Gas diffusion layer with a large-pored microporous layer having pores covered on the surface side and method for the production thereof

Abstract

The present invention relates to a gas diffusion layer for fuel cells, comprising a planar electrically conductive fibre material and a microporous layer having a high gas and water permeability, which has pores which are covered on the surface side and pores which are open on the side facing the planar electrically conductive fibre material. The invention further relates to a method for producing such a gas diffusion layer, to a fuel cell containing such a gas diffusion layer, and to the use of such a gas diffusion layer to improve the gas and / or water permeability of a fuel cell.

Description

[0001] 2022P00025WO

[0002] Dr. Nico Steiert

[0003] Applicant: Carl Freudenberg KG, 69469 Weinheim

[0004] Gas diffusion layer with a large-pored microporous layer with pores covered towards the surface and methods for its production

[0005] The present invention relates to a gas diffusion layer for fuel cells comprising a planar electrically conductive fiber material and a microporous layer with high gas and water permeability, the microporous layer having covered pores towards the surface and open pores towards the planar electrically conductive fiber material. The invention further relates to a method for producing such a gas diffusion layer, a fuel cell containing such a gas diffusion layer, and the use of such a gas diffusion layer to improve the gas and / or water permeability of a fuel cell.

[0006] BACKGROUND OF THE INVENTION

[0007] Fuel cells utilize the chemical reaction of a fuel, especially hydrogen, with oxygen to produce water, in order to generate electrical energy. In hydrogen-oxygen fuel cells, hydrogen or a hydrogen-containing gas mixture is supplied to the anode, where electrochemical oxidation takes place, releasing electrons (H₂ → 2 H₂). ++ 2 e-). Protons are transported from the anode compartment to the cathode compartment via a membrane that separates the reaction chambers gas-tight and electrically insulates them. The electrons supplied at the anode are directed to the cathode via an external circuit. Oxygen or an oxygen-containing gas mixture is supplied to the cathode, where the oxygen is reduced and electrons are absorbed. The oxygen anions formed react with the protons transported across the membrane to form water (1 / 2 O2 + 2 H2). + + 2 e- -> H2O).

[0008] For many applications, especially in automotive powertrains, proton exchange membrane fuel cells are used, also known as polymer electrolyte fuel cells or polymer electrolyte membrane fuel cells (PEMFCs). A special type is the water-oxygen fuel cell in the form of a low-temperature proton exchange membrane fuel cell (LT-PEMFC). The core component of proton exchange membrane fuel cells is a polymer electrolyte membrane (PEM) that is only open to protons (or hydronium ions, H₂O). +The membrane is permeable to water and spatially separates the oxidizing agent, generally atmospheric oxygen, from the reducing agent. A catalyst layer, forming the electrodes and typically containing platinum as the catalytically active metal, is applied to the gas-tight, electrically insulating, proton-conducting membrane on both the anode and cathode sides. The actual redox reactions and charge separations take place within these catalyst layers. The membrane and catalyst layers form a single unit, also known as a CCM (catalyst-coated membrane).

[0009] On both sides of the CCM (Cell Cell Module) there is typically a gas diffusion layer (GDL) that stabilizes the cell structure and performs transport and distribution functions for reaction gases, water, heat, and electricity. The membrane, electrodes, and gas diffusion layer form the membrane electrode assembly (MEA). Flow distribution plates (so-called bipolar plates) are arranged between the membrane electrode assemblies. These plates have channels for supplying the adjacent cathode and anode with process gases and usually also include internal cooling channels.

[0010] Gas diffusion layers for fuel cells typically consist of a conductive carbon fiber substrate coated with hydrophobic polymers, often incorporating fluoropolymers (e.g., PTFE). The fiber material is usually coated with a microporous layer (MPL) containing an electrically conductive material within a polymeric binder matrix. Common electrically conductive materials include carbon materials such as carbon black or graphite powder, while fluorinated polymers (e.g., PTFE) are frequently used as polymeric binders. The gas diffusion layers are crucial for the function and performance of the fuel cell. They transport the process components consumed and generated in the electrode reactions and conduct the electrons produced and consumed in the half-cell reactions, along with the heat generated during the reaction, to the flow distributor plates.

[0011] To ensure optimal water balance and gas transport in the fuel cell, the microplastic layer (MPL) must possess sufficient hydrophobicity and a suitable pore structure. To create pores, a pore-forming agent can be added to the compositions (MPL pastes) used to manufacture the MPL. For example, polymer particles containing a polymer that decomposes under the manufacturing conditions, such as polymethyl methacrylate (PMMA), are known to be used. Other known methods include the use of water-soluble particles that can be washed out and gas-forming compounds that outgas during thermal treatment, thus forming bubbles in the form of pores. There is also a need for gas diffusion layers with MPLs that enable very high mass transport of gases and liquids between the bipolar plates and the carbon capture and storage (CCM).The MPLs used should additionally have a surface that enables good electrical contact with the catalyst layer. Furthermore, the catalyst layer should be protected from mechanical damage and drying out. Gas diffusion layers for fuel cells, which can be single- or multi-layered, specifically in the form of a macroscopic substrate and a microporous layer arranged on top of it, are described as examples in the following documents:

[0012] DE 102016123910 A1, DE 102013207900 A1, EP 2722919 B1, DE 102023118887 A1, DE 102022131492 B3, DE 102022127234 A1 and DE 102018205571 A1.

[0013] L. Chen et al. report in J. Power Sources 467 (2020), 228355 on the influence of the gas diffusion layer structure on the performance of proton exchange membrane fuel cells. It was shown that MPLs with a porosity gradient on a thin macroporous GDL substrate exhibited the best water management. Different amounts of ammonium chloride were used as a pore-forming agent to produce MPLs with varying porosities.

[0014] G. Ren et al. report in Int. J. Hydrogen Energy 52 (2024), 1161-1172 on the improvement of the performance of proton exchange membrane fuel cells by nanostructured gas diffusion layers (nano-GDLs) with gradients regarding pore size.

[0015] CN 114430050 B describes a method for manufacturing a gas diffusion layer for a high-performance hydrogen fuel cell, comprising the following steps:

[0016] S1: Hydrophobizing a porous substrate material by immersion in a hydrophobic slurry;

[0017] S2: Production of a first composite material by pressing the porous substrate material with a prefabricated film material to form a first microporous layer. To produce the film material, carbon powder, a fluorocarbon material, a carbon-based aerogel, a fluorine-based binder, and a film-forming substance are hot-pressed into a film-like layer; and

[0018] S3: Production of the gas diffusion layer by applying a slurry to form a second microporous layer comprising carbon powder, fluorine-based binder, dispersant and water, followed by drying and sintering.

[0019] EP 4303968 A2 describes a gas diffusion layer for a fuel cell, comprising a) a planar electrically conductive fiber material and b) a microporous layer on one of the surfaces of the fiber material, wherein the gas diffusion layer has at least one property gradient with respect to at least one chemical and / or physical property with respect to its base area (in the x,y plane).

[0020] EP 4358197 A1 describes a method for producing a gas diffusion layer for a fuel cell, comprising

[0021] A) a planar electrically conductive fiber material and

[0022] B) a microporous layer on at least one of the surfaces of the fiber material, wherein the microporous layer has at least one property gradient with respect to at least one chemical and / or physical property in relation to the base area of ​​the gas diffusion layer (in the x,y plane), wherein i) a planar electrically conductive fiber material A) is provided, ii) the fiber material provided in step i) is coated with a precursor to form a microporous layer, wherein the composition of the precursor is varied to generate a gradient, iii) the coated fiber material obtained in step ii) is subjected to post-treatment at increased pressure and optionally increased temperature.

[0023] US Patent 2014 / 0134516 A1 describes a gas diffusion layer for a fuel cell, comprising: a GDL substrate and a two-layer MPL with a first MPL layer on the substrate side containing granular carbon material but no scale-like graphite, and a second MPL layer on the catalyst side containing scale-like graphite, wherein the MPL contains a concentrated region extending in a belt-like fashion substantially parallel to a bonding layer between the MPL and the GDL substrate. The thickness of the first microporous layer is in the range of 10 to 100 pm, and the thickness of the second microporous layer is less than or equal to 10 pm. In a particular embodiment, the second microporous layer contains a binder, scale-like graphite, and carbon black and / or graphite granules.The concentrated area of ​​scale-like graphite is intended to reduce the contact resistance between the catalyst layer and the MPL, and between the GDL and MPL, and to prevent the electrolyte membrane from drying out. The scale-like graphite exhibits high crystallinity and a small thickness H (extent in the z-direction) relative to the mean diameter D of the area spanned by the x- and y-axes (mean area diameter D). Preferably, the thickness H of the scale-like graphite is in the range of 0.05 pm to 1 pm, and the mean area diameter D is in the range of 5 pm to 50 pm. The mean particle diameter of the carbon granules is preferably in the range of 100 nm to 10 pm. For example, graphite granules or carbon black can be used as the carbon granules. Like the scale-like graphite, the graphite granules have high crystallinity but a low aspect ratio (ratio of mean area diameter D to thickness H).The mean particle diameter of the graphite granules is preferably in the range of 1 pm to 10 pm. Carbon black comprises fine carbon particles. The mean particle diameter of the carbon black is preferably less than or equal to 1 pm and preferably in the range of 10 nm to 100 nm. The embodiments for the second MPL layer in any case contain flat, scale-like graphite (Gf), as well as optionally scale-like graphite of smaller diameter (Gfs), graphite granules (Gg), and additionally, optionally, carbon black. The embodiments for the first MPL layer contain either only carbon black or a mixture of carbon black and graphite granules (Gg). This document does not teach the use of a two-layer MPL wherein the substrate-side (inner) layer is open-cell and has a large mean pore diameter, and the second (outer) layer is closed-cell.

[0024] KR 2023 0090754 describes a process for producing a gas diffusion layer in which a carbon fiber substrate is provided, a first mixture of carbon powder, PTFE, a pore former and a solvent is produced, in a first coating step the carbon fiber substrate is coated with the first mixture to form a first microporous layer, a second mixture of carbon powder, PTFE, and a solvent is produced, in a second coating step the carbon fiber substrate coated with the first mixture is coated with the second mixture to form a second microporous layer, and in a pore formation step the components contained in the second MPL are subjected to sintering.

[0025] The first and second MPL coatings can be applied to the same or different sides of the substrate. The second coating mixture contains no pore-forming agent or less pore-forming agent than the first coating mixture. Only the use of carbon powder in both coating mixtures is described, which can be various types of carbon black. The use of graphite is not described. Nor is the application of a two-layer MPL described, where the substrate-side (inner) layer is open-cell with a large average pore diameter and the second (outer) layer is closed-cell.

