This disclosure is directed to electrolyzers in general and, in particular, to a gas diffusion layer for an electrolyzer and method of making thereof.
Proton exchange membrane (PEM) electrolyzers may be used to convert water into separate hydrogen and oxygen streams. Such PEM electrolyzers include a PEM polymer electrolyte located between an anode and a cathode. Anode side and cathode side porous gas diffusion layers are located adjacent to the respective anode and cathodes.
In one embodiment, an anode gas diffusion layer for a PEM electrolyzer may include a porous stainless steel sheet formed by a powder metallurgical technique.
In another embodiment, a PEM electrolyzer includes an anode side flow plate, a cathode side flow plate, and a PEM polymer electrolyte located between the anode side flow plate and the cathode side flow plate. The PEM electrolyzer may further include an anode gas diffusion layer including a porous stainless steel sheet or a porous niobium sheet located between the PEM polymer electrolyte and the anode side flow plate, an anode located between the anode gas diffusion layer and the electrolyte, a cathode gas diffusion layer located between the electrolyte and the cathode side flow plate, and a cathode located between the cathode gas diffusion layer and the electrolyte.
In another embodiment, a method of making a porous stainless steel sheet configured to function as water/gas separator for a PEM electrolyzer by a powder metallurgical technique includes providing a mixture of stainless steel powder and lubricant into a die cavity, compressing the mixture of stainless steel powder and lubricant in the die cavity to form a green sheet, de-binding the green sheet, and sintering the green sheet to form the porous stainless steel sheet.
Aspects of this disclosure are best understood from the following detailed description when read with the accompanying figures. It is noted that, in accordance with the standard practice in the industry, various features are not drawn to scale. In fact, the dimensions of the various features may be arbitrarily increased or reduced for clarity of discussion.
The disclosed embodiments are described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments are shown. The foregoing may, however, be embodied in many different forms and should not be construed as being limited to the exemplary embodiments set forth herein.
All documents mentioned herein are hereby incorporated by reference in their entirety. References to items in the singular should be understood to include items in the plural, and vice versa, unless explicitly stated otherwise or clear from the text. Grammatical conjunctions are intended to express any and all disjunctive and conjunctive combinations of conjoined clauses, sentences, words, and the like, unless otherwise stated or clear from the context. Thus, the term “or” should generally be understood to mean “and/or,” and the term “and” should generally be understood to mean “and/or.”
Recitation of ranges of values herein are not intended to be limiting, referring instead individually to any and all values falling within the range, unless otherwise indicated herein, and each separate value within such a range is incorporated into the specification as if it were individually recited herein. The words “about,” “approximately,” or the like, when accompanying a numerical value, are to be construed as including any deviation as would be appreciated by one of ordinary skill in the art to operate satisfactorily for an intended purpose. Ranges of values and/or numeric values are provided herein as examples only, and do not constitute a limitation on the scope of the described embodiments. The use of any and all examples or exemplary language (“e.g.,” “such as,” or the like) is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of those embodiments. No language in the specification should be construed as indicating any unclaimed element as essential to the practice of the disclosed embodiments.
As described in U.S. Pat. No. 9,118,040, the PEM fuel cell of
The oxygen screen/frame assembly 18 shown in
Thus, the electrically insulating porous separator 12 that is described in U.S. Pat. No. 9,118,040 requires formation of through-holes 14 to establish electrical contact of the mating structures 28, 30, which adds extra expense and fabrication steps in the fuel cell stack 10.
As shown in
The anode side flow plate 52 may include a water inlet opening 58, an oxygen outlet opening 60, and the fluid flow channel 56 (e.g. a tortuous path groove) connecting the water inlet opening 58 and the oxygen outlet opening 60 in the side of the anode side flow plate 52 facing the anode gas diffusion layer 66. The fluid flow channel 56 may be located on a surface of the anode side flow plate that is configured to face the anode gas diffusion layer 66.
The anode gas diffusion layer 66 may include a porous stainless steel layer, as described in greater detail below. The cathode gas diffusion layer 70 may include a porous carbon layer. The anode 68 may include any suitable anode catalyst, such as an iridium layer. The cathode 72 may include any suitable cathode catalyst, such as a platinum layer. Other noble metal catalyst layers may also be used for the anode and/or cathodes. The polymer electrolyte 64 may include any suitable proton exchange (e.g., hydrogen ion transport) polymer membrane, such as a Nafion® membrane, which may include a sulfonated tetrafluoroethylene based fluoropolymer-copolymer having a formula C7HF13O5SC2F4.
