Systems and methods for water electrolysis of electrodes with nickel cobalt phosphorus-based compounds

Abstract

The present disclosure relates to systems and methods for water electrolysis of electrodes having nickel cobalt phosphorus-based compounds. Systems and methods for water electrolysis are provided. The system includes an electrolyte material configured for anion exchange; a first electrode including a nickel cobalt phosphorus-based compound; and a second electrode, wherein the first electrode and the second electrode are configured to exchange anions through the electrolyte material.

Description

Technical Field

[0001] The present invention relates generally to systems and methods for water electrolysis, and more specifically to systems and methods comprising electrodes having nickel-cobalt-phosphorus-based compounds. Background Technology

[0002] Interest in alternative energy sources continues to grow, particularly for applications utilizing hydrogen. Therefore, there is a sustained demand for efficient hydrogen production methods. One possible method for sustainable hydrogen production is water electrolysis. Water electrolysis, also known as "water splitting," is the process of breaking down liquid water (H2O) into oxygen (O2) and hydrogen (H2). The process involves applying a voltage to the anode and cathode to allow an electric current to flow through the water. Hydrogen is produced at the cathode, and oxygen is produced at the anode. Specifically, water electrolysis involves two half-reactions: the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) at the anode. To increase the current density and thus the amount of gas produced, water electrolysis typically involves a liquid electrolyte in the water or an ion-exchange membrane (polymer electrolyte) between the anode and cathode.

[0003] The efficiency of water electrolysis typically depends on the electrochemical catalytic performance of the electrode materials. For alkaline water electrolysis systems, the anode material is usually formed from nickel (Ni) or nickel foam. Although other materials have been found to initially provide better catalytic performance than nickel, these materials usually dissolve in the highly corrosive alkaline environment of the anode and lose their catalytic ability after a relatively short period of time.

[0004] Therefore, there is a continued need for improved gas generation systems and methods for water hydrolysis, and a continued need for improved electrode materials. Furthermore, other desirable features and characteristics of the invention will become apparent from the following detailed description and the appended claims, taken in conjunction with the accompanying drawings and the foregoing technical and background information. Summary of the Invention

[0005] This summary is provided to describe selected concepts in a simplified form, which are further described in the detailed embodiments. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to help determine the scope of the claimed subject matter.

[0006] A system for water electrolysis is provided. In one example, the system includes: an electrolyte material configured for anion exchange; a first electrode comprising a nickel-cobalt-phosphorus-based compound; and a second electrode, wherein the first and second electrodes are configured to exchange anions through the electrolyte material.

[0007] In various examples, the electrolyte material of the system may be an anion exchange membrane, the first electrode is a first catalyst layer on a first side of the anion exchange membrane, and the second electrode is a second catalyst layer on a second side of the anion exchange membrane opposite to the first side.

[0008] In various examples, the electrolyte material of the system can be an alkaline solution, and both the first and second electrodes are in contact with the alkaline solution.

[0009] In various examples, the first electrode of the system can be the anode, and the second electrode can be the cathode.

[0010] In various examples, the first electrode of the system can be a cathode, and the second electrode can be an anode.

[0011] In various examples, the second electrode of the system may include a nickel-cobalt-phosphorus-based compound.

[0012] In various examples, the first electrode of the system may comprise about 5% to 95% by weight Co (cobalt), about 5% to 95% by weight Ni (nickel), and about 5% to 20% by weight P (phosphorus).

[0013] In various examples, the first electrode of the system may include about 0.01% to 5.0% by weight of graphene or graphene oxide.

[0014] In various examples, the first electrode of the system may include one or more of the following from about 0.01 wt% to 10.0 wt%: nickel phosphide (NiP), nickel chloride (NiCl2), cobalt phosphide (CoP), cobalt chloride (CoCl2), nickel cobalt phosphide (Co-Ni-P), nickel cobalt phosphide (Ni-Co-P), iridium oxide (IrOx), ruthenium oxide (RuOx), palladium (Pd), and platinum (Pt).

[0015] In various examples, the first electrode of the system can be formed at least partially by an electrodeposition process.

[0016] A method for producing electrodes for water electrolysis is provided. In one example, the method includes: providing an electrodeposition bath containing a solution of a nickel cobalt phosphorus-based compound; and electrodepositing the solution from the electrodeposition bath onto a substrate to form a coating containing the nickel cobalt phosphorus-based compound and thus forming an electrode.

