Systems and methods for producing hydrogen gas
Patent Information
- Application Number
- JP2024520565
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2021-10-05
- Filing Date
- 2022-10-05
- Publication Date
- 2025-10-14
AI Technical Summary
Existing hydrogen gas production methods face challenges in achieving low carbon emissions and high efficiency, with high energy costs and inefficiencies due to resistive losses, electrode overpotentials, and capital costs.
The system employs a controlled electrolyzer with dynamic current density adjustment and optimized electrolyzer cell design, including baffles, ribs, and welds to manage gas and electrolyte flow, reducing power dissipation and temperature fluctuations, and using ion exchange membranes to enhance efficiency.
This approach reduces overall plant capital expenditures and operating costs while achieving efficient, low-energy hydrogen production with lower carbon emissions.
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Abstract
Description
[Technical field]
[0001] This application claims priority under 35 U.S.C. Section 119(e) to U.S. Provisional Application No. 63 / 252,552, filed October 5, 2021, and entitled “LOW COST HYDROGEN GAS PRODUCTION,” the disclosure of which is incorporated herein by reference in its entirety. [Background technology]
[0002] As electricity production transitions to lower carbon dioxide (CO2) emitting technologies, the ability to convert electricity into low or zero carbon transportation fuels is becoming an increasingly important challenge to mitigating global CO2 emissions. Among such fuel options, hydrogen gas (H2) has an inherent advantage in that its oxidation product is water. Thus, hydrogen gas represents a low carbon transportation fuel if it can be produced with low carbon emissions. Summary of the Invention [Means for solving the problem]
[0003] This disclosure describes systems and methods relating to the production of hydrogen gas (H2) via water electrolysis. In particular, this disclosure describes systems and methods that may enable low overall plant capital expenditures and provide reduced operating expenses for the production of H2 gas by water electrolysis, for example, on a cost per kilowatt or cost per H2 production capacity basis.
[0004] In one aspect, the present disclosure provides an electrolytic cell system comprising one or more electrolytic cell cells, each comprising a first half cell with a first electrode and a second half cell with a second electrode, and a controller for controlling a current applied through the one or more electrolytic cell cells, the controller controlling a current density to about 150 mA / cm 2 ~Approx. 3,000mA / cm 2and a controller configured to set the current density to a first value when a first condition is satisfied and to a second value when a second condition is satisfied.
[0005] In some embodiments of the foregoing aspect, the first value is at or below a first percentage of a maximum capacity current density of the electrolyzer cell and the second value is at or above a second percentage of a maximum capacity current density of the electrolyzer cell.
[0006] In some embodiments of the aforementioned aspect, the first percentage is 20% or less of the maximum capacity current density.
[0007] In some embodiments of the aforementioned aspect, the second percentage is 80% or greater of the maximum capacity current density.
[0008] In some embodiments of the aforementioned aspect, the first half-cell includes a tray, one or more ribs on an interior side of the tray, and a baffle plate coupled to the one or more ribs, the baffle plate partitioning a volume within the tray and providing an ascending region on a first side of the tray adjacent the first electrode and a descending region on a second side of the baffle plate opposite the first side.
[0009] In some implementations of the aforementioned aspects, the riser region encourages gas formed in the first electrode to rise and avoid the formation of gas pockets, and the faller region encourages a downward flow of electrolyte solution, the upward flow of gas and downward flow of electrolyte solution causing circulation within the reservoir that encourages thermal equilibrium within the electrolyte and reduced temperature fluctuations.
[0010] In some embodiments of the aforementioned aspects, the first half-cell includes a tray, a manifold positioned inside the tray, and an outlet tube exiting the manifold for electrolyte to exit the tray, the cross-sectional area of the manifold being configured such that electrolyte flow rate and gas flow rate through the manifold are sufficiently low to avoid slug or plug flow.
[0011] In some examples of the aforementioned aspects, the first half cell includes a tray, one or more ribs positioned vertically inside the tray, and a plurality of welds welding the first electrode to the one or more ribs, the plurality of welds forming a distributed array of welds across the electrodes that distributes current across the electrodes during operation of the electrochemical cell.
[0012] In some embodiments of the foregoing aspect, each electrolyzer cell further comprises a separator between the first half cell and the second half cell, and the number, size, and location of the plurality of welds are such that an impact of power dissipation as a function of temperature of the separator is reduced so as to reduce damage due to high localized temperatures.
[0013] In another aspect, an electrolyzer system includes a plurality of electrolyzer cells, each electrolyzer cell including a first half-cell with a first electrode, a second half-cell with a second electrode, and a separator separating the first half-cell from the second half-cell. The electrolyzer system further includes a current density through each of the plurality of electrolyzer cells of about 150 mA / cm. 2 ~Approx. 3,000mA / cm 2 and a power supply configured to apply a current through each of the plurality of electrolyzer cells such that the current density of each of the plurality of electrolyzer cells is within a current density range of 750 mA / cm. 2 a first current density range at or below 1 mA / cm 2 and a controller for dynamically controlling between a first current density range or greater and a second current density range or greater.
[0014] In some embodiments of the aforementioned aspect, the first half-cell includes a tray, one or more ribs on an interior side of the tray, and a baffle plate coupled to the one or more ribs, the baffle plate partitioning a volume within the tray and providing an ascending region on a first side of the tray adjacent the first electrode and a descending region on a second side of the baffle plate opposite the first side.
[0015] In some embodiments of the aforementioned aspects, the first half-cell includes a tray, a manifold positioned inside the tray, and an outlet tube exiting the manifold for electrolyte to exit the tray, the cross-sectional area of the manifold being configured such that electrolyte flow rate and gas flow rate through the manifold are sufficiently low to avoid slug or plug flow.
[0016] In some examples of the aforementioned aspects, the first half cell includes a tray, one or more ribs positioned vertically inside the tray, and a plurality of welds welding the first electrode to the one or more ribs, the plurality of welds forming a distributed array of welds across the electrodes that distributes current across the electrodes during operation of the electrochemical cell.
[0017] In some embodiments of the foregoing aspect, each electrolyzer cell further comprises a separator between the first half cell and the second half cell, and the number, size, and location of the plurality of welds are such that an impact of power dissipation as a function of temperature of the separator is reduced so as to reduce damage due to high localized temperatures.
[0018] In another aspect, a method for conducting electrolysis comprises increasing the current density associated with operation of the electrolytic cell to about 0.15 A / cm 2 ~3.0A / cm 2 wherein the change in current density associated with operation of the electrolytic cell is responsive to a change in demand for electricity in the region in which the electrolytic cell is located, and the change in current density includes dynamically changing the current density from about 0.15 A / cm to about 0.25 A / cm when the demand for electricity in the region in which the electrolytic cell is located increases. 2 ~3.0A / cm2 and reducing the current density to within a range of values of about 0.15 A / cm when the demand for electricity in the area in which the electrolytic cell is located decreases. 2 ~3.0A / cm 2 and increasing the value of the signal within a range of
[0019] In some embodiments of the aforementioned aspects, the change in demand occurs over a period of time when demand is increasing or decreasing.
[0020] In some embodiments of the aforementioned aspects, the increase or decrease in demand includes an increase and a decrease in demand within a period of time.
[0021] In some embodiments of the aforementioned aspects, the average demand over a period of time is increased compared to another period of time.
[0022] In some embodiments of the aforementioned aspects, the average demand over a period of time is reduced compared to another period of time.
[0023] In some embodiments of the aforementioned aspects, the time period is a time period during which demand typically increases or decreases.
[0024] In some embodiments of the aforementioned aspects, the period of time is during a particular time within a day.
[0025] In some embodiments of the aforementioned aspects, the electrolytic cell comprises at least two separate electrolytic cell cells.
[0026] In some embodiments of the aforementioned aspects, the electrolytic cell has a diameter of at least about 2.5 m. 3 The total size is:
[0027] In some embodiments of the foregoing aspects, as demand for electricity increases in the region in which the electrolyser is located, operating expenses for the electrolyser will increase unless the current density is reduced.
[0028] In another aspect, a method for conducting electrolysis includes the steps of: (a) reducing a current density associated with operation of the electrolytic cell to 20% or less of a maximum capacity of the electrolytic cell current density when the demand for electricity increases in a region in which the electrolytic cell is located; and (b) increasing a current density associated with operation of the electrolytic cell to 80% or more of a maximum capacity of the electrolytic cell current density when the demand for electricity decreases in a region in which the electrolytic cell is located.
[0029] In some implementations of the aforementioned aspects, during periods of increasing or decreasing demand, the demand for electricity increases or the demand for electricity decreases.
[0030] In some embodiments of the aforementioned aspects, the increase or decrease in demand includes an increase and a decrease in demand within a period of time.
[0031] In some embodiments of the aforementioned aspects, the average demand over a period of time is increased compared to another period of time.
[0032] In some embodiments of the aforementioned aspects, the average demand over a period of time is reduced compared to another period of time.
[0033] In some embodiments of the aforementioned aspects, the time period is a time period during which demand typically increases or decreases.
[0034] In some embodiments of the aforementioned aspects, the period of time is during a particular time within a day.
[0035] In some embodiments of the aforementioned aspects, the electrolytic cell includes at least two separate cells.
[0036] In some embodiments of the foregoing aspects, the electrolytic cell has a length of at least 2.5 m 3 The total size is:
[0037] In some embodiments of the foregoing aspects, as demand for electricity increases in the region in which the electrolyser is located, operating expenses for the electrolyser will increase unless the current density is reduced. [Brief description of the drawings]
[0038] The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments discussed in the present document.
[0039] [Figure 1] FIG. 1 is a schematic diagram of an exemplary electrolyzer cell for the electrolysis of water to produce hydrogen gas.
[0040] [Diagram 2] FIG. 2 is a schematic diagram of a stack comprising multiple electrolyzer cells configured for the electrolysis of water to produce hydrogen gas.
[0041] [Diagram 3] FIG. 3 is a front view of an exemplary pan assembly that may form an anode half cell, a cathode half cell, or both, in an electrolyzer cell.
[0042] [Figure 4] FIG. 4 is a side view of the exemplary basin assembly of FIG.
[0043] [Diagram 5] FIG. 5 is an enlarged perspective view of a top portion of the exemplary basin assembly of FIGS. 3 and 4, showing the manifold of the basin assembly.
[0044] [Figure 6] FIG. 6 is an enlarged side view of the manifold of the exemplary basin assembly of FIGS.
[0045] [Figure 7] FIG. 7 is a first perspective view conceptually illustrating electrolyte flow into the manifold of the exemplary pan assembly of FIGS.
[0046] [Figure 8] FIG. 8 is a second perspective view conceptually illustrating electrolyte flow into the manifold of the exemplary pan assembly of FIGS.
[0047] [Figure 9] FIG. 9 is a side view of a second exemplary pan assembly that may form an anode half cell, a cathode half cell, or both, in an electrolyzer cell.
[0048] [Figure 10] 10 is a front view of the second exemplary basin assembly of FIG.
[0049] [Figure 11] FIG. 11 is a perspective view of the second exemplary basin assembly of FIGS. 9 and 10 showing details of a baffle assembly located within the second exemplary basin assembly.
[0050] [Figure 12] FIG. 12 is a perspective view of the second exemplary basin assembly of FIGS. 9 and 10 with an electrode coupled to the baffle assembly.
[0051] [Figure 13] FIG. 13 is a cross-sectional side view of the second exemplary basin assembly of FIGS. 9 and 10 and a corresponding cross-sectional side view of a comparative basin assembly that does not include a baffle assembly.
[0052] [Figure 14] FIG. 14 is a schematic side view showing a simulated flow distribution of electrolyte in the second exemplary pan assembly of FIGS. 9 and 10 compared to a comparative flow distribution in a comparative pan assembly.
[0053] [Figure 15] FIG. 15 is a perspective view of a baffle plate that may form part of the baffle assembly in the second pan assembly of FIGS.
[0054] [Figure 16]FIG. 16 is a front view of a third exemplary pan assembly that may form an anode half cell, a cathode half cell, or both, in an electrolyzer cell.
[0055] [Figure 17] 17 is a cross-sectional side view of the third exemplary basin assembly of FIG. 16. FIG.
[0056] [Figure 18] FIG. 18 is an enlarged cross-sectional side view of the third exemplary basin assembly of FIGS.
[0057] [Figure 19] FIG. 19 is a perspective view of the third example basin assembly of FIGS. 16 and 17 showing details of one or more ribs within the third example basin assembly.
[0058] [Figure 20A] 20A-20C show perspective views of various alternative rib configurations for the third exemplary basin assembly of FIGS. [Figure 20B] 20A-20C show perspective views of various alternative rib configurations for the third exemplary basin assembly of FIGS. [Figure 20C] 20A-20C show perspective views of various alternative rib configurations for the third exemplary basin assembly of FIGS.
[0059] [Figure 21] FIG. 21 is a schematic diagram of an exemplary electrolyzer cell with an electrolyte temperature control system.
[0060] [Figure 22] FIG. 22 is a graph of an exemplary electricity price over the course of a typical 24 hour period.
[0061] [Diagram 23]FIG. 23 is a graph showing one example of the operation of an electrolyzer cell for the generation of hydrogen gas in accordance with the load harvesting and load shedding methods of the present disclosure.
[0062] [Figure 24] FIG. 24 is a graph showing the cost per kilogram of hydrogen gas produced for an exemplary electrolyzer cell and the improvement that can be achieved by generating hydrogen gas according to the load harvesting and load shedding methods of the present disclosure.
[0063] [Diagram 25] FIG. 25 is a graph showing optimal operating current densities for an exemplary electrolyzer cell at various electricity prices. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0064] Detailed Description The following detailed description includes references to the accompanying drawings, which form a part of the detailed description. The drawings show, by way of example, specific embodiments in which the present invention may be practiced. These embodiments, also referred to herein as "examples", are described in sufficient detail to enable those skilled in the art to practice the present invention. The exemplary embodiments may be combined, other embodiments may be utilized, or structural and logical changes may be made without departing from the scope of the present invention. While the disclosed subject matter will be described in conjunction with the enumerated claims, it is understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter. The following detailed description is therefore not to be taken in a limiting sense, and the scope of the present invention is defined by the appended claims and their equivalents.
[0065] References herein to "one embodiment," "an embodiment," "an example embodiment," and the like indicate that a described embodiment may include a particular feature, structure, or characteristic, but not all embodiments may necessarily include that particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Moreover, when a particular feature, structure, or characteristic is described in connection with one embodiment, it is understood that this is within the knowledge of one of ordinary skill in the art to affect such feature, structure, or characteristic in connection with other embodiments, whether or not explicitly described.
[0066] Values expressed in range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as limits of the range, but also all individual numerical values or subranges contained within the range as if each numerical value and subrange were explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1% by weight to about 5% by weight, but also the individual concentrations (e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, and 3.3% to 4.4%) within the range indicated. The description "about X to Y" has the same meaning as "about X to about Y" unless otherwise indicated. Similarly, the description "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z" unless otherwise indicated.
[0067] As used herein, the terms "a," "an," or "the" are used to include "one or more than one" unless the context clearly dictates otherwise. The term "or" is used to refer to a non-exclusive "or" unless otherwise indicated. Unless otherwise indicated, the phrase "at least one of," when referring to a listed group, is used to mean any combination of one or two or more of the group members. For example, the statement "at least one of A, B, and C" can have the same meaning as "A, B, C, A and B, A and C, B and C, or A, B, and C," or the statement "at least one of D, E, F, and G" can have the same meaning as "D, E, F, G, D and E, D and F, D and G, E and F, E and G, F and G, D, E, and F, D, E, and G, D, F, and G, E, F, and G, or D, E, F, and G." Commas can be used to the left or right of the decimal symbol as a separator or digit grouping symbol, e.g., "0.000,1" is equivalent to "0.0001."
[0068] In the methods described herein, steps can be performed in any order without departing from the principles of the invention, except when a time or sequence of operations is explicitly recited. Furthermore, the steps defined can be performed in parallel, unless express language recites them to be performed separately. For example, the recited act of doing X and the recited act of doing Y can be performed simultaneously in a single operation, and the resulting process would fall within the literal scope of the process. Recitation in a claim to the effect that a first step is performed, and then several other steps are subsequently performed, shall be taken to mean that the first step is performed before any of the other steps, but that the other steps may be performed in any suitable sequence, unless the sequence is further recited within the other steps. For example, a claim element reciting "step A, step B, step C, step D, and step E" shall be interpreted to mean that step A is performed first and step E is performed last, and that steps B, C, and D may be performed in any sequence between steps A and E (including one or more steps being performed in parallel with step A or step E) and the sequence still falls within the literal scope of the claimed process. A given step or subset of the steps may also be repeated.
[0069] Moreover, recited steps can be performed in parallel unless express claim language recites them as being performed separately. For example, a claimed step of doing X and a claimed step of doing Y can be performed simultaneously in a single operation, and the resulting process would fall within the literal scope of the claimed process.
[0070] The term "about" as used herein can allow for a degree of variation within a value or range, e.g., within 10%, within 5%, within 1%, within 0.5%, within 0.1%, within 0.05%, within 0.01%, within 0.005%, or within 0.001% of a stated value, or within a stated limit of a range, inclusive of the exact value or range stated.
[0071] The term "substantially" as used herein refers to a "majority of" or "mostly," such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or greater, or 100%.
[0072] In addition, phraseology or terminology employed herein and not otherwise defined should be understood to be for purposes of description only and not for purposes of limitation. Furthermore, all publications, patents, and patent documents referred to herein are incorporated herein by reference in their entirety as if individually incorporated by reference. In the event of inconsistent usage between this document and those documents so incorporated by reference, the usage in the incorporated references should be considered to support that of this document, and in the event of irreconcilable inconsistencies, the usage in this document shall prevail.
[0073] Hydrogen gas (H2) can be formed electrochemically by a water splitting reaction in which water is split into oxygen gas (O2) and H2 gas at the anode and cathode of an electrochemical cell, respectively. Examples of such electrochemical processes include, but are not limited to, proton electrolyte membrane (PEM) electrolysis and alkaline water electrolysis (AWE). In such electrochemical reactions, the operating energy required to drive the water splitting electrolysis reaction is high due to additional energy costs as a result of various energy inefficiencies. For example, to reduce unwanted migration of ionic species between the electrodes, the cathode and anode may be separated by a separator, such as a membrane, which can reduce the migration of ionic species. Although the separator can improve the overall efficiency of the cell, this may come at the cost of additional resistive losses within the cell, which in turn increases the operating voltage. Other inefficiencies in water electrolysis may include solution resistive losses, electrical conduction inefficiencies, and / or electrode overpotentials, among others. These various inefficiencies and the capital costs associated with minimizing them may play a role in the economic feasibility of H2 generation via water splitting electrolysis.
