Reinforced Proton Exchange Membrane

Abstract

A reinforced proton exchange membrane (100) is provided that includes a first layer (110) that includes a first ionomer. The first layer (110) has a first side (114) and a second side (116). The second layer (120) includes graphene oxide, the second layer (120) has a first side (124) and a second side (126), the first side (124) of the second layer (120) adjacent to the second side (116) of the first layer (110). The third layer (130) includes a second ionomer, the third layer (130) has a first side (134) and a second side (136), the first side (134) of the third layer (130) adjacent to the second side (126) of the second layer (120). The proton exchange membrane (100) may include or be formed on a support layer (140). The support layer (140) is adjacent to the first surface (114) of the first layer (110).

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63 / 293,459, filed December 23, 2021. The entire disclosures of the above-referenced applications are incorporated herein by reference.

[0002] Field The present technology relates to enhancing proton exchange membranes, including those used in membrane electrode assemblies and fuel cells containing such membrane electrode assemblies. [Background technology]

[0003] Introduction This section provides background information related to the present disclosure, but is not necessarily prior art.

[0004] Fuel cell systems can be used as power sources in many applications, such as vehicles and stationary power plants. Such systems can provide electrical power economically and with environmental and other benefits. To be commercially viable, however, fuel cell systems must exhibit sufficient reliability in operation even when exposed to conditions outside their preferred operating range.

[0005] Fuel cells convert reactants, i.e., fuel and oxidant, to produce power and reaction products. Proton exchange membrane fuel cells (PEM fuel cells), also called polymer electrolyte membrane fuel cells, can employ a membrane electrode assembly (MEA) that includes a proton exchange membrane (e.g., a proton conducting ionomer) disposed between two electrodes, i.e., a positive electrode and a negative electrode. A catalyst typically facilitates the desired electrochemical reaction at the electrodes. On each side of the MEA, separator or bipolar plates, including plates that provide flow fields for directing reactants across the surface of each electrode, and / or various types of gas diffusion media can be disposed.

[0006] In operation, the output voltage of an individual fuel cell under load may be less than 1 volt. Thus, to provide a higher output voltage, multiple fuel cells can be stacked together and connected in series to create a higher voltage fuel cell stack. End plate assemblies can be placed on either end of the fuel cell stack to hold the stack together and compress the stack components. The compression force allows for a seal and proper electrical contact between the various stack components. Fuel cell stacks can also be combined and connected in series and / or parallel with other fuel cell stacks or power sources to form larger arrays to provide higher voltages and / or currents.

[0007] Proton exchange membranes used in fuel cells may experience a wide range of operating conditions, including variations in temperature as well as relative humidity, and may be chemically and mechanically reinforced to increase the durability of the proton exchange membrane. For example, expanded polytetrafluoroethylene (e-PTFE) may be used to mechanically reinforce the membrane, while one or more antioxidants may be included in the membrane to improve its chemical stability against certain radicals, such as those generated by the Fenton reaction (e.g., hydroxyl radicals). Summary of the Invention [Problem to be solved by the invention]

[0008] Therefore, there is a continuing need to optimize the mechanical and chemical stability of proton exchange membranes to achieve the desired performance and durability requirements required for PEM fuel cells. [Means for solving the problem]

[0009] overview Consistent with the present disclosure, it has surprisingly been discovered that an optimized proton exchange membrane comprising a membrane electrode assembly and a fuel cell comprising such a proton exchange membrane, as well as a method for producing such a proton exchange membrane.

[0010] The present technology includes articles, systems, and methods relating to a proton exchange membrane including a first layer, a second layer, and a third layer. The first layer includes a first ionomer and has a first side and a second side. The second layer includes graphene oxide and has a first side and a second side, the first side of the second layer adjacent to the second side of the first layer. The third layer includes a second ionomer and has a first side and a second side, the first side of the third layer adjacent to the second side of the second layer.

[0011] A method for making a proton exchange membrane is provided that includes disposing a first layer comprising a first ionomer on a support layer. A second layer is disposed on the first layer, the second layer comprising graphene oxide. A third layer is disposed on the second layer, the third layer comprising a second ionomer. The support layer can then be removed.

[0012] Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are for purposes of illustration only and are not intended to limit the scope of the present disclosure. [Brief description of the drawings]

[0013] The drawings described herein are intended only to illustrate selected embodiments, rather than every possible embodiment, and are not intended to limit the scope of the disclosure.