[0017] In various examples, the method may include forming a solution by combining nickel sulfate, nickel chloride, cobalt sulfate, cobalt chloride, phosphorous acid, hypophosphite, and boric acid. In various examples, the method may include forming a solution by combining graphene and / or graphene oxide.

[0018] In various examples, the method may include providing an anion exchange membrane as a substrate, wherein electrodepositing a solution from an electrodeposition bath onto the substrate includes forming a first catalyst layer on a first side of the anion exchange membrane.

[0019] In various examples, the method may include forming a second catalyst layer on a second side of the anion exchange membrane, wherein the second catalyst layer comprises a nickel-cobalt-phosphorus-based compound.

[0020] In various examples, the coating formed by this method may contain about 5% to 95% by weight of Co, about 5% to 95% by weight of Ni and about 5% to 20% by weight of P.

[0021] In various examples, the method may include providing graphene in solution prior to electrodepositing the solution from an electrodeposition bath onto a substrate, wherein the coating comprises about 0.01 wt% to 5.0 wt% of graphene or graphene oxide.

[0022] In various examples, the method may include providing one or more compounds comprising one or more of the following: nickel phosphide (NiP), cobalt phosphide (CoP), nickel cobalt phosphide (Co-Ni-P), nickel cobalt phosphide (Ni-Co-P), iridium oxide (IrOx), ruthenium oxide (RuOx), palladium (Pd), and platinum (Pt), wherein the coating comprises about 0.01% to 2.0% by weight of one or more compounds.

[0023] A precursor solution for forming an electrode is provided. In one example, the precursor solution comprises a nickel-cobalt-phosphorus-based compound containing about 5% to 95% by weight of Co, about 5% to 95% by weight of Ni, and about 5% to 20% by weight of P.

[0024] In various examples, the nickel-cobalt-phosphorus-based compound of the precursor solution may contain about 0.01% to 2.0% by weight of graphene.

[0025] In various examples, the nickel cobalt phosphorus-based compound of the precursor solution may contain from about 0.01 wt% to 10.0 wt% of one or more of the following: nickel phosphide (NiP), nickel chloride (NiCl2), cobalt phosphide (CoP), cobalt chloride (CoCl2), nickel cobalt phosphide (Co-Ni-P), nickel cobalt phosphide (Ni-Co-P), iridium oxide (IrOx), ruthenium oxide (RuOx), palladium (Pd), and platinum (Pt).

[0026] Furthermore, other desired features and properties of the system, method, and precursor solution will become apparent from the following detailed description and appended claims, in conjunction with the accompanying drawings and the foregoing background information. Attached Figure Description

[0027] The invention will now be described with reference to the following figures, wherein similar numbers denote similar elements, and wherein:

[0028] Figure 1 This is a schematic diagram illustrating a system including anion exchange membranes (AEMs) according to various embodiments;

[0029] Figure 2 It is a schematic diagram illustrating a system including an anode and a cathode separated by a liquid alkaline electrolytic cell according to various embodiments;

[0030] Figure 3 This is a flowchart illustrating methods for forming electrodes according to various embodiments; and

[0031] Figure 4 This is a flowchart illustrating various implementation schemes for generating hydrogen via water electrolysis. Detailed Implementation

[0032] The following detailed descriptions are merely exemplary in nature and are not intended to limit the invention or its application and use. As used herein, the word "exemplary" means "serving as an example, instance, or illustration." Therefore, any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. All embodiments described herein are exemplary embodiments provided to enable those skilled in the art to make or use the invention, and do not limit the scope of the invention as defined by the claims. Furthermore, it is not intended to be bound by any express or implied theory presented in the foregoing technical field, background art, summary of the invention, or the following detailed descriptions.

[0033] The systems and methods disclosed herein provide for the production of hydrogen from water via water hydrolysis (i.e., water splitting). Water electrolysis involves the decomposition of water (H₂O) into oxygen (O₂) and hydrogen (H₂) by passing an electric current through the water. The system generally comprises an anode (or anode catalyst layer), a cathode (or cathode catalyst layer), and an electrolyte material separating the anode and cathode. Notably, the systems disclosed herein include at least one electrode having a compound comprising a cobalt-nickel-phosphorus (Co-Ni-P) based compound. The system can have various structures utilizing various electrolysis techniques.