[0074] The methods and systems provided herein relate to a unique electrochemical process that results in efficient, low-cost, and low-energy production of H2 gas.
[0075] Electrolyser Cell FIG 1 is a schematic diagram of a typical water electrolyzer cell 100 that uses electrical power to convert water into hydrogen and oxygen, as illustrated in FIG 1. In one embodiment, the electrolyzer cell 100 comprises two half-cells, a first half-cell 111 and a second half-cell 121. In one embodiment, the first and second half-cells 111, 121 are separated by a separator 131, such as a membrane 131. In one embodiment, the separator 131 comprises a porous or ion-exchange membrane 131. In the embodiment in which the separator 131 comprises an ion-exchange membrane, the ion-exchange membrane can be of different types, such as an anion-exchange membrane (AEM), a cation-exchange membrane (CEM), a proton-exchange membrane (PEM), a bipolar ion-exchange membrane (BEM), an ion-solvation membrane (ISM), or a microporous or nanoporous membrane.
[0076] In embodiments where the separator 131 is a cation exchange membrane, the cation exchange membrane can be a conventional membrane, such as those available from Asahi Kasei Corp. (Tokyo, Japan), or from Membrane International Inc. (Glen Rock, NJ, USA), or from Chemours Company (Wilmington, DE, USA). Examples of cation exchange membranes include, but are not limited to, membranes sold by Chemours Company under the trade name N2030WX, and membranes sold by Asahi Kasei Corp. under the trade names F8020 / F8080 or F6801. Examples of materials that can be used to form the cation exchange membrane include, but are not limited to, cation membranes that include perfluoropolymers containing anionic groups, such as sulfonic acid groups and / or carboxylic acid groups. However, it should be understood that in some embodiments, depending on the need to restrict or allow migration of certain cations or anionic species between electrolytes, cation exchange membranes that are more restrictive and therefore restrict migration of one species of cation while allowing migration of another species of cation may be used. Similarly, in some embodiments, depending on the need to restrict or allow migration of certain anion species between electrolytes, anion exchange membranes may be used that are more restrictive, thus allowing migration of one species of anion while restricting migration of another species of anion. Such restrictive cation and anion exchange membranes are commercially available and can be selected by one of skill in the art.
[0077] In some embodiments, the separator 131 can be selected such that it can function in acidic and / or alkaline electrolyte solutions, as appropriate. Other properties for the separator 131 that may be desirable include, but are not limited to, high ionic selectivity, low ionic resistance, high burst strength, and high stability in electrolyte solutions within a temperature range of room temperature up to 150° C. or higher.
[0078] In one embodiment, the separator 131 is stable within a temperature range of about 0°C to about 150°C, e.g., about 0°C to about 100°C, about 0°C to about 90°C, etc., for example, about 0°C to about 80°C, about 0°C to about 70°C, etc., for example, about 0°C to about 60°C, about 0°C to about 50°C, etc., for example, about 0°C to about 40°C, or about 0°C to about 30°C, etc.
[0079] To achieve a desired product or products in the electrolyte solution, it may be useful to use ion-specific ion exchange membranes that allow migration of one type of ion (e.g., cations for CEMs and anions for AEMs) but not another, or one type of ion and another.
[0080] In one embodiment, the first half cell 111 includes a first electrode 112, which may be located proximate to a separator 131, and the second half cell 121 includes a second electrode 122, which may be located proximate to the separator 131, for example, on the opposite side of the separator 131 from the first electrode 112. In one embodiment, the first electrode 112 is an anode for the electrolyzer cell 100 and the second electrode 122 is a cathode for the electrolyzer cell 100, and thus, in the remainder of this disclosure, the first half cell 111 may also be referred to as the anode half cell 111, the first electrode 112 may also be referred to as the anode 112, the second half cell 121 may also be referred to as the cathode half cell 121, and the second electrode 122 may also be referred to as the cathode 122. Each of the electrodes 112, 122 can be coated with one or more electrocatalysts to accelerate the reaction towards hydrogen gas (H2 gas) and / or oxygen gas (O2 gas). Examples of electrocatalysts include, but are not limited to, highly dispersed metals or alloys of platinum group metals such as platinum, palladium, ruthenium, rhodium, iridium, or combinations thereof such as platinum-rhodium, platinum-ruthenium, nickel mesh coated with ruthenium oxide (RuO2), or high surface area nickel.
[0081] The ohmic resistance of the separator 131 can affect the voltage drop across the anode 112 and the cathode 122. For example, as the ohmic resistance of the separator 131 increases, the voltage across the anode 112 and the cathode 122 can increase, and vice versa. In some embodiments, the separator 131 has a relatively low ohmic resistance and a relatively high ionic mobility. In some embodiments, the separator 131 has a relatively high hydration characteristic that increases with temperature, thus decreasing the ohmic resistance. By selecting a separator 131 with a lower ohmic resistance, as known in the art, the voltage drop across the anode 112 and the cathode 122 at a specified temperature can be reduced.
[0082] In one embodiment, the anode 112 is electrically connected to an external positive conductor 116, and the cathode 122 is electrically connected to an external negative conductor 126. When a separator 131 is wetted and in electrolytic contact with the electrodes 112 and 122, and an appropriate voltage is applied across the conductors 116 and 126, O2 gas is liberated at the anode 112 and H2 gas is liberated at the cathode 122. In one configuration, an electrolyte, for example, consisting of a solution of KOH in water, is pumped into the half cells 111, 121. For example, the electrolyte can flow into the anode half cell 111 through a first electrolyte inlet 114 and into the cathode half cell 121 through a second electrolyte inlet 124. In one embodiment, the flow of electrolyte through the anode half cell 111 traps the produced O2 gas as gas bubbles 113 that exit the anode half cell 111 through a first outlet 115. Similarly, the flow of electrolyte through the cathode half cell 121 can trap the produced H2 gas as bubbles 123 that can exit the cathode half cell 121 through a second outlet 125. The gas can be separated from the electrolyte downstream of the electrolyzer cell 100 using one or more suitable separators. In an embodiment, the produced H2 gas is dried and collected in a high pressure canister or pumped into a further process element. The O2 gas can simply be allowed to vent to the atmosphere or can be stored for other uses. In an embodiment, the electrolyte is recirculated back into the half cells 111, 121 as needed.
[0083] In one embodiment, a controller 128 can be included and can control the current applied through the electrolyzer cell 100 (e.g., by controlling the voltage applied across conductors 116 and 126). In one embodiment, the controller 128 can be configured to control the operating current density for the cell 100 (e.g., by applying a current corresponding to a desired current density based on the area of the cell 100) such that the current density for the cell 100 can be controlled (e.g., for load harvesting or load shedding, as described in more detail below).
[0084] In one embodiment, a typical voltage across the electrolyzer cell 100 is about 1.5 volts (V) to about 3.0 V. In one embodiment, the operating current density for the electrolyzer cell 100 is about 0.1 A / cm 2 ~About 3A / cm 2 Each cell 100 has a size large enough to produce very large quantities of H2 gas when operated at these current densities. In one embodiment, the cross-sectional area of each cell 100 (e.g., width x height for a rectangular cell) is about 0.25 square meters (m 2 ) ~ approx. 15m 2 , about 1m 2 ~about 5m 2 etc., for example, about 2m 2 ~about 4m 2 , about 2.25m 2 ~about 3m 2 etc., approximately 2.5m 2 ~ approx. 2.9m 2 In one embodiment, the total volume (e.g., width x height x depth) of each cell is approximately 0.1 cubic meters (m 3 ) ~ approx. 2m 3 , about 0.15m 3 ~about 1.5m 3 etc., for example, about 0.2 m 3 ~ approx. 1m 3 , about 0.25m 3 ~about 0.5m 3 etc., for example, about 0.275 m 3 ~about 0.3m 3 In one embodiment, the total volume of the entire electrolyzer system (e.g., the combined volume of all cells in all stacks in a plant) is about 1 m 3 ~about 200m 3 , about 2m 3 ~ approx. 100m 3 etc., for example, about 2.5m 3 ~About 50m 3 It is.
[0085] As will be appreciated by those skilled in the art, operating a power bus at such low voltages and high current densities can be very inefficient. Thus, typically, multiple electrolyzer cells 100 are assembled and electrically connected in series into an electrolyzer stack. Each of the multiple cells 100 can operate at lower / higher voltages and the same current densities than a single electrolyzer cell 100, making the system much more efficient. In an embodiment, the electrolyzer stack can include about five (5) electrolyzer cells 100 to about 500 electrolyzer cells 100, for example, eighty (80) electrolyzer cells 100 or more, connected in series to provide the electrolyzer stack.
[0086] Electrolyser Stack FIG. 2 shows a schematic diagram of a portion of such an electrolyzer stack 130 of electrolyzer cells 132A-132N (collectively referred to as "electrolyzer cells 132" or "electrolyzer cells 132"). Each cell 132 in the stack 130 can have any one of the structures described above with respect to the exemplary electrolyzer cell 100 of FIG. 1, for example, with one or both of the anode half cell 111 and the cathode half cell 121. In addition, each cell 132 can include one or more cell assemblies (e.g., comprising one or more pan assembly structures described below). As will be understood by one of ordinary skill in the art, the cell assembly structures (i.e., for each pan assembly) can provide for lower overall cost H2 production as described herein.
[0087] In one embodiment, the electrolyzer cells 132 are electrically connected in series with the conductors 304. In one embodiment, the stack 130 comprises a number of electrolyzer cells 132 connected in series, such as fifty (50) or more electrolyzer cells 132, sixty (60) or more electrolyzer cells 132, seventy (70) or more electrolyzer cells 132, eighty (80) or more electrolyzer cells 132, ninety (90) or more electrolyzer cells 132, one hundred (100) or more electrolyzer cells 132, one fifty (150) or more electrolyzer cells 132, two hundred (200) or more electrolyzer cells 132, three hundred (300) or more electrolyzer cells 132, etc. The individual electrolyzer cells 132 in the exemplary electrolyzer stack 130 are labeled with reference numerals 132A-132N, with only the first electrolyzer cell 132A, the second electrolyzer cell 132B, and the last electrolyzer cell 132N being shown in FIG. 2. In one embodiment, the electrical positive conductor of one cell 132A (e.g., the positive conductor 116 in FIG. 1) is electrically connected to the electrical negative conductor of the subsequent cell 132B (e.g., the negative conductor 126 in FIG. 1) using a connecting conductor 134, with the following exceptions: (a) the positive conductor of the last cell 132N at the highest voltage is connected to the power supply 136; and (2) the negative conductor of the first cell 132A at the lowest voltage is connected to the electrical circuit ground 138. In one embodiment, the power supply 136 is a constant current voltage limiting rectifier that converts grid AC power to a suitable DC power level. In one embodiment, the power supply 136 can be controlled by a controller (similar to the controller 128, described above with respect to FIG. 1 ) configured to control the current density of the electrolyzer cells 132 in the stack 130, e.g., to enable the stack to be dynamically operated with respect to load acquisition or load shedding in response to increases and decreases in demand and / or price of electricity (as described in more detail below).
[0088] Electrolyzer Cell Pan Assembly The physical configuration of the electrolyzer cell 100 can be any physical structure configured to allow for the liberation of oxygen gas at the anode 112 and hydrogen gas at the cathode 122. In one embodiment, the electrolyzer cell 100 is adapted to handle high current densities (e.g., 2 A / cm 2 The electrolyzer cell 100 may comprise components that can dynamically operate at high current densities (such as 100 sq. m or higher). By providing operation at high current densities, the electrolyzer cell 100 may enable operators to meet their targeted production rates with fewer cells, thereby reducing capital costs. Additionally, by allowing the electrolyzer cell 100 to dynamically operate over a wide range of operating current densities, the electrolyzer cell 100 may provide operators with high turndown ratios, which may enable operators to maximize production when power prices are low and reduce power consumption when power prices are high (as described in more detail below).
[0089] Operation of electrolyzer cells at high current densities can pose significant challenges, such as, but not limited to, large gas volumes produced at high current densities, significant temperature and pressure ramps, membrane erosion or fatigue, large amounts of heat generated within the cell, and / or high electrolyte flow rates. Thus, in an embodiment, each electrolyzer cell 100 can include configurations of anode and / or cathode pan assemblies that can overcome one or more of these challenges, such as, but not limited to, reducing or minimizing large temperature fluctuations of the electrolyte along the height of the cell, reducing or minimizing masking of the nominal active area with gas, reducing or minimizing the formation of stagnant gas pockets that can result in localized drying of the membrane, and / or reducing or minimizing significant pressure ramps due to slug or plug flow at the cell outlet.
[0090] Due to the large gas volume, static gas pockets may form on the electrodes or at the top of the cell. Providing a high electrolyte flow rate and taking advantage of features that cause gas levitation and generate high local shear rates can help minimize static gas pocket formation on the electrodes. However, the high electrolyte flow rate combined with the large production of gas and the large amounts of electrolyte solution entering and exiting the cell presents significant challenges associated with slug and plug flow. This type of flow can be reduced or minimized by using a defined manifold and outlet tube configuration, which is described in more detail below.
[0091] In some embodiments, a pan assembly can be used on the anode or cathode side of the electrolyzer cell 100. The pan assembly includes an effective collection system at the top of the cell and can minimize, and in some cases prevent, the formation of large stagnant gas pockets at the top of the cell. In some embodiments, the collection system includes a manifold and an outlet tube with a large cross-sectional area that effectively provides space for gas to collect and electrolyte to flow through while also reducing or minimizing the possibility of membrane masking and / or slug or plug flow. The pan assembly can provide two-phase (gas / liquid) flow that is effectively directed out of the cell.
[0092] The pan assembly, manifold, and outlet tubing are designed to ensure that the flow is uniform or substantially uniform across the width of the cell and that there is minimal pressure increase or decrease within the cell. Flow uniformity drives the need to ensure that the back pressure associated with the flow entering the manifold significantly exceeds the pressure drop along the length of the manifold, and thus the pressure within the manifold exceeds the pressure drop exiting the manifold. Maintaining an essentially constant internal pressure distribution drives the requirement to avoid slug or plug flow through the manifold and outlet tubing. Thus, the pan assembly, including the manifold and outlet tubing, can provide reliable cell operation across a wide range of electrolyte flows and high current densities.
[0093] As the current density is increased in the cell, the power dissipation can also rise dramatically. Large spatial and / or temporal temperature variations can damage the membrane. The contribution of the internal power dissipation to the cell's internal temperature distribution can be reduced or minimized through operating conditions such as the maintenance temperature, the flow rate of the inlet electrolyte, and / or the recirculation of the inlet electrolyte. A high electrolyte flow rate can provide a large amount of convective heat transfer within the cell, thereby helping to reduce or minimize the heat buildup and associated temperature rise within the cell that may otherwise result from an increase in current density. In an embodiment, the pan assembly of the electrolyzer cell includes a baffle plate configuration inside the pan assembly that can reduce or minimize the impact of increasing or decreasing power dissipation on the cell's internal temperature by helping to ensure that the electrolyte remains isothermal or substantially isothermal along the height of the cell, and thus thermal equilibrium is quickly achieved after the operating current density is changed.
[0094] In the typical electrolyzer cell 100 described above with respect to FIG. 1 , the anode half cell 111 can include an anode pan assembly that includes an anode 112 and an anode electrolyte (also referred to as “anolyte”). Similarly, the cathode half cell 121 can include a cathode pan assembly that includes a cathode 122 and a cathode electrolyte (also referred to as “catholyte”). The anode pan assembly and the cathode pan assembly can be separated by a separator 131 (e.g., a diaphragm, a membrane electrode assembly (MEA), one or more ion exchange membranes (IEM), or another type of membrane or separator). The anode pan assembly and / or the cathode pan assembly can include components such as collection systems that collect gases and electrolyte for outflow from the cell 100. The separator assembly may include one or more of an anion exchange membrane (AEM), a cation exchange membrane (CEM), or another separator, depending on the desired reactions at the anode 112 and cathode 122. Between these components, various additional separator components may be provided, for example, to separate the membrane 131 from the anode 112, to separate the membrane 131 from the cathode 122, and to provide mechanical integrity to the membrane or other separator structures. In addition to these components, individual gaskets or gasket tapes may be provided between and along the periphery of the components to seal the compartments from fluid leakage.
[0095] In one embodiment, all of the components described above are aligned parallel or near-parallel to one another, and optional perimeter bolting may be provided to stack them together in the electrochemical cell 100. In a filter press configuration, no perimeter bolting may be required. In a stack of electrochemical cells, the anode 112 of one electrochemical cell 100 can be electrically connected with the cathode 122 of an adjacent electrochemical cell. Electrical current is passed through the stack of electrochemical cells during operation.
[0096] 3-8 show several views of an exemplary pan assembly 140 that may be used as an anode pan assembly for the anode half cell 111 or as a cathode pan assembly for the cathode half cell 121 in the electrolyzer cell 100 shown in FIG. 1 or in one of the individual electrolyzer cells 132 in the stack 130 of FIG. 2. FIG. 3 is a front view of the pan assembly 140 and FIG. 4 is a cross-sectional view of the pan assembly 140. It should be understood that in the electrochemical cell 100 or 132, the pan assembly 140 may be used as an anode pan assembly or a cathode pan assembly or both, depending on the needs and reactions at the anode 112 and cathode 122. Components next to the cell, such as the anode 112 or cathode 122, can be placed on top of the pan assembly 140 shown in the front view of FIG. 3.
[0097] As illustrated in Figures 3 and 4, the pan assembly 140 includes a pan 142. Inside the depth of the pan 142 and at the top of the pan 142, a manifold 144 (shown in Figure 4) is housed. The manifold 144 can be connected to one or more outlet tubes 146 depending on the requirements for the electrolyzer cells 100. For example, the design can incorporate two, three, four, or more outlet tubes 146 on each pan assembly 140 on the same or both sides of the pan 142 to minimize the cell thickness and maximize the number of cells 100 that can fit within a particular size electrolyzer frame. Figures 5 and 6 show enlarged details of the manifold 144 and outlet tubes 146.
