforcement, for example in the form of fibers or reinforcing structures. A reinforcing structure can, for example, be introduced during the manufacturing process of the hydrocarbon membrane from an ionomer dispersion or ionomer solution. In this case, a previously formed reinforcing structure, such as ceramic materials or polymeric materials such as (bi-)axially stretched PTFE (ePTFE) or woven structures such as fabrics made of polyketone (PK) fibers, polyetherketone (PEK) fibers, polyetheretherketone (PEEK) fibers, perfluoroalkoxyalkane (PFA) fibers, or polyphenylene sulfide (PPS) fibers, is impregnated with a corresponding ionomer dispersion and subsequently dried so that the pores of the reinforcing structure are filled with ionomer.In this case, where the hydrocarbon membrane of the fuel cell membrane electrode assembly has a mechanical reinforcement, the layer thickness of the hydrocarbon membrane is advantageously from 5 to 15 pm.

[0071] If necessary, additional layers can be inserted between the protective layer and the anode or between the protective layer and the cathode. Furthermore, the invention also describes a water electrolysis cell and a fuel cell comprising the membrane electrode assembly according to the invention. The use of the membrane electrode assembly according to the invention also improves the service life of the water electrolysis cell and the fuel cell, since corrosion and oxidation of the MEA are reduced. The water electrolysis cell or the fuel cell is, in particular, a PEM water electrolysis cell or a PEM fuel cell.

[0072] The advantageous developments of the membrane electrode arrangement according to the invention also find application to the fuel cell according to the invention and the water electrolysis cell according to the invention.

[0073] Furthermore, the invention also describes a first method for producing a membrane electrode assembly as disclosed above. The method initially comprises a step of producing a protective layer dispersion comprising at least one ceramic material and at least one fluorine-containing ionomer, as set forth above for the MEA according to the invention. The ceramic material and the ionomer are dispersed or suspended in a liquid medium, for example a polar organic solvent or a mixture of polar organic solvents or water, or preferably a mixture of water and one or more polar organic solvents. Non-limiting examples of polar organic solvents are acetone, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), 1-propanol, 2-propanol, ethanol, 1-butanol, or tert-butyl alcohol.

[0074] To prepare the protective layer dispersion, the ceramic material and the fluorine-containing ionomer can be ground together in a ball mill (grinding medium: ZrO2 balls). The grinding time can be, for example, 120 minutes, but depends on the dispersibility of the ceramic material and can be adjusted accordingly.

[0075] Alternatively or additionally, ultrasound or various grinding media mills can also be used to produce dispersions. Grinding media mills include, for example, ball mills, stirred bead mills, agitator mills, attritors, and specific roller mills.

[0076] In the following description, the term "electrode" refers to both the anode and the cathode in the case of fuel cells; in the case of water electrolysis, it refers specifically to only the anode, since high potentials of > 1.5 V can occur on these electrodes and the protective layer can exert a beneficial effect. In a further process step, the protective layer dispersion is applied to an electrode or a hydrocarbon membrane. Common technologies such as slot nozzles, doctor blades, spiral applicators, screen printing, or spraying devices are used as application methods.

[0077] The protective layer dispersion is then dried to maintain the protective layer on the electrode or hydrocarbon membrane.

[0078] Once the protective coating dispersion has been applied to the electrode, a further process step can be performed to laminate the electrode with the protective coating and the hydrocarbon membrane. The lamination temperature is typically 150 to 190 °C, and the pressure is 1 to 3 MPa. The lamination time can be approximately one minute.

[0079] The above procedure also applies if the protective coating dispersion has been applied to the hydrocarbon membrane. It is then laminated to the electrode.

[0080] This first process according to the invention is easy to implement using conventional technologies and enables the production of an MEA with high oxidation and corrosion stability.

[0081] According to a second method according to the invention, the production of the MEA according to the invention first comprises the production of a protective layer dispersion, which can be carried out as described for the first method. The protective layer dispersion again comprises at least one ceramic material and at least one fluorine-containing ionomer.

[0082] The protective coating dispersion is then applied to a substrate. The substrate is inert to the protective coating dispersion, meaning it exhibits no chemical or physical reactivity with the protective coating dispersion.

[0083] In a further process step, the protective layer dispersion is dried to produce the protective layer and thus a so-called decal is obtained.

[0084] The protective layer is then transferred to the electrode or to the hydrocarbon membrane and the substrate is subsequently removed.