[0026] JP2016015216A describes a gas diffusion layer with two microporous layers that differ in thickness, porosity, and pore size. The first (inner) microporous layer has a thickness of 150 pm or less, a porosity of 80% or more, and a pore diameter ranging from 10 pm to 100 pm. The second (outer) microporous layer has a thickness ranging from 0.1 pm to 10 pm, a porosity ranging from 40% to 70%, and a pore diameter of less than 0.1 pm, with a total microporous layer thickness ranging from 10 pm to 60 pm.EP 3709409 A1 describes a microporous layer structure for a fuel cell, comprising a first (inner) layer with high water vapor permeability and a second (outer) layer with low water vapor permeability. The microporous layers exhibit a gradient between the air inlet and outlet, with the thickness of the high-permeability microporous layer increasing and the thickness of the low-permeability microporous layer decreasing in the direction of the airflow. The porosities of the microporous layers are very low. Preferably, the high-permeability microporous layer has a porosity of 45-55%, and the low-permeability microporous layer has a porosity of 30-40%.To produce the microporous layers, coating materials are used that contain exclusively finely divided carbon powder, wherein the particle size of the carbon in the coating material for producing the first layer is in the range of 30 to 60 nm, preferably 45 to 60 nm, and the particle size of the carbon in the coating material for producing the second layer is in the range of 20 to 50 nm, preferably 20 to 40 nm. The use of graphite and / or other pore-forming agents for producing the microporous layers is not described.

[0027] The present invention aims to provide a microporous layer for a gas diffusion layer for use in fuel cells, enabling a very high mass transport of gases and liquids through the gas diffusion layer, i.e., between the bipolar plates on the one hand and the membrane and catalyst layers (the COM) on the other. The microporous layers used should have a surface that allows for good electrical contact with the catalyst layer. Furthermore, the catalyst layer should be protected from mechanical damage and from drying out.

[0028] Surprisingly, it has now been found that this problem is solved by using a microporous layer in a gas diffusion layer, comprising at least two layers: a first (inner) layer, one side of which is in contact with the planar electrically conductive fiber material and the other side of which is in contact with the second (outer) layer, wherein the first layer is open-cell and has a large pore diameter, and the second layer has a smaller pore diameter than the first layer.

[0029] SUMMARY OF THE INVENTION

[0030] A first object of the invention is a gas diffusion layer for a fuel cell, comprising

[0031] A) a planar electrically conductive fiber material, B) a microporous layer containing conductive particles in a matrix of a polymeric binder, wherein the microporous layer

[0032] B1) a first open-cell layer on at least one of the surfaces of the fiber material A), and

[0033] B2) comprises a second gas- and water-permeable layer on the first layer B1), which has a smaller pore diameter than layer B1), obtainable by a process in which i) a planar electrically conductive fiber material A) is provided, ii) the fiber material provided in step i) is coated with a first coating agent to form a first microporous layer, wherein a pore-forming agent is applied to the fiber material A) prior to coating in step ii) and / or the coating agent used in step ii) contains a pore-forming agent, iii) the first coating obtained in step ii) is coated with a second coating agent to form a second microporous layer, iv) the fiber material obtained in step iii) coated with the first and the second coating agents is subjected to a treatment to generate pores from the pore-forming agent.

[0034] Another object of the invention is a gas diffusion layer for a fuel cell, comprising

[0035] A) a planar electrically conductive fiber material,

[0036] B) a microporous layer containing conductive particles in a matrix of a polymeric binder, wherein the microporous layer

[0037] B1) a first open-cell layer on at least one of the surfaces of the fiber material A), and

[0038] B2) comprises a second gas- and water-permeable layer on the first layer B1), wherein the size of the largest passage pore of the gas diffusion layer, relative to the planar electrically conductive fiber material A) and the first layer B1), determined by capillary flow porometry measurement according to ASTM F-316:2003, is at least 30.00 pm and wherein the mean pore diameter of the gas diffusion layer, relative to the planar electrically conductive fiber material A), the first layer B1) and the second layer B2), determined by capillary flow porometry measurement according to ASTM F-316:2003, is at most 8.00 pm.

[0039] In a particular embodiment, a pore-forming agent is used to form the first microporous layer B1), which is selected from a pore-forming agents which decompose upon heating to a temperature above the pore-forming temperature by forming a gas phase or which release a gas, preferably selected from a1 plastic particles, preferably selected from acrylic homo- and copolymers, polymethyl(meth)acrylates, acrylic-modified polystyrenes, especially styrene-methyl methacrylate copolymers, polyvinylidene chloride, etc.a2 expandable microspheres, preferably expandable microspheres comprising a thermoplastic shell and an enclosed gas-forming component, a3 natural polymers, preferably selected from agar, alginates, gelatin or starch, a4 gas-releasing compounds, preferably selected from alkali and ammonium hydrogen carbonates, alkali and ammonium carbonates, preferably sodium hydrogen carbonate and / or ammonium hydrogen carbonate, β pore-forming agents capable of forming pores by treatment with a solvent, preferably selected from sugars.

[0040] Y mixtures of it.

[0041] In a particular embodiment, the second coating material for forming the second microporous layer B2) is free of added pore-forming agents. The second coating material for forming the second microporous layer B2) is, in particular, free of pore-forming agents that decompose upon heating to a temperature above the pore-formation temperature, forming a gas phase, or that release a gas, and of pore-forming agents that are capable of forming pores upon treatment with a solvent. A further aspect of the invention is a method for producing a gas diffusion layer for a fuel cell, comprising

[0042] A) a planar electrically conductive fiber material,

[0043] B) a microporous layer containing conductive particles in a matrix of a polymeric binder, wherein the microporous layer

[0044] B1) a first open-cell layer on at least one of the surfaces of the fiber material A), and

[0045] B2) comprises a second gas- and water-permeable layer on the first layer B1), wherein i) a planar electrically conductive fiber material A) is provided, ii) the fiber material provided in step i) is coated with a first coating agent to form a first microporous layer, wherein a pore-forming agent is applied to the fiber material A) prior to coating in step ii) and / or the coating agent used in step ii) contains a pore-forming agent, iii) the first coating obtained in step ii) is coated with a second coating agent to form a second microporous layer, iv) the fiber material obtained in step iii) coated with the first and the second coating agent is subjected to a treatment to generate pores from the pore-forming agent.

[0046] Another object of the invention is a fuel cell comprising at least one gas diffusion layer, as defined above and below.

[0047] In a preferred embodiment, the fuel cell comprises a polymer electrolyte membrane onto which a catalyst layer is applied, the catalyst layer being in contact with the surface of the second microporous layer B2) of the gas diffusion layer. A further object of the invention is a fuel cell stack comprising a plurality of fuel cells as defined above and below.

[0048] A further aspect of the invention is the use of a gas diffusion layer, as defined above and below, in a fuel cell to improve gas and / or water permeability. Preferably, the gas diffusion layer is used in a proton exchange membrane fuel cell.

[0049] DESCRIPTION OF THE INVENTION

[0050] The microporous layers used according to the invention comprise at least two layers, a first (inner) layer and a second (outer) layer, wherein one side of the inner layer is in contact with the planar electrically conductive fiber material and the other side is in contact with the second layer, wherein the first layer is open-cell and preferably has a large mean pore diameter, and the second layer has a smaller pore diameter than the first layer. These microporous layers used according to the invention and gas diffusion layers based thereon have the following advantages:

[0051] The use of two different coating agents to produce a multilayer MPL, wherein the coating agents differ in the type of carbon-containing material used and / or the amount of carbon-containing material used and / or by the use of additional pore-forming agents, has a beneficial effect on the pore structure of the MPL.

[0052] The size, orientation, and distribution of the pores in the MPL can be specifically controlled by the properties of the carbon-containing materials used and the various pore-forming agents. In particular, it is possible to create a higher proportion of larger, open-cell pores in the inner MPL layer (layer B1) and to produce a largely closed surface with the second, outer MPL layer (layer B2).

[0053] The MPLs exhibit high porosity and pore size overall. The pores have a small diameter towards the surface (in contact with the catalyst layer) and are open towards the planar electrically conductive fiber material.

[0054] The MPL according to the invention enables a very high mass transport of gases and liquids through the gas diffusion layer, i.e. between the bipolar plates on the one hand and the membrane and the catalyst layers (the COM) on the other.

[0055] The surface of the MPL is smooth and fine-pored, allowing good electrical contact with the catalyst layer.

[0056] The complex property profile of the MPL is not negatively affected by the MPL according to the invention. The resulting MPLs exhibit good protection of the polymer membrane against fiber penetration by fibers from the GDL substrate. Properties such as hydrophobicity, protection against drying out, etc., and physicochemical properties such as Gurley gas permeability and dry diffusion length are not impaired.

[0057] Within the scope of the invention, a nonwoven fabric generally refers to a sheet-like structure consisting predominantly of individual fibers whose cohesion is essentially due to their inherent adhesion. The transformation of a nonwoven fabric into a nonwoven material by creating a stronger bond between the fibers than exists in the nonwoven fabric is achieved through nonwoven bonding processes, which are generally divided into mechanical, chemical, and thermal methods. Nonwoven fabrics and processes for their production are described in H. Fuchs, W. Albrecht, Nonwoven Fabrics, 2nd edition, Wiley-VCH, Weinheim, Germany.

[0058] Gas diffusion layers are also referred to as GDL and microporous layers as MPL.

[0059] To describe the planar fiber material A), the intermediate products manufactured therefrom, and the gas diffusion layer according to the invention, an orthogonal coordinate system can be used, wherein the base of the fiber material lies in the plane spanned by the x-axis and the y-axis (also referred to as the x,y-plane). The z-axis, orthogonal to this, serves to describe the thickness of the material or individual layers thereof. According to the description customary for fiber composite materials, the x-axis is also described as the rolling direction (machine direction, MD) and the y-axis as the cross-rolling direction (cross-machine direction, CMD or CD). Mass transport essentially occurs in the z-axis direction between the flow distributor plate (bipolar plate) and the catalyst-coated membrane (CCM).

[0060] The thickness of the conductive planar fiber material and the gas diffusion layer can be determined according to DIN 53855-1:1993-08 "Determination of the thickness of textile planar structures".

[0061] The thickness of MPL B) and MPL layers B1) and B2) can be determined by measuring a cross-section of the GDL along the z-axis (i.e., a measurement perpendicular to the surface of the GDL, or in a top view of the x,z-plane or the y,z-plane). A scanning electron microscope (SEM) can be used for this purpose. If MPL layer B1) is partially inside and partially outside the fiber material A), the portion of layer B1) located inside the fiber material A) is also taken into account when determining the thickness of polymer layer B1). In general, the layer thicknesses of layers B1) and B2) and the penetration depth of B1) into the fiber material A) can be well controlled by the application rate of the MPL pastes, their solvent content and viscosity, as well as the temperature and pressure conditions during application and post-treatment.Thus, the boundaries of the polymer layers B1) and B2) are generally easy to detect, so that by carrying out several measurements at different locations and averaging, the thicknesses of the polymer layers B1) and B2) can be determined with good accuracy.