[0034] In various embodiments, the system may include an anode and a cathode separated by an anion exchange membrane. The anion exchange membrane (AEM) is a semi-permeable membrane configured to allow anions (e.g., hydroxide ions (OH-) to pass through it. -The ion exchange membrane and water are conducted from the cathode to the anode, while also acting as a reactant barrier (e.g., hindering the transport of gases such as oxygen (O2) or hydrogen (H2)). The anode and cathode may be defined by an anode catalyst layer deposited on a first side of the ion exchange membrane (referred to as the anode side) and a cathode catalyst layer deposited on a second side of the ion exchange membrane opposite to the anode side (referred to as the cathode side). The system may also include porous transport layers (PTLs) adjacent to the anode and cathode catalyst layers, which are configured to facilitate gas diffusion. The combination of the ion exchange membrane, anode catalyst layer, cathode catalyst layer, and PTL defines the electrochemical cell. Bipolar plates may be provided to encapsulate the electrochemical cell and may include ports for transporting liquids and gases (e.g., water, hydrogen, oxygen) through it. In various embodiments, the system may include more than one electrochemical cell arranged in a stacked manner. In such embodiments, a single bipolar plate may serve as both an anode side plate and a cathode side plate of an adjacent electrochemical cell; that is, one or more bipolar plates may include flow paths, ports, channels, etc., disposed on their respective sides.

[0035] Figure 1 An exemplary first system 100 configured for electrolysis is presented, the exemplary first system including AEM 110, an anode catalyst layer 120, an anode-side porous transport layer (PTL) 130, an anode-side bipolar plate 140, a cathode catalyst layer 150, a cathode-side PTL 160, and a cathode-side bipolar plate 170.

[0036] AEM 110 can be formed from a variety of materials including certain ionomers (typically including polymers or composites). In some embodiments, AEM 110 comprises a polymeric material (main chain) having cation exchange groups (e.g., cations covalently bonded thereto) tethered thereto. Exemplary but non-limiting materials include materials based on poly(fluorenyl-co-arylpiperidinium) (PFAP) and materials based on polybenzimidazole (e.g., doped with basic salts).

[0037] In some examples, Figure 1 The anode catalyst layer 120 may comprise a cobalt-nickel-phosphorus-based compound (Co-Ni-P). In some examples, the anode catalyst layer 120 may comprise a cobalt-nickel-phosphorus-based compound having about 5% to 95% by weight of Co, about 5% to 95% by weight of Ni, and about 5% to 20% by weight of P. In other examples, the anode catalyst layer 120 may comprise various materials, including but not limited to compounds comprising phosphorus and transition metals (e.g., iron (Fe), cobalt (Co), nickel (Ni)). In various embodiments, the anode catalyst layer 120 comprises a cobalt-phosphorus-based compound (Co-P), an iron-phosphorus-based compound (Fe-P), or a nickel-phosphorus-based compound (Ni-P).

[0038] Figure 1 The cathode catalyst layer 150 may comprise various materials, including but not limited to compounds comprising noble metals (e.g., platinum (Pt), gold (Ag), palladium (Pd), iridium (Ir), rhodium (Rh), ruthenium (Ru)) and their alloys, compounds comprising rare earth oxides (e.g., neodymium (III) oxide), and compounds comprising phosphates and transition metals (e.g., iron (Fe), cobalt (Co), nickel (Ni)). In some examples, the cathode catalyst layer 150 may comprise a cobalt-nickel-phosphorus-based compound having about 5% to 95% by weight of Co, about 5% to 95% by weight of Ni, and about 5% to 20% by weight of P. In some examples, the cathode catalyst layer 150 may comprise a cobalt-nickel-phosphorus-based compound (Co-Ni-P). In other examples, the cathode catalyst layer 150 may comprise various materials, including but not limited to compounds comprising phosphorus and transition metals (e.g., iron (Fe), cobalt (Co), nickel (Ni)). In various embodiments, the cathode catalyst layer 150 includes a cobalt-phosphorus-based compound (Co-P), an iron-phosphorus-based compound (Fe-P), or a nickel-phosphorus-based compound (Ni-P).