[0085] Depending on whether the protective layer has been transferred to the electrode or to the hydrocarbon membrane by the decal process, lamination may further be carried out with either a hydrocarbon membrane or an electrode, as set forth above for the first method of the invention.

[0086] This second process according to the invention can also be easily implemented using conventional technologies and enables the production of an MEA with high oxidation and corrosion stability.

[0087] According to a third method according to the invention, as already explained above, a protective layer dispersion is first prepared which comprises at least one ceramic material and at least one fluorine-containing ionomer.

[0088] Furthermore, an electrode dispersion is prepared. The electrode dispersion comprises, in particular, at least one catalytically active substance, as described for the MEA according to the invention.

[0089] A further decal process is then carried out, in which the electrode dispersion and then the protective layer dispersion are first applied to the electrode dispersion applied to the substrate. This creates a layer arrangement: substrate / electrode dispersion / protective layer dispersion.

[0090] The dispersions are dried. No particular sequence is required. For example, the electrode dispersion can be dried or partially dried first before the protective layer dispersion is applied, or the protective layer dispersion can be applied to the not yet dried or not completely dried electrode dispersion, and both dispersions are dried simultaneously to produce the electrode layer and the protective layer on the substrate.

[0091] The decal, i.e. the dried electrode layer-protective layer arrangement, is then transferred to the hydrocarbon membrane so that the protective layer is arranged between the hydrocarbon membrane and the electrode.

[0092] The third method according to the invention makes it possible to produce an MEA with high oxidation and corrosion stability easily using conventional technologies.

[0093] The above process steps of the third process according to the invention can be followed by a step of laminating the electrode layer-protective layer assembly and the hydrocarbon membrane, as already explained for the first and second processes according to the invention. According to a fourth process according to the invention, a protective layer dispersion comprising at least one ceramic material and at least one fluorine-containing ionomer is first prepared, as already explained above.

[0094] Furthermore, an electrode dispersion (anode dispersion or cathode dispersion) is prepared. The electrode dispersion comprises, in particular, at least one catalytically active substance, as described for the MEA according to the invention.

[0095] The protective layer dispersion is then applied to the hydrocarbon membrane and subsequently the electrode dispersion is applied to the protective layer dispersion.

[0096] The dispersions are then dried to produce the electrode layer and the protective layer, whereby the dispersions can be dried sequentially or together.

[0097] The fourth process according to the invention also leads to an MEA with improved oxidation and corrosion stability, whereby the process can be easily implemented using conventional technologies.

[0098] If the MEA to be manufactured is a fuel cell membrane electrode assembly, the following fifth method according to the invention can also be used.

[0099] In a first step, as already explained for all of the above processes, a protective layer dispersion comprising at least one ceramic material and at least one fluorine-containing ionomer is prepared. An electrode dispersion is also prepared.

[0100] The electrode dispersion (anode dispersion or cathode dispersion) is then applied to a gas diffusion layer and subsequently the protective layer dispersion is applied to the electrode dispersion.

[0101] The dispersions are then dried to produce the electrode layer and the protective layer, whereby the dispersions can be dried sequentially or together.

[0102] The protective layer-electrode layer-gas diffusion layer assembly is then arranged on a hydrocarbon membrane and a lamination step as disclosed for the above methods may follow.

[0103] In an alternative process step of the fifth method, the protective layer dispersion is applied to a hydrocarbon membrane. In a further process step, the protective layer dispersion is dried to produce the protective layer. The electrode layer-gas diffusion layer assembly is then arranged on a protective layer-hydrocarbon membrane assembly, and a lamination step, as disclosed for the above methods, can follow.

[0104] The fifth process according to the invention also leads to an MEA with improved oxidation and corrosion stability, whereby the process can be easily implemented using conventional technologies.

[0105] All of the processes disclosed above may be followed by a further annealing step at a temperature range of 150 to 200 °C to strengthen the mechanical properties of the protective layer. This step may possibly coincide with one of the decal processes.

[0106] In all of the above processes, the respective counter electrode can be provided by a decal process, by direct coating, or as a gas diffusion electrode. The respective processes for the anode and cathode sides can be combined independently of each other.

[0107] The production of the MEA according to the inventive methods can be realized simply and at high production rates using state-of-the-art techniques and equipment already used in the production of fuel cell membrane electrode assemblies and water electrolysis cell membrane electrode assemblies.