[0062] Determining the area-related mass in g / m² 2 can be done according to ISO 9073-1.

[0063] The porosity of the gas diffusion layer, i.e., the composite consisting of layers A), B1), and B2), can be determined using capillary flow porometry. Capillary flow porometry measurements are described in DIN 66140:2022-02 and ASTM F-316:2003.

[0064] The structure of the gas diffusion layers according to the invention can also be characterized using computed tomography microscopy (p-CT, X-ray micro-computed tomographic microscopy). This method is particularly suitable for determining the mean pore diameters of the MPL and layers B1) and B2).

[0065] Scanning electron microscopy (SEM) can also be used to characterize the structure of the gas diffusion layers according to the invention. Scanning electron microscopy is particularly suitable for determining the mean pore diameters of layer B2.

[0066] More detailed information on capillary flow porometry, computed tomography microscopy and scanning electron microscopy can be found below under the heading "Measurement methods".

[0067] The roughness is determined using the stylus method, as described in DIN 4768-1 :1974-08 entitled "Determination of roughness parameters R a , R z , Rmax with electric stylus instruments; fundamentals" is described. Here, the mean roughness R denotes a the mean distance of a measuring point on the surface to the center line and R z This refers to the average roughness depth. The measurements can be carried out, for example, with a digital microscope suitable for determining roughness, such as the Keyence VHX-7000. The values ​​are averages from 6 measurements: 3 in the machine direction (MD) and 3 perpendicular to the machine direction (CD).

[0068] The planar electrically conductive fiber material and the gas diffusion layer used according to the invention are planar structures with a substantially two-dimensional, planar extent and a correspondingly smaller thickness. The gas diffusion layer has a base area that generally corresponds substantially to the base area of ​​the adjacent membrane with the catalyst layers and the base area of ​​the adjacent flow distributor plate of the fuel cell. The shape of the base area of ​​the gas diffusion layer can be, for example, polygonal (n-sided with n > 3, e.g., triangular, square, pentagonal, hexagonal, etc.), circular, segmented circular (e.g., semicircular), elliptical, or segmented ellipsoid. Preferably, the base area is rectangular or circular.

[0069] The gas diffusion layer comprises, as component A), at least one electrically conductive planar fiber material. Preferably, component A) comprises a fiber material selected from nonwovens, papers, woven fabrics, and combinations thereof. Suitable substrate materials are fiber materials that are themselves conductive or that can be made conductive by the addition of conductive additives, such as carbon or metal particles. Suitable substrate materials include, in principle, carbon fibers, glass fibers, fibers of organic polymers such as polypropylene, polyester, polyphenylene sulfide, polyetherketones, and mixtures thereof. The fibers contained in fiber material A) preferably comprise or consist of carbon fibers. Such fiber materials particularly advantageously fulfill the requirements of the gas diffusion layer with regard to gas diffusivity, liquid water permeability, electrical, and thermal conductivity.The fiber material A) is preferably selected from carbon fiber fabrics, carbon fiber papers, and carbon fiber nonwovens. In a preferred embodiment, the fiber material A) comprises at least one carbon fiber nonwoven or consists of a carbon fiber nonwoven.

[0070] The carbon fibers can be produced in the usual way, preferably using polyacrylonitrile fibers (PAN fibers) as the starting material.

[0071] Carbon fiber fabrics are produced by interlacing two yarn systems: warp (warp threads) and weft (weft threads). As with textiles, fiber bundles are flexibly but permanently bonded together. Carbon fiber fabrics are preferably made from oxidized, but not yet carbonized or graphitized, PAN fibers. Carbonization or graphitization, which imparts electrical conductivity to the fiber material, takes place after weaving.

[0072] Graphitized PAN fibers are preferably used to produce carbon fiber papers. These are shredded into fiber fragments in a known manner, suspended in a slurry, and a fiber layup is produced by sieving (waxing) and dried, analogous to papermaking. In a preferred embodiment, at least one binder is additionally incorporated into the paper. Suitable binders include, for example, phenolic, furan, and polyimide resins. To incorporate the binder, the paper can be impregnated with it, and the binder can optionally be subsequently cured. After impregnation and curing, the carbon fiber paper is subjected to further carbonization / graphitization to convert the binder into compounds with improved electrical conductivity. In another suitable embodiment, a filled carbon fiber paper is used to provide the fiber material A).The manufacturing process initially proceeds as previously described; however, instead of incorporating a binder and carbonization / graphitization, a filler consisting of a carbon material in a polymeric binder is introduced into the still-damp paper. Specifically, a carbon-PTFE filler is used for this purpose. This filler increases the thermal and electrical conductivity to such an extent that carbonization / graphitization becomes unnecessary.

[0073] For the production of carbon fiber nonwovens, either unoxidized or oxidized PAN fibers can be used. In a first preferred embodiment, the fibers are first laid down (carded) into a dry nap and then bonded to form a nonwoven. This can be achieved, for example, by hydro-entangling, whereby the carbon fibers are oriented, interlocked, and thus mechanically stabilized. If necessary, the thickness of the bonded nonwoven can be calibrated to a desired value. Nonwovens based on unoxidized PAN fibers are, after laying down and bonding, first subjected to oxidation at elevated temperature and under an oxygen atmosphere, and then to carbonization / graphitization under an inert gas atmosphere. Nonwovens based on oxidized PAN fibers are subjected only to carbonization / graphitization after laying down and bonding.

[0074] In a first specific embodiment, a mechanically bonded fiber material (A) is used as fiber material. In another specific embodiment, a nonwoven fabric (A) is used as fiber material, into which at least one binder has been incorporated, which may subsequently be cured. Suitable binders include, for example, phenolic, furan, and polyimide resins. The incorporation of the binder can, for example, follow carbonization / graphitization, and the resulting impregnated nonwoven fabric can then be thermally treated again (for drying and / or sintering).

[0075] The planar electrically conductive material A) is preferably a fiber composite material comprising a fiber material preferably selected from carbon fiber nonwovens, carbon fiber woven fabrics and mixtures thereof.

[0076] Specifically, the fiber composite material comprises at least one fiber material and applied to it and / or incorporated therein a1) at least one polymeric additive, a2) optionally at least one conductivity-enhancing additive, a3) optionally at least one further additive.

[0077] The polymeric additive a1) is preferably selected from fluorine-containing polymers a11), fluorine-free high-temperature-resistant polymers a12), various polymers a13) thereof, and mixtures thereof. To improve transport processes through the GDL and at the interfaces, it can be advantageous to increase the hydrophobicity of the fiber material A). Suitable polymeric additives a1), which, for example, act as binders and simultaneously increase hydrophobicity, are fluorine-containing polymers a11). In principle, fluorine-containing polymers b1) used as polymeric binders in the microporous layer are suitable as fluorine-containing polymers a11). Preferably, the fiber material then contains at least one fluorine-containing polymer a11) applied to it and / or incorporated therein. The fluorine-containing polymer a11) is preferably selected from polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers (FEP), perfluororalkoxy polymers (PFA), and mixtures thereof.Perfluoroalkoxy polymers are, for example, copolymers of tetrafluoroethylene (TFE) and perfluoroalkoxy vinyl ethers, such as perfluorovinyl propyl ether. Preferably, polytetrafluoroethylene is used as polymer a11). The fiber material can be impregnated with the fluorine-containing polymer a11) using conventional impregnation processes. For example, a PTFE dispersion can be applied in an immersion bath, the solvent evaporated, and the treated fiber material sintered at elevated temperatures, generally at least 300 °C.

[0078] Preferably, the mass fraction of the polymeric additive a1) is 0.5 to 50%, preferably 1 to 40%, based on the mass of the electrically conductive material A). In a special embodiment, the polymeric additive a1) comprises at least one fluorine-containing polymer a11). Preferably, the mass fraction of the fluorine-containing polymer a11) is then 0.5 to 40%, preferably 1 to 30%, based on the mass of the electrically conductive material A).

[0079] In a preferred embodiment, the polymeric additive a1) comprises at least one fluorine-free, high-temperature-resistant polymer a12), such as those used according to the invention as component b2) for the production of the microporous layer B). The fluorine-free, high-temperature-resistant polymer a12) is then preferably selected from polyaryletherketones, polyphenylene sulfides, polysulfones, polyethersulfones, semi-aromatic (co)polyamides, polyimides, polyamideimides, polyetherimides, and mixtures thereof. Preferably, the mass fraction of the fluorine-free polymer a12) is then 0.5 to 40%, preferably 1 to 30%, based on the mass of the fiber material A).

[0080] In a particular embodiment, the binder a1) comprises a mixture of at least one fluorine-containing polymer a11) and at least one fluorine-free, high-temperature-resistant polymer a12). Preferably, the total mass fraction of the polymers a11) and a12) is then 0.5 to 40%, preferably 1 to 30%, based on the mass of the electrically conductive material A).

[0081] The additive a1) can comprise at least one further polymer a13) different from a11) and a12). Suitable polymers a13) are selected, for example, from phenolic resins, furan resins, polyimide resins, and mixtures thereof. Specifically, the polymeric additive a1) contains various further polymers a13) from the fluorinated polymers a11) and the polymers a12) in a weight fraction of at most 5%, preferably at most 1%, particularly preferably at most 0.5%, and especially at most 0.1%, based on the total weight of the electrically conductive material A). Applied to and / or incorporated therein. Even more specifically, the electrically conductive material A) contains no additions of further polymers a13) different from the fluorinated polymers a11) and the polymers a12).

[0082] In many cases, the fiber material A) used as an electrically conductive material already possesses good electrical and thermal conductivity due to the carbon fibers it contains, even without conductivity-enhancing additives. However, to further improve its electrical and thermal conductivity, the fiber material A) can be additionally equipped with at least one conductivity-enhancing additive a2). Preferably, the conductivity-enhancing additive a2) is selected from metal particles, carbon black, graphite, graphene, carbon nanotubes (CNTs), carbon nanofibers, and mixtures thereof. Preferably, the conductivity-enhancing additive a2) comprises or consists of carbon black. The fiber material A) can be equipped with at least one conductivity-enhancing additive a2) in conjunction with, for example, the polymeric additive a1) and / or further additives a3).