[0039] In various examples, the anode catalyst layer 120 and / or the cathode catalyst layer 150 may contain one or more of graphene or graphene oxide from about 0.01 wt% to 5.0 wt%, and / or one or more of the following from about 0.01 wt% to 10.0 wt%: nickel phosphide (NiP), nickel chloride (NiCl2), cobalt phosphide (CoP), cobalt chloride (CoCl2), nickel cobalt phosphide (Co-Ni-P), nickel cobalt phosphide (Ni-Co-P), iridium oxide (IrOx), ruthenium oxide (RuOx), palladium (Pd), and platinum (Pt).

[0040] The anode-side PTL 130 and cathode-side PTL 160 can be formed from various materials that provide high electronic conductivity, high gas diffusion, and optionally high corrosion resistance. In various embodiments, the anode-side PTL 130 and cathode-side PTL 160 may comprise a mesh or matrix formed of a metallic material having a coating comprising a metal or alloy chemically similar to the corresponding anode catalyst layer 120 or cathode catalyst layer 150 (e.g., comprising the same transition metal). In various embodiments, the anode-side PTL 130 and / or cathode-side PTL 160 comprise a mesh formed of, for example, titanium, aluminum, nickel, copper, zinc, or stainless steel (e.g., SS 304, SS 316, SS 430, SSA-286, etc.) and having a coating comprising a transition metal-based compound, such as a cobalt-based alloy, an iron-based alloy, or a nickel-based alloy. In various embodiments, the anode-side PTL 130 and / or the cathode-side PTL 160 may be electrically connected to the corresponding anode catalyst layer 120 or cathode catalyst layer 150, such that the anode-side PTL 130 and / or the cathode-side PTL 160 form part of the corresponding electrode.

[0041] The anode-side bipolar plate 140 and the cathode-side bipolar plate 170 can be formed from a variety of rigid materials, optionally possessing high corrosion resistance. In various embodiments, the anode-side bipolar plate 140 and the cathode-side bipolar plate 170 may comprise metal, ceramic, polymer, or composite plates having a coating thereon, the coating comprising a metal or alloy chemically similar to the corresponding anode catalyst layer 120 or cathode catalyst layer 150 (e.g., comprising the same transition metal). In various embodiments, the anode-side PTL 130 and / or the cathode-side PTL 160 comprise metal plates (e.g., titanium, aluminum, nickel, copper, zinc, or stainless steel (e.g., SS304, SS 316, SS 430, SSA-286, etc.)) having a coating comprising a transition metal-based compound, such as a cobalt-based alloy, an iron-based alloy, or a nickel-based alloy.

[0042] The system and method are not limited to embodiments including ion exchange membranes. For example, in various embodiments, the system may include an anode and a cathode separated by an alkaline electrolyzer configured to exchange anions (e.g., hydroxide ions (OH-)). - The electrolyzer conducts from the cathode to the anode, where hydrogen gas is generated on the cathode side. An exemplary but non-limiting electrolyzer may include a liquid alkaline solution of sodium hydroxide or potassium hydroxide. Figure 2 An exemplary second system 200 configured for electrolysis is presented, the exemplary second system including an electrolytic cell 210, an anode 220, and a cathode 250. The anode 220 and / or cathode 250 may comprise materials such as those pointed out above for the anode catalyst layer 120 and the cathode catalyst layer 150.

[0043] The first system 100 and the second system 200 can be produced using various technologies and technical means. For example, Figure 3 This is a flowchart illustrating a non-limiting method 300 for producing an electrode. Method 300 may begin at 310. At 320, method 300 may include providing an electrodeposition bath containing a precursor solution comprising a nickel-cobalt-phosphorus-based compound. At 330, method 300 may include electrodepositing the precursor solution from the electrodeposition bath onto a substrate to form a coating containing a nickel-cobalt-phosphorus-based compound and thus forming an electrode. The method may end at 340. Various detailed examples of components for the production system 100 are described below.

[0044] In various embodiments, the anode catalyst layer 120 can be formed by providing an ion exchange membrane (e.g., AEM 110) and electroplating a metallic coating thereon. As a specific but non-limiting example, the anode catalyst layer 120 can be formed by providing an AEM 110, positioning at least a portion of the AEM 110 in a nickel cobalt phosphate precursor solution, and depositing a coating comprising, for example, a nickel cobalt phosphate-based alloy on the AEM 110 via an electroplating process. In various embodiments, the anode 220 can be formed by providing a core material (e.g., titanium, stainless steel, etc.), positioning at least a portion of the core material in a nickel cobalt phosphate precursor solution, and depositing a coating comprising, for example, a nickel cobalt phosphate-based alloy on the core material via an electroplating process.