[0108] Further details, advantages, and features of the present invention will become apparent from the following description of exemplary embodiments with reference to the drawings. It shows:

[0109] Fig. 1 shows an MEA according to a first embodiment in section.

[0110] Fig. 1 shows only the essential components of the MEA. All other components are omitted for clarity.

[0111] In detail, Fig. 1 shows an MEA 1 that can be used for a fuel cell or an electrolysis cell.

[0112] The MEA 1 is shown in section and comprises an anode 2, a cathode 3 and a hydrocarbon membrane 4 located between the anode 2 and the cathode 3. Between the hydrocarbon membrane 4 and the anode 2 there is a protective layer 5 which protects the MEA 1 from corrosion and oxidation processes.

[0113] This protective mechanism is evident, for example, when using the MEA in a fuel cell when operating under cold and wet conditions or during rapid transients where the fuel cell cells experience hydrogen starvation at the anode, meaning that insufficient hydrogen is supplied to the anode to maintain the stack current and provide sufficient electrons, driving the affected cells into voltage reversal. Under such a cell reversal condition, the anode voltage rises to values ​​that can be far higher than the cathode voltage (e.g., >1.5 V vs. RHE). This can cause the anode side of the fuel cells to rapidly corrode and fail, which is prevented by the MEA according to the invention.

[0114] The above-mentioned advantageous effects are also evident when the MEA is used in a water electrolysis cell. Here, oxygen evolution at the anode occurs at potentials above the thermodynamic potential for water splitting, which is 1.23 V versus RHE. Typical anode potentials are well above this value due to reaction overpotentials, usually between 1.5 V and 2.0 V. In this voltage range, carbons are unstable and are oxidized over time. These oxidation processes are also prevented by the MEA according to the invention.

[0115] These unexpected beneficial effects are due to the structure of the MEA 1, as shown in Fig. 1. Here, between the hydrocarbon membrane 2 and the anode 3, there is a protective layer 5 comprising at least one ceramic material 6 and at least one fluorine-containing ionomer 7, wherein the ceramic material 6 is distributed within the fluorine-containing ionomer 7. The total volume of ceramic material 6 is in particular in a range of 17 to 76 volume%, based on the total volume of the protective layer 5.

[0116] The ceramic material 6 is advantageously selected from oxides, nitrides, carbides, silicides, borides, and mixtures thereof, of at least one selected from silicon, tantalum, niobium, zinc, titanium, zirconium, cerium, tungsten, antimony, or mixtures thereof. Furthermore, the ceramic material 6 is particularly stable to reduction with respect to hydrogen. For this purpose, it is advantageously selected from Nb2Ü5, Ta2Ü5, SiÜ2, WO3, ZrÜ2, and mixtures thereof.

[0117] The equivalent weight of the proton-conductive polymer (7) of the protective layer is less than 1050 g / mol and in particular less than 950 g / mol and in particular less than 850 g / mol, so that even with a limited amount of ionomer, a sufficient number of proton-conductive sulfonic acid groups are present and thus the protective layer as a whole has a high proton conductivity.

[0118] A layer thickness S of the protective layer 5 is in particular in a range of 0.1 to 10 μm, so that the protective effect is particularly efficient with the lowest possible volume and weight. The hydrocarbon membrane 4 comprises in particular sulfonated polyether ketones, sulfonated polyetheretherketones, sulfonated polyketone ketones, sulfonated polyphenylenes, sulfonated phenylated polyphenylenes, and mixtures thereof.

[0119] The cathode 3 comprises at least one platinum-containing catalyst, wherein a loading of the cathode 3 with catalyst, expressed in platinum weight per unit area of ​​the cathode 3, in particular between 0.02 and 1 mgPt / cm 2 and the catalyst is supported in particular on a carbon-containing support.

[0120] The anode 2 also comprises at least one catalyst comprising iridium oxide or an iridium-ruthenium mixed oxide, optionally supported on a base metal oxide such as, in particular, titanium oxide or niobium oxide.

[0121] The anode 2 may further advantageously comprise a hydrogen oxidation reaction catalyst, in particular a platinum-containing hydrogen oxidation reaction catalyst, wherein the loading of the anode 2 with platinum-containing hydrogen oxidation catalyst expressed in platinum weight per unit area of ​​the anode 2 is in particular from 0.01 to 0.2 mgPt / cm 2 amounts.

[0122] In addition to the above written description of the invention, reference is hereby explicitly made to the graphic representation of the invention in Fig. 1 for its supplementary disclosure.