[0083] Preferably, the mass fraction of the conductivity-enhancing additive a2) is 0.5 to 45%, preferably 1 to 25%, based on the mass of the fiber material A). In a particular embodiment, the conductivity-enhancing additive a2) comprises or consists of carbon black and has a mass fraction of 0.5 to 45%, preferably 1 to 25%, based on the mass of the fiber material A).

[0084] The fiber materials A) may additionally contain at least one further additive a3). These include, for example, surfactants. The addition of at least one further additive a3) to the fiber material A) can be carried out together with the polymeric additive a1) and / or conductivity-enhancing additives a2). Preferably, the total mass fraction of further additives a3) is 0 to 80%, preferably 0 to 50%, based on the mass of the fiber material A).

[0085] The fiber material A) preferably has a thickness in the range of 50 to 500 pm, particularly preferably from 100 to 400 pm. This thickness refers to the unfinished, uncompressed state of the fiber material A), i.e., before the GDL is installed in a fuel cell.

[0086] The fiber material A) can be equipped with components a1) and optionally a2) and / or a3) by conventional methods. An aqueous dispersion is preferably used for equipping the fiber material A). Suitable coating and impregnation processes are described in more detail below. In a particular embodiment, the fiber material A) equipped with components a1) and optionally a2) and / or a3) is subjected to a thermal treatment (drying and / or sintering). The thermal treatment of the fiber material A) preferably takes place at a temperature of at least 250 °C, more preferably at least 300 °C, and particularly in a range of 300 to 450 °C. The thermal treatment can also be carried out after the application of the microporous layer B), as described in more detail below.

[0087] Microporous layer B)

[0088] The gas diffusion layer according to the invention consists of a multilayer composite based on a planar, electrically conductive fiber material A) and a microporous layer (MPL) B) on one of the surfaces of the fiber material A).

[0089] The microporous layer B) contains conductive particles in a matrix of a polymeric binder, wherein the microporous layer

[0090] B1) a first open-cell layer on at least one of the surfaces of the fiber material A), and

[0091] B2) comprises a second gas- and water-permeable layer on top of the first layer B1).

[0092] Preferably the polymeric binder contains at least one polymer selected from fluorine-containing polymers b1) fluorine-free, high-temperature-resistant polymers b2) and mixtures thereof.

[0093] The polymeric binder used to produce the MPL can have the same or different compositions in layers B1) and B2). The following information regarding suitable and preferred polymeric binders and their quantities applies equally to both layers B1) and B2).

[0094] In a preferred embodiment, the polymeric binder contains at least one fluorine-containing polymer (b1). The fluorine-containing polymer (b1) is preferably selected from polytetrafluoroethylenes, tetrafluoroethylene-hexafluoropropylene copolymers, perfluoroalkoxy polymers, and mixtures thereof. Preferably, polytetrafluoroethylene is used as polymer (b2).

[0095] In a further preferred embodiment, the polymeric binder contains at least one fluorine-free, high-temperature-resistant polymer b2). The fluorine-free, high-temperature-resistant polymer b2) is preferably selected from polyaryletherketones, polyphenylene sulfides, polysulfones, polyethersulfones, semi-aromatic (co)polyamides, polyimides, polyamideimides, polyetherimides and mixtures thereof.

[0096] The polymer b2) is specifically selected from among so-called high-performance plastics, which are characterized by properties such as a high glass transition temperature, a high melting point, good temperature resistance, good chemical resistance, and good mechanical properties. Preferably, the polymers b1) have a continuous operating temperature (continuous service temperature) of at least 150°C. In particular, the polymers b2) are thermoplastics.

[0097] Preferably, the polymers used are (b2) semi-aromatic and aromatic polymers.

[0098] The polymers b2) are preferably selected from polyaryletherketones (PAEK), polyphenylene sulfides (PPS), polysulfones (PSU), polyethersulfones (PES), semi-aromatic (co)polyamides (high temperature polyamides, HTPA), polyimides (PI), polyamide-imides (PAI), polyether-imides (PEI) and mixtures (blends) thereof.

[0099] Suitable polymers b2) also include (partially) aromatic polyesters, such as PET or PBT, polycarbonates (PC) and temperature-resistant melamines, such as melamine foams filled with nanoporous SiO2 aerogels.

[0100] In a preferred embodiment, the polymer component b1) comprises at least one polyaryletherketone. Specifically, the polymer component b1) consists of at least one polyaryletherketone. Polyaryletherketones (PAEKs) are semi-crystalline thermoplastics with an alternating structure in which an aryl group is followed by either a keto group (carbonyl group) or an ether group, the proportions of keto and ether groups being variable and differing in the substitution pattern on the aryl rings. Suitable polyaryletherketones b1) are polyetherketones (PEK), polyetheretherketones (PEEK), polyetherketoneketones (PEKK), etc. Preferably, the polymer component b2) comprises at least one polyetheretherketone or consists of at least one polyetheretherketone.

[0101] Suitable semi-aromatic (co)polyamides b2) are the polymers designated as high-temperature polyamides (HTPA). These are semi-crystalline or amorphous, thermoplastic, semi-aromatic polyamides. Preferably, they contain at least one aromatic dicarboxylic acid polymerized within them, in particular selected from terephthalic acid, isophthalic acid, and mixtures of terephthalic acid and isophthalic acid. Preferred semi-aromatic (co)polyamides b2) are selected from PA 6.T, PA 10.T, PA 12.T, PA 6.1, PA 10.1, PA 12.1, PA 6.T / 6.I, PA 6.T / 6, PA 6.T / 10T, PA 10.T / 6.T, PA 6.T / 12.T, PA12.T / 6.T, and mixtures thereof. Another special embodiment of the polyamides b2) is polyphthalamide (PPA). Suitable polyimides b2) are polysuccinimide (PSI), polybismaleimide (PBMI), polyimide sulfone (PISO) and polymethacrylimide (PMI).

[0102] In particular, the polymeric binder contains at least one fluorine-containing polymer b1) and at least one fluorine-free, high-temperature-resistant polymer b2).

[0103] In a preferred embodiment, the polymeric binder comprises at least one polymer b1) and at least one polymer b2), wherein b1) comprises or consists of polytetrafluoroethylene (PTFE) and b2) comprises or consists of a polyetheretherketone (PEEK).

[0104] Optionally, the polymeric binder contains at least one other polymer different from polymers b1) and b2). Suitable polymers are those mentioned above as polymeric additives a13) of the fiber material A).

[0105] Preferably, the polymeric binder is used to produce the microporous layer B) in an amount of 0.5 to 50 wt.%, particularly preferably 1.0 to 40 wt.%, and especially 10 to 25 wt.%, based on the total weight of the coating material used to produce the microporous layer B). The total weight of the coating material used to produce the microporous layer B) is the sum of the weights of the coating materials used to produce the first and second coatings. Similarly, the amount of polymeric binder by weight is the sum of the weights of the polymeric binders contained in the first and second coating materials.

[0106] Preferably the solids content of the first coating material for producing the first layer B1) of the microporous layer B) is 1 to 50 wt.%, particularly preferably 2 to 25 wt.%, in particular 4 to 18 wt.%.

[0107] Preferably the solids content of the second coating material for producing the second layer B2) of the microporous layer B) is 1 to 50 wt.%, particularly preferably 2 to 25 wt.%, in particular 4 to 18 wt.%.

[0108] Preferably, the first and second coating compositions comprise at least one solvent and dispersant selected from water, water-miscible liquids, and mixtures thereof. Preferably, water is used as the first and / or second solvent and dispersant.

[0109] Preferably, for the production of the first layer B1) of the microporous layer B), the polymeric binder is used in an amount by weight of 0.2 to 10 wt.%, particularly preferably 0.5 to 5 wt.%, in particular 0.8 to 4 wt.%, based on the weight of the first coating material used to produce the first layer B1).

[0110] Preferably, for the production of the second layer B2) of the microporous layer B), the polymeric binder is used in a weight quantity of 0.2 to 10 wt.%, particularly preferably 0.5 to 5 wt.%, in particular 0.8 to 4 wt.%, based on the weight of the second coating material used to produce the second layer B1).

[0111] Preferably, the weight ratio of the first coating material to the second coating material is in a range of 50.0 : 50.0 to 95.0 : 5.0, particularly preferably in a range of 60.0 : 40.0 to 90.0 : 10.0.

[0112] According to the invention, the microporous layer B) comprises conductive particles in a matrix of a polymeric binder. The conductive particles are preferably selected from carbon black, graphite, graphene, carbon nanotubes (CNTs), carbon nanofibers, and mixtures thereof. Carbon black, graphite, or a mixture thereof is preferred. As will be explained in more detail below, the carbon-containing component of the microporous layer (MPL) influences the pore properties and the mass transport through the gas diffusion layer. Without being bound to any specific theory, it is assumed that the influence of the carbon-containing component on the pore properties and the mass transport is based, among other things, on steric effects. This applies particularly to the use of carbon black and graphite. These components can then both function as conductive materials and be used specifically to modify the pore properties and the mass transport.To achieve larger pores, however, the use of at least one different pore-forming agent will generally be necessary (hereinafter also referred to as "additional pore-forming agent"). Such pore-forming agents, which decompose upon heating to a temperature above the pore-forming temperature, forming a gas phase, or which release a gas, or which are capable of forming pores through treatment with a solvent, are described in more detail below.

[0113] Preferably, the amount of conductive particles by weight is 0.5 to 45 wt.%, particularly preferably 0.8 to 40 wt.%, in particular 1.0 to 20 wt.%, especially 3.0 to 15 wt.%, based on the total weight of the coating material used to produce the microporous layer B).

[0114] Preferably, the weight of conductive particles in the first layer B1) is 0.5 to 45 wt.%, particularly preferably 0.8 to 40 wt.%, in particular 1.0 to 20 wt.%, and specifically 3.0 to 15 wt.%, based on the weight of the first coating material used to produce the first layer B1). Preferably, the weight of conductive particles in the second layer B2) is 0.5 to 45 wt.%, particularly preferably 0.8 to 40 wt.%, in particular 1.0 to 20 wt.%, and specifically 3.0 to 15 wt.%, based on the weight of the second coating material used to produce the second layer B1).

[0115] The previously specified weight quantities of conductive particles in MPL B) or in layers B1) and B2) serve to improve conductivity. If the carbon-containing components are also to be used to modify the porosity or mass transport in MPL B) or in layers B1) and B2), this quantity can be increased if necessary.

[0116] It was found that the use of two different coating agents to produce a multilayer MPL, wherein the coating agents differ in the type and / or quantity of carbon-containing material used and possibly additional pore-forming agents, has a beneficial effect on the pore structure of the MPL.