[0098] In one embodiment, the depth D of the manifold 144 ManifoldThe cross-sectional area of the manifold 144 and / or the size of the outlet tube 146 are selected such that the pan assembly 140 provides a relatively large cross-sectional area of the manifold 144 to not only reduce or minimize the occurrence of slug and plug flow in a two-phase system, but also to provide sufficient space between the walls of the manifold 144 and the electrode (e.g., the anode or cathode, depending on whether the pan assembly 140 forms an anode pan or cathode pan) that is placed above the pan 142 for gas and electrolyte to have unimpeded flow and for the membrane to remain wet. Manifold And / or the cross-sectional area of the manifold 144 and / or the size of the outlet tube 146 can also dictate the overall thickness of the cell 100 .
[0099] In one embodiment of the basin assembly 140, the manifold 144 is spaced apart from the depth D of the basin 142. Pan Approximately 0.25 (25%) to approximately 0.75 (75%) of the depth D Pan Approximately 0.25 (25%) to approximately 0.6 (60%) of the depth D of the tray 142 Pan For example, the depth D of the tray 142 is about 0.25 (25%) to about 0.5 (50%). Pan Approximately 0.25 (25%) to approximately 0.4 (40%) of the depth D of the tray 142 Pan For example, the depth D of the tray 142 is about 0.25 (25%) to about 0.3 (30%). Pan Approximately 0.3 (30%) to approximately 0.75 (75%) of the depth D of the tray 142 Pan For example, the depth D of the tray 142 is about 0.3 (30%) to about 0.6 (60%). Pan Approximately 0.3 (30%) to approximately 0.5 (50%) of the depth D of the tray 142 Pan For example, the depth D of the tray 142 is about 0.3 (30%) to about 0.4 (40%). Pan Approximately 0.4 (40%) to approximately 0.75 (75%) of the depth D of the tray 142 Pan For example, the depth D of the tray 142 is about 0.4 (40%) to about 0.6 (60%). Pan Approximately 0.4 (40%) to approximately 0.5 (50%) of the depth D of the tray 142 PanFor example, the depth D of the tray 142 is about 0.5 (50%) to about 0.75 (75%). Pan Approximately 0.5 (50%) to approximately 0.6 (60%) of the depth D of the tray 142 Pan 5 and 6 ) is about 0.6 (60%) to about 0.75 (75%) of Manifold has.
[0100] In one embodiment, manifold 144 has an upwardly tapered portion at the top (seen in most detail in FIG. 6 ) that creates an interior volume or area above the upper edge of membrane 131, located next to the electrode, that provides a small area for the gas-rich mixture to form without causing membrane 131 to dry out.
[0101] An exemplary flow path for gas and electrolyte mixing through the pan assembly 140 is shown in Figures 7 and 8 by dotted line 148. As can be seen in Figures 7 and 8, in one embodiment, the two-phase gas and electrolyte flow path 148 passes upward from the main portion of the pan 142, to the top of the manifold 144, then through a set of notches 150 in the top of the manifold 144, and downward into the manifold 144. The gas and electrolyte can then exit through an exit tube 146.
[0102] To accommodate the large volumes of gas and electrolyte solution flowing through the manifold 144 and outlet tube 146, e.g., due to high current densities and high flow rates, and to reduce or minimize the occurrence of slug and plug flow, in one embodiment, the cross-sectional area of the manifold 144 and outlet tube 146 is large enough to maintain a superficial liquid velocity of the electrolyte of about 0.35 m / sec or less, e.g., about 0.25 m / sec or less, about 0.2 m / sec or less, such as about 0.15 m / sec or less, about 0.1 m / sec or less, such as about 0.08 m / sec or less, about 0.05 m / sec or less, such as about 0.01 m / sec or less. The cross-sectional area of the manifold 144 and the outlet tube 146 is large enough to maintain a superficial gas velocity (e.g., O2 gas from the anode pan or H2 gas produced from the cathode pan) of about 5 m / sec or less, e.g., about 4.5 m / sec or less, about 4 m / sec or less, etc., such as about 3.5 m / sec or less, about 3 m / sec or less, etc., such as about 2.5 m / sec or less, about 2 m / sec or less, etc., such as about 1.5 m / sec or less, about 1 m / sec or less.
[0103] As described herein, in some embodiments, the cross-sectional area of the manifold 144 (e.g., the depth D of the pan 142) can be adjusted to accommodate high current densities and high flow rates. Pan Depth D of manifold 144 of about 0.25 (25%) to about 0.75 (75%) Manifold The dimensions of the 12.5" x 12.5" x 12.5" (mm 2 ) ~ approx. 6,200mm 2 For example, about 520 mm 2 ~ approx. 6,000mm 2 , about 520mm 2 ~ approx. 5,000mm 2 For example, about 520 mm 2 ~ approx. 4,000mm 2 , about 520mm 2 ~ approx. 3,000mm2 For example, about 520 mm 2 ~ approx. 2,000mm 2 , about 520mm 2 ~ approx. 1,000mm 2 For example, about 600 mm 2 ~Approx. 6,200mm 2 , about 600 mm 2 ~ approx. 6,000mm 2 For example, about 600 mm 2 ~ approx. 5,000mm 2 , about 600 mm 2 ~ approx. 4,000mm 2 For example, about 600 mm 2 ~ approx. 3,000mm 2 , about 600 mm 2 ~ approx. 2,000mm 2 For example, about 600 mm 2 ~ approx. 1,000mm 2 , about 800 mm 2 ~Approx. 6,200mm 2 For example, about 800 mm 2 ~ approx. 6,000mm 2 , about 800 mm 2 ~ approx. 5,000mm 2 For example, about 800 mm 2 ~ approx. 4,000mm 2 , about 800 mm 2 ~ approx. 3,000mm 2 For example, about 800 mm 2 ~ approx. 2,000mm 2 , about 800 mm 2 ~ approx. 1,000mm 2 For example, about 1,000 mm 2 ~Approx. 6,200mm 2 , about 1,000 mm 2 ~ approx. 6,000mm 2 For example, about 1,000 mm 2 ~ approx. 5,000mm 2 , about 1,000 mm 2 ~ approx. 4,000mm 2 For example, about 1,000 mm 2 ~ approx. 3,000mm 2 , about 1,000 mm 2 ~ approx. 2,000mm 2For example, about 2,000 mm 2 ~Approx. 6,200mm 2 , about 2,000 mm 2 ~ approx. 6,000mm 2 For example, about 2,000 mm 2 ~ approx. 5,000mm 2 , about 2,000 mm 2 ~ approx. 4,000mm 2 For example, about 2,000 mm 2 ~ approx. 3,000mm 2 , about 3,000 mm 2 ~Approx. 6,200mm 2 For example, about 3,000 mm 2 ~ approx. 6,000mm 2 , about 3,000 mm 2 ~ approx. 5,000mm 2 For example, about 3,000 mm 2 ~ approx. 4,000mm 2 , about 4,000 mm 2 ~ approx. 62,000mm 2 For example, about 4,000 mm 2 ~ approx. 6,000mm 2 , about 4,000 mm 2 ~ approx. 5,000mm 2 For example, about 5,000 mm 2 ~Approx. 6,200mm 2 , about 5,000 mm 2 ~ approx. 6,000mm 2 etc.
[0104] In some embodiments where the cross-sectional area of the manifold 144 is as listed above, the outlet tube 146 fluidly connected to the manifold 144 may be about 26 millimeters (mm) to about 89 mm, e.g., about 26 mm to about 80 mm, about 26 mm to about 75 mm, etc., such as about 26 mm to about 70 mm, about 26 mm to about 60 mm, etc., such as about 26 mm to about 50 mm, about 26 mm to about 40 mm, etc., such as about 26 mm to about 30 mm, about 30 mm to about 89 mm, etc., such as about 30 mm to about 80 mm, about 30 mm to about 75 mm, etc., such as about 30 mm to about 70 mm, about 30 mm to about 60 mm, etc., such as about 30 mm to about 50 mm. m, about 30 mm to about 40 mm, for example, about 40 mm to about 89 mm, about 40 mm to about 80 mm, for example, about 40 mm to about 75 mm, about 40 mm to about 70 mm, for example, about 40 mm to about 60 mm, about 40 mm to about 50 mm, for example, about 50 mm to about 89 mm, about 50 mm to about 80 mm, for example, about 50 mm to about 75 mm, about 50 mm to about 70 mm, for example, about 50 mm to about 60 mm, about 60 mm to about 89 mm, for example, about 60 mm to about 80 mm, about 60 mm to about 75 mm, for example, about 70 mm to about 89 mm, about 70 mm to about 80 mm, for example, about 70 mm to about 75 mm Outlet (shown in FIG. 5).
[0105] One skilled in the art will appreciate that what may be considered a "high electrolyte flow rate" may be compared to the size of the electrochemical cell 100. For a relatively narrow cell, e.g., about 300 mm to about 600 mm wide, a "high flow rate" may correspond to a flow rate of about 200 kg / hr, while for a large commercial size cell, e.g., about 2 meters (m) to about 3 m wide, a "high flow rate" may correspond to a flow rate of about 800 kg / hr or more, e.g., about 1,000 kg / hr or more, about 1,350 kg / hr or more, etc., e.g., about 1,500 kg / hr or more, about 1,750 kg / hr or more, e.g., about 2,000 kg / hr or more, about 2,250 kg / hr or more, etc., e.g., about 2,500 kg / hr or more, about 2,700 kg / hr or more, etc. The cross-sectional area of the manifold 144, the cross-sectional area of the outlet tube 146, and / or the baffle assembly can accommodate the high electrolyte flow rates and high gas flow rates associated with operation at high current densities as described herein, and can provide superficial liquid velocities of about 0.2 m / sec or less and gas flow rates of about 3 m / sec or less so that slug and plug flows are unlikely to develop.
[0106] In some examples, the pan assembly can include a baffle assembly inside the pan assembly, which can reduce or minimize the effects of high current density and / or fluctuating power dissipation on the internal temperature profile along the height of the electrolyzer cell. The baffle assembly can be suspended within the pan assembly, for example, between the back pan wall and the electrode. In an example, the baffle assembly includes one or more ribs inside the pan. The one or more ribs can include one or more notches. A baffle plate with one or more slots can be included and configured to fit over the one or more ribs such that corresponding structures of the baffle plate can fit into the one or more notches of the one or more ribs.
[0107] 9-15 show several views of a pan assembly 160, including an exemplary baffle assembly 162. Similar to the pan assembly 140 described above with respect to FIGS. 3-8, the pan assembly 160 can be used as a structure for one or both of the anode half cell 111 and the cathode half cell 121 in the electrolyzer cell 100 of FIG. 1. For example, if the pan assembly 160 is used to form a portion of the anode half cell 111, the pan assembly 160 can be an anode pan assembly. Similarly, if the pan assembly 160 is used to form a portion of the cathode half cell 121, the pan assembly 160 can be a cathode pan assembly. Like the pan assembly 140, the pan assembly 160 includes a pan 164 (e.g., an anode pan and / or a cathode pan) and an outlet tube 166. The pan assembly 160 can also include a manifold 168 through which the electrolyte and produced gases can flow before exiting the pan assembly 160 through an exit tube 166, which can be similar to or the same as the manifold 144 described above with respect to the pan assembly 140. In other words, the pan assemblies that form either the anode assembly or the cathode assembly, or both, can include features of both the pan assembly 140 described above with respect to Figures 3-8 and the pan assembly 160 described below.
[0108] In one embodiment, the baffle assembly 162 of the basin assembly 160 includes a baffle plate 170 that fits within the basin 162. In one embodiment, the baffle plate 170 includes one or more slots 172 (seen in best detail in FIG. 10). Each slot 172 can interact with a corresponding rib 174 (shown in FIGS. 9, 11, and 12), with the one or more ribs 174 and the baffle plate 170 forming the baffle assembly 162. The baffle plate 170 can have any number of slots 172 depending on the number of ribs 174 in the baffle assembly 162. The number of slots can be, for example, 1 to about 200 in the baffle plate 170. The baffle plate 170 can be fitted over the ribs 174 in the basin 164. In certain embodiments, the one or more ribs 174 are perpendicular or substantially perpendicular to the baffle plate 170 and to the overall orientation of the pan 164. In other words, in certain embodiments, the baffle plate 170 is parallel or substantially parallel to a major surface of the pan 164, such as a back wall 178 of the pan 164. An electrode 176 associated with the pan assembly 160 (e.g., the anode 112 if the pan assembly 160 is an anode pan assembly, or the cathode 122 if the pan assembly 160 is a cathode pan assembly) can be attached to the top of the pan assembly 160, e.g., on the side of the baffle assembly 162 opposite the back wall 178 of the pan 164.
[0109] In one embodiment, the one or more ribs 174 can each include one or more structures for positioning the baffle plate 170 relative to the basin 164 and / or relative to the electrode 176. In one embodiment, these structures include one or more notches on each rib 174 that slidably engage with corresponding slots 172 on the baffle plate 170 to position the baffle plate 170 relative to the basin 164 such that the baffle plate 170 is suspended relative to the electrode 176 and / or relative to a back wall 178 of the basin 164 at a location defined by the baffle plate 170, as can be seen, for example, in Figures 9, 11, and 12. The notches in the ribs 174 are not visible in the figures because the notches are filled with the baffle plate 170. The distance of the baffle plate 170 from the electrode 176 and from the back wall 178 of the basin 164 can be changed by modifying the depth of the notches along the ribs 174 .
[0110] The positioning of the slots 172 within the baffle plate 170, the length of the slots 172, and / or the distance between the slots 172 can affect the fitting of the baffle plate 170 onto one or more ribs 174. In one embodiment, the baffle plate 170 is a solid plate with the slots 172 formed therein, as shown in most detail in FIG. 10. In other embodiments, the baffle plate can be an expanded metal plate or mesh. In one embodiment, the baffle plate 170 is made from a conductive metal, such as, but not limited to, nickel, stainless steel, and the like. In another embodiment, the baffle plate 170 is made from a polymeric material. In either case, the baffle plate 170 can be configured to snap into place using features on the ribs 174.
[0111] As previously described, the contribution of internal power dissipation to the internal temperature distribution within the electrolyzer cell 100 can be reduced or minimized through operating conditions such as the temperature and flow rate of electrolyte flowing through the half cells 111, 121 (e.g., through the pan assembly 160 forming the half cells 111, 121). A high electrolyte flow rate can help increase, and in some embodiments, maximize, convective heat transfer within the electrolyzer cell 100, thereby reducing or minimizing heat buildup and corresponding associated temperature rise within the cell 100 that may otherwise result from the high current densities described herein. As discussed above, operating at high electrolyte flow rates and high current densities can lead to slugging or plug flow at the cell outlet, which can result in pressure build-up and down that may shorten the life of the membrane 131. The pan assemblies 140, 160 described herein, along with the manifold 144 and outlet configurations and / or baffle assemblies 162, are designed to reduce or minimize slug and plug flow. In particular, the baffle assembly 162 can provide mixing of the electrolyte as it flows through the pan assembly 160 and enhance convective heat transfer within the electrolyte during electrolysis.
[0112] In some embodiments, the baffle assembly 162 is designed and positioned in such a way that gas produced at the electrode 176 may mix with the electrolyte on the side of the baffle plate 170 closest to the electrode 176, resulting in a relatively low density column and defining a riser section. The low density mixture may rise relatively quickly through the riser section. Once above the top of the baffle plate, the gas may break away and flow into the manifold 168 and then into the outlet tube 166. A small portion of the electrolyte may then fall back down the side of the baffle plate 170 closer to the back wall 178 of the pan 164 (i.e., the side opposite the electrode 176) into the faller region, thereby creating a circulation loop. This circulation loop formed in the pan assembly 160 (with the ascending section 180 on the side of the baffle plate 170 closer to the electrode 176 and the descending section 182 on the side of the baffle plate 170 opposite the electrode 176) is conceptually illustrated in FIG. 13, which is compared to a comparative pan assembly 184 that does not include a baffle assembly, such as one with a baffle plate like the baffle plate 170, such that there is no resulting formation of a circulation pattern. FIG. 14 shows vector plots of the simulated flow distribution of electrolyte in the pan assembly 160 with the baffle plate 170 included (left side of FIG. 14) and the comparative pan assembly 184 without the baffle assembly (right side of FIG. 14). As can be seen in FIG. 14, without the baffle plate, the electrolyte solution slowly rises upward through the comparative pan assembly 184. The gas evolved at electrode 176 affects the electrolyte flow, dragging some of the electrolyte upward and knocking some of the electrolyte to the side. Gas levitation is evident along the top left wall (adjacent electrode 176) in comparative pan assembly 184. Comparative pan assembly 184 without a baffle plate does not result in the formation of a weak electrolyte circulation, while pan assembly 160 including baffle plate 170 creates a strong circulation within pan assembly 160.14, the flow in the riser section 180, e.g., the side of the baffle plate 170 closest to the electrode 176, is strongly directed upward due to gas buoyancy, and the flow in the faller section 182, e.g., the side of the baffle plate 170 closest to the back wall 178 of the pan assembly 160, is strongly directed downward. The relatively high velocities and shear rates in the riser section 180 help sweep gas away from the electrode 176 and provide efficient top-to-bottom mixing within the pan assembly 160, driving increased convective cooling.
[0113] The baffle assembly 162 can be used to create a fast-flowing circulation loop so that as the electrolyte flows through the pan assembly 160, it remains substantially isothermal. Due to the high degree of top-to-bottom mixing and circulation, fast thermal equilibration of the electrolyte can be achieved as it flows into and through the pan assembly 160. Another advantage is that relatively cool electrolyte can be introduced into the pan assembly 160 where it can equilibrate with the warm circulating electrolyte fluid. The circulation rate (i.e., the number of times the recirculation loop is circulated during the electrolyte transition through the pan assembly 160) can be anywhere from 1 to 200. A high circulation rate can also help drive higher shear rates adjacent to the membrane 131, sweeping gas away from the membrane 131, and / or enhancing or maximizing heat transfer from the membrane 131 to the electrode 176.