[0123] Production of membrane electrode assemblies according to the invention in the form of catalyst-coated membranes (CCM)

[0124] Catalyst-coated membranes (CCM) were prepared from anode catalyst layers containing 50 mass% Pt on graphitized carbon with a platinum loading of 0.05 mg Pt / cm 2 and cathode catalyst layers containing 50 mass% PtCo on carbon with a platinum loading of 0.50 mg Pt / cm 2 Catalyst-coated membranes (CCMs) were then prepared using a decal process (standard decal transfer method), in which an ionomer membrane was sandwiched between an anode layer and a cathode layer on the other side of the membrane. The active area of ​​both catalyst layers was 71 mm x 62 mm, and the membrane size was 100 mm x 100 mm. Table 1 summarizes the CCM compositions.

[0125] An anode catalyst ink was prepared by mixing a Pt / C (50 wt% Pt on carbon) catalyst and an iridium oxide catalyst in water, organic solvents, and a D79-25BS PFSA ionomer dispersion from Solvay Specialty Polymers. The platinum-to-iridium mass ratio was 1:1. The ionomer-to-carbon mass ratio was 0.8:1. The anode catalyst ink was milled for 120 minutes in a ball mill (grinding medium: ZrO2 balls with a diameter of 1 mm). An anode catalyst layer was prepared by applying and drying the catalyst ink to a substrate (decal process).

[0126] A cathode catalyst ink was prepared by mixing a PtCo / C (50 wt% PtCo on carbon) catalyst, water, organic solvents, and a D79-25BS PFSA ionomer dispersion from Solvay Specialty Polymers. The ionomer-to-carbon mass ratio was 1:1. The cathode catalyst ink was milled for 120 minutes in a ball mill (grinding media: ZrO2 balls with a diameter of 1 mm). A cathode catalyst layer was prepared by applying and drying the catalyst ink to a substrate (decal process).

[0127] Example 1 (hydrocarbon membrane with protective layer)

[0128] To prepare the protective layer dispersion, 0.83g Nb2Ü5 (BET surface area 6.2 m 2 / g), 1.40 g of D79-25BS (Solvay, PFSA ionomer dispersion, 25 mass%), and 7.77 g of organic solvent were mixed and ground for 120 minutes in a ball mill (grinding medium: ZrO2 balls with a diameter of 1 mm). The mass ratio of the metal oxide to ionomer was 2.37:1. This corresponded to a volume fraction of niobium oxide of 52 volume%. The conversion was carried out using the density of the niobium oxide of 4.6 g / cm 3 and the density of the ionomer of 2.1 g / cm 3 The anode was then coated with the protective coating dispersion using a spiral doctor blade (4 pm wire diameter) and dried in an oven at 120 °C for 5 minutes. The resulting thickness of the protective coating, measured by scanning electron microscopy, was approximately 200 nm.

[0129] The anode and cathode layers were prepared as described above. A 7-μm-thick sPEEK hydrocarbon membrane was used to fabricate the CCM. The hydrocarbon membrane was sandwiched between the protective layer-anode assembly and the cathode and laminated at a temperature of 160 °C and a pressure of 3 MPa for 1 minute. The substrates (decals) were then removed.

[0130] Example 2 (hydrocarbon membrane with protective layer)

[0131] To prepare the protective layer dispersion, 0.59 g of Nb2Ü5 (BET surface area 6.2 m 2 / g), 2.36 g of D79-25BS (Solvay, PFSA ionomer dispersion, 25 mass%), and 7.05 g of organic solvent were mixed and ground for 120 minutes in a ball mill (grinding medium: ZrO2 balls with a diameter of 1 mm). The mass ratio of the metal oxide to ionomer was 1:1. This corresponded to a volume fraction of niobium oxide of 31 volume%. The conversion was carried out using the density of the niobium oxide of 4.6 g / cm 3 and the density of the ionomer of 2.1 g / cm 3 The anode was then coated with the protective coating dispersion using a spiral doctor blade (4 pm wire diameter) and dried in an oven at 120 °C for 5 minutes. The resulting thickness of the protective coating, measured by scanning electron microscopy, was approximately 200 nm.

[0132] The anode and cathode layers were prepared as described above. A 7-μm-thick sPEEK hydrocarbon membrane was used to fabricate the CCM. The hydrocarbon membrane was sandwiched between the protective layer-anode assembly and the cathode and laminated at a temperature of 160 °C and a pressure of 3 MPa for 1 minute. The substrates (decals) were then removed.

