Surface protonated hydrocarbon support structures for fuel cell and electrolyzer membranes

Abstract

Aspects of the present disclosure include a surface-protonated hydrocarbon support for fuel cell and electrolyzer membranes. An exemplary proton exchange membrane (PEM) electrochemical cell includes a proton generating electrode having an anode, a proton consuming electrode including a cathode, and a proton exchange membrane positioned between the proton generating electrode and the proton consuming electrode. The proton exchange membrane further includes a surface-protonated porous hydrocarbon reinforcement layer. The surface-protonated porous hydrocarbon reinforcement layer can include a surface-protonated non-fluorinated or partially fluorinated hydrocarbon support matrix. The surface-protonated porous hydrocarbon reinforcement layer can be protonated by a chemical reaction process, such as a sulfonation process, using at least one of an acid or a sulfonating agent, or by a physical treatment process, such as an impregnation process in the presence of a dilute ionomer solution.

Description

Technical Field

[0001] This disclosure relates to hydrogen fuel cells and electrolysis, and more particularly to surface protonated hydrocarbon support structures for use in fuel cells and electrolyzer membranes. Background Technology

[0002] Hydrogen fuel cells and related technologies have emerged as promising clean energy solutions, offering high efficiency and zero emissions for a wide range of applications, from transportation (e.g., personal and commercial vehicles, ships, aircraft, etc.) to stationary power generation. In a hydrogen fuel cell, hydrogen enters through the anode, where it is split into protons and electrons. Protons pass through the electrolyte membrane, while electrons flow through external circuitry, generating electricity. At the cathode, protons, electrons, and oxygen combine to produce water. Hydrogen fuel cells are typically implemented in fuel cell stacks, which are components of multiple individual hydrogen fuel cells connected in series to increase total voltage and power output.

[0003] Hydrogen fuel cells typically require a supply of hydrogen fuel provided via one or more electrolysis cells. An electrolysis cell is a device that uses electrical energy to drive a non-spontaneous chemical reaction that separates water (H₂O) into hydrogen (H₂) and oxygen (O₂) gases. An electrolysis cell typically includes an anode, a cathode, and an electrolyte. When an electric current is applied between the anode and cathode, water molecules split at the anode to produce oxygen and protons (H₂O). + At the cathode, protons combine with electrons to produce hydrogen gas. Summary of the Invention

[0004] In one exemplary embodiment, the vehicle includes an electric motor, a battery, and a fuel cell stack including a proton exchange membrane (PEM) electrochemical cell. The fuel cell stack is electrically connected to at least one of the electric motor or the battery. The PEM electrochemical cell includes a proton generating electrode (anode), a proton consuming electrode (cathode), and a proton exchange membrane located between the anode and the cathode. The proton generating electrode, the proton consuming electrode, and the proton exchange membrane collectively define a membrane electrode assembly (MEA). The proton exchange membrane includes a surface-protonated porous hydrocarbon reinforcement layer. The PEM electrochemical cell also includes an anode-side gas diffusion layer on the proton generating electrode, a cathode-side gas diffusion layer on the proton consuming electrode, a first flow field connected to the anode-side gas diffusion layer, and a second flow field connected to the cathode-side gas diffusion layer.

[0005] In some embodiments, the surface-protonated porous hydrocarbon reinforcement layer comprises a surface-protonated non-fluorinated or partially fluorinated hydrocarbon support matrix.

[0006] In some embodiments, the surface-protonated porous hydrocarbon reinforcement layer comprises at least one of sulfonated polyether ether ketone (SPEEK) and polysulfone (PSU).

[0007] In some embodiments, the non-fluorinated or partially fluorinated hydrocarbon support matrix is ​​protonated by using a sulfonation method employing at least one of an acid or a sulfonating agent.

[0008] In some embodiments, the non-fluorinated or partially fluorinated hydrocarbon support matrix is ​​protonated by an impregnation process in the presence of a diluted ionomer solution.

[0009] In some embodiments, the proton exchange membrane (PEM) includes a bottom ionomer layer, a top ionomer layer, and an ionomer-filled porous support layer between the bottom ionomer layer and the top ionomer layer.

[0010] In some embodiments, the ionomer-filled porous support layer comprises a porous hydrocarbon matrix and an ionomer filled in the matrix.

[0011] In another exemplary embodiment, the PEM electrochemical cell includes a proton-generating electrode comprising an anode, a proton-consuming electrode comprising a cathode, and a proton exchange membrane located between the proton-generating electrode and the proton-consuming electrode. The proton-generating electrode, the proton-consuming electrode, and the proton exchange membrane collectively define an MEA. The proton exchange membrane also includes a surface-protonated porous hydrocarbon reinforcement layer. The PEM cell includes an anode-side gas diffusion layer on the proton-generating electrode, a cathode-side gas diffusion layer on the proton-consuming electrode, a first flow field connected to the anode-side gas diffusion layer, and a second flow field connected to the cathode-side gas diffusion layer.