[0045] In various examples, the precursor solution may contain a nickel-cobalt-phosphorus-based compound comprising, for example, about 5% to 95% by weight of Co, about 5% to 95% by weight of Ni, and about 5% to 20% by weight of P. In various examples, the precursor solution may contain about 0.01% to 5.0% by weight of graphene. In various examples, the precursor solution may contain about 0.01% to 10.0% by weight of one or more of the following: nickel phosphide (NiP), nickel chloride (NiCl2), cobalt phosphide (CoP), cobalt chloride (CoCl2), nickel cobalt phosphide (Co-Ni-P), nickel cobalt phosphide (Ni-Co-P), phosphorous acid, hypophosphite, boric acid, iridium oxide (IrOx), ruthenium oxide (RuOx), palladium (Pd), and platinum (Pt).

[0046] In various embodiments, one or more intermediate layers may be provided between the anode catalyst layer 120 and the ion exchange membrane (e.g., AEM 110). For example, in some embodiments, a cobalt-based alloy may be deposited onto the AEM 110 via electroplating, and then the anode catalyst layer 120 may be formed thereon by electroplating a coating comprising, for example, a cobalt-nickel phosphate-based alloy.

[0047] In various embodiments, the cathode catalyst layer 150 can be formed by providing an ion exchange membrane (e.g., AEM 110) and electroplating a metallic coating thereon. As a specific but non-limiting example, the cathode catalyst layer 150 can be formed by providing an AEM 110 and electroplating thereon to produce a coating comprising, for example, a cobalt-based alloy.

[0048] In various embodiments, the anode-side PTL 130 and the cathode-side PTL 160 can be formed by providing a metal wire mesh (e.g., titanium, stainless steel, etc.) and electroplating the metal wire mesh with a metal coating. As a specific but non-limiting example, the anode-side PTL 130 and the cathode-side PTL 160 can be formed by providing a stainless steel wire mesh and electroplating thereon to produce a coating containing a cobalt-based alloy.

[0049] In various embodiments, the anode-side bipolar plate 140 and the cathode-side bipolar plate 170 can be formed by providing a metal plate (e.g., titanium, stainless steel, etc.) and electroplating the metal plate with a metal coating. As a specific but non-limiting example, the anode-side bipolar plate 140 and the cathode-side bipolar plate 170 can be formed by providing a stainless steel plate and electroplating thereon to produce a coating containing a cobalt-based alloy.

[0050] Exemplary materials for certain layers of the anode-side PTL 130, anode-side bipolar plate 140, cathode-side PTL 160, and cathode-side bipolar plate 170, and exemplary methods for depositing certain layers of the anode catalyst layer 120, anode 220, cathode catalyst layer 150, cathode 250, anode-side PTL 130, anode-side bipolar plate 140, cathode-side PTL 160, and cathode-side bipolar plate 170 are disclosed in U.S. Patent Application Publication No. 2019 / 0292674A1 by Ilgar et al., the entire contents of which are incorporated herein by reference.

[0051] The systems disclosed herein (including the first system 100 and the second system 200) provide a method for generating hydrogen and oxygen from water via water electrolysis. For example, Figure 4This is a flowchart illustrating a non-limiting method 400 for generating hydrogen. Method 400 may begin at 410 and provide one or more electrochemical cells, such as those described herein with respect to the first system 100, at 420. An electrolyte solution (e.g., water, KOH, etc.) may be supplied to the electrochemical cells at 430, and a voltage (e.g., 1.23V or higher) may then be applied between the anode (e.g., anode catalyst layer 120) and cathode (e.g., cathode catalyst layer 150) of the electrochemical cells at 440. When the voltage is applied at 440, water in the electrolyte solution decomposes into oxygen (O2) at the anode and into hydrogen (H2) at the cathode. Method 400 may include collecting, storing, and / or using the generated hydrogen and / or generated oxygen at 450. Method 400 may end at 460.

[0052] The systems disclosed herein (including first system 100 and second system 200) may be part of a larger system configured for various purposes, such as hydrogen generation, oxygen generation, and / or power generation. In various embodiments, the system is part of an industrial system configured for hydrogen production. In various embodiments, the system is part of a fuel cell configured for power generation.