[0014] [Figure 1] FIG. 1 is a schematic cross-sectional view of a first embodiment of a proton conducting membrane constructed in accordance with the present technology.

[0015] [Diagram 2] FIG. 2 is a schematic cross-sectional view of a second embodiment of a proton conducting membrane constructed in accordance with the present technology.

[0016] [Diagram 3] FIG. 1 is a schematic cross-sectional view of a third embodiment of a proton conducting membrane constructed in accordance with the present technology.

[0017] [Figure 4] FIG. 1 is a schematic cross-sectional view of a fourth embodiment of a proton conducting membrane constructed in accordance with the present technology.

[0018] [Diagram 5] FIG. 11 is a schematic cross-sectional view of a fifth embodiment of a proton conducting membrane constructed in accordance with the present technology.

[0019] [Figure 6] FIG. 11 is a schematic cross-sectional view of a sixth embodiment of a proton conducting membrane constructed in accordance with the present technology. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] Detailed Description The following description of the technology is merely exemplary in nature of the subject matter, manufacture and use of one or more inventions, and is not intended to limit the scope, application or use of any particular inventions claimed in this application or any other application which may claim priority from this application, or any patents issued therefrom. For the disclosed methods, the order of steps shown is exemplary in nature, and therefore, unless otherwise specified, the order of steps may differ in various embodiments, including cases where certain steps may be performed simultaneously. As used herein, "A" and "an" indicate that there is "at least one" of an item, and where possible, there may be more than one of such items. Unless otherwise expressly stated, all numerical values ​​herein are understood to be modified by the word "about," and all geometric and spatial descriptors are understood to be modified by the word "substantially" in describing the broadest scope of the technology. When applied to a numerical value, "about" indicates that some imprecision in the value is allowed by calculation or measurement (such as approaching the accuracy of the value to some extent, being approximately close to or reasonably close to the value, almost). If for any reason the imprecision afforded by "about" and / or "substantially" is not otherwise understood according to its ordinary meaning in the art, then as used herein, "about" and / or "substantially" will at least account for the variation that can result from ordinary methods of measuring or using such parameters.

[0021] Although embodiments of the present technology are described and claimed herein using the open-ended term "comprising" as a synonym for non-limiting terms such as including, containing, or having, embodiments may alternatively be described using more limiting terms such as "consisting of" or "consisting essentially of." Thus, for any given embodiment that recites materials, components, or process steps, the present technology also specifically includes embodiments that consist of or consist essentially of such materials, components, or process steps, but excludes additional materials, components, or methods (consisting of) and additional materials, components, or methods (consisting essentially of) that affect critical properties of the embodiment, even if the additional materials, components, or methods are not expressly recited in this application. For example, a recitation of a composition or method reciting elements A, B, and C specifically contemplates embodiments consisting of, as well as embodiments consisting essentially of, A, B, and C, excluding element D, as may be recited in the art, even if element D is not expressly described as excluded herein.

[0022] As described herein, the disclosure of a range includes the endpoints and includes all separate values ​​and further divided ranges within the entire range unless otherwise indicated. Thus, for example, a range of "from A to B" or "from about A to about B" includes A and B. The disclosure of a value and range of values ​​for a particular parameter (amount, weight percent, etc.) does not exclude other values ​​and ranges of values ​​useful herein. It is contemplated that two or more specific exemplary values ​​for a given parameter may define the endpoints of a range of values ​​that may be claimed for that parameter. For example, if a parameter X is exemplified herein as having a value A and is also exemplified herein as having a value Z, it is contemplated that the parameter X may have a value ranging from about A to about Z. Similarly, the disclosure of two or more ranges of values ​​for a parameter (whether such ranges are overlapping, overlapping, or separate) is contemplated to encompass all possible combinations of the ranges of values ​​that may be claimed using the endpoints of the disclosed ranges. For example, when a parameter X is exemplified herein as having a value in the range of 1 to 10, 2 to 9, or 3 to 8, it is also contemplated that the parameter X may have values ​​in other ranges, including 1 to 9, 1 to 8, 1 to 3, 1 to 2, 2 to 10, 2 to 8, 2 to 3, 3 to 10, 3 to 9, etc.