[0117] The components used to adjust the properties of layer B1) and layer B2) are preferably selected from carbon black, graphite particles, expanded graphite, various pore-forming agents, and mixtures thereof. These components are also referred to as "porosity-modifying components." The term "porosity-modifying components" generally refers to components that influence the formation and / or properties of the resulting pores. It thus also includes components such as carbon black, graphite particles, and expanded graphite, which are primarily used to improve conductivity and / or to create a more closed surface in layer B2).

[0118] The porosity-modifying components, which differ from carbon black, graphite particles, and expanded graphite, are also referred to as "additional pore-formers." These are specifically components that can be removed from the microporous layer by forming pores. These additional pore-formers can also be used as standalone pore-formers.

[0119] soot

[0120] Within the scope of the invention, the term carbon black refers to a material consisting essentially of fine carbon particles. Carbon black suitable for use in the microporous layer B), the first layer B1), and the second layer B2) preferably has a mean particle diameter, based on the primary particles (nodules), of at most 1000 nm (1 pm), preferably at most 500 nm. Preferably, the carbon black used according to the invention has a mean particle diameter, based on the primary particles, in the range of 10 to 400 nm, particularly preferably from 20 to 300 nm. The mean particle diameter and the electron microscopic surface area can be determined according to ASTM standard D-3849-87 (Standard Test Method for Carbon Black - Morphological Characterization of Carbon Black Using Electron Microscopy).

[0121] The carbon black used according to the invention preferably has a BET surface area of ​​10 to 1500 m². 2 / g, preferably 20 to 600 m2 / g, especially preferably 50 to 500 m 2 / g, on. The BET surface area value is determined according to ASTM standard D 6556-04.

[0122] The soot used according to the invention is preferably selected from acetylene soot, flame soot, crack soot, channel soot, plasma soot, gas soot, furnace soot, Ketjen soot and mixtures thereof.

[0123] Graphite particles

[0124] In principle, graphite particles of different morphologies, such as slate-shaped, spherical, etc., are suitable for use in the microporous layer B), the first layer B1) and the second layer B2). The term "graphite particles" within the meaning of the invention includes non-expanded graphite.

[0125] The size distribution of the graphite particles used according to the invention can be monomodal or can include several maxima and be, for example, bimodal or polymodal.

[0126] The aspect ratio of diameter to thickness (D / H) (i.e., of mean diameter in the plane of greatest extent D to thickness H) of the graphite particles is preferably in a range of 1 to 3 . expanded graphite

[0127] Expanded graphite and methods for its production are known to those skilled in the art. Natural graphite, such as flake graphite, can serve as the starting material. This graphite consists of layers of honeycomb-arranged carbon atoms and is capable of intercalating molecules between the graphite layers. The intercalation of compounds such as acids results in so-called expanded graphite, which expands to many times its original volume at elevated temperatures. Intercalated graphite is frequently used to produce expanded graphite. This graphite is obtained by treating graphite with a strong acid, preferably concentrated sulfuric acid, in combination with an oxidizing agent, or by treatment with concentrated nitric acid.

[0128] The expanded graphite used according to the invention for use in the microporous layer B), the first layer B1) and the second layer B2) preferably has an aspect ratio of mean diameter in the plane of greatest extent D to thickness H (D / H) in a range of 10 to 1000.

[0129] Other pore-forming agents

[0130] In a preferred embodiment, at least one pore-forming agent is used to adjust the properties of layer B1) which is different from soot, graphite particles and expanded graphite (“further pore-forming agent”).

[0131] Preferably, a pore-forming agent is used to form the first microporous layer B1), which is selected from

[0132] Pore-forming agents that decompose upon heating to a temperature above the pore-forming temperature, forming a gas phase or releasing a gas,

[0133] Pore-forming agents that lead to the formation of pores through treatment with a

[0134] solvents are able to

[0135] Mixtures thereof.

[0136] In particular, the pore-forming agents used to form the first microporous layer B1), which decompose upon heating to a temperature above the pore-forming temperature to form a gas phase or which release a gas, are selected from: a1 plastic particles, preferably selected from acrylic homo- and copolymers, polymethyl(meth)acrylates, acrylic-modified polystyrenes, especially styrene-methyl methacrylate copolymers, polyvinylidene chloride, etc.; a2 expandable microspheres, preferably expandable microspheres comprising a thermoplastic shell and an enclosed gas-forming component; a3 natural polymers, preferably selected from agar, alginates, gelatin or starch; a4 gas-releasing compounds, preferably selected from alkali and ammonium hydrogen carbonates, alkali and ammonium carbonates, preferably sodium hydrogen carbonate and / or ammonium hydrogen carbonate, and mixtures thereof.

[0137] In a special embodiment, at least one expandable microsphere is used as a pore-forming agent to form the first microporous layer B1).

[0138] Suitable expandable microspheres can, for example, comprise volatile physical blowing agents, such as hydrocarbons or halogenated hydrocarbons, encapsulated in thermoplastic shells. Physical blowing agents serve to make the expandable microspheres foamable. The shells of the expandable microspheres preferably comprise at least one thermoplastic. The shells of the expandable microspheres are preferably selected from acrylic homo- and copolymers, polymethyl methacrylates, acrylic-modified polystyrenes, especially styrene-methyl methacrylate copolymers, polyvinylidene chloride, and mixtures thereof.

[0139] Expandable microspheres suitable for the invention preferably have a mean particle size in the range of about 1 to 300 pm, particularly preferably 5 to 250 pm.

[0140] Suitable commercially available microspheres are the EXPANCEL brands from the company Nouryon, NL.

[0141] In particular, the pore-forming agents used to form the first microporous layer B1), which is enabled to form pores upon treatment with a solvent, are selected from carbohydrates such as sugars, cellulose, or cellulose derivatives such as methylcellulose. In a preferred embodiment, at least one sugar is used as the pore-forming agent. These can preferably be washed out with water, forming pores.

[0142] Preferably, the first coating agent used to form the first microporous layer B1) comprises at least one further pore-forming agent in a total amount of 0.01 to 50 wt.%, particularly preferably 0.1 to 5 wt.%, based on the total weight of the first coating agent.

[0143] In a first embodiment, the first coating material used to form the first microporous layer B1) comprises carbon black, graphite particles, and other pore-forming components as porosity-modifying elements. In other words, no further porosity-modifying component is added to the first coating material in this embodiment.

[0144] In a second embodiment, the first coating material used to form the first microporous layer B1) comprises carbon black and graphite particles as porosity-modifying components. In other words, no further porosity-modifying component is added to the first coating material in this embodiment.

[0145] Preferably, the first coating material used to form the first microporous layer B1) comprises carbon black and graphite particles in a weight ratio of 1:0.5 to 1:10, particularly preferably from 1:1 to 1:6. This applies to both the aforementioned first embodiment (porosity-modifying components: carbon black, graphite particles, and other pore-forming agents) and the aforementioned second embodiment (porosity-modifying components: carbon black and graphite particles). In a first embodiment, the second coating material used to form the second microporous layer B2) comprises carbon black and expanded graphite as porosity-modifying components. In other words, no further porosity-modifying component is added to the second coating material in this embodiment.

[0146] In a second embodiment, the second coating material used to form the second microporous layer B2) contains carbon black as a porosity-modifying component. In other words, no further porosity-modifying component is added to the second coating material in this embodiment.

[0147] Preferably, the second coating material used to form the second microporous layer B2) comprises carbon black and expanded graphite in a weight ratio of 1 : 0 to 1 : 10.

[0148] In a particular embodiment, the second coating agent for forming the second microporous layer B2) is free of any added pore-forming agents. In particular, the second coating agent for forming the second microporous layer B2) is free of added pore-forming agents that decompose upon heating to a temperature above the pore-formation temperature, forming a gas phase or releasing a gas, and of pore-forming agents capable of forming pores through treatment with a solvent.

[0149] It is preferred that the second coating agent for forming the second microporous layer B2) is completely free of pore-forming agents that decompose upon heating to a temperature above the pore-forming temperature, forming a gas phase or releasing a gas, and of pore-forming agents capable of forming pores upon treatment with a solvent. Preferably, the second coating agent for forming the second microporous layer B2) contains pore-forming agents that decompose upon heating to a temperature above the pore-forming temperature, forming a gas phase or releasing a gas, and pore-forming agents capable of forming pores upon treatment with a solvent, in an amount in the range of 0 to 0.00005 wt.%, based on the total weight of the second coating agent, particularly preferably 0 to 0.00001 wt.%.-%, based on the total weight of the second coating material, in particular 0 wt.%, based on the total weight of the second coating material.

[0150] A structural analysis of the MPL B) and the layers B1) and B2) can be performed, as previously described, using computed tomography microscopy (p-CT) or scanning electron microscopy (SEM). Preferably, the microporous layer B) has a thickness, determined by scanning electron microscopy, of 5 to 100 pm (micrometers), preferably 10 to 50 pm (micrometers). This thickness refers to the uncompressed state of the microporous layer B), i.e., before the GDL is installed in a fuel cell.

[0151] Preferably, layer B1) has a thickness, determined by scanning electron microscopy, of 5 to 99 pm, preferably 10 to 49 pm. This thickness refers to the uncompressed state of layer B1), i.e., before the GDL is installed in a fuel cell.

[0152] Preferably, layer B2) has a thickness, determined by scanning electron spectroscopy, of 1 to 20 pm, preferably 1 to 10 pm. This thickness refers to the uncompressed state of layer B2), i.e., before the GDL is installed in a fuel cell.

[0153] Preferably, the ratio of the thickness of layer B1) to the thickness of layer B2) is at least 1.5 : 1, preferably at least 2.0 : 1.

[0154] The gas diffusion layer according to the invention preferably has a thickness (total thickness of fiber material A) and MPL B)), determined according to DIN 53855-1 :1993-08, in the range of 50 to 1000 pm, particularly preferably from 75 to 500 pm. This thickness refers to the uncompressed state of the GDL.

[0155] Determining the area-related mass (also known as basis weight) in g / m² 2 can be done according to EN 29073-1 :1992.

[0156] Pore ​​sizes

[0157] The determination of the pore size distribution and porosity of the gas diffusion layer, i.e., the composite of layers A), B1) and B2), can be carried out using capillary flow porometry, as previously described.

[0158] The characterization of the pore size distribution and porosity of layers B1) and B2) can be carried out specifically using computed tomography microscopy (p-CT, X-ray micro-computed tomographic microscopy) or scanning electron microscopy (SEM). Reference is made to the information under the heading "Measurement Methods" in this regard.

[0159] The pore size can exhibit a monomodal, bimodal, or polymodal distribution curve. A bimodal or polymodal distribution curve can be achieved, for example, by using different porosity-modifying components (e.g., a mixture of carbon black and graphite particles). Preferably, layer B1) has a mean pore diameter, determined by computed tomography microscopy (p-CT), of 12.00 to 100.00 pm, particularly preferably 15.00 to 80.00 pm.