[0114] The positioning of the baffle plate 170 relative to the electrode 176 and relative to the rear wall 178 of the receiving pan 164 and / or the width W of the baffle plate 170 (as shown in FIG. 15 ) Baffle and length L Bafflecan affect the velocity of the electrolyte through the riser section 180 and the faller section 182, thereby affecting the circulation rate of the electrolyte within the pan assembly 160. It has been found that if the baffle plate 170 is located farther than a defined critical distance from the electrode 176, the circulation pattern of the riser section 180 and the faller section 182 may not form. Specifically, it has been found that when the gap between the baffle plate 170 and the electrode 176 is too large, the free convection in the relatively light, gas-rich zone adjacent the electrode 176 rises relatively quickly compared to the electrolyte which rises more slowly further away from the electrode 176. The resulting shear force may drag some of the electrolyte upward, which may then drop downward on the side of the baffle plate 170 closer to the electrode 176 as the gas escapes into the manifold 168 at the top of the pan assembly 160, resulting in a weak circulation forming on the side of the baffle plate 170 closest to the electrode 176. In such a configuration, the baffle plate 170 may not split between the ascending and descending sections, and a strong circulating current may not form. On the other hand, if the baffle plate 170 is too close to the electrode 176, the space between the electrode 176 and the baffle plate 170 may fill with gas as it forms at the electrode 176, completely blocking the electrolyte flow in the space between the baffle plate 170 and the electrode 176. A high volume fraction of gas in the space between the baffle plate 170 and the electrode 176 may result in masking of the membrane and / or the electrode 176 and poor electrical and thermal transport.
[0115] As shown in FIG. 13, the depth D of the tray 164 Pan , the relative depth D of the baffle plate 170 to the electrode 176 Baffle , Total height H of tray 164 Pan Height H of baffle plate 170 Baffle , and / or within the basin 164 (e.g., the vertical distance H from the top edge of the baffle plate 170 to the top wall of the basin 164 Topand the corresponding vertical distance H from the bottom edge of the baffle plate 170 to the bottom wall of the receiving pan 164. Bot The vertical location of the baffle plate 170 (as dictated by) can affect the circulation pattern of the electrolyte within the pan 164.
[0116] In one embodiment, the distance of the baffle plate 170 from the electrode 176 (i.e., the relative depth D of the baffle as illustrated in FIG. 13) Baffle ) is about 5 mm to about 25 mm, for example, about 5 mm to about 15 mm, about 5 mm to about 12 mm, etc., for example, about 5 mm to about 10 mm, about 5 mm to about 8 mm, etc., for example, about 5 mm to about 6 mm, for example, about 6 mm to about 25 mm, about 6 mm to about 15 mm, etc., for example, about 6 mm to about 12 mm, about 6 mm to about 10 mm, etc., for example, about 6 mm to about 8 mm, for example, about 8 mm to about 25 mm, about 8 mm to about 15 mm, etc., for example, about 8 mm to about 12 mm, for example, about 8 mm to about 10 mm, for example, about 10 mm to about 25 mm, about 10 mm to about 15 mm, etc., for example, about 10 mm to about 12 mm, about 12 mm to about 25 mm, etc., for example, about 12 mm to about 15 mm. In some embodiments, the distance D of the baffle plate 170 from the electrode 176 Baffle is equal to the depth of the notch on the rib 174.
[0117] In one embodiment, the distance D from the baffle plate 170 to the electrode 176 is Baffle The total depth D of the tray is 164 Pan 0.25 (25%) to 0.5 (50%) of the total depth D of the tray 164. Pan Approximately 0.25 (25%) to approximately 0.4 (40%) of the total depth D of the tray 164 Pan For example, the total depth D of the tray 164 is about 0.25 (25%) to about 0.3 (30%). Pan Approximately 0.3 (30%) to approximately 0.5 (50%) of the total depth D of the tray 164 Pan The ratio is about 0.4 (40%) to about 0.5 (50%).
[0118] In one embodiment, the height H of the baffle plate 170 BaffleThe positioning is such that this creates a space (H in FIG. 13) above the receiving tray 164 for the flow of gas and liquid. Top ) and / or at its bottom a space (H in FIG. 13 Bot In some embodiments where the manifold 168 and the baffle plate 170 are both within the basin assembly 160, the depth of the manifold 168 and the depth D of the basin 164 are Pan Depending on where the baffle plate 170 is located relative to the electrode 176, the baffle plate 170 may extend behind the manifold 168 (e.g., between the manifold 168 and the electrode 176) toward the top of the basin 164, or the baffle plate 170 may terminate below the manifold 168. In either case, there may be space between the baffle plate 170 and the top and / or bottom of the basin 164 for gas and liquid flow.
[0119] In one embodiment, the space H between the bottom edge of the baffle plate 170 and the bottom wall of the basin 164 is Bot is about 6 mm to about 75 mm, for example, about 6 mm to about 65 mm, about 6 mm to about 50 mm, etc., for example, about 6 mm to about 40 mm, about 6 mm to about 30 mm, etc., for example, about 6 mm to about 20 mm, about 6 mm to about 10 mm, etc., for example, about 10 mm to about 75 mm, about 10 mm to about 65 mm, etc., for example, about 10 mm to about 50 mm, about 10 mm to about 40 mm, etc., for example, about 10 mm to about 30 mm, about 10 mm to about 20 mm, etc., for example, about 10 mm to about 15 mm, about 20 mm for example, about 30 mm to about 75 mm, for example, about 20 mm to about 65 mm, about 20 mm to about 50 mm, for example, about 20 mm to about 40 mm, about 20 mm to about 30 mm, for example, about 30 mm to about 75 mm, about 30 mm to about 65 mm, for example, about 30 mm to about 50 mm, about 30 mm to about 40 mm, for example, about 40 mm to about 75 mm, about 40 mm to about 65 mm, for example, about 50 mm to about 75 mm, about 50 mm to about 65 mm, for example, about 60 mm to about 75 mm.
[0120] In some embodiments, the space H between the top edge of the baffle plate 170 and the top wall of the pan 164 or the bottom of the manifold 168 may be Top is about 6 mm to about 150 mm, for example, about 6 mm to about 140 mm, about 6 mm to about 130 mm, etc., for example, about 6 mm to about 120 mm, about 6 mm to about 110 mm, etc., for example, about 6 mm to about 100 mm, about 6 mm to about 80 mm, etc., for example, about 6 mm to about 70 mm, about 6 mm to about 50 mm, etc., for example, about 6 mm to about 25 mm, about 10 mm to about 150 mm, etc., for example, about 10 mm to about 140 mm m, about 10 mm to about 130 mm, for example, about 10 mm to about 120 mm, about 10 mm to about 110 mm, for example, about 10 mm to about 100 mm, about 10 mm to about 80 mm, for example, about 10 mm to about 70 mm, about 10 mm to about 50 mm, for example, about 10 mm to about 25 mm, about 25 mm to about 150 mm, for example, about 25 mm to about 140 mm, about 25 mm to about 130 mm, for example About 25 mm to about 120 mm, about 25 mm to about 110 mm, etc., for example, about 25 mm to about 100 mm, about 25 mm to about 80 mm, etc., for example, about 25 mm to about 70 mm, about 25 mm to about 50 mm, etc., for example, about 50 mm to about 150 mm, about 50 mm to about 140 mm, etc., for example, about 50 mm to about 130 mm, about 50 mm to about 120 mm, etc., for example, about 50 mm to about 110 mm, about 50 mm to about 100 mm, etc., for example, about 50 mm to about 80 mm, about 50 mm to about 70 mm, etc., for example, about 100 mm to about 150 mm, about 100 mm to about 140 mm, etc., for example, about 100 mm to about 130 mm, about 100 mm to about 120 mm, etc., for example, about 125 mm to about 150 mm, about 125 mm to about 140 mm, etc., for example, about 130 mm to about 150 mm, about 75 mm to about 120 mm, etc. It should be understood that any of the above dimensions for the space between the baffle plate and the bottom of the anode and / or cathode pan and the dimensions for the space between the baffle plate and the top of the anode and / or cathode pan or the bottom of the manifold may be combined to achieve an optimal circulation pattern of the electrolyte.
[0121] In some embodiments, the anode and / or cathode pan assemblies provided herein, along with the aforementioned manifold and outlet tube and / or baffle assemblies, provide several advantages such as, but not limited to, accommodating the aforementioned high flow rates of anolyte or catholyte and / or reducing or minimizing the occurrence of slug or plug flow, reducing or minimizing large spatial and / or temporal temperature changes, reducing or minimizing pressure changes due to multiphase flow within the cell, for example to less than 0.5 psi, and / or reducing or minimizing membrane erosion and / or fatigue.
[0122] As described above, operation of an electrolyzer cell at high current densities can pose significant challenges, including, but not limited to, the large amounts of heat generated within the cell. In electrolyzer cells that produce large amounts of gas at high current densities, the gas / electrolyte mixture can have a lower specific heat, lower density, and / or lower thermal conductivity than the electrolyte alone. Thus, the heat removal efficiency of the electrolyte can be reduced as gas retention increases. If gas pockets mask areas of the electrodes, local temperatures can rise rapidly. If significant areas of the electrodes are masked, the unmasked areas will have to work more, which will increase local Joule heating. Such developed local hot spots can damage the membrane. As the current density is increased in the cell, power dissipation can also rise dramatically. Large spatial and / or temporal temperature variations can also damage the membrane.
[0123] 16-19 and 20A-20C show an illustrative embodiment of a pan assembly 190 that may be used as an anode pan assembly for the anode half cell 111 or as a cathode pan assembly for the cathode half cell 121, or both, in the electrolyzer cell 100 shown in FIG 1. The pan assembly 190 includes a plurality of ribs 194 with a defined geometry and / or spacing and / or through the use of one or more welds 196 that couple an electrode 198 of the pan assembly 190 to the ribs 194, the welds 196 having a defined weld density and cross-sectional configuration to reduce or minimize power dissipation to improve temperature distribution during operation of the cell. The pan assembly 190 may also include features of the pan assembly 140 described above with respect to Figures 3-8 (e.g., a manifold and outlet tube through which the electrolyte and produced gas may flow before exiting the pan assembly 190, which may be similar to or the same as the manifold 144 and outlet tube 146 described above with respect to the pan assembly 140), and / or features of the pan assembly 160 described above with respect to Figures 9-15 (e.g., a baffle assembly, which may be similar to or the same as the baffle assembly 162 described above with respect to the pan assembly 160). In other words, the pan assemblies that form either the anode assembly or the cathode assembly, or both, may include features of the pan assembly 140 described above with respect to Figures 3-8 and / or the pan assembly 160 described above with respect to Figures 9-15, in addition to the features of the pan assembly 190 described below.
[0124] The rib geometry, rib spacing, and / or weld density and cross-sectional configuration within the pan assembly 190 can reduce or minimize the effects of one or more of these challenges, such as by, without limitation, distributing the current more effectively across the pan assembly 190 and reducing the opportunity for hot spot formation, reducing or avoiding large spatial and / or temporal temperature variations of the electrolyte along the height of the pan assembly 190, and / or reducing or minimizing membrane damage due to hot spots.
[0125] As described below, the design of the pan assembly 190, which includes one or more ribs 194 and welds 196, can provide efficient current distribution across the effective area of the cell when operating at high current densities. The cross-sectional area of the ribs 194 and welds 196 can also allow the cell to be more efficient for operational and economic purposes.
[0126] 3-15, the pan assembly 190 can be used as a structure for one or both of the anode half cell 111 and the cathode half cell 121 in the electrolyzer cell 100 of FIG. 1, i.e., the pan assembly 190 can form the anode half cell 111 such that the pan assembly 190 is an anode pan assembly, and / or the pan assembly 190 can form the cathode half cell 121 such that the pan assembly 190 is a cathode pan assembly. The pan 192 can include an interior for receiving an electrolyte (i.e., anolyte if the pan assembly 190 is an anode pan assembly, or catholyte if the pan assembly 190 is a cathode pan assembly) and an electrode 198 (i.e., the anode 112 in the anode pan assembly 190 or the cathode 122 in the cathode pan assembly 190). The anode pan assembly and the cathode pan assembly can be separated by a separator (i.e., membrane 131), which can be, for example, one or more of a diaphragm, a membrane electrode assembly (MEA), or an ion exchange membrane (IEM). The pan assembly 190 can further include components such as a collection system (e.g., a manifold such as manifold 144 or 168 described above) that collects gas and electrolyte for outflow from the pan assembly 190. Various additional separator components can be provided, for example, to separate one or more membranes from the anode, to separate one or more membranes from the cathode, to separate one membrane from another membrane (e.g., to separate an anion exchange membrane (AEM) from a cation exchange membrane (CEM)), and / or to provide mechanical integrity to one or more membranes. In addition to these components, individual gaskets or gasket tapes may be provided between and along the periphery of the components to seal the compartments from fluid leakage.
[0127] In one embodiment, the basin assembly 190 includes a basin 192, one or more ribs 194 positioned vertically inside the basin 192, an electrode 198 coupled to the one or more ribs 194, and one or more welds 196 welding the electrode 198 to the one or more ribs 194. FIG. 16 is a front view of an illustrative embodiment of the basin assembly 190, FIG. 17 is a side cross-sectional view of the basin assembly 190, and FIG. 18 is an enlarged view of the cross-section taken along line 18 in FIG. 17. The figures show one or more structures that may form the one or more ribs 194. In particular, as can be seen in the view of FIG. 18, in one embodiment, the one or more ribs 194 can be perpendicular or substantially perpendicular to a major dimension of the basin 192. For example, one or more ribs 194 may each be perpendicular or approximately perpendicular to one or more major surfaces of the pan 192 , such as the electrode 198 or the rear pan wall 200 .
[0128] An electrode 198 can be disposed on top of the basin 192 and on top of the one or more ribs 194. As can be seen, in certain embodiments, the electrode 198 can be welded to the one or more ribs 194 using one or more welds 196. In certain embodiments, the one or more ribs 194 are each coupled to a rear wall 200 of the basin 192 by one or more tabs 202, which are coupled to the rear wall 200 using one or more tab welds 204.
[0129] In one embodiment, the electrode 198 can be electrically coupled to an electrical current provided through one or more welds 196. During operation of a cell using the pan assembly 190 to form a cathode half cell, electrical current flows through the welds 196 of the cathode pan assembly 190 into the cathode (e.g., the electrode 198 of the cathode pan assembly 190). The electrical current then flows from the cathode 198 to one or more ribs 194 of the cathode pan assembly 190. The electrical current then flows through the one or more ribs 194 of the cathode pan assembly 190, through the tabs 202, and finally into a conductor contacting the pan 192 of the cathode pan assembly 190 (e.g., to the anode half cell of an adjacent cell or to a contact plate). During operation of a cell using the pan assembly 190 to form an anode half cell, current flows from a conductor contacting the pan 192 of the anode pan assembly 190 (e.g., from the cathode half cell of an adjacent cell or from a contact plate) through the tabs 202 to the ribs 194 of the anode pan assembly 190, then to the anode (e.g., the electrode 198 of the anode pan assembly 190), and then into a conductor that is electrically connected to one or more of the welds 196 of the anode pan assembly 190. As described above, the one or more ribs 194 can be welded to the back wall 200 of the pan 192 via the tabs 202 and tab welds 204. In one embodiment, the tabs 202 set the spacing of the tab welds 204 between the bottom of the ribs 194 and the back wall 200 of the pan 192. Because current flows between the back wall 200 of the pan 192 and the electrode 198 through the ribs 194, the tabs 202 can provide a proper weld cross-section between the ribs 194 and the pan 192. The tabs 202 can facilitate better current distribution across an effective area and provide electrical contact between the ribs 194 and the pan 192. However, in other embodiments, the ribs 194 can be welded directly to the back wall 200 of the pan 192 and not connected through a tab.
[0130] The geometry and spacing of one or more ribs 194 can dictate current flow through the pan assembly 190. The geometry of the ribs 194 can include, but is not limited to, the number of ribs 194 (as shown in FIG. 19 ), the height H of the ribs 194, and the spacing of the ribs 194. Rib , the physical design of the ribs 194, the pitch P between adjacent ribs 194 Ribs , and / or the thickness T of the rib 194 Rib As current flows through the welds 196, the geometry, spacing or density, and / or cross-sectional area of the welds 196 can also affect the current flow through the basin assembly 190. As increasingly higher currents flow through the cell, the density and cross-sectional area of the welds 196 can significantly affect local Joule heating and avoid membrane damage from local hot spots. Provided herein are specific geometries, spacing, and cross-sectional areas of the ribs 194 and welds 196 that can promote efficient operation of an electrochemical cell composed of one or two of the basin assemblies 190 at high current densities.
[0131] The physical configuration, i.e., overall shape, of the one or more ribs 194 can be selected for one or more purposes. For example, one or more of the ribs 194 can be a solid plate, such as a solid plate of conductive metal, such as the example rib 194A shown in FIG. 20A. In another embodiment, the one or more ribs 194 can include one or more holes or openings that allow electrolyte to move laterally within the pan 192, such as one or more ribs 194B having holes 206 as shown in FIG. 20B. In an embodiment, the one or more ribs 194 include one or more notches for receiving one or more other structures, such as rib 194C shown in FIG. 20C, which includes one or more notches 208 for receiving a portion of a baffle plate 210 (described in more detail below). In certain embodiments, one or more ribs 194 can include both holes 206 and notches 208, similar to rib 194C shown in FIG. 20C, or can include only holes 206 or only notches 208.
[0132] The number of ribs 194 on the inside of the basin 192 can affect the current distribution and power dissipation within the basin assembly 190. In one embodiment, the number of ribs 194 on the inside of the tray 192 may be 1-75 ribs 194, 1-60 ribs 194, etc., e.g., 1-50 ribs 194, 1-40 ribs 194, etc., e.g., 1-30 ribs 194, 1-20 ribs 194, etc., 1-10 ribs 194, etc., e.g., 1-5 ribs 194, 5-75 ribs 194, etc., e.g., 5-60 ribs 194, 5-50 ribs 194, etc., e.g., 5-40 ribs 194, 5-30 ribs 194, etc., e.g., 5-20 ribs 194, 5-10 ribs 194, etc., e.g., 10-75 ribs 194, 10-60 ribs 194, etc., e.g., 10-50 ribs 194, 94, 10 to 40 ribs 194, for example, 10 to 30 ribs 194, 10 to 20 ribs 194, for example, 20 to 75 ribs 194, 20 to 60 ribs 194, for example, 20 to 50 ribs 194, 20 to 40 ribs 194, for example, 20 to 30 ribs 194, 30 to 75 ribs 194, for example For example, 30-60 ribs 194, 30-50 ribs 194, etc., for example, 30-40 ribs 194, 40-75 ribs 194, etc., for example, 40-60 ribs 194, 40-50 ribs 194, etc., for example, 50-75 ribs 194, 50-60 ribs 194, etc., for example, 60-75 ribs 194. For example, the pan assembly 190 shown in Figures 16-19 and 20A-20C shows a pan 192 containing five (5) ribs 194.