[0023] When an element or layer is referred to as being "on," "engaged to," "connected to," or "coupled to" another element or layer, it can be directly on, directly embedded in, directly connected to, or directly coupled to the other element or layer, or there may be intervening elements or layers present. In contrast, when an element is referred to as being "directly on," "directly engaged to," "directly connected to," or "directly coupled to" another element or layer, there may not be intervening elements or layers present. Other terms used to describe relationships between elements should be interpreted similarly (e.g., "between" and "directly between," "adjacent" and "directly adjacent," etc.). As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0024] In this specification, terms such as first, second, third, etc. may be used to describe various elements, components, regions, layers, and / or portions, but these elements, components, regions, layers, and / or portions are not limited by these terms. These terms may only be used to distinguish one element, component, region, layer, or portion from another region, layer, or portion. As used in this specification, terms such as "first," "second," and other numerical terms do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer, or portion discussed below may be referred to as a second element, component, region, layer, or portion without departing from the disclosure of the exemplary embodiments.

[0025] Spatially relative terms, such as "inner," "outer," "beneath," "below," "lower," "above," "upper," and the like, may be used herein to facilitate describing the relationship of one element or feature to another element or feature as shown in the figures. Spatially relative terms may be intended to encompass various orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in a figure is inverted, an element described as "below" or "below" another element or feature would be positioned "above" the other element or feature. Thus, the exemplary term "below" may encompass both an above and below orientation. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein may be interpreted accordingly.

[0026] The present technology focuses on optimized proton exchange membranes that provide improved mechanical and chemical stability in the operating environment encountered within a PEM fuel cell. In this manner, the proton exchange membranes can be used to achieve the desired performance and durability requirements required for PEM fuel cells. The proton exchange membranes presented herein can include a first layer, a second layer, and a third layer. The first layer can include a first ionomer and can have a first side and a second side. The second layer can include graphene oxide and can have a first side and a second side, where the first side of the second layer can be adjacent to the second side of the first layer. The third layer can include a second ionomer and can have a first side and a second side, where the first side of the third layer can be adjacent to the second side of the second layer. In certain embodiments, the first side of the second layer can be directly adjacent to the second side of the first layer, and the first side of the third layer can be directly adjacent to the second side of the second layer. The proton exchange membrane may also include a support layer adjacent to the first surface of the first layer, and the support layer may also be directly adjacent to the first surface of the first layer. Thus, the second layer may be sandwiched between the first and second layers. The construction of the proton exchange membrane provides improved mechanical stability, including stability against changes in humidity and temperature, as well as improved chemical stability. Such proton exchange membranes constructed according to the present disclosure also provide improved stability against oxidation inhibition caused thereby, and may minimize migration of antioxidants from the membrane.

[0027] A support layer, configured as, for example, a blank or web, can be used in forming a proton exchange membrane. For example, the support layer may provide a stable platform on which successive layers can be placed, applied, or formed in various ways to produce a proton exchange membrane. The support layer can include a fluoropolymer layer, which can facilitate subsequent removal from the formed proton exchange membrane. Certain methods of producing a proton exchange membrane include providing a support layer as a blank or web, where the support layer can include a fluoropolymer layer. A first layer including a first ionomer can be placed on or applied to the support layer. A second layer including graphene oxide can be placed on or applied to the first layer. A third layer including a second ionomer can be placed on or applied to the second layer. Removal of the support layer can leave a proton exchange membrane including the second layer sandwiched between the first and second layers.

[0028] The support layer may include the following aspects: The support layer may be configured as a blank of a given size or a continuous web of material. The support layer may include a fluoropolymer layer. The fluoropolymer layer may include one or more of various fluoropolymers, such as polytetrafluoroethylene (PTFE), polyethylenetetrafluoroethylene (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene (FEP), polyethylenechlorotrifluoroethylene (ECTFE), perfluoroelastomer (FFPM), perfluoropolyether (PFPE), and perfluorosulfonic acid (PFSA). Embodiments include those in which the support layer is comprised solely of a fluoropolymer layer, as well as those in which the support layer may also include combinations of other polymers, elastomers, and materials, for example, the fluoropolymer layer may be applied as a release layer onto other materials or layers of materials. The release layer may be applied by spray coating, dip coating, or the like. If the support layer includes a fluoropolymer layer, the thickness of the fluoropolymer layer can be from about 0.1 mil (2.54 microns) to about 5 mils (127 microns).