In operation, water is provided into the fluid flow channel 56 through the water inlet opening 58. The water flows through the fluid flow channel 56 and through the anode gas diffusion layer 66 to the anode 68. The water is electrochemically separated into oxygen and hydrogen at the anode 68 upon application of an external current or voltage between the anode 68 and the cathode 72. The oxygen diffuses back through the anode gas diffusion layer 66 to the anode side flow plate 52 and exits the PEM electrolyzer 50 through the oxygen outlet opening 60. Hydrogen ions diffuse through the polymer electrolyte 64 to the cathode 72 and then exit the PEM electrolyzer 50 through the cathode gas diffusion layer 70 and the hydrogen outlet opening 62 in the cathode side flow plate 54.
A porous stainless steel layer (e.g., sheet) may be used as the anode gas diffusion layer 66 (i.e., transport layer). Conventional porous stainless steel sheet production methods include tape casting and screen printing followed by sintering. Stainless steels are a family of iron-based alloys that contain a minimum of approximately 11% chromium, and also include carbon (e.g., from 0.03% to greater than 1.00%), and one or more of nitrogen, aluminum, silicon, sulfur, titanium, nickel, copper, selenium, niobium, and/or molybdenum.
In other embodiments, the porous stainless steel layer (e.g., sheet) that is used as the anode gas diffusion layer 66 is formed by a powder metallurgical technique, in which stainless steel powder is pressed into a porous stainless steel sheet using a compaction process. The compacted sheet is then sintered to yield the anode gas diffusion layer 66 with an established metallurgical bond. The porous stainless steel sheet may have a porosity in a range from approximately 40% to approximately 60%.
Operations in a powder metallurgy compaction cycle may include lowering the lower punch 104 from an elevated position to expose a die cavity 106 as shown, for example, in
The compacted green stainless steel sheet 114 may be provided onto a moving belt (not shown) which moves the compacted green stainless steel sheet 114 through one or more belt furnaces (not shown). The compacted green stainless steel sheet 114 may first be annealed at a first temperature in a de-binding process to burn out the organic lubricant (i.e., binder), followed by annealing at a second (e.g., greater) temperature to sinter the de-lubricated stainless steel sheet. The resulting sintered porous stainless steel sheet may then be positioned in the electrolyzer (e.g., the PEM electrolyzer 50 of
In one embodiment, the porosity of the anode gas diffusion layer 66 may be selected to provide a bubble point pressure of at least 10 pounds per square inch (psi), such as 10 to 60 psi. For example, the average pore size (e.g., diameter) may be less than 5 microns, such as 1 to 3 microns in the porous stainless steel sheet. While a porous stainless steel sheet is described above, in an alternative embodiment, the porous sheet may include a porous niobium sheet.
In one embodiment shown in
The porosity difference may be a continuous porosity gradient in which the porosity increases continuously from the first major side 66a to the second major side 66b (i.e. between opposing major surfaces). Alternatively, the porosity may change in a stepwise fashion such that the first major side 66a and the second major side 66b of the anode gas diffusion layer 66 have different respective porosities from one another. To form different porosity regions, a different amount of lubricant may be added to top and bottom sections of the stainless steel powder 112 in the die cavity 106 in a continuous gradient or in a stepwise manner. The anode gas diffusion layer 66 may have a greater porosity in the first major side 66a that is made from a powder section containing a greater lubricant concentration than in the second major side 66b that is made from a powder section containing a lower lubricant concentration.
The lubricant concentration in the die cavity 106 may be formed by two or more different passes of the powder shoe 110 in which the stainless steel powder 112 to lubricant ratio is different (e.g., higher or lower) in different passes. The die cavity 106 may be partially filled during a first pass of the powder shoe 110 with a first portion of the mixture of the stainless steel powder 112 and lubricant having a first ratio of stainless steel powder 112 to lubricant. The die cavity 106 may then be further filled during a second pass of the powder shoe 110 with a second portion of the mixture of the stainless steel powder 112 and lubricant. The second portion may have a second ratio of stainless steel powder 112 to lubricant that is different from the first ratio. A lower ratio of stainless steel powder 112 to lubricant results in a higher porosity during the de-binding anneal operation.
