HIGH SURFACE AREA PLATING FOR OXYGEN EVOLUTION ELECTRODES
20250323282 ยท 2025-10-16
Inventors
- Anthony Edwards SULLIVAN (Reading, MA, US)
- Jeremy HITT (Charlestown, MA, US)
- Muhammad NASIR (Revere, MA, US)
- Anne Katherine HICKEY (Cambridge, MA, US)
- Daniel Louis BECERRA (Pittsburgh, PA, US)
- Zachary Dean KAUFMAN (Pittsburgh, PA, US)
Cpc classification
International classification
Abstract
Oxygen evolution electrodes having high surface area plating and methods of forming such oxygen evolution electrodes are described. According to one aspect, an electrode for an oxygen evolution reaction (OER) may include a substrate including at least one surface and a layer of nickel coated on the at least one surface of the substrate. The at least one surface of the substrate has a first surface area, the layer of nickel has a second surface area, and a ratio of the second surface area to the first surface area is greater than about 10:1 and less than about 50:1.
Claims
1. A method of making an oxygen evolution electrode for a metal-air battery, the method comprising: at least partially immersing a cathode and an anode in a solution, the solution including cations of a metal; applying electric current between the cathode and the anode in the solution, the electric current generating bubbles on at least one surface of a substrate of the cathode as the cations of the metal chemically reduce around the bubbles on the at least one surface of the substrate and form a layer of the metal on the at least one surface of the substrate; and with the layer formed on the surface of the substrate, removing the substrate from the solution.
2. The method of claim 1, wherein the solution further includes ammonium cations.
3. The method of claim 1, herein the solution is an aqueous solution, and the bubbles on the at least one surface of the substrate are hydrogen.
4. The method of claim 3, wherein at least partially immersing the cathode and the anode in the solution includes dissolving a metal salt in water.
5. The method of claim 4, wherein the metal salt includes a nickel salt, and the layer formed on the at least one surface of the substrate of the cathode includes nickel.
6. The method of claim 5, wherein the nickel salt includes nickel chloride.
7. The method of claim 3, wherein at least partially immersing the cathode and the anode in the solution includes dissolving ammonium chloride in the aqueous solution.
8. The method of claim 3, wherein at least partially immersing the cathode and the anode in the solution includes dissolving ammonium sulfamate in the aqueous solution.
9. The method of claim 1, wherein at least a portion of the at least one surface of the substrate is flat.
10. The method of claim 1, wherein at least one portion of the at least one surface of the substrate is three-dimensional.
11. The method of claim 10, wherein the at least one portion of the surface of the substrate includes a mesh, defines perforations, or a combination thereof.
12. The method of claim 1, wherein, at least along the surface, the substrate is formed of nickel, steel, copper, or a combination thereof.
13. An electrode for an oxygen evolution reaction (OER), the electrode comprising: a substrate including at least one surface; and a layer of nickel coated on the at least one surface of the substrate, the at least one surface of the substrate has a first surface area, the layer of nickel has a second surface area, and a ratio of the second surface area to the first surface area is greater than about 10:1 and less than about 50:1.
14. The electrode of claim 13, wherein the substrate is formed of nickel, steel, copper, or a combination thereof.
15. The electrode of claim 13, wherein at least a portion of the at least one surface of the substrate is three-dimensional.
16. The electrode of claim 15, wherein at least one portion of the at least one surface of the substrate is a mesh.
17. The electrode of claim 13, wherein the layer of nickel defines a plurality of pores.
18. The electrode of claim 17, wherein at least a subset of the plurality of pores has a size of greater than about 1 micron and less than about 100 microns.
19. The electrode of claim 18, wherein average pore size of the plurality of pores is greater than 20 microns and less than 40 microns.
20. A battery comprising the electrode of claim 13.
Description
DESCRIPTION OF THE DRAWINGS
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[0022] Like reference symbols in the various drawings indicate like elements.
DETAILED DESCRIPTION
[0023] Embodiments will be described in detail with reference to the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. References made to particular examples and implementations are for illustrative purposes and are not intended to limit the scope of the claims. The following description of the embodiments of the disclosure is not intended to limit the disclosure to these embodiments but rather to enable a person skilled in the art to make and use this disclosure. Unless otherwise noted, the accompanying drawings are not drawn to scale.