[0133] Comparative example 1 (hydrocarbon membrane)

[0134] The anode and cathode layers were prepared as described above. No protective layer was used. The same type of hydrocarbon membrane as in Example 1, with a thickness of 7 pm, was used to fabricate the CCM.

[0135] Comparative example 2 (PFSA membrane)

[0136] The anode and cathode layers were prepared as described above. No protective layer was used. A 12 pm thick PFSA membrane was used to fabricate the CCM.

[0137] Comparative example 3 (hydrocarbon membrane)

[0138] Anode and cathode layers were prepared as described above. A protective layer consisting solely of ionomer was used. For this purpose, 1.40 g of D79-25BS (Solvay, PFSA ionomer dispersion, 25 mass%) and 7.77 g of organic solvent were mixed. The anode was then coated with the protective layer dispersion using a spiral doctor blade (8 μm wire diameter) and dried in an oven at 120 °C for 5 minutes. The resulting layer thickness of the protective layer was approximately 200 nm. The same hydrocarbon membrane type as in Example 1, with a thickness of 7 μm, was used to fabricate the CCM.

[0139] Fuel cell test

[0140] Electrochemical tests were carried out using a 38 cm 2 The experiments were carried out in a large PEM single cell equipped with graphitized serpentine flow plates. The single cell was thermally controlled by a thermocouple, using heat-resistant hot plates for heating and a fan for air cooling. The gases were humidified using a humidifier bubbler. The single cell was operated in a countercurrent flow pattern.

[0141] All fabricated CCMs were coated with carbon-based gas diffusion layers on both sides of the membrane electrode assemblies (CCMs). All CCM samples were coated with incompressible glass fiber reinforced PTFE gaskets, resulting in a 10 vol% compression of the GDL. Before conducting fuel depletion tests on the MEA samples, the single cell was heated under hydrogen / air for 8 hours at 1 A / cm 2and a pressure of 1.5 bar a bs, conditioned. The temperature of the single cell Tzeiie was 80 °C and the humidifier temperatures were 80 °C (anode) and 80 °C (cathode).

[0142] Fuel depletion test (cell reversal)

[0143] The cells were subjected to an extended voltage reversal test, which consisted of a current of 0.2 A / cm 2 while the fuel cell was operated with air on the cathode side and nitrogen on the anode side (this simulates the fuel depletion case). The end of the test was reached when the average cell voltage fell below -1.5 V. The time required to reach -1.5 V was calculated as the extended reversal tolerance time.

[0144] The carbon dioxide (CO2) content was measured at the anode outlet using a Binos 100 2M sensor from Fisher-Rosemont GmbH & Co (Germany), whereby the measuring principle is based on the use of a non-dispersive infrared (NDIR) photometer.

[0145] Adhesion test

[0146] To determine adhesion, full-surface CCMs (i.e., the anode and cathode were the same size as the membrane) measuring 50 x 50 mm were fabricated and immersed in boiling water for 4 hours. In cases of good adhesion, the bond between both electrodes and the membrane remained intact; in cases of poor adhesion, one or both electrodes detached from the membrane.

[0147] Example 1, which features the inventive protective layer between the anode and the membrane in a fuel cell configuration, demonstrated significantly improved cell reversal tolerance compared to a CCM with a hydrocarbon membrane without such a protective layer (Comparative Example 1). Furthermore, Example 1 demonstrated cell reversal tolerance at the same level as a corresponding CCM with a PFSA membrane without a protective layer according to the invention. Comparative Example 3 featured a protective layer between the anode and membrane that did not contain a ceramic component. Due to the poor adhesion between the hydrocarbon membrane and the PFSA protective layer, a determination of the cell reversal tolerance was not possible. Table 1

[0148] List of reference symbols

[0149] 1 membrane electrode assembly

[0150] 2 anode

[0151] 3 Cathode 4 Hydrocarbon membrane

[0152] 5 protective layer

[0153] 6 ceramic material

[0154] 7 fluorinated ionomer

[0155] S Layer thickness of the protective layer

Claims

Claims 1. Membrane electrode assembly (1) comprising an anode (2), a cathode (3) and a hydrocarbon membrane (4) located between the anode (2) and the cathode (3), further comprising a protective layer (5) which is arranged between the anode (2) and the hydrocarbon membrane (4) and / or between the cathode (3) and the hydrocarbon membrane (4), wherein the protective layer (5) comprises at least one ceramic material (6) and a fluorine-containing ionomer (7), wherein the ceramic material (6) is distributed in the fluorine-containing ionomer (7).