[0012] In some embodiments, the surface-protonated porous hydrocarbon reinforcement layer comprises a surface-protonated non-fluorinated or partially fluorinated hydrocarbon support matrix.

[0013] In some embodiments, the surface-protonated porous hydrocarbon reinforcement layer comprises at least one of SPEEK and PSU.

[0014] In some embodiments, the non-fluorinated or partially fluorinated hydrocarbon support matrix is ​​protonated by using a sulfonation method employing at least one of an acid or a sulfonating agent.

[0015] In some embodiments, the non-fluorinated or partially fluorinated hydrocarbon support matrix is ​​protonated by an impregnation process in the presence of a diluted ionomer solution.

[0016] In some embodiments, the PEM includes a bottom ionomer layer, a top ionomer layer, and an ionomer-filled porous support layer between the bottom ionomer layer and the top ionomer layer.

[0017] In some embodiments, the ionomer-filled porous support layer comprises a porous hydrocarbon matrix and an ionomer filled in the matrix.

[0018] In yet another exemplary embodiment, a method may include forming a proton-generating electrode including an anode, forming a proton-consuming electrode including a cathode, and forming a proton exchange membrane located between the proton-generating electrode and the proton-consuming electrode. The proton-generating electrode, the proton-consuming electrode, and the proton exchange membrane collectively define an MEA. The proton exchange membrane includes a surface-protonated porous hydrocarbon reinforcement layer. The method includes forming an anode-side gas diffusion layer on the proton-generating electrode, forming a cathode-side gas diffusion layer on the proton-consuming electrode, connecting a first flow field to the anode-side gas diffusion layer, and connecting a second flow field to the cathode-side gas diffusion layer.

[0019] In some embodiments, the surface-protonated porous hydrocarbon reinforcement layer comprises a surface-protonated non-fluorinated or partially fluorinated hydrocarbon support matrix.

[0020] In some embodiments, the surface-protonated porous hydrocarbon reinforcement layer comprises at least one of SPEEK and PSU.

[0021] In some embodiments, the non-fluorinated or partially fluorinated hydrocarbon support matrix is ​​protonated by using a sulfonation method employing at least one of an acid or a sulfonating agent.

[0022] In some embodiments, the non-fluorinated or partially fluorinated hydrocarbon support matrix is ​​protonated by an impregnation process in the presence of a diluted ionomer solution.

[0023] In some embodiments, the PEM includes a bottom ionomer layer, a top ionomer layer, and an ionomer-filled porous support layer between the bottom ionomer layer and the top ionomer layer.

[0024] In some embodiments, the ionomer-filled porous support layer comprises a porous hydrocarbon matrix and an ionomer filled in the matrix.

[0025] The above-described features and advantages, as well as other features and advantages, of this disclosure will become apparent when taken in conjunction with the accompanying drawings and the following detailed description. Attached Figure Description

[0026] Other features, advantages, and details appear as examples only in the following detailed description, with reference to the accompanying drawings.

[0027] Figure 1 It is a vehicle configured according to one or more embodiments;

[0028] Figure 2A An electrolyzer according to one or more embodiments is described;

[0029] Figure 2B A fuel cell according to one or more embodiments is described;

[0030] Figure 3A The protonation process for forming a protonation support matrix for use in fuel cells and electrolyzer membranes, according to one or more embodiments, is described.

[0031] Figure 3B An exemplary reaction of a protonation process according to one or more embodiments is described;

[0032] Figure 4 A method for manufacturing a proton exchange membrane (PEM) using a surface-protonated hydrocarbon support and an ionomer solution for use in fuel cells and electrolyzers, according to one or more embodiments, is described; and

[0033] Figure 5 It is a flowchart according to one or more embodiments. Detailed Implementation

[0034] The following description is exemplary in nature and is not intended to limit this disclosure, its application or use.

[0035] Understanding and optimizing proton exchange membrane (PEM) type electrochemical cells, such as hydrogen fuel cells and electrolyzers (also known as electrolyzers), has become crucial for the widespread adoption and commercialization of hydrogen fuel cell technology. One of the key components in PEM type electrochemical cells is the membrane electrode assembly (MEA). In PEM cells, the MEA serves as the core functional unit where the main electrochemical reactions occur, converting chemical energy into electrical energy (in fuel cells) or electrical energy into chemical energy (in electrolyzers). More specifically, in PEM fuel cells, the MEA facilitates the oxidation of hydrogen at the anode and the reduction of oxygen at the cathode, producing electricity and the byproduct water, while in PEM electrolyzers, the MEA facilitates the splitting of water into hydrogen and oxygen using electricity.

[0036] Despite their potential, optimizing the design and fabrication of PEMs and MEAs remains challenging. For example, ensuring mechanical stability without compromising performance remains an unresolved issue. To illustrate, consider that these membranes typically include a support layer made of materials such as expanded polytetrafluoroethylene (ePTFE) or hydrocarbon substructures to enhance mechanical stability. Unfortunately, while these materials are suitable for providing mechanical reinforcement, their drawback is that they do not conduct protons, negatively impacting the overall proton conductivity of the membrane. This reduction in proton conductivity can lead to decreased performance and efficiency in the underlying fuel cell and electrolyzer, limiting their commercial viability and widespread adoption.