In another embodiment, the formation of the anode gas diffusion layer 66 (e.g., see
In another embodiment, a noble metal coating (e.g., gold or platinum group metal coating) may be formed on the anode gas diffusion layer 66 during the powder metallurgy process. Forming such a coating during the powder metallurgy process may streamline the process of forming such a coating and may further reduce a cost associated with the coating. To form a coating in this way, for example, a noble metal powder may be provided into the die cavity 106 below and above the stainless steel powder 112. The powder mixture may then be compressed using the upper punch 102 and the lower punch 104, as described above with reference to
In an example embodiment, the die cavity 106 may be partially filled with a noble metal powder and lubricant mixture during a first pass of the powder shoe 110. Then, in a second pass of the powder shoe 110, the die cavity 106 may be additionally filled with a stainless steel powder 112 and lubricant mixture. Lastly, in a third pass the of the powder shoe 110, the die cavity 106 may be filed with a noble metal powder and lubricant mixture. The process may be simplified by using two or more powder shows 110 each having respective different powders or powder mixtures. For example, a first powder shoe 110 having the noble metal powder and lubricant mixture may be used during the first and the third passes. Similarly, a second powder shoe 110 filled with the stainless steel powder and lubricant mixture may be used during the second shoe pass. In this way, a noble metal/stainless steel/noble metal powder tri-layer may be formed in the die cavity 106. The tri-layer may be then compressed to form a porous stainless steel plate coated on both major surfaces by the noble metal.
In another embodiment, a different de-binding and sintering protocol may be used to obtain a continuous noble metal coating on the first major side 66a and on the second major side 66b of the anode gas diffusion layer 66 (e.g., see
In another embodiment, the method of forming the anode gas diffusion layer 66 may include control of silicide formation. For example, some metal alloys form silicide phases during sintering (e.g., see J. D. Bolton, M. Youseffi & B. S. Becker (1998) Silicide Phase Formation and Its Influence on Liquid Phase Sintering in 316L Stainless Steel with Elemental Silicon Additions, Powder Metallurgy 41:2, (1998) 93-101, available at https://www.tandfonline.com/doi/abs/10.1179/pom.1998.41.2.93, which incorporated herein by reference in its entirety). For example, silicon addition to 316L stainless steel causes liquid silicide phase formation during sintering. The liquid silicide phases generate large pores in the stainless steel parts after sintering is completed.
In one embodiment, the powder metallurgy process may be carried out using a stainless steel powder 112 with a silicon content that is less than 0.1 weight percent silicon (e.g., 0 to 0.01 weight percent silicon). In this way, the substantial absence of silicon in the stainless steel powder 112 avoids or reduces formation of bulk stainless steel silicide phases and/or surface silicide phases. Thus, undesirable surface properties of the anode gas diffusion layer 66 may be avoided.
In another embodiment, silicide formation control may include a using stainless steel powder 112 with at least 1 weight percent silicon (e.g., 1 to 10 weight percent silicon) dispersed throughout the die cavity 106 in the powder metallurgy process used to form the anode gas diffusion layer 66. In this way, bulk silicide phases may be intentionally formed throughout a thickness of the anode gas diffusion layer 66 during sintering (e.g., liquid phase sintering). Such bulk silicide phases may act to increase pore formation. Thus, the porosity of the anode gas diffusion layer 66 may be increased by intentionally generating silicide-phase pores during sintering. The resulting bulk silicide phases may be distributed throughout the anode gas diffusion layer 66, and as such, may not be concentrated on the surface of the anode gas diffusion layer 66. In this way, undesirable surface effects due to surface silicide phases may be avoided or reduced.
Thus, in some embodiments, the porous stainless steel sheet may have a porosity that is in a range from approximately 40% to approximately 60%. The porous stainless steel sheet may have an average pore size of less than 5 microns or may have an average pore size of 1 to 3 microns. The anode gas diffusion layer may include a first major side that has a greater porosity than an opposite second major side of the porous stainless steel sheet. The first major side of the porous stainless steel sheet may be configured to face an anode side flow plate, and the second major side of the porous stainless steel sheet may be configured to face an anode. The first major side of the porous stainless steel sheet may have a porosity that is at least 10 percent greater than a porosity of the opposite second major side of the porous stainless steel sheet. In other embodiments, the porous stainless steel sheet may have continuous porosity gradient in which the porosity increases continuously from the first major side to the second major side. The porous stainless steel sheet may further include a noble metal coating. The porous stainless steel sheet may further include bulk and/or surface silicide phases.
It will be appreciated that the methods and systems described above are set forth by way of example and not of limitation. Numerous variations, additions, omissions, and other modifications will be apparent to one of ordinary skill in the art. In addition, the order or presentation of method operations in the description and drawings above is not intended to require this order of performing the recited operations unless a particular order is expressly required or otherwise clear from the context. Thus, while particular embodiments have been shown and described, it will be apparent to those skilled in the art that various changes and modifications in form and details may be made therein without departing from the scope of the disclosure.
This application claims the benefit of Provisional Patent Application No. 63/074,866, filed on Sep. 4, 2020, the entire contents of which are incorporated herein by reference.
Number | Date | Country | |
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63074866 | Sep 2020 | US |