[0053] The systems and methods disclosed herein offer various advantages over certain existing systems and methods. For example, embodiments including an anode catalyst layer 120 having a nickel-cobalt-phosphorus-based compound can provide high electrolysis efficiency, improved corrosion resistance relative to, for example, nickel-based or stainless steel-based anodes, and improved abundance and reduced cost relative to, for example, platinum and rare earth oxides.

[0054] In this document, relational terms such as "first" and "second" may be used only to distinguish one entity or action from another, and do not necessarily require or imply any actual such relationship or order between such entities or actions. Unless expressly defined by the language of the claims, numerical ordinal numbers such as "first," "second," "third," etc., merely indicate different individuals among a plurality and do not imply any order or sequence. Unless expressly defined by the language of the claims, any sequence of text in the claims does not imply that the processing steps must be performed in a chronological or logical order according to such a sequence. Without departing from the scope of the invention, the method steps may be interchanged in any order, provided that such interchange does not contradict the language of the claims and is not logically absurd.

[0055] Furthermore, depending on the context, the use of terms such as “connected” or “coupled to” when describing the relationship between different components does not imply that a direct physical connection must be made between these components. For example, two components can be physically, electronically, logically, or in any other way connected to each other by one or more additional components.

[0056] While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be understood that numerous variations exist. It should also be understood that one or more exemplary embodiments are merely examples and are not intended to limit the scope, applicability, or construction of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient roadmap for implementing exemplary embodiments of the invention. It should be understood that various changes can be made to the function and arrangement of the elements described in the exemplary embodiments without departing from the scope of the invention as set forth in the appended claims.

Claims

1. A system for water electrolysis, the system comprising: An electrolyte material configured for anion exchange; A first electrode, the first electrode comprising a nickel-cobalt-phosphorus-based compound; and The second electrode, wherein the first electrode and the second electrode are configured to exchange the anions through the electrolyte material.

2. The system according to claim 1, wherein the electrolyte material is an anion exchange membrane, the first electrode is a first catalyst layer on a first side of the anion exchange membrane, and the second electrode is a second catalyst layer on a second side of the anion exchange membrane opposite to the first side.

3. The system according to claim 1, wherein the electrolyte material is an alkaline solution, and both the first electrode and the second electrode are in contact with the alkaline solution.

4. The system of claim 1, wherein the first electrode comprises: Approximately 5% to 95% by weight of Co; Approximately 5% to 95% by weight of Ni; and Approximately 5% to 20% by weight of P.

5. The system of claim 1, wherein the first electrode comprises about 0.01% to 5.0% by weight of graphene or graphene oxide.

6. The system of claim 1, wherein the first electrode comprises about 0.01% to 10.0% by weight of one or more of the following: nickel phosphide (NiP), nickel chloride (NiCl2), cobalt phosphide (CoP), cobalt chloride (CoCl2), nickel cobalt phosphide (Co-Ni-P), nickel cobalt phosphide (Ni-Co-P), iridium oxide (IrOx), ruthenium oxide (RuOx), palladium (Pd), and platinum (Pt).

7. A method for producing an electrode for water electrolysis, the method comprising: Provides an electrodeposition bath containing a solution of nickel-cobalt-phosphorus-based compounds; as well as The solution is electrodeposited from the electrodeposition bath onto the substrate to form a coating containing the nickel-cobalt-phosphorus-based compound and thus form the electrode.

8. The method of claim 7, wherein the coating comprises: Approximately 5% to 95% by weight of Co; About 5% to 95% by weight of Ni; and Approximately 5% to 20% by weight of P.

9. The method of claim 7, further comprising providing graphene in the solution prior to electrodepositing the solution from the electrodeposition bath onto the substrate, wherein the coating comprises about 0.01 wt% to 5.0 wt% of graphene or graphene oxide.

10. The method of claim 7, further comprising providing one or more compounds comprising one or more of the following: nickel phosphide (NiP), nickel chloride (NiCl2), cobalt phosphide (CoP), cobalt chloride (CoCl2), nickel cobalt phosphide (Co-Ni-P), nickel cobalt phosphide (Ni-Co-P), iridium oxide (IrOx), ruthenium oxide (RuOx), palladium (Pd), and platinum (Pt), wherein the coating comprises from about 0.01% by weight to 10.0% by weight of the one or more compounds.

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