2. Membrane electrode assembly (1) according to claim 1, wherein the hydrocarbon membrane (4) comprises sulfonated polyether ketones, sulfonated polyether ether ketones, sulfonated polyketone ketones, sulfonated polyphenylenes, sulfonated phenylated polyphenylenes and mixtures thereof and / or wherein a total volume of the ceramic material (6) in the protective layer (5) based on the total volume of the protective layer (5) is at least 17% by volume and in particular at least 25% by volume and in particular at least 30% by volume and / or wherein a total volume of the ceramic material (6) in the protective layer (5) based on the total volume of the protective layer (6) is less than 76% by volume, in particular less than 65% by volume and in particular less than 54% by volume and / or wherein a specific surface area of ​​the ceramic material (6), measured according to BET, is 5 to 800 m 2 / g and especially 20 to 500 m 2 / g and / or wherein the ceramic material (6) has a weight loss of less than 2 mass% when the ceramic material is exposed to a 3.3 vol% hydrogen stream in argon for 12 hours at a temperature of 80 °C and / or wherein the ceramic material (6) is selected from at least one of oxides, nitrides, carbides, silicides, borides and mixtures thereof, of at least one selected from silicon, tantalum, niobium, zinc, titanium, zirconium, cerium, tungsten, antimony or mixtures thereof and in particular is selected from Nb2O5, Ta2O5, SiO2, WO3, ZrO2 and mixtures thereof and / or wherein the equivalent weight of the proton-conductive polymer (7) of the protective layer is less than 1050 g / mol and in particular less than 950 g / mol and in particular less than 850 g / mol and / or wherein a layer thickness (S) of the protective layer (5), measured by means of Scanning electron microscopy, smaller than 10 pm, especially smaller than 5 pm and in particular less than 3 pm and / or wherein a layer thickness (S) of the protective layer (5) is greater than or equal to 0.1 pm, in particular greater than or equal to 0.15 pm and in particular greater than or equal to 0.2 pm.

3. Membrane electrode arrangement (1) according to one of the preceding claims, wherein the cathode (3) comprises at least one platinum-containing catalyst, wherein a loading of the cathode (3) with catalyst, expressed in platinum weight per unit area of ​​the cathode (3), in particular from 0.02 to 1 mgPt / cm 2 , especially from 0.05 to 0.6 mgPt / cm 2 and in particular from 0.1 to 0.4 mgPt / cm 2 wherein the catalyst is in particular supported and wherein the support of the catalyst comprises in particular carbon.

4. Membrane electrode assembly (1) according to one of the preceding claims, wherein the anode (2) comprises at least one oxygen evolution catalyst, wherein the oxygen evolution catalyst comprises in particular iridium oxide or an iridium-ruthenium mixed oxide, and / or wherein the oxygen evolution catalyst is supported, in particular on a base metal oxide, in particular titanium oxide or niobium oxide.

5. Membrane electrode assembly (1) according to one of the preceding claims, wherein the anode (2) further comprises a hydrogen oxidation reaction catalyst, in particular a platinum-containing hydrogen oxidation reaction catalyst, wherein the loading of the anode (2) with platinum-containing hydrogen oxidation catalyst expressed in platinum weight per unit area of ​​the anode, in particular from 0.01 to 0.2 mgPt / cm 2 and in particular from 0.03 to 0.1 mgPt / cm 2wherein the hydrogen oxidation reaction catalyst is supported in particular on a carbon-containing support.

6. Membrane electrode assembly (1) according to one of the preceding claims, wherein the membrane electrode assembly (1) is a water electrolysis cell membrane electrode assembly.

7. Membrane electrode assembly (1) according to one of claims 1 to 5, wherein the membrane electrode assembly (1) is a fuel cell membrane electrode assembly.

8. Membrane electrode assembly (1) according to claim 6 with claim 4, wherein a loading of the anode (2) with catalyst, expressed in iridium weight per Unit area of ​​the anode (2) from 0.05 to 2 mglr / cm 2 , especially from 0.1 to 1.5 mglr / cm 2 and in particular from 0.2 to 1 mglr / cm 2 amounts.