[0024] As used herein unless specified otherwise, the recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value within a range is incorporated into the specification as if it were individually recited herein.
[0025] The following examples are provided to illustrate various embodiments of the present systems and methods of the present disclosure. These examples are for illustrative purposes, may be prophetic, and should not be viewed as limiting, and do not otherwise limit the scope of the present disclosure.
[0026] The various embodiments of systems, equipment, techniques, methods, activities, and operations set forth in this specification may be used for various other activities and in other fields in addition to those set forth herein. Additionally, these embodiments, for example, may be used with other equipment or activities that may be developed in the future and with existing equipment or activities which may be modified, in-part, based on the teachings of this specification. Further, the various embodiments and examples set forth in this specification may be used with each other, in whole or in part, and in different and various combinations. Thus, for example, the configurations provided in the various embodiments of this specification may be used with each other. Thus, the configurations provided in the various embodiments of this specification may be used with each other. For example, the components of an embodiment having A, A and B and the components of an embodiment having A, C and D can be used with each other in various combination, e.g., A, C, D, and A. A C and D, etc., in accordance with the teaching of this Specification. The scope of protection afforded the present disclosure should not be limited to a particular embodiment, configuration or arrangement that is set forth in a particular embodiment, example, or in an embodiment in a particular figure.
[0027] As used herein, unless stated otherwise, room temperature is 25 C. And, standard temperature and pressure is 25 C. and 1 atmosphere. Unless expressly stated otherwise all tests, test results, physical properties, and values that are temperature dependent, pressure dependent, or both, are provided at standard ambient temperature and pressure.
[0028] Unless otherwise specified or made clear from the context, all references to mean particle size herein shall be understood to refer to mean particle size on a weight percentage basis. Thus, some references to mean particle size herein may occasionally omit specific mention of weight percentage basis for the sake of clarity and readability.
[0029] Embodiments of the present disclosure include apparatuses, systems, and methods for long-duration, and ultra-long-duration energy storage. Herein, long duration and/or ultra-long duration may refer to periods of energy storage of 8 hours or longer, such as periods of energy storage of 8 hours, periods of energy storage ranging from 8 hours to 20 hours, periods of energy storage of 20 hours, periods of energy storage ranging from 20 hours to 24 hours, periods of energy storage of 24 hours, periods of energy storage ranging from 24 hours to a week, periods of energy storage ranging from a week to a year (e.g., such as from several days to several weeks to several months), etc. In other words, long duration and/or ultra-long duration energy storage devices or systems may refer to energy storage devices or systems that may be configured to store energy over time spans of days, weeks, or seasons. For example, the energy storage devices or systems may be configured to store energy generated by solar cells during the summer months, when sunshine is plentiful and solar power generation exceeds power grid requirements, and discharge the stored energy during the winter months, when sunshine may be insufficient to satisfy power grid requirements.
[0030] According to other embodiments, the present invention includes apparatus, systems, and methods for energy storage at shorter durations of less than about 8 hours. For example, the electrochemical cells may be configured to store energy generated by solar cells during the diurnal cycle, where the solar power generation in the middle of the day may exceed power grid requirements, and discharge the stored energy during the evening hours, when the sunshine may be insufficient to satisfy power grid requirements. As another example, said invention may include energy storage used as backup power when the electricity supplied by the power grid is insufficient, for installations including homes, commercial buildings, factories, hospitals, or data centers, where the required discharge duration may vary from a few minutes to several days.
[0031] An electrochemical cell, such as a battery, stores electrochemical energy by using a difference in electrochemical potential generating a voltage difference between the positive and negative electrodes. This voltage difference produces an electric current if the electrodes are connected by a conductive element. In a battery, the negative electrode and positive electrode are connected by external and internal resistive elements in series. Generally, the external element conducts electrons, and the internal element (electrolyte) conducts ions. Because a charge imbalance cannot be sustained between the negative electrode and positive electrode, these two flow streams must supply ions and electrons at the same rate. In operation, the electronic current can be used to drive an external device. A rechargeable battery can be recharged by applying an opposing voltage difference that drives an electric current and ionic current flowing in the opposite direction as that of a discharging battery in service.