[0160] Preferably, layer B2) has a mean pore diameter, determined by scanning electron microscopy (SEM), of 0.005 to 10.00 pm, preferably 0.010 to 5.00 pm, in particular 0.5 to 5.00 pm.

[0161] Manufacturing process

[0162] Another object of the invention is a method for producing a gas diffusion layer for a fuel cell, comprising

[0163] A) a planar electrically conductive fiber material,

[0164] B) a microporous layer containing conductive particles in a matrix of a polymeric binder, wherein the microporous layer

[0165] B1) a first open-cell layer on at least one of the surfaces of the fiber material A), and

[0166] B2) comprises a second closed-cell, gas- and water-permeable layer on the first layer B1), wherein i) a planar electrically conductive fiber material A) is provided, ii) the fiber material provided in step i) is coated with a first coating agent to form a first microporous layer, wherein a pore-forming agent is applied to the fiber material A) prior to coating in step ii) and / or the coating agent used in step ii) contains a pore-forming agent, iii) the first coating obtained in step ii) is coated with a second coating agent to form a second microporous layer, iv) the fiber material obtained in step iii) coated with the first and the second coating agent is subjected to a treatment to generate pores from the pore-forming agent.

[0167] In step i) of the process according to the invention, at least one fiber material A) is provided, with reference being made in full to the previously given descriptions regarding suitable and preferred fiber materials. The fiber materials can be equipped with conventional binders and / or additives before use in step ii), as also described above. Conventional impregnation processes can be used for this purpose. The optionally equipped fiber material A) can be subjected to thermal treatment (drying and / or sintering) before use in step ii).

[0168] The fiber material A) provided in step i) is coated in step ii) with a first coating agent to form a first microporous layer B1). Preferably, the fiber material is coated and / or impregnated with an aqueous composition containing at least one polymeric binder, conductive particles, at least one pore-forming component, and optionally further additives. Certain carbon-containing compounds, as mentioned above, can be used as conductive particles and as porosity-modifying components. In this case, the amount used is selected to fulfill both purposes. It is possible for all components required to form the first microporous layer B1) to be used in a single composition for coating the fiber material A).It is also possible to coat the fiber material A) with two or more coating agents, each containing one or more components. Regarding suitable and preferred polymeric binders, conductive particles, and porosity-modifying components, reference is made in full to the previously stated descriptions.

[0169] The fiber material A) coated with the first coating agent can be dried before the application of the second coating agent. Drying can be carried out at an elevated temperature and / or reduced pressure. If a pore-forming agent is used to create the first microporous layer, which decomposes into a gas phase or releases a gas when heated to a temperature above the pore-forming temperature, drying is carried out at a temperature below the pore-forming temperature. In a specific embodiment, the fiber material A) coated with the first coating agent is not dried before the application of the second coating agent.

[0170] The fiber material A) obtained in step ii) and coated with the first coating agent to form the first microporous layer B1) is coated in step iii) with a second coating agent to form a second microporous layer. Preferably, an aqueous composition is used for the coating, containing at least one polymeric binder, conductive particles, at least one porosity-modifying component, and optionally further additives. Certain carbon-containing compounds, as mentioned previously, can again be used as conductive particles and as a porosity-modifying component. It is possible for all components for forming the second microporous layer B2) to be used in a single coating composition.It is also possible to apply the coating to form the second microporous layer using two or more coating agents, each containing one or more components. Regarding suitable and preferred polymeric binders, conductive particles, and porosity-modifying components, reference is made in full to the previously stated descriptions.

[0171] In step iv), the fiber material obtained in step iii) coated with the first and second coating agents is subjected to a treatment to generate pores from the pore-forming agent.

[0172] If at least one pore-forming agent is used to form the microporous layers, which decomposes upon heating to a temperature above the pore-forming temperature, forming a gas phase, or which releases a gas, the treatment for generating pores in step iv) comprises heating to a temperature above the pore-forming temperature. Generally, the coated fiber material is heated to a temperature in the range of 100 to 600°C, preferably 150 to 500°C. The heating duration is preferably 1 to 180 minutes, more preferably 2 to 120 minutes.

[0173] If a pore-forming agent capable of forming pores through treatment with a solvent is used to create the microporous layers, the treatment for generating pores in step iv) comprises eluting the pore-forming agent. A preferred solvent is water. Finally, a thermal treatment is carried out, e.g., in a drying and sintering furnace. This can, for example, involve first drying at a temperature of 100 to 200°C and then sintering at a temperature of 300 to 500°C.

[0174] The application of the MPL layers in steps ii) and iii) can be carried out in various ways. While spraying, screen printing, or Meyer-Rod processes are frequently used in batch production, doctor blade, slot nozzle, and engraving roller processes are preferred for continuous coating. The MPL layer thickness and penetration depth can be influenced by the coating process parameters as well as the viscosity of the coating.

[0175] Properties: The microporous layer and / or the gas diffusion layer generally exhibit advantageous properties with respect to the following parameters:

[0176] Pore ​​structure of the MPL: in particular, the inner MPL layer has a high proportion of larger, open-cell pores.

[0177] The surface of the MPL is essentially closed, allowing good electrical contact with the catalyst layer.

[0178] The MPL according to the invention enables a very high mass transport of gases and liquids through the gas diffusion layer, i.e. between the bipolar plates on the one hand and the membrane and the catalyst layers (the CCM) on the other.

[0179] The advantageous properties regarding porosity and mass transport are evident, for example, in the following parameters: Gurley gas permeability, dry diffusion length, bubble point and largest through-pore (bubble point).

[0180] Fuel cell

[0181] Another object of the invention is a fuel cell comprising at least one gas diffusion layer as defined above, or obtainable by a method as defined above.

[0182] In principle, the gas diffusion layer according to the invention is suitable for all conventional fuel cell types. Preferably, the fuel cell according to the invention is a proton exchange membrane fuel cell (PEMFC). Proton exchange membrane fuel cells are also known as polymer electrolyte fuel cells (PEFCs). Reference is made in full to the previously given descriptions of the structure of fuel cells.

[0183] The fuel cells according to the invention preferably comprise a polymer electrolyte membrane onto which a catalyst layer is applied on the anode and cathode sides, forming the electrodes. Preferably, a gas diffusion layer (GDL) is located on the anode and / or cathode side in contact with the catalyst layer. The fuel cells specifically have a polymer electrolyte membrane onto which a catalyst layer is applied, which is in contact with the surface of the microporous layer B) of a gas diffusion layer according to the invention. Specifically, the fuel cells have a gas diffusion layer according to the invention on the cathode side, wherein the catalyst layer is in contact with the surface of the microporous layer B) of the gas diffusion layer.More specifically, the fuel cells have a gas diffusion layer according to the invention on the cathode side and on the anode side, wherein both the cathode layer and the anode layer are in contact with the surface of the microporous layer B) of a gas diffusion layer according to the invention.

[0184] In one embodiment, the cathode material can contain at least one hygroscopic material to prevent the cathode from drying out. This allows the cathode to retain more water, thus reducing the electrode resistance. Preferably, at least one heteropoly acid, such as zirconium phosphate (ZrP) and zirconium solid-state particles (ZrSPP), or oxides such as ZrÜ2, TiÜ2, and SiÜ2, is used as the hygroscopic material.

[0185] An advantage of the invention is that the gas diffusion position can be specifically adapted to the structural conditions of the fuel cell, the operating media flowing through it, and / or the operating parameters of the fuel cell.

[0186] Another object of the invention is the use of a gas diffusion layer, as previously defined, or obtainable by a method as previously defined, in a proton exchange membrane fuel cell.

[0187] FIGURE DESCRIPTION

[0188] Figure 1 illustrates the representation of the measured values ​​of a capillary flow porometry with wet curve, dry curve and semi-dry curve as well as the bubble point, the mean pore diameter and the smallest pore diameter.

[0189] Figure 2a shows a scanning electron microscope image of the top view of the surface of a gas diffusion layer according to the invention with a carbon black cover layer B2) on an underlying open-cell layer B1), which was obtained by using a spherical pore former.

[0190] Figure 2b shows a p-CT scan (3D view, oblique top view) of the gas diffusion layer from Figure 2a.

[0191] Figure 2c shows a p-CT scan (cross-section) of the gas diffusion position from Figure 2a.

[0192] MEASURING METHODS

[0193] The characterization of the through pores relevant to the material transport properties of the gas diffusion layers is carried out using capillary flow porometry, sometimes also simply referred to as "porometry." Capillary flow porometry measurements are described in DIN 66140:2022-02 and ASTM F-316.2003. Capillary flow porometry measurements consist of two steps. In the first step, the gas diffusion layer is saturated with a liquid that wets as ideally as possible (contact angle close to 0 °C) so that all accessible pores are completely filled with the liquid. The sample is then placed in a porometry instrument and subjected to a steadily increasing pressure on the upstream side.

[0194] Initially, all pores are filled with the wetting medium, and no flow occurs through the material. As the pressure increases, the liquid is extruded from the pores. The largest pores are opened first. The bubble point (also called the first bubble point or FBP) is the pressure at which the first gas flow occurs. It is a measure of the size of the largest through-pore. The gas flow through the sample increases with increasing pressure as more and more smaller pores are opened. Once all pores are open, the gas flow increases almost linearly with increasing pressure. The resulting curve is called the "wet curve."

[0195] The second measurement step is performed without the pores being filled with a wetting fluid. This yields a "dry curve," which combines with the quasi-linear part of the wet curve. The "half-dry curve" is calculated by dividing the flow rate values ​​with respect to the applied pressure by 2. The smallest pore diameter is located at the intersection of the wet and dry curves. The mean flow pore size is located at the intersection of the wet and half-dry curves. Using the Young-Laplace equation P = 4xyx cos(0) / D, where P = pressure, y = surface tension, 0 = contact angle, and D = pore diameter, the pore size distribution is obtained as a function of the applied pressure and based on the surface tension of the wetting fluid. When using standard wetting fluids (e.g.,Perfluorinated hydrocarbons or ethers with surface tensions in the range of about 15 to 25 dyn / cm) and pressures up to 35 bar can detect pore sizes down to a minimum of about 15 nm.

[0196] Subsequently, each measurement was repeated three times and the mean value determined. Porefil with a surface tension of 26 dyn / cm² was used as the wetting fluid, and air was used as the gas. The measurements were taken at room temperature. A POROLUX® 500 porometer was used as the measuring instrument. The sample area was 298.6 mm². 2 The final pressure of the three measurements was 1 bar, 1 bar and 1.5 bar (gauge pressure in each case). Measurement points for wet measurement: 200, measurement points for dry measurement: 100, pressure rise: 120 s / bar.