9. Membrane electrode assembly (1) according to claim 7 with claim 4, wherein a loading of the anode (2) with catalyst, expressed in iridium weight per unit area of ​​the anode (2), of 0.005 to 0.05 mglr / cm 2 , especially from 0.006 to 0.03 mglr / cm 2 amounts.

10. Membrane electrode assembly (1) according to claim 6 or 8, wherein a layer thickness of the hydrocarbon membrane (4) is 150 pm or less or wherein the hydrocarbon membrane (4) has a mechanical reinforcement and a layer thickness of the hydrocarbon membrane (4) is from 20 to 120 pm, in particular from 30 to 100 pm.

11. Membrane electrode assembly (1) according to claim 7 or 9, wherein a layer thickness of the hydrocarbon membrane (4) is 20 pm or less or wherein the hydrocarbon membrane (4) has a mechanical reinforcement and a layer thickness of the hydrocarbon membrane (4) is from 5 to 15 pm.

12. Water electrolysis cell comprising a membrane electrode assembly (1) according to one of claims 1 to 6, 8 or 10.

13. Fuel cell comprising a membrane electrode assembly (1) according to one of claims 1 to 5, 7, 9 or 11.

14. A method for producing a membrane electrode assembly (1) according to one of claims 1 to 11, comprising the steps: Producing a protective layer dispersion comprising at least one ceramic material (6) and at least one fluorine-containing ionomer (7), - applying the protective layer dispersion to the anode (2) or the cathode (3) or the hydrocarbon membrane (4) and Drying the protective layer dispersion while maintaining the protective layer (5) on the anode (2) or the cathode (3) or the hydrocarbon membrane (4).

15. A method for producing a membrane electrode assembly (1) according to one of claims 1 to 11, comprising the steps: Producing a protective layer dispersion comprising at least one ceramic material (6) and at least one fluorine-containing ionomer (7), - Applying the protective layer dispersion to a substrate, Drying the protective layer dispersion to produce the protective layer (5) and transferring the protective layer (5) to the anode (2) or the cathode (3) or the hydrocarbon membrane (4).

16. A method for producing a membrane electrode assembly (1) according to one of claims 1 to 11, comprising the steps: Producing a protective layer dispersion comprising at least one ceramic material (6) and at least one fluorine-containing ionomer (7), Producing an anode dispersion or cathode dispersion, - Applying the anode dispersion or cathode dispersion to a substrate, - Applying the protective layer dispersion to the anode dispersion or the cathode dispersion, Drying the dispersions to produce the anode layer and the protective layer (5) in the form of an anode layer-protective layer arrangement or the cathode layer and the protective layer (5) in the form of a cathode layer-protective layer arrangement and Transferring the dried anode layer-protective layer assembly or cathode layer-protective layer assembly to the hydrocarbon membrane (4), the method optionally further comprising a step of laminating the anode layer-protective layer assembly and the hydrocarbon membrane (4).

17. A method for producing a membrane electrode assembly (1) according to any one of claims 1 to 5 with claims 7, 9 or 11, comprising the steps: Producing a protective layer dispersion comprising at least one ceramic material (6) and at least one fluorine-containing ionomer (7), Producing an anode dispersion or cathode dispersion, - Applying the anode dispersion or the cathode dispersion to a Gas diffusion layer, - Applying protective layer dispersion to the anode dispersion or the Cathode dispersion, Drying the dispersions to produce the anode layer and the protective layer (5) in the form of an anode layer-protective layer- Gas diffusion layer arrangement or cathode layer and the protective layer (5) in the form of a cathode layer-protective layer-gas diffusion layer arrangement and - Arranging the dried anode layer-protective layer-gas diffusion layer arrangement or cathode layer-protective layer-gas diffusion layer arrangement on the hydrocarbon membrane (4).

18. A method for producing a membrane electrode assembly (1) according to any one of claims 1 to 5 with claims 7, 9 or 11, comprising the steps: Producing a protective layer dispersion comprising at least one ceramic material (6) and at least one fluorine-containing ionomer (7), Producing an anode dispersion or cathode dispersion, - applying the protective layer dispersion to the hydrocarbon membrane (4), - Applying the anode dispersion or the cathode dispersion to the protective layer dispersion and Drying the dispersions to produce the anode layer or cathode layer and the protective layer (5).

19. The method according to any one of claims 14 to 18, further comprising a step of annealing in a temperature range of 150 to 200 °C.

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