[0133] A cross-sectional perspective view of an exemplary basin assembly 190 is shown in FIG. 19. The electrode 198 and welds 196 are not shown in FIG. 19. As explained above, the basin assembly 190 includes one or more ribs 194 positioned vertically within the basin 192, e.g., the ribs 194 are coupled to a back wall 200 of the basin 192 with tabs 202 or the like, and the ribs 194 extend from the back wall 200 toward the electrode. In FIG. 19, the pitch, i.e., distance, between two adjacent ribs 194 is P Rib and the height of one or more ribs 194 is HRib and the thickness of one or more ribs 194 is labeled T Rib 19. The ribs 194 are shown in FIG. 19 as including holes 206 and notches 208 for electrolyte migration. The notches 208 facilitate fitting of a defined section of the baffle plate 210 into a space formed by the notches 208 to secure the baffle plate 210 to the one or more ribs 194. The baffle plate 210 can be similar to or the same as the baffle plate 170, described above with respect to the pan assembly 160 of FIGS. 9-15. In one embodiment, the one or more ribs 194 are made from a conductive metal, such as, but not limited to, nickel, stainless steel, etc.
[0134] It should be understood that the holes 206 and notches 208 may not be present, for example, the ribs 194 may each be formed from a solid plate, such as rib 194A of FIG. 20A, or the ribs 194 may have notches 208 but no holes 206, or the ribs 194 may have holes 206 but no notches 208. The holes 206, if present, need not be any particular shape or size. For example, the holes 206 can be circular openings, slits, perforations, or a mesh.
[0135] In one embodiment, the length L of one or more ribs 194 Rib(FIG. 16) is about 0.25 meters (m) to about 1.5 m, for example, about 0.25 m to about 1.2 m, about 0.25 m to about 1 m, etc., for example, about 0.25 m to about 0.8 m, about 0.25 m to about 0.6 m, etc., for example, about 0.25 m to about 0.5 m, about 0.25 m to about 0.4 m, etc., for example, about 0.25 m to about 0.3 m, about 0.5 m to about 1.5 m, etc., for example, about 0.5 m to about 1.2 m, about 0.5 m to about 1 m, etc., for example, about 0.5m to about 0.8m, about 0.5m to about 0.6m, etc., for example, about 0.6m to about 1.5m, about 0.6m to about 1.2m, etc., for example, about 0.6m to about 1m, about 0.6m to about 0.8m, etc., for example, about 0.7m to about 1.5m, about 0.7m to about 1.2m, etc., for example, about 0.7m to about 1m, about 0.7m to about 0.8m, etc., for example, about 0.8m to about 1.5m, about 0.8m to about 1.2m, etc., for example, about 0.8m to about 1m.
[0136] In one embodiment, the length of the notch 208 in each of the one or more ribs 194 is from about 5 millimeters (mm) to about 100 mm, e.g., from about 5 mm to about 80 mm, from about 5 mm to about 60 mm, etc., such as from about 5 mm to about 50 mm, from about 5 mm to about 40 mm, etc., such as from about 5 mm to about 30 mm, from about 5 mm to about 20 mm, etc., such as from about 5 mm to about 10 mm, from about 10 mm to about 100 mm, etc., such as from about 10 mm to about 50 mm, from about 10 mm to about 40 mm. m, for example, about 10 mm to about 30 mm, about 10 mm to about 20 mm, for example, about 20 mm to about 100 mm, about 20 mm to about 50 mm, for example, about 20 mm to about 40 mm, about 20 mm to about 30 mm, for example, about 30 mm to about 100 mm, about 30 mm to about 50 mm, for example, about 30 mm to about 40 mm, about 40 mm to about 100 mm, for example, about 40 mm to about 50 mm, about 50 mm to about 100 mm, for example, about 75 mm to about 100 mm.
[0137] In one embodiment, the thickness T of one or more ribs 194 Rib is about 1 mm to about 3 mm, for example, about 1 mm to about 2.5 mm, about 1 mm to about 2 mm, etc., for example, about 1 mm to about 1.5 mm, about 2 mm to about 3 mm, etc., for example, about 2 mm to about 2.5 mm, about 2.5 mm to about 3 mm, etc.
[0138] In one embodiment, the height H of one or more ribs 194 Rib is about 10 mm to about 110 mm, for example, about 10 mm to about 100 mm, about 10 mm to about 75 mm, etc., for example, about 10 mm to about 70 mm, about 10 mm to about 60 mm, etc., for example, about 10 mm to about 50 mm, about 10 mm to about 40 mm, etc., for example, about 10 mm to about 30 mm, about 20 mm to about 110 mm, etc., for example, about 20 mm to about 75 mm, about 20 mm to about 70 mm, etc., for example, about 20 mm to about 60 mm, about 20 mm to about 50 mm, etc., for example, about 20 mm to about 40 mm, about 20 mm to about 30 mm, etc., for example, about 30 mm to about 110 mm, about 30 mm to about 75 mm, etc. For example, about 30 mm to about 70 mm, about 30 mm to about 60 mm, etc., for example, about 30 mm to about 50 mm, about 30 mm to about 40 mm, etc., for example, about 40 mm to about 110 mm, about 40 mm to about 75 mm, etc., for example, about 40 mm to about 70 mm, about 40 mm to about 60 mm, etc., for example, about 40 mm to about 50 mm, about 50 mm to about 110 mm, etc., for example, about 50 mm to about 75 mm, about 50 mm to about 70 mm, etc., for example, about 50 mm to about 60 mm, about 60 mm to about 110 mm, etc., for example, about 60 mm to about 75 mm, about 70 mm to about 110 mm, etc., for example, about 70 mm to about 80 mm.
[0139] In one embodiment, the pitch P between two adjacent ribs 194 Ribis about 40 mm to about 200 mm, for example, about 40 mm to about 150 mm, about 40 mm to about 140 mm, etc., for example, about 40 mm to about 130 mm, about 40 mm to about 120 mm, etc., for example, about 40 mm to about 110 mm, about 40 mm to about 100 mm, etc., for example, about 40 mm to about 80 mm, about 40 mm to about 70 mm, etc., for example, about 60 mm to about 200 mm, about 60 mm to about 150 mm, etc., for example, about 60 mm to about 140 mm, about 60 mm to about 130 mm, etc., for example, about 60 mm to about 120 mm, about 60 mm to about 110 mm, etc., for example, about 60 mm to about 100 mm, about 60 mm to about 80 mm, etc., for example, about 80 mm to about 200 mm, about 80 mm to about 150 mm, etc., for example, about 80 mm to about 100 mm, about 100 mm to about 200 mm, etc., for example, about 100 mm to about 150 mm, about 100 mm to about 140 mm, etc., for example, about 100 mm to about 130 mm, about 100 mm to about 120 mm, etc., for example, about 125 mm to about 200 mm, about 125 mm to about 150 mm, etc., for example, about 125 mm to about 140 mm, about 130 mm to about 150 mm, etc., for example, about 75 mm to about 120 mm.
[0140] 18 and 20A-20C, the electrode 198 can be welded to the top of one or more ribs 194 using a number of welds 196. In one embodiment, the electrode 198 is a planar electrode or an expanded metal or mesh. In embodiments in which electrode 198 is an expanded metal or mesh, the thickness of each strand forming the mesh can be from about 0.5 mm to about 3 mm, e.g., from about 0.5 mm to about 2.5 mm, from about 0.5 mm to about 2 mm, etc., for example, from about 0.5 mm to about 1.5 mm, from about 0.5 mm to about 1 mm, etc., for example, from about 1 mm to about 3 mm, from about 1 mm to about 2.5 mm, etc., for example, from about 1 mm to about 2 mm, from about 1 mm to about 1.5 mm, etc., for example, from about 1.5 mm to about 3 mm, from about 1.5 mm to about 2.5 mm, etc., for example, from about 1.5 mm to about 2 mm, from about 2 mm to about 3 mm, etc., for example, from about 2.5 mm to about 3 mm.
[0141] The geometry, spacing, density, and / or cross-sectional area of the welds 196 can affect the current flow through the pan assembly 190. As the operating current density increases and more current flows through the cell, the density of the welds 196 (e.g., the cross-sectional area of the welds 196 and the spacing between the welds 196) can affect local Joule heating. The density of the welds 196 can be selected to reduce or minimize the room for film damage due to the formation of local hot spots. The example welds 196 in FIGS. 20A-20C are illustrated as spots. However, the welds 196 can be in the form of lines, spots, patterns, or any other shape, or combinations thereof. For example, a spot welder can form the welds 196 as spots, while a laser welder can produce the welds 196 as lines and / or spots and / or patterns. The patterns in which the welds 196 may be formed include, but are not limited to, combinations of dots, arrays of dots, dashed lines, spots, lines, and line segments, which may be arranged in a pattern of any geometrically regular shape, such as a generally rectangular geometry, a generally circular geometry, or a generally hexagonal geometry, or may be arranged in an irregular shape.
[0142] Examples of welding techniques that may be used to form the weld 196 include, but are not limited to, laser welding, TiG welding, and spot welding, e.g., resistance spot welding. Laser welding involves welding the entire length L of the rib 194 to the electrode 198. Rib Length L of one of the ribs 194 up to and including Rib For example, when one or more ribs 194 are solid plates (e.g., rib 194A in FIG. 20A ) or plates with holes (e.g., rib 194B in FIG. 20B ) that do not include a notch 208, the overall length L of rib 194 for joining rib 194 to electrode 198 may be less than 100 mm. RibThere may be a single linear weld 196 along the rib 194. Laser welding or TiG welding may also be used to create a weld 196 in the form of a line segment. For example, when one or more of the ribs 194 include a notch 208 (e.g., rib 194C in FIG. 20C), there may be a segment of the weld line across a portion of the rib 194 that contacts the electrode 198 but does not span the notch 208. Laser welding can also produce weld patterns with dots, arrays of dots, dashed lines, spots, line segments, long lines, and any defined geometry, such as oval, rectangular, circular, hexagonal, or combinations thereof. The weld geometry may be dictated by the shape of the weld tip and anvil, such as when the weld is created using resistance welding. TiG welds may be created manually and can be in arbitrary shapes.
[0143] In one embodiment, the geometry of the welds 196 includes the number of welds within the pan 192. The number of welds 196 connecting the electrodes 198 to the ribs 194 can affect the current distribution and power dissipation within the pan assembly 190. In one embodiment, the number of welds 196 per rib 194 (such as the exemplary spot welds 196 shown in FIGS. 18 and 20A-20C ) in the form of spots is between 10 and 50 welds 196 per rib 194, e.g., between 10 and 40 welds 196 per rib 194, between 10 and 30 welds 196 per rib 194, etc., e.g., between 10 and 20 welds 196 per rib 194, between 20 and 50 welds 196 per rib 194, e.g., between 20 and 40 welds 196 per rib 194, between 20 and 30 welds 196 per rib 194, e.g., between 30 and 40 welds 196 per rib 194, between 35 and 40 welds 196 per rib 194, e.g., between 40 and 50 welds 196 per rib 194.
[0144] In one embodiment, the distance between welds 196 in the form of spot welds is, independently in the X direction and the Y direction, about 25 mm to about 200 mm, for example, about 25 mm to about 150 mm, about 25 mm to about 100 mm, etc., for example, about 25 mm to about 75 mm, about 25 mm to about 50 mm, etc., for example, about 50 mm to about 200 mm, about 50 mm to about 150 mm, etc., for example, about 50 mm to about 100 mm, about 50 mm to about 75 mm, etc., for example, about 75 mm to about 200 mm, about 75 mm to about 150 mm, etc., for example, about 75 mm to about 100 mm, about 100 mm to about 200 mm, etc., for example, about 100 mm to about 150 mm.
[0145] In one embodiment, the number of welds 196 per rib 194, in the form of line welds or line section welds, may range from 1 to 75 welds 196 per rib 194, e.g., 1 to 70 welds 196 per rib 194, 1 to 60 welds 196 per rib 194, etc., e.g., 1 to 50 welds 196 per rib 194, 1 to 4 ... 1-30 welds 196 per rib 194, 1-20 welds 196 per rib 194, etc., e.g., 1-10 welds 196 per rib 194, 2-75 welds 196 per rib 194, etc., e.g., 2-70 welds 196 per rib 194, 2-60 welds 196 per rib 194, etc., e.g., 2-50 welds 196 per rib 194, 2-40 welds 196 per rib 194, etc. 196, e.g., 2-30 welds 196 per rib 194, 2-20 welds 196 per rib 194, etc., e.g., 2-10 welds 196 per rib 194, 10-75 welds 196 per rib 194, e.g., 10-70 welds 196 per rib 194, 10-60 welds 196 per rib 194, etc., e.g., 10-50 welds 196 per rib 194 , 10 to 40 welds 196 per rib 194, for example, 10 to 30 welds 196 per rib 194, 10 to 20 welds 196 per rib 194, for example, 25 to 75 welds 196 per rib 194, 25 to 50 welds 196 per rib 194, for example, 50 to 75 welds 196 per rib 194, 60 to 75 welds 196 per rib 194, etc.
[0146] In an embodiment, the distance between welds 196 when in the form of line welds or line section welds is, independently in the X and Y directions, about 40 mm to about 200 mm, e.g., about 40 mm to about 150 mm, about 40 mm to about 100 mm, etc., for example, about 40 mm to about 75 mm, about 75 mm to about 200 mm, etc., for example, about 75 mm to about 150 mm, about 75 mm to about 100 mm, etc., for example, about 100 mm to about 200 mm, about 100 mm to about 150 mm, etc., for example, about 150 mm to about 200 mm.
[0147] In one embodiment, when one or more ribs 194 include one or more notches 208 and a weld 196 includes one or more line segments in which the electrode 198 is welded to a ridge of the rib 194 formed between the notches 208, the line segment of a particular weld 196 can extend along the entire length of the ridge between the notches 208 or along only a partial length of the ridge between the notches 208. In an embodiment, the length of the line section weld 196 is the length of the ridge between the notches 208, or the length of the line section weld 196 is about 0.25 m to about 1 m, such as about 0.25 m to about 0.8 m, such as about 0.25 m to about 0.6 m, such as about 0.25 m to about 0.5 m, such as about 0.25 m to about 0.4 m, such as about 0.25 m to about 0.3 m, such as about 0.5 m to about 1 m, such as about 0.5 m to about 0.8 m, such as about 0.5 m to about 0.6 m, such as about 0.6 m to about 1 m, such as about 0.6 m to about 0.8 m, such as about 0.7 m to about 1 m, such as about 0.7 m to about 0.8 m, such as about 0.8 m to about 1 m.
[0148] In an embodiment, the distance between two adjacent line section welds 196 is about 5 mm to about 100 mm, for example, about 5 mm to about 80 mm, about 5 mm to about 60 mm, etc., for example, about 5 mm to about 50 mm, about 5 mm to about 40 mm, etc., for example, about 5 mm to about 30 mm, about 5 mm to about 20 mm, etc., for example, about 5 mm to about 10 mm, about 10 mm to about 100 mm, etc., for example, about 10 mm to about 50 mm, about 10 mm to about 40 mm, etc., for example, about 10 mm. m to about 30 mm, about 10 mm to about 20 mm, etc., for example, about 20 mm to about 100 mm, about 20 mm to about 50 mm, etc., for example, about 20 mm to about 40 mm, about 20 mm to about 30 mm, etc., for example, about 30 mm to about 100 mm, about 30 mm to about 50 mm, etc., for example, about 30 mm to about 40 mm, about 40 mm to about 100 mm, etc., for example, about 40 mm to about 50 mm, about 50 mm to about 100 mm, etc., for example, about 75 mm to about 100 mm.
[0149] In an embodiment, the cross-sectional area of each weld 196 is approximately 6 square millimeters (mm 2 ) ~ approx. 3,300mm 2 , for example, about 6 mm 2 ~ approx. 3,000mm2 , about 6mm 2 ~ approx. 2,000mm 2 etc., for example, about 6 mm 2 ~ approx. 1,000mm 2 , about 6mm 2 ~ approx. 500mm 2 etc., for example, about 6 mm 2 ~about 300mm 2 , about 6mm 2 ~ approx. 100mm 2 etc., for example, about 50 mm 2 ~Approx. 3,300mm 2 , about 50 mm 2 ~ approx. 3,000mm 2 etc., for example, about 50 mm 2 ~ approx. 2,000mm 2 , about 50 mm 2 ~ approx. 1,000mm 2 etc., for example, about 50 mm 2 ~ approx. 500mm 2 , about 50 mm 2 ~about 300mm 2 etc., for example, about 50 mm 2 ~ approx. 100mm 2 , about 100 mm 2 ~Approx. 3,300mm 2 etc., for example, about 100 mm 2 ~ approx. 3,000mm 2 , about 100 mm 2 ~ approx. 2,000mm 2 etc., for example, about 100 mm 2 ~ approx. 1,000mm 2 , about 100 mm 2 ~ approx. 500mm 2 etc., for example, about 100 mm 2 ~about 300mm 2 , about 500 mm 2 ~Approx. 3,300mm 2 For example, about 500 mm 2 ~ approx. 3,000mm 2 , about 500 mm 2 ~ approx. 2,000mm 2 For example, about 500 mm 2 ~ approx. 1,000mm 2 , about 1,000 mm 2 ~Approx. 3,300mm 2For example, about 1,000 mm 2 ~ approx. 3,000mm 2 , about 1,000 mm 2 ~ approx. 2,000mm 2 For example, about 2,000 mm 2 ~ approx. 3,000mm 2 , about 2,500 mm 2 ~ approx. 3,000mm 2 etc.
[0150] In one embodiment, the geometry, spacing or density, and / or cross-sectional area of the welds 196 are such that the ratio of the cross-sectional area of the electrode 198 to the total cross-sectional area of the welds 196 is from about 15:1 to about 2,000:1, e.g., from about 15:1 to about 1,000:1, from about 15:1 to about 500:1, etc.