[0037] This disclosure describes the fabrication and use of surface-protonated hydrocarbon support structures for fuel cell and electrolyzer membranes. The designs described herein aim to improve both the mechanical stability and proton conductivity of the proton exchange membrane, thereby optimizing the performance of the fuel cell and electrolyzer. Surface protonation can be achieved through various methods, such as sulfonation with concentrated acids and / or other reagents (see [link to documentation]). Figure 3A Step 304 and Figure 3B ) and / or pretreatment of the support material by impregnation with a diluted ionomer solution (see Figure 3A (Step 306). These methods increase the proton density on the surface of the supporting material, promote better ionomer absorption, and improve the overall proton conductivity of the membrane.

[0038] According to an exemplary embodiment, the vehicle is in Figure 1The vehicle 100 is generally indicated by 100. The vehicle 100 is shown in the form of an automobile having a body 102. The body 102 includes a passenger compartment 104, within which a steering wheel, front seats, and rear passenger seats (not shown separately) are arranged. Several components are arranged within the body 102, including, for example, a fuel cell 106 (also referred to as a “fuel cell stack”), a hydrogen fuel storage tank 108, an intake manifold 110, a battery 112, and an electric motor 114, which is configured to use electrical energy to provide output torque to output components 116 (each component is shown in a projection near the front of the vehicle 100). The fuel cell 106 receives a flow of hydrogen or other fuel gases from the hydrogen fuel storage tank 108 and a flow of air including oxygen from the intake manifold 110. The fuel cell 106 may include an air compressor unit (not shown separately) for pressurizing the air to a desired pressure. The fuel cell 106 may directly supply electrical energy to the electric motor 114 and / or the fuel cell 106 may supply electrical energy to the battery 112 for storage and later use. Output component 116 can provide output torque for, for example, providing prime mover power to vehicle 100. In some embodiments, vehicle 100 receives hydrogen fuel from electrolyzer 118 (electrolyte) configured to produce hydrogen, and in some embodiments, delivers the hydrogen to hydrogen fuel storage tank 108 and / or fuel cell 106.

[0039] The fuel cell 106, hydrogen fuel storage tank 108, intake manifold 110, battery 112, electric motor 114, and electrolyzer 118 are shown for illustrative purposes only. It should be understood that the configuration, location, size, arrangement, etc., of these components are not intended to be particularly limited, and all such configurations (including multi-motor configurations) are within the scope of this disclosure. Furthermore, although this disclosure is discussed primarily in the context of the configuration of fuel cell 106 and electrolyzer 118 for vehicle 100, the aspects described herein can be similarly incorporated into any system (vehicle, building, or otherwise) having a hydrogen fuel cell-based electric and / or energy storage system, and all such configurations and applications are within the scope of this disclosure. In particular, electrolyzer 118 can be configured as a completely separate unit for independent hydrogen and oxygen production (potentially for servicing vehicle 100 and / or other downstream applications). As will be discussed in more detail herein, fuel cell 106 and / or electrolyzer 118 can be modified to include a surface-protonated hydrocarbon support structure.

[0040] Figure 2A An electrolyzer 118 according to one or more embodiments is depicted. For example... Figure 2AAs shown, the electrolyzer 118 includes a proton generating electrode (referred to as anode 202), a proton consuming electrode (referred to as cathode 204), and a proton exchange membrane 206 (or simply membrane 206) between the anode 202 and the cathode 204. The combination of anode 202, membrane 206, and cathode 204 together defines a membrane electrode assembly (MEA) 210.

[0041] In an electrolyzer-type configuration, protons (H) + The oxygen and protons are generated in the anode 202 and pass through the membrane 206 to the cathode 204. More specifically, the anode 202 is responsible for the oxidation of water molecules during the electrolysis process, producing oxygen and protons (H+). + The cathode 204 is responsible for the generation of protons (H+) and electrons during the electrolysis process. + The reduction of protons and electrons at the anode 202 to form hydrogen gas. Protons generated at the anode 202 pass through membrane 206 to the cathode 204. Cathode 204 facilitates the efficient recombination of protons that have passed from the anode 202 through membrane 206 with electrons that have traveled through external circuitry (e.g., power supply 208). In some embodiments, the anode 202 (anode) and cathode 204 (cathode) are coupled to power supply 208, which supplies current to the anode 202 and cathode 204, such that water supplied to the electrolyzer 118 can be decomposed into hydrogen and oxygen gas.

[0042] In some embodiments, the electrolyzer 118 includes a porous transport layer (PTL) 212 on the anode 202 and a gas diffusion layer (GDL) 214 (sometimes referred to as a diffusion medium or DM) on the cathode 204.