[0197] Computed tomography microscopy

[0198] The structure of the gas diffusion layers according to the invention can be characterized using computed tomography microscopy (p-CT, X-ray micro-computed tomographic microscopy). Such a method is described by Odaya et al. in "X-ray Tomography Analysis of Porosity Distributions in Gas Diffusion Layers of Proton Exchange Membrane Fuel Cells," Electrochimica Acta, Volume 152, January 10, 2015, pages 464–472 (https: / / doi.org / 10.1016 / j.electacta.2014.11.143). This method also allows the determination of the mean pore diameters of the MPL and layers B1) and B2).

[0199] The structure of the gas diffusion layers according to the invention can also be characterized using scanning electron microscopy (SEM). Such a method is described by Farmer et al. in "Assessing porosity of proton exchange membrane fuel cell gas diffusion layers by scanning electron microscope image analysis," Journal of Power Sources 197 (2012) 1-11, (doi:10.1016 / j.jpowsour.2011.08.064). This method also allows, in particular, the determination of the mean pore diameters of layer B2.

[0200] Porosity values ​​determined using different measurement methods are not directly comparable. The methods employed capture different aspects of porosity, such as the material's behavior when filled or permeated with various liquids and gases, or the determination of the material structure using an imaging technique. Furthermore, only values ​​determined on samples with a comparable layer structure can be compared (e.g., based on fiber material A and only the first microporous layer B1), or based on fiber material A, the first microporous layer B1), and the second microporous layer B2). mass

[0201] Determining the area-related mass in g / m² 2 was carried out according to ISO 9073-1.

[0202] thickness of the Fiber material and the

[0203] The thickness of the conductive sheet fiber material and the gas diffusion layer was determined according to DIN 53855-1:1993-08 "Determination of the thickness of textile sheet structures". The determination of the thickness at a specific compressive force (e.g., as in the following tests at 0.025 MPa or at 6.0 MPa) is also described in the DIN standard.

[0204] The Gurley gas permeability was determined perpendicular to the material plane using a Gurley densometer from Gurley Precision Instruments according to ISO 5636-5. The measurement time is recorded in seconds up to 100 cm. 3 Air at a constant pressure difference perpendicularly through the GDL sample with a flow area of ​​6.42 cm² 2 have flowed.

[0205] T dry diffusion length

[0206] The dry diffusion length was determined using a stationary Wicke-Kallenbach cell. The dry diffusion length refers to the actual distance, in pm, that a gas molecule travels through the planar fibrous material a) the microporous layer b).

[0207] roughness

[0208] The roughness was determined using the stylus method as described in DIN 4768-1:1974-08.

[0209] The mean roughness R was determined a (mean distance of a measuring point on the surface to the center line) and the average roughness depth R z The measurements were performed using a Mahr measuring device Mahrsurf XCR20 with a free probe MFW-250. The values ​​are averages from 6 measurements: 3 in the machine direction (MD) and 3 perpendicular to the machine direction (CD).

[0210] The following conditions were chosen for the measurement:

[0211] Button = MFW-250. Touch diamond radius 2pm, cone angle 60°

[0212] LC (GS) = 2.5mm = Cut Off = LT+LM

[0213] LT = 17.5 mm = Sensing distance = 2.5 mm lead time and 2.5 mm follow time for the Gaussian filter to rise and fall. This 2 x 2.5 mm travel is not taken into account in the measurement.

[0214] LM = 12.5mm = measuring distance used to determine the roughness value

[0215] Z = 5 = Number of individual measurements for the Rz value. The measurement path (profile) is divided into 5 symmetrical segments (= LM / 5). The mean value is calculated from each segment. The Rz value is then averaged from these 5 mean values.

[0216] VB = ±250pm = measuring range of the button

[0217] Profile resolution per measuring section = 100,000 steps

[0218] Linearity ≤ 1%

[0219] Sensing force (measuring force) = 0.8 mN

[0220] Sampling speed 0.5 mm / sec.

[0221] PREFERRED FORMS OF THE INVENTION

[0222] 1. Gas diffusion layer for a fuel cell, comprising

[0223] A) a planar electrically conductive fiber material, B) a microporous layer containing conductive particles in a matrix of a polymeric binder, wherein the microporous layer

[0224] B1) a first open-cell layer on at least one of the surfaces of the fiber material A), and

[0225] B2) comprises a second gas- and water-permeable layer on the first layer B1), which has a smaller pore diameter than layer B1), obtainable by a process in which i) a planar electrically conductive fiber material A) is provided, ii) the fiber material provided in step i) is coated with a first coating agent to form a first microporous layer, wherein a pore-forming agent is applied to the fiber material A) prior to coating in step ii) and / or the coating agent used in step ii) contains a pore-forming agent, iii) the first coating obtained in step ii) is coated with a second coating agent to form a second microporous layer, iv) the fiber material obtained in step iii) coated with the first and the second coating agents is subjected to a treatment to generate pores from the pore-forming agent.Gas diffusion layer for a fuel cell, comprehensive.

[0226] A) a planar electrically conductive fiber material,

[0227] B) a microporous layer containing conductive particles in a matrix of a polymeric binder, wherein the microporous layer

[0228] B1) a first open-cell layer on at least one of the surfaces of the fiber material A) and B2) a second gas- and water-permeable layer on the first layer B1), wherein the size of the largest through-pore of the gas diffusion layer, relative to the planar electrically conductive fiber material A) and the first layer B1), determined by capillary flow porometry measurement according to ASTM F-316:2003, is at least 30.00 pm and wherein the mean pore diameter of the gas diffusion layer, relative to the planar electrically conductive fiber material A), the first layer B1) and the second layer B2), determined by capillary flow porometry measurement according to ASTM F-316:2003, is at most 8.00 pm.

[0229] 3. Gas diffusion layer according to claim 1 or 2, wherein a pore-forming agent is used to form the first microporous layer B1), which is selected from a pore-forming agents which decompose upon heating to a temperature above the pore-forming temperature to form a gas phase or which release a gas, preferably selected from a1 plastic particles, preferably selected from acrylic homo- and copolymers, polymethyl(meth)acrylates, acrylic-modified polystyrenes, especially styrene-methyl methacrylate copolymers, polyvinylidene chloride, etc.a2 expandable microspheres, preferably expandable microspheres comprising a thermoplastic shell and an enclosed gas-forming component, a3 natural polymers, preferably selected from agar, alginates, gelatin or starch, a4 gas-releasing compounds, preferably selected from alkali and ammonium hydrogen carbonates, alkali and ammonium carbonates, preferably sodium hydrogen carbonate and / or ammonium hydrogen carbonate, β pore-forming agents capable of forming pores by treatment with a solvent, preferably selected from sugars.

[0230] Y mixtures of it.

[0231] 4. Gas diffusion layer according to one of claims 1 or 3, wherein a pore-forming agent is used to form the first microporous layer B1) which decomposes upon heating to a temperature above the pore-forming temperature to form a gas phase or which releases a gas and the treatment for generating pores in step iv) comprises heating to a temperature above the pore-forming temperature, or a pore-forming agent is used to form the first microporous layer B1) which is capable of forming pores by treatment with a solvent and the treatment for generating pores in step iv) comprises eluting the pore-forming agent.

[0232] 5. Gas diffusion layer according to one of the preceding claims, wherein the second coating material for forming the second microporous layer B2) is free of added pore-forming agents, in particular free of pore-forming agents which decompose upon heating to a temperature above the pore-forming temperature by forming a gas phase or which release a gas and pore-forming agents which are capable of forming pores by treatment with a solvent.

[0233] 6. Gas diffusion layer according to any of the preceding claims, wherein the fiber material A) is selected from carbon fiber nonwovens, carbon fiber woven fabrics, carbon fiber papers and combinations thereof.

[0234] 7. Gas diffusion layer according to one of the preceding claims, wherein the mean pore diameter of layer B1), determined by computed tomography microscopy (p-CT), is at least 50%, preferably at least 90%, of the thickness of layer B1), determined by computed tomography microscopy.

[0235] 8. Gas diffusion layer according to one of the preceding claims, wherein the mean pore diameter of layer B1), determined by computed tomography microscopy (p-CT), is 12.00 to 100.00 pm, preferably 15.00 to 80.00 pm.

[0236] 9. Gas diffusion layer according to one of the preceding claims, wherein the mean pore diameter of layer B2), determined by scanning electron microscopy (SEM), is 0.005 to 10.00 pm, preferably 0.010 to 5.00 pm.

[0237] 10. Gas diffusion layer according to any one of the preceding claims, wherein a first coating material containing porosity-modifying components, selected from carbon black, graphite particles, and mixtures thereof, is used to form the first microporous layer B1). Gas diffusion layer according to any one of the preceding claims, wherein a first coating material containing a mixture of carbon black and graphite particles, preferably in a weight ratio of carbon black to graphite particles in the range of 1:0.5 to 1:10, particularly preferably from 1:1 to 1:6, is used to form the first microporous layer B2). Gas diffusion layer according to any one of the preceding claims, wherein a second coating material containing porosity-modifying components, selected from carbon black, expanded graphite, and mixtures thereof, is used to form the second microporous layer B2).Gas diffusion layer according to any one of the preceding claims, wherein a second coating material is used to form the second microporous layer B1), which contains as porosity-modifying components a carbon material consisting exclusively of carbon black or a mixture of carbon black and expanded graphite particles. Gas diffusion layer according to any one of the preceding claims, wherein a second coating material is used to form the second microporous layer B2), which contains carbon black and expanded graphite in a weight ratio of 1:0 to 1:10. Method for producing a gas diffusion layer for a fuel cell, comprising.

[0238] A) a planar electrically conductive fiber material,

[0239] B) a microporous layer containing conductive particles in a matrix of a polymeric binder, wherein the microporous layer

[0240] B1) a first open-cell layer on at least one of the surfaces of the fiber material A), and

[0241] B2) comprises a second gas- and water-permeable layer on the first layer B1), wherein i) a planar electrically conductive fiber material A) is provided, ii) the fiber material provided in step i) is coated with a first coating agent to form a first microporous layer, wherein a pore-forming agent is applied to the fiber material A) prior to coating in step ii) and / or the coating agent used in step ii) contains a pore-forming agent, iii) the first coating obtained in step ii) is coated with a second coating agent to form a second microporous layer, iv) the fiber material obtained in step iii) coated with the first and the second coating agent is subjected to a treatment to generate pores from the pore-forming agent.

[0242] 16. Fuel cell comprising at least one gas diffusion layer as defined in any one of embodiments 1 to 14, or obtainable by a method as defined in embodiment 15.

[0243] 17. Fuel cell according to claim 16, comprising a polymer electrolyte membrane on which a catalyst layer is applied, wherein the catalyst layer is in contact with the surface of the second microporous layer B2) of the gas diffusion layer.