[0032] As used herein, the term commercially electroplated nickel surface or grammatical variants thereof shall be understood to refer to a smooth nickel surface, an example of which is shown in
[0033] Referring now to
[0034] The electrochemical cell 100 is merely an example of one electrochemical cell configuration according to various embodiments and is not intended to be limiting. Other configurations, such as electrochemical cells with different type meshes and/or without the mesh 105, electrochemical cells with different type frames and/or without the frame 108, electrochemical cells with different type current collectors and/or without the current collectors 107, electrochemical cells with reservoir structures, electrochemical cells with different type backing plates and/or without the backing plates 106, electrochemical cells with different type insulation and/or without insulation, and/or electrochemical cells with different type heaters and/or without the heater 150, may be substituted for the example configuration of the electrochemical cell 100 shown in
[0035] In some embodiments, a plurality of electrochemical cells 100 in
[0036] Referring now to
[0037] In various embodiments, the electrolyte 20 may be an aqueous or non-aqueous alkaline, neutral, or acidic solution. For example, the electrolyte solution may contain potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH) or combinations of these.
[0038] In some embodiments, a battery 10 may include a separator 16 that allows transfer of ions between the electrodes 12, 14 via the electrolyte. In some embodiments, a separator may be chosen based on an ability to allow selective transfer of desired molecules or materials while substantially limiting or preventing transfer of undesired molecules or materials. For example, some separator membranes are ion-selective and allow the transfer of negative (or positive) ions while substantially preventing transfer of positive (or negative) ions. In other examples, separator materials may be chosen based on an ability to allow or prevent the cross-over of gas bubbles from one side (associated with one electrode) to the opposite side (associated with the counter-electrode).
[0039] In various embodiments, the container 18 may be made of any suitable materials and construction capable of containing the electrolyte, electrodes, and at least a minimum amount of gas pressure. For example, the container 18 may be made of metals, plastics, composite materials, or others. In some embodiments, the battery container 18 may be sealed so as to prevent the escape of any gases generated during operation of the battery.
[0040] In some embodiments, the battery container 18 may include a pressure relief valve to allow release of gases when a gas pressure within the battery container 18 exceeds a pre-determined threshold.
[0041] While the electrodes 12, 14 are shown substantially spaced apart in the figures, in some embodiments the electrodes may be very close to one another or even compressed against one another with a separator 16 in between. Furthermore, although the figures may illustrate a single positive electrode 12 and a single negative electrode 14, battery systems within the scope of the present disclosure may also include two or more positive electrodes 12 and/or two or more negative electrodes 14.
[0042] Referring now to
[0043] Having described certain aspects of the electrochemical cell 100 and the battery 10, attention is now directed to the description of certain aspects of the positive electrode 103 and the positive electrode 12. For example, the positive electrode 103 and/or the positive electrode 12 may be an oxygen evolution electrode (OEEs) (also sometimes referred to as oxygen evolution reaction (OER) electrode). An OEE produces oxygen (O.sub.2) gas via electrolysis.
[0044] Referring now to
[0045] In use, as compared to smoother layers of nickel formed using commercial nickel electroplating (such as the commercially electroplated nickel surface shown in
[0046] Competing considerations of manufacturing cost and electrochemical performance are effectively balanced at a ratio of the second surface area of layer 254 of nickel to the first surface area of the at least one surface 252 of the substrate 250 greater than about 10:1 and less than about 50:1 (with approximations at each end of the range intended to account for manufacturing tolerances). Specifically, ratios below 10:1 do not demonstrate significant performance improvement relative to the degenerate case of a commercially nickel electroplated surface. Further, or instead, ratios greater than 50:1 increase cost-namely, materials cost and capital equipment cost required for handling high-current density associated with the techniques described herein-without corresponding gains in improvement in performance relative to ratios greater than about 10:1 and less than about 50:1.