[0043] PTL 212 facilitates the uniform distribution of the reactant stream (typically water) across anode 202 and into membrane 206. PTL 212 also aids in the efficient removal of byproducts, such as oxygen, from electrolyzer 118. In some embodiments, PTL 212 is made of materials providing a combination of high conductivity, chemical stability, mechanical strength, and porosity, such as, for example, sintered titanium, stainless steel, and nickel-based materials (such as nickel foam). In some embodiments, PTL 212 is connected to flow field 216 via flow channels and manifolds (not shown separately). In some embodiments, flow field 216 serves as an inlet point (one or more) for the reactant stream (typically water) between anode 202 and membrane 206, which is necessary for the electrochemical reactions occurring within MEA 210. Conversely, flow field 216 may include one or more outlet manifolds (not shown separately) to ensure the efficient removal of oxygen and excess water from electrolyzer 118.

[0044] GDL 214 facilitates the collection and discharge of hydrogen generated in MEA 210. In some embodiments, GDL 214 is connected to flow field 218 via flow channels and manifolds (not separately indicated). In some embodiments, flow field 218 serves as an outlet point for hydrogen generated in MEA 210. In some embodiments, GDL 214 is made of a material that provides a combination of high conductivity, chemical stability, mechanical strength, and porosity, such as, for example, carbon fiber paper, carbon cloth, and other carbon-based materials.

[0045] In some embodiments, membrane 206 is a solid polymer dielectric that conducts protons (H). + The anode 202 and / or cathode 204 act as an insulator for electrons, ensuring that protons generated at the anode 202 can pass through to the cathode 204 while preventing mixing of product gases. In some embodiments, the anode 202 and / or cathode 204 are catalyst layers attached (laminated or directly coated) to both sides of the membrane 206. The anode 202 and / or cathode 204 may include finely dispersed catalyst particles, such as platinum (Pt) or iridium (Ir), supported on carbon particles. These catalyst layers facilitate electrochemical reactions: at the anode 202, water molecules are oxidized to produce oxygen, protons, and electrons, while at the cathode 204, protons and electrons combine to form hydrogen. In some embodiments, the anode 202 contains finely dispersed catalyst particles, such as iridium (Ir) and / or titanium oxide particles, while the cathode 204 contains finely dispersed catalyst particles, such as platinum (Pt), supported by carbon particles. The catalyst layer can be coated on membrane 206, coated on PTL 212, coated on GDL 214, and / or transferred to any one or all of membrane 206, PTL 212 and GDL 214.

[0046] Figure 2B A fuel cell 106 according to one or more embodiments is depicted. The fuel cell 106 is related to... Figure 2A The electrolyzer 118 discussed is similarly configured, except that, in the fuel cell configuration, the anode 202 and cathode 204 are connected to a load 220 (e.g., an electric motor, etc.). Figure 1 The electric motor 114 and load 220 are powered by current generated by fuel cell 106, and PTL 212 is replaced by a second GDL 222. Current is generated within fuel cell 106 as water is produced by the reaction of hydrogen and oxygen. Specifically, hydrogen is oxidized at anode 202, conducts electrons through load 222, and conducts protons through membrane 206. During this process, oxygen is reduced at cathode 204 to form water.

[0047] like Figure 2BAs shown, the fuel cell 106 includes an anode 202, a cathode 204, and a membrane 206 between the anode 202 and the cathode 204. The combination of the anode 202, membrane 206, and cathode 204 together defines an MEA 210. In a fuel cell configuration, these components work together to convert the chemical energy from hydrogen and oxygen into electrical energy through an electrochemical reaction, which is consistent with... Figure 2A The electrolyzer configurations differ in each case. Figure 2A The electrolyzer configuration in the fuel cell uses electrical energy to split water into hydrogen and oxygen. In the fuel cell configuration, the anode 202 is where hydrogen (H2) is supplied and oxidized. Protons generated at the anode 202 pass through membrane 206 to the cathode 204, while electrons are conducted away from the anode 202, thus generating a current that can be used to power the load 220. In this configuration, the cathode 204 is where oxygen (O2) is supplied and reduced. At the cathode 204, protons (H2) that have passed through membrane 206 are oxidized. + ) and electrons that have already traveled through load 220 (e - It combines with oxygen molecules to form water (H2O). GDL 214 and flow field 218 help deliver oxygen (typically as air) to MEA 210 and remove water from fuel cell 106. Conversely, GDL 222 and flow field 216 help deliver hydrogen to MEA 210 and remove excess hydrogen from fuel cell 106.

[0048] Figure 3A The image depicts a method for forming an electrolyzer (e.g., according to one or more embodiments) Figure 2A Electrolyzer 118) and fuel cell (e.g.) Figure 2B The protonation process 300 of the protonation support matrix for the membrane of the fuel cell 106. The protonation process 300 can be operated as a batch or continuous process as needed. Figure 3A As shown, in some embodiments, the protonation process 300 begins at step 301, preparing a support matrix 302.

