The present disclosure is directed to moisture and carbon dioxide management systems for electrochemical cells, and more in particular, to electrochemical cells comprising air breathing cathodes and utilizing a liquid ionically conductive medium.
Many types of electrochemical cells utilize a liquid ionically conductive medium to support electrochemical reactions within the cell. Electrochemical cells may utilize an air breathing electrode coupled to a fuel electrode, comprising any suitable fuel. For example, a metal-air electrochemical cell system may comprise a plurality of cells, each having a fuel electrode serving as an anode at which metal fuel is oxidized, and an air breathing oxidant reduction electrode at which oxygen from ambient air is reduced. The liquid ionically conductive medium in such cells may communicate the oxidized/reduced ions between the electrodes.
In various ionically conductive mediums, evaporation, electrolysis (e.g. water splitting on recharge or during self-discharge) or other loss of moisture from the ionically conductive medium, may be detrimental to the electrochemical cell, particularly for cells requiring water to operate. For example, salting of the ionically conductive medium due to water loss, may clog an oxidant electrode of the electrochemical cell, reducing its performance or, in extreme cases, resulting in complete cell failure. Such salting or other failures may occur, for example, where an air-side of the oxidant electrode, or a portion thereof, is excessively dry. Additionally, a decrease in water content in the ionically conductive medium may decrease the medium's solvating capacity, i.e., its ability to dissolve solutes, or increase the percentage concentration of solutes in the medium, affecting the functionality of the ironically conductive medium.
Metal-air electrochemical cells are utilized in a wide variety of environmental conditions, including very hot and dry environments. These cells may have limited effectiveness and/or life as a result of the loss of moisture from the liquid ionically conductive medium.
Electrochemical cell water conservation and management systems have been developed such as U.S. patent application Ser. No. 14/176,888, filed Feb. 10, 2014, Fluidic Inc., which provides an example of a battery water management system; the entirety of which is hereby incorporated by reference in its entirety.
The disclosure is directed to an electrochemical cell, such as a metal-air electrochemical cell that can effectively operate in a wide range of environmental conditions, including very arid environments. Many electrochemical reactions benefit from an oxygen rich air supply or an airflow with reduced carbon dioxide. In addition, in alkaline fuel cells or rechargeable battery systems comprising an alkaline electrolyte, carbon dioxide can react with the electrolyte to form potassium carbonate, which lowers the conductivity of the electrolyte by decreasing the hydroxide concentration and decreasing the solubility of a metal species, such as zinc. In addition, precipitation of carbonate within the pores of the air electrode can damage the electrode, expand the pore structure and lead to leakage. It is to be understood that some embodiments of the moisture, i.e. water, and carbon dioxide management system described herein, may be utilized in various electrochemical cells, including fuel cells and in particular, alkaline fuel cells and polymer electrolyte membrane (PEM) fuel cells. In alkaline electrochemical cells, such as metal-air batteries, that use air breathing electrodes which have open communication to air at ambient conditions, carbon dioxide is absorbed from the air into the electrolyte through the air breathing electrode, and moisture (water) is lost from the electrolyte to the air (ambient) through evaporation through the air breathing electrode. This disclosure utilizes multiple mechanisms and/or methods, e.g., four, to decrease the amount of carbon dioxide absorbed from the air and moisture lost to the air, e.g., in accordance with one embodiment: a carbon dioxide scrubber to remove carbon dioxide from the air prior to it entering the air breathing electrode chamber; a humidity exchange membrane (HEM) which transfers moisture lost through evaporation into the air stream leaving the air breathing electrode chamber back into the air stream entering the air breathing electrode chamber; an air recirculation mechanism that directs a portion of carbon dioxide depleted, humidity laden air leaving the air breathing electrode chamber back into the air stream entering the air breathing electrode chamber; and a vent filter that catches and returns electrolyte liquid droplets leaving the cell as a mist due to gas generated during normal cell electrochemical reactions and returning that liquid back to the cell. These mechanisms may operate independently or dependently to reduce the amount of carbon dioxide absorbed into the electrolyte and to reduce the amount of moisture lost from the cell.
The summary of the disclosure is provided as a general introduction to some of the embodiments of the disclosure, and is not intended to be limiting. Additional example embodiments including variations and alternative configurations of the disclosure are provided herein.
The accompanying drawings are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure, and together with the description serve to explain the principles of the disclosure.
Corresponding reference characters indicate corresponding parts throughout the several views of the figures. The figures represent an illustration of some of the embodiments of the present disclosure and are not to be construed as limiting the scope of the disclosure in any manner. Further, the figures are not necessarily to scale, some features may be exaggerated to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.
As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the disclosure. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
Certain exemplary embodiments of the present disclosure are described herein and are illustrated in the accompanying figures. The embodiments described are only for purposes of illustrating the present disclosure and should not be interpreted as limiting the scope of the disclosure. Other embodiments of the disclosure, and certain modifications, combinations and improvements of the described embodiments, will occur to those skilled in the art and all such alternate embodiments, combinations, modifications, improvements are within the scope of the present disclosure.