[0029] Each layer (e.g., first and second layers) that includes an ionomer may include the following aspects. Embodiments include those in which the ionomer in each layer is the same, while other embodiments include those in which the ionomer in the various layers is different. The ionomer may include a sulfonated tetrafluoroethylene-based fluoropolymer copolymer, such as DuPont's Nafion™ fluoropolymer copolymer. The ionomer equivalent weight (EW) of the ionomer in the first layer and / or the third layer may be, for example, from about 700 g / mol to about 1,100 g / mol. The thickness of the first layer and / or the third layer may be from about 2.54 microns to about 127 microns. It is also possible for the first and third layers to be substantially the same.

[0030] The second layer including graphene oxide may include the following aspects: The graphene oxide may include functionalized graphene oxide having various ionized units, such as sulfonic acid units. For example, the graphene oxide may be functionalized by various methods to include various functional groups. Certain embodiments include those in which the graphene oxide may be functionalized by using 3-mercaptopropyltrimethoxysilane (MPTMS) as a sulfonic acid functional group precursor.

[0031] The second layer including graphene oxide may also include an antioxidant. In certain embodiments, the antioxidant includes cerium oxide, the cerium oxide being present at about 0.01 mg / cm. 2 ~about 0.3mg / cm 2 The second layer may include a functionalized graphene oxide and an antioxidant (e.g., cerium oxide). Additionally, the second layer may include a functionalized graphene oxide, an antioxidant (e.g., cerium oxide), and an ionomer, such as a proton form ionomer and / or a sodium form ionomer. The thickness of the second layer may be from about 2.5 microns to about 5 microns.

[0032] Graphene oxide has excellent physical, chemical and mechanical properties that can surprisingly strengthen the proton exchange membranes presented herein. Graphene oxide can be easily processed and coated as one or more thin films, and graphene oxide itself can act as an excellent antioxidant. The graphene oxide layer can pass protons but prevent gases from passing through, resulting in special properties for use as a reinforcing layer in the present proton exchange membranes. Graphene oxide can also be processed in aqueous / alcoholic media of various concentrations and coated as a sandwich layer to other constituent layers, for example, a second layer containing graphene oxide can be sandwiched between the first and third layers in the construction of a proton exchange membrane. Graphene oxide can strengthen the entire proton exchange membrane structure.

[0033] The proton exchange membrane can be used in a variety of applications. A membrane electrode assembly can include one or more proton exchange membranes as shown herein with one or more electrodes. For example, the proton exchange membrane can be disposed between two electrodes, such as a positive electrode and a negative electrode. Such a membrane electrode assembly can be used in one or more fuel cells, including various fuel cell stacks. Individual fuel cells or stacks including fuel cells having one or more proton exchange membranes as shown herein can be used as power generation devices in a variety of applications, including providing power for vehicles.

[0034] The present technology provides various methods for manufacturing proton exchange membranes. For example, one or more of the various constituent layers may be placed on top of another layer by various means including laminating successive layers, coated by one or more rollers, calendered, sprayed, or deposited on top of one another to form a complete layered or partial proton exchange membrane, which may then be further combined or laminated to form a complete membrane. Other constituent layers may be applied to and / or transferred from a web of a given constituent layer. Similarly, other constituent layers may be applied to individual blanks having a given dimension of the given constituent layer.

[0035] A given method of making a proton exchange membrane may include providing a support layer, such as a blank or web, that includes a fluoropolymer layer. A first layer that includes an ionomer may be disposed on the fluoropolymer layer. A second layer that includes graphene oxide may be disposed on the first layer. A third layer that includes an ionomer may be disposed on the second layer. The support layer may be removed leaving the proton exchange membrane that includes the second layer sandwiched between the first and second layers. Disposing the various layers on top of one another may include various means of coating, laminating, calendering, spraying, deposition, or other membrane forming techniques, as applicable.

[0036] Therefore, the present technology can enhance the durability of proton exchange membrane applications and provide economic benefits. In some embodiments, the proton exchange membrane can simultaneously improve mechanical and chemical durability. It has been observed that in other proton exchange membranes, a certain amount of antioxidant (e.g., CeO2) can leach out of the proton exchange membrane and adversely affect the performance of the fuel cell. However, the proton exchange membrane provided by the present technology can stabilize the added antioxidant and minimize the migration of the antioxidant from the membrane. EXAMPLES

[0037] Exemplary embodiments of the present technology are illustrated with reference to the several figures accompanying this specification.