[0049] The support matrix 302 can be made from a range of suitable PEM support materials, such as non-fluorinated or partially fluorinated hydrocarbon materials. While not intended to be particularly limiting, exemplary non-fluorinated hydrocarbon materials include poly(ether ether ketone) (PEEK) and polysulfone (PSU). Examples of partially fluorinated hydrocarbon materials include poly(vinylidene fluoride) (PVDF) and poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP). These materials can be selected based on their mechanical properties, chemical stability, and compatibility with the desired proton exchange membrane to enhance the overall performance of the underlying fuel cell and electrolyzer. In some embodiments, the support matrix 302 comprises one or both of PEEK and PSU. The support matrix 302 may have a woven or non-woven porous structure as needed. For example, a woven structure may include materials such as woven PEEK fibers or woven PSU fibers, which may be interwoven to form a mesh structure. On the other hand, a non-woven structure may include materials such as non-woven PEEK pads or non-woven PSU pads, which are formed by bonding fibers together randomly or in a specific pattern without weaving. Depending on the requirements, the support matrix 302 may have a uniform or non-uniform pore size distribution. For example, a uniform pore size distribution can be achieved using a precisely controlled manufacturing process to produce a consistent pore size throughout the support matrix 302, such as in the case of sintered PEEK or PSU materials. On the other hand, a non-uniform pore size distribution can be achieved by using techniques that create a range of pore sizes within the support matrix 302, such as electrospinning or phase separation methods.

[0050] In some embodiments, prior to sulfonation, the support matrix 302 undergoes a surface cleaning process to remove any contaminants or impurities. This can be done using solvents, detergents, or other cleaning agents as needed. In some embodiments, prior to sulfonation, the cleaned support matrix 302 is dried to remove any residual cleaning agents and moisture.

[0051] As will be described in further detail herein, the supporting matrix 302 may undergo chemical protonation (refer to step 304) or physical protonation (refer to step 306). In other words, step 301 may be followed by either chemical protonation step 304 or physical protonation step 306. Steps 304 and 306 will be described sequentially herein.

[0052] In some embodiments, the sulfonation process itself involves, in step 304, treating the support matrix 302 with a sulfonating agent to transfer sulfonic acid groups (e.g., -SO3H groups or other H groups) to the substrate. +The supporting matrix 302 is introduced onto the surface of the hydrocarbon material by introducing functional groups. Specifically, step 304 results in the formation of a protonated supporting matrix 308a having chemically bonded functional groups 310. In other words, step 304 results in the chemical protonation of the supporting matrix 302. As used herein, chemical protonation refers to bonding materials through covalent interactions (e.g., electron sharing). Sulfonation can be achieved using concentrated sulfuric acid (H2SO4) and / or other sulfonating agents. In some embodiments, the supporting matrix 302 is immersed in a sulfonating agent (e.g., H2SO4) for a predetermined duration, which may vary depending on the desired level of sulfonation. The concentration of the sulfonating agent, reaction time, temperature, and pressure may also be increased or decreased to achieve the desired degree of surface protonation. More specifically, increasing the concentration of the sulfonating agent (e.g., concentrated sulfuric acid) generally results in a higher degree of sulfonation because a more concentrated solution provides a greater quantity of sulfonated material available for reaction with the hydrocarbon material, resulting in the introduction of more sulfonic acid groups onto the surface. Conversely, reducing the concentration of the sulfonating agent will result in a lower degree of sulfonation because less sulfonated material is available. Prolonging the duration of the sulfonation reaction allows the sulfonating agent to interact with the hydrocarbon material for a longer period, leading to a higher degree of sulfonation, while reducing the reaction time tends to reduce the exposure of the hydrocarbon material to the sulfonating agent. Higher temperatures generally accelerate the sulfonation reaction by increasing the kinetic energy of the molecules involved. This can enhance the reactivity of the sulfonating agent, leading to a higher degree of sulfonation and more sulfonic acid groups on the surface. On the other hand, lower temperatures slow down the reaction kinetics, reducing the reactivity of the sulfonating agent. This results in a lower degree of sulfonation because the reaction proceeds more slowly and fewer sulfonic acid groups are introduced onto the surface. Higher pressures can increase the concentration of the sulfonating agent in contact with the hydrocarbon material, potentially enhancing the sulfonation reaction. This can lead to a higher degree of sulfonation and more sulfonic acid groups on the surface. Conversely, lower pressures reduce the concentration of the sulfonating agent in contact with the hydrocarbon material, which can reduce the sulfonation reaction. This results in a lower degree of sulfonation and fewer sulfonic acid groups on the surface. In any case, during the sulfonation reaction, the sulfonating agent reacts with the hydrocarbon material in the support matrix 302, introducing sulfonic acid groups. This results in an increase in proton density at the surface of the protonated support matrix 308a, thereby enhancing its proton conductivity. Notably, the appearance of the support matrix 302 and / or the protonated support matrix 308a may not change before and after the sulfonation process. However, the sulfonation process leads to the chemical protonation of the support matrix 302, which can be characterized using, for example, X-ray fluorescence (XRF) and energy-dispersive X-rays (EDX) to detect the presence of SO3H or other proton donor functional groups (e.g., microscale detection).