[0151] In one embodiment, the geometry, spacing or density, and / or cross-sectional area of the welds 196 are configured to allow a current density through each weld 196 of approximately 20 amperes per square millimeter (A / mm 2 ) when the cell 190 is operating at its maximum current density. 2 ) or less, e.g., about 19 A / mm 2 or less, 18A / mm 2 or less, for example, about 17 A / mm 2 or less, about 16A / mm 2 or less, for example, about 15 A / mm 2 or less, about 14A / mm 2 or less, for example, about 13 A / mm 2 or less, about 12.5A / mm 2 or less, for example, about 12 A / mm 2 or less, about 11A / mm 2 or less, for example, about 10 A / mm 2 or less, about 9A / mm 2 or less, for example, about 8 A / mm 2 or less, or about 5A / mm 2~ approx. 20A / mm 2 , about 7.5A / mm 2 ~about 15A / mm 2 For example, about 7.5 A / mm 2 ~ approx. 10A / mm 2 It is as if.
[0152] In one specific and non-limiting example, the welds 196 are in the form of spot welds, there are 10-50 welds 196 per rib 194, the distance between adjacent spot welds 196 is about 25 mm to about 200 mm (in the X and Y directions independently), and the cross-sectional area of each spot weld 196 is about 6 mm. 2 ~Approx. 3,300mm 2 and the current density through each spot weld 196 is 6 A / mm 2 or less, e.g., 4A / mm 2 In another specific and non-limiting example, the welds 196 are in the form of line welds, there are 1-75 welds 196 per rib 194, the distance between adjacent line welds 196 is about 40 mm to about 200 mm (independently in the X and Y directions), and the cross-sectional area of each line weld 196 is about 6 mm 2 ~Approx. 3,300mm 2 and the current density through each weld 196 is 6 A / mm 2 or less, e.g., 4A / mm 2 Or less.
[0153] In one embodiment, an electrochemical cell 100 including a pan assembly with one or any combination of the structures described above with respect to the pan assemblies 140, 160, 190 for one or both of the anode half cell 111 and the cathode half cell 121 can achieve a current of about 300 mA / cm 2 ~Approx. 6,000mA / cm 2 , for example, about 300 mA / cm 2 ~Approx. 5,000mA / cm 2 , about 300mA / cm 2 ~Approx. 4,000mA / cm 2 For example, about 300 mA / cm2 ~Approx. 3,000mA / cm 2 , about 300mA / cm 2 ~Approx. 2,000mA / cm 2 For example, about 300 mA / cm 2 ~Approx. 1,000mA / cm 2 , about 300mA / cm 2 ~about 800mA / cm 2 For example, about 300 mA / cm 2 ~about 600mA / cm 2 , about 300mA / cm 2 ~about 500mA / cm 2 etc., for example, about 500 mA / cm 2 ~Approx. 6,000mA / cm 2 , about 500mA / cm 2 ~Approx. 5,000mA / cm 2 etc., for example, about 500 mA / cm 2 ~Approx. 4,000mA / cm 2 , about 500mA / cm 2 ~Approx. 3,000mA / cm 2 etc., for example, about 500 mA / cm 2 ~Approx. 2,000mA / cm 2 , about 500mA / cm 2 ~Approx. 1,000mA / cm 2 etc., for example, about 500 mA / cm 2 ~about 800mA / cm 2 , about 500mA / cm 2 ~about 600mA / cm 2 etc., for example, about 600 mA / cm 2 ~Approx. 6,000mA / cm 2 , about 600mA / cm 2 ~Approx. 5,000mA / cm 2 etc., for example, about 600 mA / cm 2 ~Approx. 4,000mA / cm 2 , about 600mA / cm 2 ~Approx. 3,000mA / cm 2 etc., for example, about 600 mA / cm 2 ~Approx. 2,000mA / cm 2 , about 600mA / cm 2 ~Approx. 1,000mA / cm 2 etc., for example, about 600 mA / cm2 ~about 800mA / cm 2 , about 800mA / cm 2 ~Approx. 6,000mA / cm 2 etc., for example, about 800 mA / cm 2 ~Approx. 5,000mA / cm 2 , about 800mA / cm 2 ~Approx. 4,000mA / cm 2 etc., for example, about 800 mA / cm 2 ~Approx. 3,000mA / cm 2 , about 800mA / cm 2 ~Approx. 2,000mA / cm 2 etc., for example, about 800 mA / cm 2 ~Approx. 1,000mA / cm 2 , approx. 1,000mA / cm 2 ~Approx. 6,000mA / cm 2 For example, about 1,000 mA / cm 2 ~Approx. 5,000mA / cm 2 , approx. 1,000mA / cm 2 ~Approx. 4,000mA / cm 2 For example, about 1,000 mA / cm 2 ~Approx. 3,000mA / cm 2 , approx. 1,000mA / cm 2 ~Approx. 2,000mA / cm 2 For example, about 2,000 mA / cm 2 ~Approx. 6,000mA / cm 2 , approx. 2,000mA / cm 2 ~Approx. 5,000mA / cm 2 For example, about 2,000 mA / cm 2 ~Approx. 4,000mA / cm 2 , approx. 2,000mA / cm 2 ~Approx. 3,000mA / cm 2 For example, about 3,000 mA / cm 2 ~Approx. 6,000mA / cm 2 , approx. 3,000mA / cm 2 ~Approx. 5,000mA / cm 2 For example, about 3,000 mA / cm 2 ~Approx. 4,000mA / cm 2 , approx. 4,000mA / cm 2~Approx. 6,000mA / cm 2 For example, about 4,000 mA / cm 2 ~Approx. 5,000mA / cm 2 , approx. 5,000mA / cm 2 ~Approx. 6,000mA / cm 2 In some embodiments, the electrochemical cell 100, including any one of the pan assemblies 140, 160, 190 for one or both of the anode half cell 111 and the cathode half cell 121, can operate at a current density of about 300 mA / cm. 2 ~Approx. 3,000mA / cm 2 , about 300mA / cm 2 ~Approx. 2,000mA / cm 2 For example, about 300 mA / cm 2 ~Approx. 1,000mA / cm 2 , about 300mA / cm 2 ~about 800mA / cm 2 For example, about 300 mA / cm 2 ~about 600mA / cm 2 , about 300mA / cm 2 ~about 500mA / cm 2 For example, about 300 mA / cm 2 ~about 400mA / cm 2 It operates at a high current density of .
[0154] In one embodiment, the pan assembly, comprising one or any combination of the structures described above with respect to the pan assemblies 140, 160, 190, can accommodate a high flow rate of electrolyte (either anolyte through the anode pan assembly or catholyte through the cathode pan assembly), e.g., from about 200 kilograms per hour (kg / hr) to about 10,000 kg / hr, from about 200 kg / hr to about 9,000 kg / hr, etc., from about 200 kg / hr to about 8,000 kg / hr, from about 200 kg / hr to about 7,000 kg / hr, etc., e.g., from about 20 0 kg / hour to about 6,000 kg / hour, about 200 kg / hour to about 5,000 kg / hour, etc., for example, about 200 kg / hour to about 4,000 kg / hour, about 200 kg / hour to about 3,000 kg / hour, etc., for example, about 200 kg / hour to about 2,000 kg / hour, about 200 kg / hour to about 1,000 kg / hour, etc., for example, about 500 kg / hour to about 10,000 kg / hour, about 500 kg / hour to about 9,000 kg / hour, etc., for example, about 500 kg / hour to about 8,000 kg / hour, about 500 kg / hour to about 7,000 kg / hour, etc., for example, about 500 kg / hour to about 6,000 kg / hour, about 500 kg / hour to about 5,000 kg / hour, etc., for example, about 500 kg / hour to about 4,000 kg / hour, about 500 kg / hour to about 3,000 kg / hour, etc., for example, about 500 kg / hour to about 2,000 kg / hour, about 500 kg / hour to about 1,000 kg / hour, etc., for example, about 800 kg / hour to about 10,000 kg / hour, about 800 kg / hour to about 9,000 kg / hour, etc., for example, about 800 kg / hour to about 8,000 kg / hour, about 800 kg / hour to about 7,000 kg / hour, etc., for example, about 800 kg / hour For example, about 800 kg / hour to about 6,000 kg / hour, about 800 kg / hour to about 5,000 kg / hour, etc., for example, about 800 kg / hour to about 4,000 kg / hour, about 800 kg / hour to about 3,000 kg / hour, etc., for example, about 800 kg / hour to about 2,000 kg / hour, about 800 kg / hour to about 1,000 kg / hour, etc., for example, about 1,000 kg / hour to about 10,000 kg / hour, about 1,000 kg / hour to about 9,000 kg / hour, etc., for example, about 1,000 kg / hour to about 8,000 kg / hour, about 1,000 kg / hour to about 7,000 kg / hour, etc., for example, about 1,000 kg / hour to about 6,000 kg / hour, about 1,000 kg / hour to about 5,000 kg / hour, etc., for example, about 1,000 kg / hour to about 4,000 kg / hour, about 1,000 kg / hour to about 3,000 kg / hour, etc., for example, about 1,000 kg / hour to about 2,000 kg / hour, about 3,000 kg / hour to about 10,000 kg / hour, etc., for example, about 3,000 kg / hour to about 9,000 kg / hour, about 3,000 kg / hour to about 8,000 kg / hour, etc., for example, about 3,000 kg / hour to about 7,000 kg / hour, about 3,000 kg / hour to about 6,000 kg / hour, etc., for example, about 3,000 kg / hour to about 5,000 kg / hour, about 5,000 kg / hour to about 10,000 kg / hour, etc., for example, about 5,000 kg / hour to about 8,000 kg / hour, about 5,000 kg / hour to about 6,000 kg / hour, etc., for example, about 6,000 kg / hour to about 10,000 kg / hour, about 6,000 kg / hour to about 8,000 kg / hour, etc., for example, about 8,000 kg / hour to about 10,000 kg / hour.
[0155] In one embodiment, a pan assembly having one or any combination of the structures described above with respect to the pan assembly 140, 160, 190 can provide a superficial liquid velocity of electrolyte through the pan assembly 140, 160, 190 of 0.1 m / sec or less, e.g., 0.08 m / sec or less, 0.05 m / sec or less, etc., e.g., 0.01 m / sec or less.
[0156] Temperature Control Control of temperature within an electrochemical cell can be important for the operation of the cell. During operation, the current density through the cell can often be varied, for example, to take advantage of increases and decreases in electricity prices (as explained below). To maximize separator performance and life, it is generally preferred to maintain the separator within a small range of temperatures. If the temperature of the electrolyte inlet into the electrochemical cell is held constant or substantially constant while the current density is changed significantly, the temperature at the separator will vary significantly.
[0157] The inventors have discovered that the flow rates of electrolyte through the anode and cathode half cells of the electrochemical cell 100 can be set such that the resulting temperature of the electrolyte outlet stream can be maintained within a prescribed range at the highest expected operating current density using a convenient temperature for the inlet stream. FIG. 21 shows an exemplary electrochemical cell 300 configured for temperature control to maintain the temperature of a separator 331 within the cell 300. The cell 300 is similar to the exemplary cell 100 described above with respect to FIG. 1. For example, like the cell 100, the electrochemical cell 300 comprises two half cells, a first half cell 311 and a second half cell 321. In one embodiment, the first and second half cells 311, 321 are separated by a separator 331, such as a membrane 331.
[0158] The first half cell 311 can include a first electrode 312 that can be located proximate to a separator 331, and the second half cell 321 can include a second electrode 322 that can be located proximate to the separator 331, for example, on an opposite side of the separator 331 from the first electrode 312. In an embodiment, the first electrode 312 is an anode for the cell 300 and the second electrode 322 is a cathode for the cell 300, and thus the first half cell 311 can also be referred to as an anode half cell 311, the first electrode 312 can also be referred to as an anode 312, the second half cell 321 can also be referred to as a cathode half cell 321, and the second electrode 322 can also be referred to as a cathode 322. Each of the electrodes 312, 322 can be coated with one or more electrocatalysts, such as, but not limited to, highly dispersed metals or alloys of platinum group metals, such as platinum, palladium, ruthenium, rhodium, iridium, or combinations thereof, such as platinum-rhodium, platinum-ruthenium, or nickel mesh coated with ruthenium oxide (RuO2), to accelerate the reaction toward hydrogen gas (H2 gas) and / or oxygen gas (O2 gas).
[0159] The anode 312 can be electrically connected to an external positive conductor 316, and the cathode 322 can be electrically connected to an external negative conductor 326. When a separator 331 is wetted and in electrolytic contact with the electrodes 312 and 322, and an appropriate voltage is applied across the conductors 316 and 326, O2 gas is liberated at the anode 312, or H2 gas is liberated at the cathode 322, or both. In one configuration, an electrolyte, for example consisting of a solution of KOH in water, is pumped into the half cells 311, 321. For example, the electrolyte can flow into the anode half cell 311 through a first electrolyte inlet 314 and into the cathode half cell 321 through a second electrolyte inlet 324. In one embodiment, the flow of electrolyte through the anode half cell 311 can trap the produced O2 gas as gas bubbles 313 that exit the anode half cell 311 through a first outlet 315. Similarly, the flow of electrolyte through the cathode half cell 321 can trap the produced H 2 gas as gas bubbles 323, which can exit the cathode half cell 321 through a second outlet 325.
[0160] By referencing a look-up table, an operator can set the temperature of the inlet streams 314, 324 as a function of the current density at which the cell 300 is currently operating such that the resulting temperature of the outlet streams 315, 325 does not increase or decrease significantly, for example, such that the temperature of the outlet streams 315, 325 is within a defined temperature spread of the target temperature. In another example, the temperature of the inlet streams 314, 324 can be varied to maintain the temperature of the separator 331 at a constant or substantially constant set point (which may be determined by measuring the temperature of one or both of the outlet streams 325, 315 and calculating the temperature of the separator 331 based on one or more of the temperatures of the outlet streams 315, 325 and the operating current density). In an embodiment, the inlet temperature control is automated through one or more controllers 340, 342 (e.g., a first controller 340 configured for temperature control of the first inlet stream 314 and a second controller 342 configured for temperature control of the second outlet stream 324 based on the temperature of the second outlet stream 325), such as a programmable logic controller ("PLC"). The temperature control can be tied to one or more of the current density setting (e.g., the current across the electrolyzer cell 300 per area of the electrodes 312, 322), the voltage across the electrolyzer cell 300, and the temperature of the corresponding outlet streams 315, 325. In some embodiments, the temperature control can be automated using a proportional-integral-derivative ("PID") controller, or a feed-forward control scheme, or both. In an embodiment, the inlet temperature control is controlled via feed-forward control based on the current density set point and the voltage observed across the electrolyzer cell 300. In another embodiment, in addition to feedforward control by current density, the temperature of the corresponding electrolyte outlet 315, 325 can also be used to control the temperature of the inlet 314, 324 via a PID controller tuned for a slow response, which can allow the temperature of the outlet 315, 325 to fine-tune the temperature of the inlet 314, 324 after a fast response from the feedforward controller.
[0161] In one embodiment shown in Figure 21, control of the temperature of the inlet streams 314, 324 is effectively accomplished using a mixed approach with cooling heat exchangers 344, 346 that can cool at least a portion of the hot electrolyte return as it flows from the electrolyte outlets 315, 325 to the corresponding electrolyte inlets 314, 315. In the embodiment of Figure 21, a first cooling heat exchanger 344 is configured to cool the electrolyte in the first outlet stream 315 exiting the anode half cell 311 before it is recycled to the first inlet stream 314. A similar second cooling heat exchanger 346 is configured to cool the electrolyte in the second outlet stream 325 exiting the cathode half cell 321 before it is recycled to the second inlet stream 324. In one embodiment, the electrolyte recirculation configuration can include bypass lines 350, 352 (e.g., a first bypass line 350 to bypass the first cooling heat exchanger 344 and a second bypass line 352 to bypass the second cooling heat exchanger 346) configured to allow some or all of the recirculated electrolyte to bypass the cooling heat exchangers 344, 346 such that the bypassed portion of the electrolyte is not cooled and remains at or near the high temperature at the electrolyte outlets 315, 325. Corresponding bypass control valves 354, 356 can be included to modulate the proportion of the recirculated electrolyte that flows through the cooling heat exchangers 344, 346 and the proportion that would flow through the bypass lines 350, 352 (e.g., a first control valve 354 to modulate the flow through the first cooling heat exchanger 344 and the first bypass line 350 and a second control valve 356 to modulate the flow through the second cooling heat exchanger 346 and the second bypass line 352). 21, the bypass control valves 354, 356 are installed on the bypass lines 350, 352. However, those skilled in the art will understand that the control valves could be located in the inlet lines feeding into the cooling heat exchangers 344, 346 or the outlet lines exiting the cooling heat exchangers 344, 346 and would still achieve the same effect of modulating the ratio of electrolyte flowing through the heat exchangers 344, 346 and the bypass lines 350, 352.
[0162] The streams flowing through the cooling heat exchangers 344, 346 and the bypass lines 350, 352 are then mixed to achieve a defined set point temperature. For example, if it is desired that the temperature of the electrolyte fed to the cell 300 via the inlets 314, 324 be higher than its current temperature, the control valves 354, 356 can be controlled to allow a lower proportion of electrolyte to flow through the cooling heat exchangers 344, 346 relative to the proportion of electrolyte flowing through the bypass lines 350, 352 such that a relatively smaller amount of electrolyte is cooled by the cooling heat exchangers 344, 346, and thus the temperature of the electrolyte after mixing the two streams is higher. Similarly, if it is desired that the temperature of the electrolyte fed to the cell 300 be lower than its current temperature, the control valves 354, 356 can be controlled to flow a higher proportion of electrolyte through the cooling heat exchangers 344, 346 relative to the proportion flowing through the bypass lines 350, 352 so that a relatively greater amount of electrolyte is cooled by the cooling heat exchangers 344, 346 and therefore the temperature of the electrolyte after mixing the two streams will be lower.