[0038] Referring to FIG. 1, a first embodiment of a proton conducting membrane is shown generally at 100. A first layer 110 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 114 and a second side 116. In certain embodiments, the first layer 110 may include ePTFE and / or porous PTFE, which is an expanded PTFE that is also porous to accommodate the ionomer. A second layer 120 (e.g., graphene oxide) has a first side 124 and a second side 126, with the first side 124 of the second layer 120 adjacent to the second side 116 of the first layer 110. A third layer 130 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 134 and a second side 136, with the first side 134 of the third layer 130 adjacent to the second side 126 of the second layer 120. There can be a support layer 140 (e.g., ePTFE) having a first side 144 and a second side 146, and the proton conducting membrane 100 can be formed by disposing the first side 114 of the first layer 110 on the second side 146 of the support layer 140. This can be followed by disposing a second layer 120 on the first layer 110, and a third layer 130 on the second layer 120, either sequentially or simultaneously.

[0039] Referring to FIG. 2, a second embodiment of a proton conducting membrane is shown generally at 200. A first layer 210 (e.g., an ionomer with an EW of 700-1100 g / mol) has a first side 214 and a second side 216. In certain embodiments, the thickness of the first layer 210 can range from 0.1 mils to 5 mils. A second layer 220 (e.g., an H +A second layer 220 (e.g., a functionalized graphene oxide) has a first side 224 and a second side 226, with the first side 224 of the second layer 220 adjacent to the second side 216 of the first layer 210. A third layer 230 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 234 and a second side 236, with the first side 234 of the third layer 230 adjacent to the second side 226 of the second layer 220. A support layer 240 (e.g., ePTFE having a thickness of 3-5 mils) having a first side 244 and a second side 246 is present, and the proton conducting membrane 200 can be formed by disposing the first side 214 of the first layer 210 on the second side 246 of the support layer 240. This can be followed by disposing the second layer 220 on the first layer 210, either sequentially or simultaneously, and disposing the third layer 230 on the second layer 220.

[0040] 3, a third embodiment of a proton conducting membrane is shown generally at 300. A first layer 310 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 314 and a second side 316. A second layer 320 (e.g., graphene oxide+CeO2) has a first side 324 and a second side 326, with the first side 324 of the second layer 320 adjacent to the second side 316 of the first layer 310. A third layer 330 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 334 and a second side 336, with the first side 334 of the third layer 330 adjacent to the second side 326 of the second layer 320. A support layer 340 (e.g., ePTFE) having a first side 344 and a second side 346 is present, and the proton conducting membrane 300 can be formed by disposing a first side 314 of a first layer 310 on the second side 346 of the support layer 340. This can then be followed by disposing a second layer 320 on the first layer 310, and a third layer 330 on the second layer 320, either sequentially or simultaneously.

[0041] 4, a fourth embodiment of a proton conducting membrane is shown generally at 400. A first layer 410 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 414 and a second side 416. A second layer 420 (e.g., functionalized graphene oxide+CeO2) has a first side 424 and a second side 426, with the first side 424 of the second layer 420 adjacent to the second side 416 of the first layer 410. A third layer 430 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 434 and a second side 436, with the first side 434 of the third layer 430 adjacent to the second side 426 of the second layer 420. A support layer 440 (e.g., 3-5 mil thick ePTFE) having a first side 444 and a second side 446 is present, and the proton conducting membrane 400 can be formed by disposing a first side 414 of a first layer 410 on the second side 446 of the support layer 440. This can then be followed by disposing a second layer 420 on the first layer 410, and a third layer 430 on the second layer 420, either sequentially or simultaneously.

[0042] 5, a fifth embodiment of a proton conducting membrane is shown generally at 500. A first layer 510 (e.g., an ionomer with an EW of 700-1100 g / mol) has a first side 514 and a second side 516. A second layer 520 (e.g., graphene oxide+CeO2+H + A second layer 520 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 524 and a second side 526, with the first side 524 of the second layer 520 adjacent to the second side 516 of the first layer 510. A third layer 530 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 534 and a second side 536, with the first side 534 of the third layer 530 adjacent to the second side 526 of the second layer 520. A support layer 540 (e.g., PTFE) is present having a first side 544 and a second side 546, and the proton conducting membrane 500 can be formed by disposing the first side 514 of the first layer 510 on the second side 546 of the support layer 540. This can be followed by disposing the second layer 520 on the first layer 510, either sequentially or simultaneously, and disposing the third layer 530 on the second layer 520.