[0053] In some embodiments, at step 306, the sulfonation process involves physically protonating the support matrix 302 by immersing it in a diluted ionomer. As used herein, physical protonation, as opposed to chemical protonation (refer to step 304), refers to attaching the material via non-covalent interactions. These interactions may include hydrogen bonds, van der Waals forces, electrostatic interactions, and / or physical trapping within the material matrix. In some embodiments, at step 306, the support matrix 302 is treated with an ionomer dispersion (also referred to as an ionomer solvent). The ionomer dispersion (not specifically indicated) may be made of materials such as perfluorosulfonic acid (PFSA), sulfonated PEEK (SPEEK), or other suitable ionomers. In some embodiments, treatment via the ionomer dispersion results in the formation of a protonated support matrix 308b having physically bound functional groups 312. While not intended to be particularly limiting, physically bound functional groups 312 may include, for example, physically bound ionomer molecules, such as -R-SO3H.

[0054] Additionally or alternatively, the protonation of the support matrix 302 can occur using other processes, such as plasma treatment or X-ray irradiation. For example, the support matrix 302 (or the fibers that will constitute the support matrix 302) can be exposed to a plasma environment, which is a partially ionized gas containing ions, electrons, and optionally neutral substances. During plasma treatment, reactive sites in the matrix fibers can react with the plasma material to form new functional groups, such as hydroxyl (-OH) or carboxyl (-COOH) groups, which can enhance the proton conductivity of the support matrix 302. While not particularly limiting, plasma treatment can include, for example, oxygen plasma treatment, hydrogen plasma treatment, and mixed gas plasma treatment. In another example, the support matrix 302 (or the fibers that will constitute the support matrix 302) can be subjected to X-ray irradiation. Exposure to relatively high-energy X-ray photons can cause ionization and the formation of reactive substances within the matrix fibers. These reactive substances can lead to the breaking of chemical bonds and the formation of new functional groups, such as hydroxyl (-OH) or carboxyl (-COOH) groups, which can enhance the proton conductivity of the supporting matrix 302. X-ray irradiation can be fine-tuned by adjusting the X-ray dose, exposure time, environmental conditions, etc., to achieve the desired level of surface modification (e.g., protonation).

[0055] After the sulfonation reaction is complete (chemical, physical, or otherwise), the sulfonated support matrix 302 is removed from the sulfonating agent (e.g., sulfonic acid groups, diluted ionomers, etc.). In some embodiments, the support matrix 302 is rinsed with, for example, deionized water to remove any residual acid or byproducts. In some embodiments, the sulfonated support matrix 302 may undergo a neutralization step to ensure that any remaining acidic groups are neutralized. This can be done using a neutralizing agent such as sodium hydroxide (NaOH) or ammonium hydroxide (NH4OH). In some embodiments, the neutralized support matrix 302 is then rinsed again with deionized water to remove any residual neutralizing agent. In some embodiments, the sulfonated and neutralized support matrix 302 is dried to remove any remaining moisture. This can be done using an oven or vacuum drying process, if necessary.

[0056] Alternatively, protonation may occur before or simultaneously with the fabrication of the support matrix 302. In this case, the protonation process (e.g., chemical, physical, plasma, X-ray irradiation, etc., as previously discussed herein, refer to steps 304 and 306) may be applied directly to the fibers used to produce the support matrix 302 (not separately indicated). In other words, protonation may occur before, after, or both before and after the fabrication of the support matrix 302.

[0057] like Figure 3A As shown, the sulfonation process (chemical or physical) results in the generation of protons (chemically bonded functional groups 310 or physically bonded functional groups 312, respectively) on the surface of the support matrix 302 (not separately indicated). The protons generated at the protonated surface of the support matrix 308a or 308b increase surface hydrophilicity, thereby promoting ionomer absorption and facilitating the PEM manufacturing process (see [link]). Figure 4 The protons generated at the surfaces of the protonated support substrates 308a and 308b also increase the proton density of the resulting PEM, thereby improving membrane proton conductivity and fuel cell or electrolyzer performance (depending on the implementation).

[0058] Figure 3B An example protonation reaction based on a chemical sulfonation method according to one or more embodiments is described (see, for example...). Figure 3A Step 304). (As in...) Figure 3BAs shown, the PEM support material (here, PEEK) undergoes sulfonation (resulting in surface protonation) to form sulfonated PEEK (or SPEEK). During this process, one or more hydrogen (H) atoms in the benzene functional groups of the PEEK are replaced by sulfonic acid (-SO3H) functional groups. Notably, the accessibility of hydrogen atoms in the sulfonic acid functional groups is greater than that when confined to the benzene functional groups. In other words, the sulfonated PEM support material can be considered as a surface-protonated hydrocarbon support structure.

[0059] Figure 4 A process 400 for forming PEM 206 according to one or more embodiments is described, the PEM 206 having a surface-protonated hydrocarbon support and serving as an electrolyzer (e.g. Figure 2A Electrolyzer 118) and fuel cell (e.g.) Figure 2B The reinforced layer of the membrane in the fuel cell 106 is a filled ionomer. Method 400 can be operated as a batch or continuous process, depending on the need. Figure 4 As shown, the isomer impregnation process 400 begins with the preparation of a protonated support matrix 308a or 308b (see [link to documentation]). Figure 3A ) and ionomer solution 401.