[0244] 18. Fuel cell stack comprising a plurality of fuel cells as defined in one of embodiments 16 or 17.

[0245] 19. Use of a gas diffusion layer as defined in any of embodiments 1 to 14, or obtainable by a method as defined in embodiment 15, in a fuel cell to improve gas and / or water permeability.

[0246] The invention is explained using the following examples, which are not to be understood as limiting.

[0247] EXAMPLES

[0248] I) Production of gas diffusion layers

[0249] The following components were used in the production of the gas diffusion layers to adjust the properties of the pores and the gas and water permeability:

[0250] Soot: A commercial furnace black was used. The BET surface area value according to ASTM standard D 6556-04 was <100 m². 2 / G.

[0251] Graphite particles

[0252] Synthetic graphite particles were used. The average particle size D90 according to ASTM standard D3849-87 was <45 pm. Expanded graphite

[0253] A commercially available expanded graphite with a particle size D90 according to ASTM standard D3849-87 of <50 pm was used.

[0254] Pore-forming agents

[0255] Spherical PMMA plastic particles were used as pore-forming agents. The particle size D90 according to ASTM standard D3849-87 was <50 pm.

[0256] Production example 1

[0257] To produce a sheet-like electrically conductive material, a nonwoven fabric made of 100% carbon fibers with a composition as specified in Table 2 was used. For finishing the nonwoven fabric, an impregnation composition was mixed containing 70% carbon black and 30% PTFE (based on the solids content). Finishing was carried out by foulard impregnation with an aqueous dispersion at a concentration of 15% of the finishing weight based on the mass of the GDL substrate (corresponding to 10 g / m²). 2 ). This was followed by drying for 5 minutes at 160 °C and sintering for 10 minutes at 400 °C.

[0258] To produce the gas diffusion layers according to the invention, a first inner and a second outer MPL coating were applied to the substrate thus obtained. The comparison gas diffusion layers have only a single MPL layer. The composition of the coating materials (pastes) for producing the MPLs is shown in Table 1. The coating weight for the gas diffusion layers according to the invention was 10 g / m². 2 for the inner layer and 5 g / m² 2 for the outer layer. For the comparison gas diffusion layers, the equipment weight was 25 g / m². 2 For comparison example V1 and 15 g / m² 2 for comparison example V2.

[0259] Table 1: Composition of the pastes for the production of MPLs 2022P00025WG

[0260] 41

[0261] Exp. Gr. = expanded graphite

[0262] For the MPL coating, the MPL paste was first applied to the fiber material by squeegeeing to create the inner layer, which acts as a polymeric binder.

[0263] The material contained PTFE as well as carbon black, optionally graphite particles and optionally another pore-forming agent in distilled water. The fiber material was then dried at 120 °C. Subsequently, in the gas diffusion layers according to the invention, the MPL paste for the production of the outer layer, which contained PTFE as a polymeric binder as well as carbon black and / or expanded graphite, was applied by doctor blade.

[0264] The fiber material was then dried at 120 °C and sintered at 400 °C. The resulting MPL loading is shown in Table 2. The values ​​from the application-related measurements are shown in Table 3.

[0265] II) Application-related measurements

[0266] Table 2

[0267] Table 3 a) Comparative example b) for comparative examples V1 and V2 relating to the composite of nonwoven fabric A) and M PL layer B1); for examples 1 and 2 according to the invention relating to the composite of

[0268] Nonwoven fabric A), inner M PL layer B1) and outer M PL layer B2)

Claims

PATENT CLAIMS 1. Gas diffusion layer for a fuel cell, comprising A) a planar electrically conductive fiber material, B) a microporous layer containing conductive particles in a matrix of a polymeric binder, wherein the microporous layer B1) a first open-cell layer on at least one of the surfaces of the fiber material A), and B2) comprises a second gas- and water-permeable layer on the first layer B1), which has a smaller pore diameter than layer B1), obtainable by a process in which i) a planar electrically conductive fiber material A) is provided, ii) the fiber material provided in step i) is coated with a first coating agent to form a first microporous layer, wherein a pore-forming agent is applied to the fiber material A) prior to coating in step ii) and / or the coating agent used in step ii) contains a pore-forming agent, iii) the first coating obtained in step ii) is coated with a second coating agent to form a second microporous layer, iv) the fiber material obtained in step iii) coated with the first and the second coating agents is subjected to a treatment to generate pores from the pore-forming agent.

2. Gas diffusion layer for a fuel cell, comprising A) a planar electrically conductive fiber material, B) a microporous layer containing conductive particles in a matrix of a polymeric binder, wherein the microporous layer B1) a first open-cell layer on at least one of the surfaces of the fiber material A) and B2) comprises a second gas- and water-permeable layer on the first layer B1), wherein the size of the largest passage pore of the gas diffusion layer, relative to the planar electrically conductive fiber material A) and the first layer B1), determined by capillary flow porometry measurement according to ASTM F-316:2003, is at least 30.00 pm and wherein the mean pore diameter of the gas diffusion layer, relative to the planar electrically conductive fiber material A), the first layer B1) and the second layer B2), determined by capillary flow porometry measurement according to ASTM F-316:2003, is at most 8.00 pm.

3. Gas diffusion layer according to claim 1 or 2, wherein a pore-forming agent is used to form the first microporous layer B1), which is selected from a pore-forming agents which decompose upon heating to a temperature above the pore-forming temperature to form a gas phase or which release a gas, preferably selected from a1 plastic particles, preferably selected from acrylic homo- and copolymers, polymethyl(meth)acrylates, acrylic-modified polystyrenes, especially styrene-methyl methacrylate copolymers, polyvinylidene chloride, etc.a2 expandable microspheres, preferably expandable microspheres comprising a thermoplastic shell and an enclosed gas-forming component, a3 natural polymers, preferably selected from agar, alginates, gelatin or starch, a4 gas-releasing compounds, preferably selected from alkali and ammonium hydrogen carbonates, alkali and ammonium carbonates, preferably sodium hydrogen carbonate and / or ammonium hydrogen carbonate. Pore-forming agents capable of forming pores upon treatment with a solvent, preferably selected from sugars, Y mixtures of it.

4. Gas diffusion layer according to one of claims 1 or 3, wherein a pore-forming agent is used to form the first microporous layer B1) which decomposes upon heating to a temperature above the pore-forming temperature to form a gas phase or which releases a gas and the treatment for generating pores in step iv) comprises heating to a temperature above the pore-forming temperature, or a pore-forming agent is used to form the first microporous layer B1) which is capable of forming pores by treatment with a solvent and the treatment for generating pores in step iv) comprises eluting the pore-forming agent.

5. Gas diffusion layer according to one of the preceding claims, wherein the second coating material for forming the second microporous layer B2) is free of added pore-forming agents, in particular free of pore-forming agents which decompose upon heating to a temperature above the pore-forming temperature by forming a gas phase or which release a gas and pore-forming agents which are capable of forming pores by treatment with a solvent.

6. Gas diffusion layer according to any of the preceding claims, wherein the fiber material A) is selected from carbon fiber nonwovens, carbon fiber woven fabrics, carbon fiber papers and combinations thereof.

7. Gas diffusion layer according to one of the preceding claims, wherein the mean pore diameter of layer B1), determined by computed tomography microscopy (p-CT), is at least 50%, preferably at least 90%, of the thickness of layer B1), determined by computed tomography microscopy.

8. Gas diffusion layer according to one of the preceding claims, wherein the mean pore diameter of layer B1), determined by computed tomography microscopy (p-CT), is 12.00 to 100.00 pm, preferably 15.00 to 80.00 pm.

9. Gas diffusion layer according to one of the preceding claims, wherein the mean pore diameter of layer B2), determined by scanning electron microscopy (SEM), is 0.005 to 10.00 pm, preferably 0.010 to 5.00 pm.

10. Gas diffusion layer according to one of the preceding claims, wherein the mean pore diameter of layer B2), determined by scanning electron microscopy (SEM), is 0.5 to 5.0 pm.

11. Gas diffusion layer according to one of the preceding claims, wherein a first coating material containing porosity-modifying components selected from carbon black, graphite particles and mixtures thereof is used to form the first microporous layer B1).

12. Gas diffusion layer according to one of the preceding claims, wherein a first coating material containing a mixture of carbon black and graphite particles is used to form the first microporous layer B1).

13. Gas diffusion layer according to one of the preceding claims, wherein a first coating agent is used to form the first microporous layer B1) which contains a mixture of carbon black and graphite particles in a weight ratio of carbon black to graphite particles in a range of 1 : 0.5 to 1 : 10, particularly preferably from 1 : 1 to 1 :

6.

14. Gas diffusion layer according to one of the preceding claims, wherein a second coating material is used to form the second microporous layer B2) which contains porosity-modifying components selected from carbon black, expanded graphite and mixtures thereof.

15. Gas diffusion layer according to one of the preceding claims, wherein a second coating material is used to form the second microporous layer B2), which contains as porosity-modifying components a carbon material consisting exclusively of soot or containing a mixture of soot and expanded graphite particles.

16. Gas diffusion layer according to one of the preceding claims, wherein a second coating material is used to form the second microporous layer B2), which contains carbon black and expanded graphite in a weight ratio of 1 : 0 to 1 :

10.

17. Method for producing a gas diffusion layer for a fuel cell, comprising A) a planar electrically conductive fiber material, B) a microporous layer containing conductive particles in a matrix of a polymeric binder, wherein the microporous layer B1) a first open-cell layer on at least one of the surfaces of the fiber material A), and B2) comprises a second gas- and water-permeable layer on the first layer B1), wherein i) a planar electrically conductive fiber material A) is provided, ii) the fiber material provided in step i) is coated with a first coating agent to form a first microporous layer, wherein a pore-forming agent is applied to the fiber material A) prior to coating in step ii) and / or the coating agent used in step ii) contains a pore-forming agent, iii) the first coating obtained in step ii) is coated with a second coating agent to form a second microporous layer, iv) the fiber material obtained in step iii) coated with the first and the second coating agent is subjected to a treatment to generate pores from the pore-forming agent.

18. Fuel cell comprising at least one gas diffusion layer as defined in any one of claims 1 to 16, or obtainable by a method as defined in claim 17.

19. Fuel cell according to claim 18, comprising a polymer electrolyte membrane on which a catalyst layer is applied, wherein the catalyst layer is in contact with the surface of the second microporous layer B2) of the gas diffusion layer.

20. Fuel cell stack comprising a plurality of fuel cells as defined in claim 18 or 19.

21. Use of a gas diffusion layer as defined in any one of claims 1 to 16, or obtainable by a method as defined in claim 17, in a fuel cell to improve gas and / or water permeability.

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