[0043] 6, a sixth embodiment of a proton conducting membrane is shown generally at 600. A first layer 610 (e.g., an ionomer with an EW of 700-1100 g / mol) has a first side 614 and a second side 616. A second layer 620 (e.g., a functionalized graphene oxide+CeO2+Na + A second layer 620 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 624 and a second side 626, with the first side 624 of the second layer 620 adjacent to the second side 616 of the first layer 610. A third layer 630 (e.g., an ionomer having an EW of 700-1100 g / mol) has a first side 634 and a second side 636, with the first side 634 of the third layer 630 adjacent to the second side 626 of the second layer 620. A support layer 640 (e.g., ePTFE having a thickness of 0.1-5 mils) having a first side 644 and a second side 646 is present, and the proton conducting membrane 600 can be formed by disposing the first side 614 of the first layer 610 on the second side 646 of the support layer 640. This can be followed by disposing the second layer 620 on the first layer 610, either sequentially or simultaneously, and disposing the third layer 630 on the second layer 620.

[0044] Exemplary embodiments are shown so that the disclosure will be thorough and fully convey the scope of the present disclosure to those skilled in the art. Many specific details are shown, such as examples of specific components, devices and methods, so that the embodiments of the present disclosure can be fully understood. It is clear to those skilled in the art that specific details need not be adopted, and that the exemplary embodiments can be embodied in many different forms, and none of them should be construed as limiting the scope of the present disclosure. In some exemplary embodiments, well-known methods, well-known device structures and well-known technologies are not described in detail. Equivalent changes, modifications and variations of some embodiments, materials, compositions and methods can be made within the scope of the present technology, resulting in substantially similar results.

Claims

1. A proton exchange membrane comprising: a first layer comprising a first ionomer and having a first side and a second side; a second layer comprising graphene oxide and having a first side and a second side, the first side of the second layer adjacent to the second side of the first layer; a third layer comprising a second ionomer and having a first side and a second side, the first side of the third layer being adjacent to the second side of the second layer; A proton exchange membrane comprising:

2. the first surface of the second layer is directly adjacent to the second surface of the first layer; and the first surface of the third layer is directly adjacent to the second surface of the second layer. The proton exchange membrane of claim 1.

3. The proton exchange membrane of claim 1 , further comprising a support layer adjacent said first surface of said first layer.

4. The proton exchange membrane of claim 3 , wherein the support layer is directly adjacent the first surface of the first layer.

5. The proton exchange membrane of claim 3 , wherein the support layer comprises a fluoropolymer.

6. 2. The proton exchange membrane of claim 1, wherein the first ionomer, the second ionomer, or each of the first ionomer and the second ionomer comprises a sulfonated tetrafluoroethylene-based fluoropolymer copolymer.

7. 2. The proton exchange membrane of claim 1, wherein said first layer and said second ionomer are substantially identical.

8. 10. The proton exchange membrane of claim 1, wherein the graphene oxide comprises a functionalized graphene oxide having ionized units.

9. The proton exchange membrane of claim 8 , wherein the ionizable units comprise sulfonic acid units.

10. The proton exchange membrane of claim 1 , wherein the second layer comprises an antioxidant.

11. The proton exchange membrane of claim 10 , wherein the antioxidant comprises cerium oxide.

12. 10. The proton exchange membrane of claim 1, wherein the graphene oxide comprises a functionalized graphene oxide and the second layer comprises cerium oxide.

13. 2. The proton exchange membrane of claim 1, wherein the graphene oxide comprises a functionalized graphene oxide and the second layer comprises cerium oxide and a proton-type ionomer.

14. 2. The proton exchange membrane of claim 1, wherein the graphene oxide comprises a functionalized graphene oxide and the second layer comprises a cerium oxide and a sodium ion type ionomer.

15. 13. A method for manufacturing a proton exchange membrane comprising: Membrane electrode assembly.

16. A fuel cell comprising the membrane electrode assembly of claim 15.

17. A vehicle comprising the fuel cell of claim 16.

18. A method for producing a proton exchange membrane, comprising the steps of: disposing a first layer over the support layer, the first layer comprising a first ionomer; disposing a second layer over the first layer, the second layer comprising graphene oxide; disposing a third layer over the second layer, the third layer comprising a second ionomer; The method includes:

19. The method of claim 18 , further comprising removing the support layer.

20. A method for manufacturing a membrane electrode assembly, comprising the steps of: Producing a proton exchange membrane according to the method of claim 18; disposing a first electrode on one side of the proton exchange membrane; disposing a second electrode on the other side of the proton exchange membrane; The method includes:

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