[0060] In some embodiments, prior to protonation, the protonated support matrix 308a or 308b undergoes a surface cleaning process to remove any contaminants or impurities. This can be done using solvents, detergents, or other cleaning agents as needed. In some embodiments, prior to sulfonation, the protonated support matrix 308a or 308b is dried to remove any residual cleaning agents and moisture.

[0061] like Figure 4 As further shown, the protonated support matrix 308a or 308b and the ionomer solution 401 are combined and processed in PEM manufacturing step 402 to define membrane 206. In some embodiments, step 402 involves coating the protonated support matrix 308a or 308b with a first ionomer solution layer, then drawing the first ionomer solution into the protonated support matrix, and then coating the protonated support matrix (not separately indicated) with a second ionomer solution coating. The second ionomer solution may or may not be the same ionomer material as the first ionomer solution layer. The resulting bottom ionomer layer 404 and top ionomer layer 406 may comprise materials such as perfluorosulfonic acid (PFSA), sulfonated PEEK (SPEEK), or other suitable ionomers dispersed in a suitable solvent (such as water, alcohol, and / or other organic solvent mixtures). Figure 4As shown, the result of step 402 is the formation of a three-layer membrane 206: a bottom ionomer layer 404, a top ionomer layer 406, and a reinforcing layer 408 (also referred to as an ionomer-filled surface protonated porous hydrocarbon reinforcing layer). In some embodiments, process 400 may include multilayer coating before and / or after the inhalation process. The membrane manufacturing process may also include heat treatment, characterization (thickness monitoring, defect inspection, etc.) between and / or after each coating and inhalation process. The membrane may be produced on top of a backing substrate, or directly on an electrode layer, or on an electrode layer on top of a gas diffusion layer.

[0062] In some embodiments, membrane 206 is formed on a backing substrate and / or electrode layer (not shown separately) before, during, or after the introduction of the ionomer solution 401. While not intended to be particularly limited, the backing substrate may include, for example, glass, polymer films (e.g., polyethylene terephthalate (PET), polyimide (PI), polypropylene (PP), polyethylene (PE), polyvinylidene fluoride (PVDF), etc.), metal foils (e.g., aluminum foil, stainless steel foil, copper foil, nickel foil, etc.), ceramics (e.g., alumina, zirconium oxide, silicon carbide, etc.), composite materials (e.g., glass fiber reinforced polymers, carbon fiber polymers, etc.), silicon wafers, etc. The electrode layer (if present) may include any suitable anodic or cathode electrode material, such as platinum, iridium, ruthenium, nickel, palladium, cobalt, iron, their oxides (e.g., iridium oxide), their alloys (e.g., nickel-iron alloys), and combinations thereof.

[0063] Now for reference Figure 5 A flowchart 500, based on one embodiment, generally illustrates the use of a surface-protonated hydrocarbon support structure for fuel cells and electrolyzer membranes. (Reference) Figure 1-4 Describe flowchart 500, and flowchart 500 may include Figure 5 Additional steps not depicted. Although depicted in a specific order, Figure 5 The blocks depicted can be rearranged, subdivided, and / or combined.

[0064] At block 502, the method includes forming a proton generating electrode including an anode.

[0065] At block 504, the method includes forming a proton-consuming electrode including a cathode.

[0066] At block 506, the method includes forming a proton exchange membrane located between a proton generating electrode and a proton consuming electrode. The proton generating electrode, the proton consuming electrode, and the proton exchange membrane collectively define the MEA. The proton exchange membrane includes a surface-protonated porous hydrocarbon reinforcement layer.

[0067] At block 508, the method includes forming an anode-side gas diffusion layer on the proton-generating electrode.

[0068] At block 510, the method includes forming a cathode-side gas diffusion layer on the proton-consuming electrode.

[0069] At block 512, the method includes connecting a first flow field to the anode-side gas diffusion layer.

[0070] At block 514, the method includes connecting a second flow field to the cathode-side gas diffusion layer.

[0071] In some embodiments, the surface-protonated porous hydrocarbon reinforcement layer comprises a surface-protonated non-fluorinated or partially fluorinated hydrocarbon support matrix.

[0072] In some embodiments, the surface-protonated porous hydrocarbon reinforcement layer comprises at least one of sulfonated polyether ether ketone (SPEEK) and polysulfone (PSU).

[0073] In some embodiments, a non-fluorinated or partially fluorinated hydrocarbon support matrix is ​​protonated by using a sulfonation method employing at least one of an acid or a sulfonating agent.

[0074] In some embodiments, the non-fluorinated or partially fluorinated hydrocarbon support matrix is ​​protonated by an impregnation process in the presence of a diluted ionomer solution.

[0075] In some embodiments, the PEM includes a bottom ionomer layer, a top ionomer layer, and an ionomer-filled porous support layer (optionally, one or more reinforcing layers) between the bottom ionomer layer and the top ionomer layer.