[0163] In one embodiment, flow control valves 360, 362 (e.g., a first flow control valve 360 for controlling the flow rate of electrolyte to the first inlet 314 and a second flow control valve 362 for controlling the flow rate of electrolyte to the second inlet 324) located downstream of the mixing point can ensure that the feed rate of electrolyte to the inlets 314, 324 remains constant or substantially constant. In another embodiment (not shown), temperature control valves (similar to the control valves 354, 356 of FIG. 21) can control the flow rate through the cooling heat exchangers 344, 346 and flow control valves can control the flow rate through the heat exchanger bypass lines 350, 352. In one embodiment, the cooling heat exchangers 344, 346 are at least slightly oversized (in terms of the flow rates that the heat exchangers 344, 346 can accommodate or the heat exchange capacity of the heat exchangers 344, 346) so that the combination of the cooling heat exchangers 344, 346 and the bypass lines 350, 352 can provide adequate temperature and flow control. The inventors have found that this type of temperature control for the electrolyte inlet streams 314, 324 can provide fast and linear or near-linear inlet temperature control compared to controlling the temperature of the inlet streams 314, 324 by varying the amount of cooling water being pumped to the cooling heat exchangers 344, 346.
[0164] The combination of fast linear temperature control of the inlets 314, 324 and a feedforward controller that sets an inlet temperature set point based on the current density or the voltage observed across the cell 300 or both can provide stable temperature control for the outlet streams 315, 325 when changing the current density (e.g., when changing the current density applied across the cell 300 to change the H2 production rate to account for changes in electricity pricing, as described in more detail below). Such rapid temperature management can minimize thermal shock to the separator 331, electrodes 312, 322, and other components of the cell 300 while compensating for rapid changes in current density. Dynamic Cellular Operation for Improved Overall Operating Costs.
[0165] The various structural aspects of the electrolyzer cell and other supporting apparatus described above, i.e., the manifold 144 and outlet tube 146 configuration of the exemplary pan assembly 140 to accommodate high gas production rates and high electrolyte flow rates (as described above with respect to FIGS. 3-8), the baffle plate assembly 162 of the exemplary pan assembly 160 to further accommodate high gas production rates and high electrolyte flow rates and aid in temperature distribution within the electrolyte flowing through the pan assembly (as described above with respect to FIGS. 9-15), the ribs 194 and welds 196 for coupling the electrodes 198 to the ribs 194 for power and current distribution and improved temperature distribution (as described above with respect to FIGS. 16-19 and 20A-20C), and the temperature control subsystem for maintaining electrolyte temperature during operation of the cell in response to changes in current density (as described above with respect to FIG. 21), enable the overall water electrolysis H2 gas generation system to be flexible and dynamically adapt to a wide range of operating parameters. In particular, the structural and systemic aspects described herein can enable an electrolyzer cell to operate over a wide range of current densities while still being able to accommodate wide inequalities in heat generation, temperature fluctuations, and gas production rates. For example, an electrolyzer cell with one or more of these features can achieve a current density of about 150 milliamps per square centimeter (mA / cm 2 ) ~ approx. 3,000mA / cm 2 As high as 250mA / cm 2 ~Approx. 2,750mA / cm 2 etc., for example, about 500 mA / cm 2 ~Approx. 2,500mA / cm 2 , about 750mA / cm 2 ~Approx. 2,250mA / cm 2 For example, about 1,000 mA / cm 2 ~Approx. 2,000mA / cm 2The structural and systemic aspects described herein also enable the electrolyzer cell to accommodate a wide range of electrolyte flow rates and gas production rates while still reducing or minimizing slug or plug flow of electrolyte or produced gases through and / or exiting the electrolyzer cell.
[0166] These structural and systematic aspects may enable the electrolyzer cells to be operated at a higher than specified current density and / or a higher than specified gas production rate (i.e., a "nominal" current density and / or a "nominal" H2 gas production rate for the electrolyzer cells or for the plant as a whole) when electricity demand and / or the price of electricity are below a specified threshold and / or during periods when electricity demand and / or the price of electricity are decreasing, which will hereinafter also be referred to as "load harvesting" to take advantage of situations when electricity demand and / or the price of electricity are below a specified threshold. Similarly, the electrolyzer cells are configured to be operated at a current density lower than a specified current density and / or a H2 gas production rate lower than a specified gas production rate (i.e., a "nominal" current density and / or a "nominal" H2 gas production rate for the electrolyzer cells as a whole or for the plant) during periods when the demand for electricity and / or the price of electricity exceeds a specified threshold and / or when the price and / or demand is increasing, which will hereinafter also be referred to as "load shedding" to take advantage of situations when the demand for electricity and / or the price of electricity exceeds a specified threshold or when the price or demand is increasing. In some examples, the electrolyzers described herein are configured to operate at a current density lower than a specified current density and / or a H2 gas production rate lower than a specified gas production rate (i.e., a "nominal" current density and / or a "nominal" H2 gas production rate for the electrolyzer cells as a whole or for the plant 2 ~3.0A / cm 2 However, the device is configured to operate within a range of current density values of 3.0 A / cm 2 and / or 0.15A / cm 2 It should be understood that other ranges and values of current densities, including current density values below, are also suitable for use with the electrolytic cells and methods described herein.
[0167] As will be understood by one of ordinary skill in the art, the price or demand for electricity can vary greatly depending on the location of the electrolyzer cell, and therefore, unless otherwise stated herein, the term "price" or "demand" as used herein when referring to electricity is the price or demand for electricity in the relevant region in which the electrolyzer cell is located.
[0168] The electrolyzer cells described herein can also be manufactured at a relatively low capital expenditure ("CapEx") compared to conventional water splitting electrolysis cells. As used herein, the terms "capital expenditure" and "CapEx" refer to the capital expenses incurred to engineer, design, procure, and construct the electrolyzer cells and supporting equipment (e.g., piping, deionized water generation, pumps for electrolyte and water circulation, gas handling and storage, electrical rectifiers, electrical transformers, and electrical bus connections).
[0169] The relatively low CapEx costs required to design and build the electrolyzer cells of the present disclosure can enable the electrolyzer cells to be designed to be capable of accommodating a maximum current density that is higher than a "nominal" current density (corresponding to a nominal desired H2 gas production rate for which the entire plant is designed), e.g., a current density associated with an optimal current density for which the electrolyzer cells are designed. In other words, if the overall plant is designed for an average H2 gas production capacity (corresponding to a particular cell size and nominal current density), the cells can be designed with one or more of the structural features described above that enable the electrolyzer cells to achieve a higher current density (and thus a higher H2 gas production rate) without making the cell design uneconomical. For example, the H2 gas production rate designed for the entire plant can be about 1 A / cm 2However, in accordance with the present disclosure, electrolyzer cells may be adapted to operate at a nominal operating current density of approximately 1.5 A / cm because they are capable of utilizing electrical demand and / or prices below thresholds and / or declining demand and / or prices set forth in the context of load acquisition. 2 or higher, for example, about 1.6 A / cm 2 or higher, about 1.7A / cm 2 or higher, for example, about 1.75 A / cm 2 or higher, about 1.8A / cm 2 or higher, for example, about 1.9 A / cm 2 or higher, about 2A / cm 2 or higher, for example, about 2.1 A / cm 2 or higher, about 2.2A / cm 2 or higher, for example, about 2.25 A / cm 2 or higher, about 2.3A / cm 2 or higher, for example, about 2.4 A / cm 2 or higher, about 2.5A / cm 2 or higher, for example, about 2.6 A / cm 2 or higher, about 2.7A / cm 2 or higher, for example, about 2.75 A / cm 2 or higher, about 2.8A / cm 2 or higher, for example, about 2.9 A / cm 2 or higher, about 3A / cm 2 or higher, for example, about 3.1 A / cm 2 or higher, about 3.2A / cm 2 or higher, for example, about 3.25 A / cm 2 or higher, about 3.3A / cm 2 or higher, for example, about 3.4 A / cm 2 or higher, about 3.5A / cm 2The cells can be designed to handle substantially higher current densities, such as current densities that are at or above the nominal H2 gas production rate and current density. Similarly, the support equipment for the cells (e.g., piping, deionized water generation, pumps for electrolyte and water circulation, gas processing and storage, electrical rectifiers, electrical transformers, and electrical bus connections) can also be "upsized" relative to what would be required for the nominal H2 gas production rate and nominal current density to take advantage of the higher heat distribution and larger H2 gas handling requirements associated with potential load draw situations and load draws.
[0170] The relatively low CapEx of the electrolyzer cells and their supporting equipment described herein is such that it may still be economical from a capital investment standpoint to operate the electrolyzer cells of the present disclosure at a lower current density and / or a lower H2 gas production rate (which may be the same as or different from a specified current density or a specified H2 gas production rate associated with a load harvest situation, e.g., the specified current density may be a percentage of the nominal current density and / or the specified H2 gas production rate may be a percentage of the nominal H2 gas production rate) when load shedding is performed to reduce overall operating expenditures ("OpEx") when the demand and / or price of electricity is above a threshold and / or increasing demand and / or price. As used herein, the terms "operating expenditures" and "OpEx" refer to the ongoing costs of generating hydrogen gas using electrolyzer cells and other supporting equipment, which may include, but are not limited to, electricity costs, operating labor, regular ongoing maintenance, insurance, engineering and supervisory operations, short-term consumables, and selling and administrative expenses. In contrast, a typical electrolyzer cell, which has a higher CapEx cost, cannot economically produce hydrogen in a load curtailment situation, even if this reduces the OpEx, because the CapEx of the typical electrolyzer cell is so high.
[0171] The electrolyzer cell and overall system of the present disclosure allow for dynamic control of current density, which allows the electrolyzer cell to effectively and efficiently load shed and load harvest compared to existing electrolyzer cells. As described in more detail below, the ability of the electrolyzer cell to operate over a wide range of current densities and gas production rates allows the systems and methods described herein to provide strategic and dynamic operation of the electrolyzer cell for H2 gas production, such that the average cost for H2 gas production is reduced, and in some cases minimized, over the course of long-term operation of the system. In certain examples, the electrolyzer cell provides current densities of less than 1 ampere per square centimeter (A / cm 2 ) or greater (resulting in a corresponding maximum H2 gas production rate), e.g., about 1.5 A / cm 2 Maximum achievable current density of, for example, about 2.0 A / cm 2 Maximum achievable current density, e.g., about 2.5 A / cm 2 , for example, about 3A / cm 2 Maximum achievable current density of, for example, about 3.5 A / cm 2 In addition, the electrolyzer cell and entire system of the present disclosure can be designed to operate at a maximum achievable current density of about 750 milliamps per square centimeter (mA / cm 2 ) or less than the minimum economically viable current density (resulting in a corresponding minimum H2 gas production rate), e.g., about 600 mA / cm 2 The minimum economically viable current density, e.g., about 500 mA / cm 2 The minimum economically viable current density, e.g., about 400 mA / cm 2 The minimum economically viable current density is approximately 300mA / cm 2 A minimum economically viable current density, e.g., about 250 mA / cm 2 The minimum economically viable current density, e.g., about 200 mA / cm 2 The minimum economically viable current density, e.g., about 150 mA / cm 2Thus, the maximum achievable current density for the electrolyzer cell can be approximately 3 A / cm 2 (i.e., about 3,000mA / cm 2 ), and approximately 150mA / cm 2 In an embodiment, the electrolyzer cell may be configured to operate at a current density as low as about 5% of the maximum achievable current density (i.e., 3,000 mA / cm 2 150mA / cm 2 ), which means that the electrolyzer cell has a 95% load shedding and load gain operating range (i.e., 5% to 100% of maximum achievable current density).
[0172] The ability of the electrolyzer cells to dynamically operate at high and low current densities can enable operators to dynamically respond to electricity prices and / or electricity demand and load acquisition when electricity prices and / or demand are low and / or decreasing, and to load shedding when electricity prices and / or demand are high and / or increasing. For example, if the demand for electricity increases over a period of time, the OpEx for the electrolyzer cells will increase by a corresponding amount over the same period due to the increase in the price of electricity, unless the operating current density of the electrolyzer cells is dynamically reduced. Thus, in a load shedding situation, a dynamic reduction in current density dynamically reduces the OpEx, having the effect of countering the expected rise in OpEx associated with an increase in demand.
[0173] In other words, the operating current density of the electrolyzer cells can be varied in response to a period of time when the demand for electricity and / or the price of electricity is increasing or decreasing. An increase or decrease in demand can include an increase in demand (e.g., if the demand during a first period is lower than during a subsequent second period) or a decrease in demand (e.g., if the demand during a first period is higher during a subsequent second period). Similarly, an increase or decrease in price can include an increase in price (e.g., if the price of electricity during a first period is lower than during a subsequent second period) or a decrease in price (e.g., if the price of electricity during a first period is higher during a subsequent second period). Dynamic operation of the electrolyzer cells can be particularly useful during periods of time when the demand for electricity and / or the price of electricity are known to increase or decrease (i.e., are known to increase or decrease), such as during periods spanning overnight hours through mid-afternoon to early evening.
[0174] Electrolyzer cells can be designed to achieve a maximum capacity. As used herein, the term "maximum capacity" when referring to an electrolyzer cell refers to the maximum current density that the electrolyzer cell can reliably achieve (taking into account the ability of the electrolyzer cell to avoid or minimize damage to the separators of the cell and / or to dissipate heat generated to remove gases being produced in the cell without slug or plug flow of gas or electrolyte). In one embodiment, the maximum capacity current density is 1.5 A / cm. 2 or more, e.g., 1.6A / cm 2 or higher, 1.7A / cm 2 or greater, 1.75A / cm 2 or higher, 1.8A / cm 2 or higher, 1.9A / cm 2 or higher, 2A / cm 2 or higher, 2.1A / cm 2 or higher, 2.2A / cm 2 or higher, 2.25A / cm 2 or higher, 2.3A / cm 2 or higher, 2.4A / cm 2or higher, 2.5A / cm 2 or higher, 2.6A / cm 2 or higher, 2.7A / cm 2 or greater, 2.75A / cm 2 or higher, 2.8A / cm 2 or higher, 2.9A / cm 2 or higher, 3A / cm 2 or higher, 3.1A / cm 2 or higher, 3.2A / cm 2 or higher, 3.25A / cm 2 or higher, 3.3A / cm 2 or higher, 3.4A / cm 2 or greater than 2.5A / cm 2 It is.
[0175] In one embodiment, "load shedding" (i.e., a situation in which the operating current density of the electrolyzer cell is reduced in response to high or increasing demand or price for electricity) refers to reducing the operating current density of the electrolyzer cell to 30% or less of maximum capacity, e.g., 29% or less of maximum capacity, 28% or less of maximum capacity, 27% or less of maximum capacity, 26% or less of maximum capacity, 25% or less of maximum capacity, 24% or less of maximum capacity, 23% or less of maximum capacity, 22% or less of maximum capacity, 21% or less of maximum capacity, 20% or less of maximum capacity, 19% or less of maximum capacity, 18% or less of maximum capacity, or the like. including a reduction to below, 17.5% or less of maximum capacity, 17% or less of maximum capacity, 16% or less of maximum capacity, 15% or less of maximum capacity, 14% or less of maximum capacity, 13% or less of maximum capacity, 12.5% or less of maximum capacity, 12% or less of maximum capacity, 11% or less of maximum capacity, 10% or less of maximum capacity, 9% or less of maximum capacity, 8% or less of maximum capacity, 7.5% or less of maximum capacity, 7% or less of maximum capacity, 6% or less of maximum capacity, or 5% or less of maximum capacity.
[0176] In one embodiment, "load harvest" (i.e., a situation in which the operating current density of the electrolyzer cells is increased in response to low or decreasing electricity demand or price) refers to increasing the operating current density to 70% or greater of maximum capacity, 75% or greater of maximum capacity, 76% or greater of maximum capacity, 77% or greater of maximum capacity, 77.5% or greater of maximum capacity, 78% or greater of maximum capacity, 79% or greater of maximum capacity, 80% or greater of maximum capacity, 81% or greater of maximum capacity, 82% or greater of maximum capacity, 82.5% or greater of maximum capacity, 83% or greater of maximum capacity, 84% or greater of maximum capacity, 85% or greater of maximum capacity, 86% or greater of maximum capacity, 87% or greater of maximum capacity, 88% or greater of maximum capacity, 89% or greater of maximum capacity, 90% or greater of maximum capacity, 91% or greater of maximum capacity, 92% or greater of maximum capacity, 93% or greater of maximum capacity, 94% or greater of maximum capacity, 95% or greater of maximum capacity, 96% or greater of maximum capacity, 97% or greater of maximum capacity, 98% or greater of maximum capacity, 99% or greater of maximum capacity, 10 ... or greater than maximum capacity, 87.5% of maximum capacity, 88% of maximum capacity, 89% of maximum capacity, 90% of maximum capacity, 91% of maximum capacity, 92% of maximum capacity, 92.5% of maximum capacity, 93% of maximum capacity, 94% of maximum capacity, 95% of maximum capacity, 96% of maximum capacity, 97% of maximum capacity, 97.5% of maximum capacity, 98% of maximum capacity, 98.5% of maximum capacity, 99% of maximum capacity, 99.5% of maximum capacity, 99.9% of maximum capacity, or maximum capacity (i.e., 100%) of maximum capacity).
[0177] In an embodiment, the electrolyzer system (i.e., including all of the electrolyzer cells in the plant) can generate at least about 1 kilogram of H gas per hour (kg H2 / hr), at least about 1.5 kg H2 / hr, at least about 5 kg H2 / hr, at least about 10 kg H2 / hr, at least about 25 kg H2 / hr, at least about 50 kg H2 / hr, at least about 100 kg H2 / hr, at least about 500 kg H2 / hr, at least about 1,000 kg H2 / hr, at least about 1,500 kg H2 / hr, at least about 2,000 kg H2 / hr, at least about 2,500 kg H2 / hr, at least about 3,000 kg H2 / hr, at least about 3,500 kg H2 / hr, at least about 4,000 kg H2 / hr, at least about 4,500 kg H2 / hr, or at least about 5,000 kg H2 / hr, etc. In an embodiment, the electrolyzer system can generate up to about 30,000 kg H2 / hr, e.g., up to about 25,000 kg H2 / hr, up to about 20,000 kg H2 / hr, up to 15,000 kg H2 / hr, or up to 10,000 kg H2 / hr. As will be appreciated by one of ordinary skill in the art, the actual mass of H2 gas produced by the electrolyzer system will depend on many factors, including the area of each electrolyzer cell, the number of electrolyzer cells in the electrolyzer system, and the current density at which the electrolyzer cells are operated. In an embodiment, the mass of H2 gas that can theoretically be generated per ampere of current supplied to the electrolyzer cell is about 3.761×10 -5 kg H2 / hr. Therefore, the theoretical mass of H2 gas that an electrolyzer system can generate is equal to the total amperes supplied for electrolysis, which in turn is equal to the current density applied to the electrolyzer cells times the total area of the electrolyzer cells (or area per electrolyzer cell times the number of cells times the current density).