[0047] In instances of the electrode 212 having a ratio of the second surface area of layer 254 of nickel to the first surface area of the at least one surface 252 of the substrate 250 in the range of greater than about 10:1 and less than about 50:1, the layer 254 of nickel may define a plurality of pores 253 such that the structure of the layer 254 of nickel is cauliflower-like, including micron-sized nodules making up a larger porous framework (as shown in
[0048] In general, the substrate 250 may be formed of any one or more materials upon which nickel may be electroplated and, further or instead, may be in any one or more shapes of the electrode 212 corresponding to end-use in a particular configuration of an electrochemical cell (e.g., the electrochemical cell 100 in
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[0050] As shown in step 462, the exemplary method 460 may include at least partially immersing a cathode 471 and an anode 472 in a solution 474. The solution 474 may include cations of a metal (e.g., nickel), and the cathode 471 may include the substrate 250 to be coated. For example, the solution 474 may include ammonium cations. Continuing with this example, the cations of the metal may correspond to cations of any metal compatible with ammonium cations in the solution 474. As described above, the substrate 250 may be any one or more of various different shapes, sizes, and/or materials useful for cost-effectively accommodating a particular end-use. Thus, in some instances, at least a portion of the at least one surface 252 of the substrate 250 may be flat. Additionally, or alternatively, at least a portion of the at least one surface 252 of the substrate 250 may be three-dimensional. For example, the at least one portion of the at least one surface 252 of the substrate may include a mesh, define perforations, or a combination thereof. Further, or instead, at least along the at least one surface 252 of the substrate 250, the substrate 250 may be formed of nickel, steel, copper, or a combination thereof.
[0051] In certain implementations, the solution 474 may be aqueous such that the bubbles generated on the at least one surface 252 of the substrate 250, as described in greater detail below, are hydrogen. For example, at least partially immersing the cathode 471 and the anode 472 in the solution 474 in step 462 may include dissolving a metal salt in water. As a specific example, the metal salt may include a nickel salt such that the layer 254 formed on the at least one surface 252 of the substrate 250 of the cathode 471 includes nickel. In some instances, the nickel salt may include nickel chloride. Additionally, or alternatively, at least partially immersing the cathode 471 and the anode 472 in the solution 474 may include dissolving ammonium chloride in the solution 474 in instances in which the solution 474 is an aqueous solution. Dissolving ammonium chloride in the solution 474 in such instances may be useful for balancing competing considerations associated with using current to achieve rapid plating of the metal while also current to achieve robust formation of bubbles (hydrogen bubbles in the case of ammonium chloride in an aqueous solution). That is, although the addition of ammonium chloride to the solution 474 in instances in which the solution is aqueous decreases the concentration of the metal cations in the solution 474, the reaction of the ammonium cations favors hydrogen generation such that current may be used efficiently to achieving rapid plating around a significant concentration of bubbles on the at least one surface 252 of the substrate 250, as described in greater detail below. While the use of ammonium chloride in the solution 274 has been described as being useful for achieving balance between plating and bubble generation, it shall be appreciated that dissolving other material (e.g., ammonium sulfamate) that forms ammonium cations in the aqueous solution may be additionally or alternatively used to achieve such a balance.
[0052] As shown in step 464, the exemplary method 460 may include applying electric current between the cathode 471 and the anode 472 in the solution 474. For example, the electric current may be applied between the substrate 250 and the anode 472 using a power supply 476. The electric current may generate bubbles on the at least one surface 252 of the substrate 250 of the cathode 471 as the cations of the metal chemically reduce around the bubbles on the at least one surface 252 of the substrate 250 and form the layer 254 of the metal on the at least one surface 252 of the substrate 250. That is, the bubbles on the at least one surface 252 of the substrate 250 form a scaffold around which the cations of the metal in the solution 474 chemically reduce to form the layer with a rough texture that corresponds to high surface area of the metal in the layer.
[0053] As shown in step 466, the exemplary method 460 may include, with the layer formed on the surface of the substrate, removing the substrate from the solution.
[0054] The foregoing method descriptions are provided merely as illustrative examples and are not intended to require or imply that the steps of the various embodiments must be performed in the order presented. As will be appreciated by one of skill in the art the order of steps in the foregoing embodiments may be performed in any order. Words such as thereafter, then, next, etc. are not necessarily intended to limit the order of the steps; these words may be used to guide the reader through the description of the methods. Further, any reference to claim elements in the singular, for example, using the articles a, an or the is not to be construed as limiting the element to the singular.
[0055] The preceding description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the described embodiment. Further, any step of any embodiment described herein can be used in any other embodiment. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the following claims and the principles and novel features disclosed herein.