[0076] The term “a” does not indicate a limitation of quantity, but rather that at least one of the referenced items is present. Unless the context clearly indicates otherwise, the term “or” means “and / or”. Throughout the specification, the reference to “aspect” means that a particular element described in connection with that aspect (e.g., a feature, structure, step, or characteristic) is included in at least one aspect described herein and may or may not be present in other aspects. Furthermore, it should be understood that the described elements may be combined in any suitable manner in the aspects.

[0077] Furthermore, as used in this disclosure, phrases such as "at least one of A, B, or C" or "at least one of A, B, and C" should be interpreted as selecting at least one from the group including "A, B, and C". Unless explicitly stated otherwise in conjunction with specific examples in this disclosure, this phrasing does not imply "at least one of A, at least one of B, and at least one of C". As used in this disclosure, the example "at least one of A, B, or C" would cover any of the following selections: {A}, {B}, {C}, {A,B}, {A,C}, {B,C}, and {A,B,C}.

[0078] When an element, such as a layer, film, region, or substrate, is referred to as being “on” another element, it can be directly on the other element, or there may be intermediate elements present. Conversely, when an element is referred to as being “directly” on another element, there are no intermediate elements present.

[0079] Unless otherwise stated herein, all test standards are the most recent standards in force as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which a test standard appears.

[0080] Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains.

[0081] While the foregoing disclosure has been described with reference to exemplary embodiments, those skilled in the art will understand that various changes can be made and elements can be substituted with equivalents without departing from its scope. Furthermore, many modifications can be made to adapt particular situations or materials to the teachings of this disclosure without departing from the basic scope of this disclosure. Therefore, it is intended that this disclosure be limited to the specific embodiments disclosed, but will include all embodiments falling within its scope.

Claims

1. A vehicle comprising: Electric motor; A battery, which is electrically connected to the motor; and A fuel cell stack, the fuel cell stack including a proton exchange membrane electrochemical cell, the proton exchange membrane electrochemical cell being electrically connected to at least one of the electric motor or the battery, the proton exchange membrane electrochemical cell comprising: A proton-generating electrode, which includes an anode; A proton-consuming electrode, which includes a cathode; A proton exchange membrane is located between the proton generating electrode and the proton consuming electrode, the proton generating electrode, the proton consuming electrode and the proton exchange membrane together defining a membrane electrode assembly (MEA), the proton exchange membrane including a surface-protonated porous hydrocarbon reinforcement layer; Anode-side gas diffusion layer on the proton generating electrode; Cathode-side gas diffusion layer on the proton-consuming electrode; A first flow field, which is connected to the anode-side gas diffusion layer; and The second flow field is connected to the cathode-side gas diffusion layer.

2. The vehicle of claim 1, wherein the surface-protonated porous hydrocarbon reinforcement layer comprises a surface-protonated non-fluorinated or partially fluorinated hydrocarbon support matrix.

3. The vehicle according to claim 2, wherein the surface-protonated porous hydrocarbon reinforcement layer comprises at least one of sulfonated polyether ether ketone (SPEEK) and polysulfone (PSU).

4. The vehicle according to claim 2, wherein the non-fluorinated or partially fluorinated hydrocarbon support matrix is ​​protonated by using a sulfonation method of at least one of an acid or a sulfonating agent.

5. The vehicle according to claim 2, wherein the non-fluorinated or partially fluorinated hydrocarbon support matrix is ​​protonated by an impregnation process in the presence of a diluted ionomer solution.

6. The vehicle of claim 1, wherein the surface protonated porous hydrocarbon reinforcement layer comprises a bottom ionomer layer, a top ionomer layer, and an ionomer-filled porous support layer between the bottom ionomer layer and the top ionomer layer.

7. The vehicle of claim 6, wherein the ionomer-filled porous support layer comprises a porous hydrocarbon matrix and an ionomer filled in the hydrocarbon support matrix.

8. A proton exchange membrane (PEM) electrochemical cell, comprising: A proton-generating electrode, which includes an anode; A proton-consuming electrode, which includes a cathode; A proton exchange membrane is located between the proton generating electrode and the proton consuming electrode, the proton generating electrode, the proton consuming electrode and the proton exchange membrane together defining a membrane electrode assembly (MEA), the proton exchange membrane including a surface-protonated porous hydrocarbon reinforcement layer; Anode-side gas diffusion layer on the proton generating electrode; Cathode-side gas diffusion layer on the proton-consuming electrode; A first flow field, which is connected to the anode-side gas diffusion layer; and The second flow field is connected to the cathode-side gas diffusion layer.

9. The PEM electrochemical cell according to claim 8, wherein the surface-protonated porous hydrocarbon reinforcement layer comprises a surface-protonated non-fluorinated or partially fluorinated hydrocarbon support matrix.

10. The PEM electrochemical cell according to claim 9, wherein the surface-protonated porous hydrocarbon reinforcement layer comprises at least one of sulfonated polyether ether ketone (SPEEK) and polysulfone (PSU).

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