[0178] As discussed in more detail below, the ability to dynamically load harvest and load shedding can result in an overall average cost per kilogram ($ / kg) of H2 gas production that is lower than is possible with conventional electrolyzer cells operated in a steady-state mode. In some examples, discussed in more detail below, the dynamic load harvest and load shedding of the present disclosure can enable a reduction in the cost of electricity required to produce the same amount of H2 gas by about 20% to about 40% or more (e.g., even as much as 50% or more).
[0179] FIG. 22 is a graph illustrating a typical price of electricity over a 24-hour period (e.g., from midnight to midnight the next day) according to data collected by the Electric Reliability Council of Texas ("ERCOT"). Data line 400 represents the average price of electricity in US dollars per megawatt hour ($ / MWh) at a particular time of day. Data lines 402 and 404 represent one standard deviation above and one standard deviation below the average price at each particular time of day, respectively. As can be seen from FIG. 22, the price of electricity tends to remain relatively steady from hour 1 (i.e., midnight) until about hour 10 (i.e., 9:00 AM), at which point the average price rises fairly sharply with large fluctuations to above $60 / MWh. The high average price and high volatility remain until about hour 19 or hour 20 (e.g., 6-7:00 PM), at which point the average price begins to drop downward toward the more stable prices observed at the start of the day. In other words, the price of electricity tends to be low and has little variance during the night and early morning hours, and then tends to rise and have large variance during the day and afternoon hours. The ability to dynamically operate electrolyzer cells through load shedding and load harvesting allows an operator to, for example, operate electrolyzer cells at high loads (i.e., e.g., below 1 A / cm) during periods of low electricity pricing (i.e., during night hours such as hours 1-10 and after about hour 22 in the graph of FIG. 22). 2By allowing the electrolyzer cells to operate at high loads (i.e., high current densities, above a prescribed current density, for example, above a prescribed current density, etc.) and then operating the electrolyzer cells at low loads (i.e., low current densities, below a prescribed current density, for example) during periods of high electricity pricing (i.e., during the daytime hours from hours 10 to 22 in the graph of FIG. 22), the systems and methods described herein can dynamically respond to electricity prices and enable achieving overall electricity costs that are less than those that would be incurred by conventional steady state operation, as described below.
[0180] FIG. 23 illustrates an example scenario involving changes in electricity pricing and how the systems and methods described herein may be dynamically operated in a load-taking and load-shedding mode to reduce the overall average price of H2 gas production compared to conventional operation of the electrolyzer cells at a constant or substantially constant current density and H2 gas production rate that does not consider the current price of electricity. Data lines 406 correspond to the increasing and decreasing price of electricity over the course of a full two-day operation. Lines 408 show that the electrolyzer cells are operated to take load during periods when the price of electricity is below a defined lower price threshold (e.g., about $25 per MWh in the example of FIG. 23), the current density is tapered when the price of electricity exceeds a defined lower price threshold, and the electrolyzer cells are shut off (i.e., 0 A / cm2) when the price of electricity exceeds a defined upper price threshold (e.g., about $40 per MWh in the example of FIG. 23). 2 23. Data line 410 is a data series of operating current densities of electrolyzer cells according to the present disclosure at various times over the course of the same two days when operated at a "nominal" current density (e.g., about 1 A / cm for the example of FIG. 23) at which the electrolyzer cells are designed to be operated. 2 ) In other words, data line 410 represents "conventional" operation of the electrolyzer cells at the capacity for which they were designed. As can be seen in Figure 23, if the electrolyzer cells were operated continuously at their nominal current density sustainedly, the average price of electricity over the two days represented by the data in Figure 23 would be $28 per MWh.
[0181] In the example of FIG. 23, the electrolyzer cells are configured to reduce load harvest current density (e.g., about 2 A / cm) when the price of electricity is below a prescribed lower price threshold (e.g., when the price is ≦$25 per MWh in the example of FIG. 23). 2 ), and when the price of electricity is between a specified lower price threshold and a specified upper price threshold, it is operated at a variable load shedding current density (e.g., when the price is between $25 / MWh and $40 / MWh in the example of FIG. 23, the current density is between 0 and 2 A / cm depending on the price of electricity). 2 ) and is shut off if the price exceeds a specified upper price threshold (e.g., 0 A / cm when the price exceeds $40 / MWh in the example of FIG. 23). 2 In the example scenario shown in FIG. 23, the average current density over the course of two days is about 1.6 A / cm (as represented by data line 412). 2 , which is equal to 1 A / cm during conventional operation of the electrolyzer cell. 2 23 )。 Also, the average cost of electricity consumed over the course of two days of operation was about $22 per MWh (represented by data line 414), which corresponds to about a 20% reduction in the cost of electricity during the load acquisition and load shedding operations of the present disclosure. In other words, in the example scenario shown in FIG. 23 , not only was the cost of electricity substantially lower than conventional operation of the electrolyzer cell (i.e., about $22 / MWh vs. about $28 / MWh, i.e., 20% less electricity cost over the same period), but the same electrolyzer cell was able to consume a substantially higher average current density (i.e., about 1.6 A / cm on average). 2 to 1A / cm 2 , i.e., about 60% higher). As will be appreciated by one of ordinary skill in the art, this means that the same electrolyzer cell was capable of producing substantially more H gas at substantially lower operating costs (since the production rate of H gas is proportional to the current density).
[0182] The example scenarios and threshold electricity prices of Figure 23 are provided for illustrative purposes only and are not intended to limit the scope of the present disclosure. One skilled in the art will understand that the operating current density of the electrolyzer cell and the threshold electricity price that triggers the adjustment of the operating current density can be varied and still be encompassed by the present disclosure. As described above, electrolyzer cells that may be incorporated into the load harvesting and load shedding systems and methods of the present disclosure can be used over a wide range of current densities, for example, up to about 0.15 A / cm 2 from the lower limit of 3A / cm 2 This large dynamic range of operating current densities may allow an operator to choose, with considerable flexibility, a minimum electricity price threshold for beginning the transition from the load harvest current density to the load shedding current density, and a maximum electricity price threshold for operating the load shedding current density or shutting down the electrolyzer cells completely, and to include one or more additional intermediate price thresholds for setting one or more intermediate operating current densities.
[0183] One skilled in the art will also understand that the particular operating current density per price threshold may be selected based on aspects of the particular electrolyzer cell, including, but not limited to, the optimal current density for the particular electrolyzer cell (e.g., the current density that is most efficient at producing H2 gas based on the mass of H2 gas produced per MW of electricity consumed, which itself may depend on the price of electricity), the maximum current density that the electrolyzer cell can achieve (e.g., depending on the ability of the electrolyzer cell to remove the gas produced and / or dissipate the heat generated), or the cost per kilogram of H2 gas produced for the electrolyzer cell at various current densities and various prices of electricity per MWh.
[0184] Figures 24 and 25 show an example of these considerations for a particular electrolyzer cell. Figure 24 shows a cost curve (represented by line 416) for a particular exemplary electrolyzer cell. The cost curve 416 corresponds to a total levelized cost per kilogram of H2 gas produced at different operating current densities when the price of electricity is $26.6 / MWh. For this example, i.e., electrolyzer cell, the cost curve 416 corresponds to a production cost of about $1.91 per kg of H2 gas produced at about 1.12 A / cm2. 2 24 has a minimum point 418 at a current density of about 1.66 A / cm. The cost curve 416 in FIG. 24 corresponds to the cost if the electrolyzer cell is operated at a constant current density, rather than the cost if the load acquisition and load shedding methods of the present disclosure are implemented. In other words, the cost curve 416 corresponds to an exemplary electrolyzer cell operated in a conventional manner, similar to line 410 in FIG. 23. However, if the load acquisition and load shedding methods of the present disclosure are implemented (e.g., similar to the example described above with respect to FIG. 23), the effective optimal current density for the same exemplary electrolyzer cell (at data point 420) is about 1.66 A / cm. 2 (the minimum point 418 on the conventional cost curve 416 for 1.19 A / cm 2 416), the average cost per kilogram of H2 is reduced to about $1.69 / kg H2 (about an 11.5% reduction compared to $1.91 / kg H2 for the minimum point 418 on the conventional cost curve 416).
[0185] FIG. 25 shows a graph of optimal current density (represented by data line 422) for a particular example electrolyzer cell as a function of the price of electricity. As used herein, the term "optimum current density" refers to the current density that achieves the minimum cost per kilogram of H2 produced at a particular electricity price. In an embodiment, the optimal current density for each electricity price can be determined, for example, by finding the minimum point on the cost curve associated with each electricity price, in a manner very similar to that implemented in FIG. 24. In the embodiment of FIG. 25, when the price falls below $35 / MWh (i.e., $0.035 / kWh), the electrolyzer cell achieves approximately 2 A / cm 2The optimal current density is at or above the maximum current density at which the exemplary electrolyzer cell can operate, such that the electrolyzer cell can start up at its maximum current density of 100 kWh (e.g., the electrolyzer cell can be operated in full load harvesting mode). At a price of about $35 / MWh, the optimal current density begins to fall as prices rise, such that, in some examples, the operating current density for the electrolyzer cell can be tapered as electricity prices rise above $35 / MWh. In other words, in the example of FIG. 25, $35 / MWh is a defined lower price threshold that corresponds to the beginning of the transition between load harvesting and load shedding (as described above with respect to FIG. 23). As shown in FIG. 25, when the price of electricity reaches about $50 / MWh, the optimal current density for the exemplary electrolyzer cell reaches zero (0) (ignoring other considerations such as the cost of shutdown and start-up labor, wear on plant equipment, and the like). Thus, when prices are higher than $50 / MWh, the exemplary electrolyzer cell can be shut down. In other words, in the example of FIG. 25, $50 / MWh is the defined upper price threshold (as described above with respect to FIG. 23). One skilled in the art will appreciate that the exact price point for the defined upper price threshold can be varied from the actual price point at which the optimal current density reaches zero, and that the amount of variance can depend on one or more factors, including, but not limited to, capital expenditures (e.g., CapEx) for the exemplary electrolyzer cells and other supporting equipment, the overall size of the electrolyzer cells in the plant (e.g., size of the cell stack), the current price at which the produced H2 gas can be sold, and other operating expenses (such as the cost of labor to start up the plant or to shut down and start up the plant, or the price of water, or the cost of regular maintenance for the electrolyzer cells and supporting equipment). In fact, the "optimum" current density at any point along the optimal current density curve 422 can be varied from a theoretical or calculated optimal current density based on one or more of these same factors.
[0186] The above detailed description includes references to the accompanying drawings, which form a part of the detailed description. The drawings show, by way of illustration, specific embodiments in which the invention may be practiced. These embodiments are also referred to herein as "examples." Such examples may include elements in addition to those shown or described. However, the inventors also contemplate examples in which only those elements shown or described are provided. The inventors also contemplate examples using any combination or permutation of those elements shown or described (or one or more aspects thereof), either with respect to a particular example (or one or more aspects thereof) or with respect to other examples (or one or more aspects thereof) shown or described herein.
[0187] In the event of a conflicting usage between this document and any document so incorporated by reference, the usage in this document shall control.
[0188] The terms "a" or "an" are used herein, as is common in patent documents, to include "one or more than one," independent of any other instance or usage of "at least one" or "one or more." The term "or" is used herein to refer to a non-exclusive "or," such that "A or B" includes "A but not B," "B but not A," and "A and B," unless otherwise indicated. The terms "including" and "in which" are used herein as the plain English equivalents of the respective terms "comprising" and "wherein." Also, in the following claims, the terms "including" and "comprising" are open-ended, i.e., systems, devices, articles, compositions, formulations, or processes that include elements in addition to those listed after such terms in a claim, are still considered to be within the scope of that claim. Also, in the following claims, the terms "first," "second," and "third," etc. are used merely as labels and are not intended to impose numerical requirements on their purposes.
[0189] The method embodiments described herein can be at least partially machine or computer implemented. Some embodiments can include a computer-readable medium or machine-readable medium encoded with instructions operable to configure an electronic device to perform the methods as described in the above embodiments. Such method implementations can include code, such as microcode, assembly language code, higher level language code, or the like. Such code can include computer-readable instructions for performing various methods. The code can form part of a computer program product. Furthermore, in some embodiments, the code can be tangibly stored on one or more volatile, non-transitory, or non-volatile tangible computer-readable media, such as during execution or at other times. Examples of these tangible computer-readable media can include, but are not limited to, hard disks, removable magnetic disks, removable optical disks (e.g., compact disks and digital video disks), magnetic cassettes, memory cards or sticks, random access memory (RAM), read-only memory (ROM), and the like.
[0190] The above description is intended to be illustrative and not restrictive. For example, the above described embodiments (or one or more aspects thereof) may be used in combination with each other. Other embodiments may also be used by those of skill in the art upon review of the above description. The Abstract is provided to comply with 37 C.FR §1.72(b) to enable the reader to quickly ascertain the nature of the present technical disclosure. It should be considered with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. Also, in the above detailed description, various features may be grouped together to simplify the disclosure. This should not be construed as intending that an unclaimed disclosed feature is essential to any claim. Rather, the subject matter of the invention may lie in less than all features of a particular disclosed embodiment. Thus, the following claims are incorporated herein as examples or embodiments into the detailed description, with each claim standing on its own as a separate embodiment, and it is contemplated that such embodiments may be combined with each other in various combinations or permutations. The scope of the invention should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.
Claims
1. An electrolytic cell system, the electrolytic cell system comprising: one or more electrolytic cell, each of the one or more electrolytic cell comprising a first half-cell with a first electrode, a second half-cell with a second electrode, and a separator between the first half-cell and the second half-cell; a controller configured to control a current density applied through each of the one or more electrolyzer cells; Equipped with the controller is configured to dynamically adjust the current density applied through each of the one or more electrolyzer cells within a current density range of 150 mA / cm to 3,000 mA / cm in response to changes in the price of electricity in a region in which the electrolyzer system is located; The dynamic adjustment of the current density by the controller comprises: operating the one or more electrolyzer cells at a first current density within the range of 150 mA / cm 2 to 3,000 mA / cm 2 when the price of electricity in the region is a first defined price; increasing the current density applied through each of the one or more electrolyzer cells above the first current density in the range of 150 mA / cm 2 to 3,000 mA / cm 2 when the price of electricity in the region decreases below the first defined price; reducing the current density applied through each of the one or more electrolyzer cells below the first current density in the range of 150 mA / cm 2 to 3,000 mA / cm 2 when the price of electricity in the region increases above the first defined price; 1. An electrolyzer system comprising:
2. The dynamic adjustment of the current density by the controller comprises: reducing the current density applied through each of the one or more electrolyzer cells to no more than a first fraction of a maximum capacity current density of the one or more electrolyzer cells when the price of electricity in the region exceeds the first defined price; increasing the current density applied through each of the one or more electrolyzer cells to greater than or equal to a second fraction of the maximum capacity current density when the price of electricity in the region decreases below a second predetermined price; Including, 2. The electrolyzer system of claim 1, wherein the second specified price is lower than the first specified price.
3. The dynamic adjustment of the current density by the controller comprises: operating each of the one or more electrolyzer cells at a variable current density between the first fraction and the second fraction of the maximum capacity current density when the price of electricity in the region is between the first specified price and the second specified price.
3. The electrolytic cell system of claim 2, further comprising:
4. An electrolytic cell system as described in claim 3, wherein the variable current density is dependent on and inversely correlated with the price of electricity in the region.
5. An electrolytic cell system as described in claim 2, wherein the first proportion of the maximum capacity current density is 25%.
6. An electrolytic cell system as described in claim 2, wherein the second proportion of the maximum capacity current density is 75%.
7. The electrolytic cell system of claim 1, wherein the first percentage of the maximum capacity current density results in a current density of 750 mA / cm 2 or less, and the second percentage of the maximum capacity current density results in a current density of 1 mA / cm 2 or more.
8. An electrolytic cell system as described in claim 1, wherein the electrolytic cell system comprises at least two separate electrolytic cell cells.
9. The electrolyzer system of claim 1, wherein the one or more electrolyzer cells have a total size of at least about 2.5 m 3 .
10. A method for conducting electrolysis, the method comprising: dynamically adjusting the current density associated with operation of said electrolyzer within a range of values between 150 mA / cm 2 and 3,000 mA / cm 2 in response to changes in the price of electricity in the region in which said electrolyzer is located. Including, The dynamic adjustment of the current density associated with operation of the electrolytic cell comprises: operating the electrolytic cell at a first current density within the range of values between 150 mA / cm2 and 3,000 mA / cm2 when the price of electricity in the region is a first specified price; increasing the current density of the electrolytic cell above the first current density within a range of values between about 150 mA / cm2 and about 3,000 mA / cm2 when the price of electricity in the region decreases below the first defined price; reducing the current density of the electrolytic cell below the first current density within a range of values between about 150 mA / cm 2 and 3,000 mA / cm 2 when the price of electricity in the region increases above the first defined price; A method comprising:
11. Dynamically adjusting the current density associated with operation of the electrolytic cell comprises: reducing a current density to no more than a first fraction of a maximum capacity current density of the electrolytic cell when the price of electricity in the region exceeds the first defined price; increasing the current density to greater than or equal to a second percentage of the maximum capacity current density of the electrolytic cell when the price of electricity in the region decreases below a second predetermined price; Including, The method of claim 10 , wherein the second specified price is lower than the first specified price.
12. Dynamically adjusting the current density associated with operation of the electrolytic cell comprises: operating the electrolyzer at a variable current density between the first fraction and the second fraction of the maximum capacity current density when the price of electricity in the region is between the first specified price and the second specified price. The method of claim 11 further comprising:
13. The method of claim 12, wherein the variable current density is dependent on and inversely correlated with the price of electricity in the region.
14. The method of claim 11, wherein the first percentage of the maximum capacity current density is 25%.
15. The method described in claim 11, wherein the second percentage of the maximum capacity current density is 75%.