An exemplary moisture and carbon dioxide system in accordance with embodiments of this disclosure may comprise a recirculation mechanism wherein at least a portion of the air exiting the electrochemical cell is recirculated back into the air inflow to the cell. Many electrochemical cells produce heat and an exhaust flow that is high in humidity and therefore conserving this moisture through recirculation can effectively conserve the moisture in the system.
An exemplary moisture and carbon dioxide management system in accordance with embodiments of this disclosure comprises a humidity exchange membrane (HEM), for transfer of moisture from the outflow of air from a chamber containing the air breathing electrode of the electrochemical cell to the air inflow of said chamber. The HEM comprises a moisture exchange material, such as a membrane comprising an ionomer, such as perfluorosulfonic acid polymer, for example. A HEM separates air inflow to the cell from air exiting the electrochemical cell, such as from the oxidant reduction electrode air chamber, whereby moisture from the air exiting the cell is transferred through the humidity exchange membrane to the air inflow due to a relative humidity (RH) difference across the membrane (air outflow at high RH, air inflow at low RH). The air exiting the oxidant reduction electrode air chamber, or air chamber outflow, is warm and humid and therefore can carry a relatively high amount of moisture which enables the HEM to work effectively. This exiting air picks up moisture from the liquid ionically conductive medium as it flows through the cell and is heated due to the increased heat from the chemical reactions. The air chamber outflow may be hotter and contain a relatively high moisture content. For example, the air chamber outflow may be 10° C., 20° C., 30° C., or 40° C. hotter than the air inflow. The electrochemical reactions within the cell heat the air chamber and also humidify the air chamber air. For example, the air chamber outflow may have a relative humidity of more than about 70%, more than about 80%, more than about 90%, more than about 95%, and substantially fully saturated, depending on the flow rates, size of the system and environmental conditions. As an example, air inflow may be very dry, at only 20% relative humidity at 30° C. and may pass by a HEM module having air chamber outflow on the opposing side of the HEM at 90% relative humidity at 50° C., to increase the air inflow humidity to about 70% before entering the cell. A HEM may be configured in a module comprising multiple layers, folds, pleats or corrugations of the HEM to increase the amount of surface area that the air stream must flow over, thereby increase the amount of moisture transferred. In accordance with an embodiment, a marketed or manufactured HEM or HEM module may be used. An exemplary HEM or HEM module is available from DPoint Technologies, Vancouver, BC, Canada, for example, and may be used in the disclosed system. However, this example is not intended to be limiting.
An exemplary moisture and carbon dioxide management system in accordance with embodiments of this disclosure comprises a recirculation feature, such as a valve or other mechanism, that may be configured to reintroduce some of the air chamber outflow directly back into the air inflow, thereby increasing the moisture level of the air inflow. When an electrochemical cell is located in a very arid environment, recirculation of the outflow air into the air inflow can effectively conserve moisture in the system. A recirculation feature may be configured upstream, prior to the inflow air reaching the HEM, or downstream of the HEM. In one embodiment, it may be preferred to locate a recirculation feature upstream of the HEM, whereby the outflow air flows past the HEM, thereby maintaining the HEM in a warm moist state, prior to recirculation. As described herein, in some embodiments, a HEM may work more effectively when maintained in a warm and moist condition. A recirculation feature may be a valve that is operated by a control system or may be a baffle that is automatically controlled by pressure. A control system may monitor the moisture level within and external to the system, such as relative humidity, RH, of the air inflow, the air outflow, the ambient RH, the liquid electrolyte level and the like to determine when and how much recirculation to include into the air inflow. The air exiting the oxidant reduction electrode air chamber, or air chamber outflow, is warm and humid and a portion or amount thereof may be recirculated into the air inflow. In one embodiment, a valve is opened and closed to control when the air chamber outflow is recirculated and what portion or amount is recirculated. For example, in very arid environments, a high proportion of the air chamber outflow may be recirculated, such as about 40% or more, about 50% or more, about 70% or more, about 90% or more, or all of the air chamber outflow or any portion between and including the percentages provided. The remaining air chamber outflow may be passed through the air flow device and out of the cell.
For example, in one embodiment, an exemplary electrochemical cell may utilize a recirculation feature that provides about 50% of the inflow to the cell from air outflow from the cell. The ambient air, or inlet air may comprise about 400 ppm carbon dioxide, 50% RH, and 21.2% oxygen. The air outflow from the cell may have a reduced carbon dioxide concentration, such as about 0%, due to the scrubber and/or reaction within the cell, 100% RH, and a reduced oxygen concentration of about 12%. When the ambient air and air outflow from the cell are mixed through the recirculation feature the inlet airflow to the cell will have a 200 ppm carbon dioxide concentration, about 75% RH, and 18% oxygen. The electrochemical cell may be configured to run at a three or four stoichiometry for oxygen and therefore a slightly reduced oxygen concentration will not create a loss of power generation potential. In addition, there will be a large benefit from the increase humidity level and reduced carbon dioxide level which will result in extending the life of the electrochemical cell.
An exemplary moisture and carbon dioxide management system in accordance with embodiments of this disclosure comprises a mist elimination system that may be incorporated to control the loss of liquid ionically conductive medium, such as an electrolyte. A mist elimination system may comprise a baffle or valve, a filter, a hydrogen recombination catalyst, a neutralizer and a hydrophobic filter. An exemplary mist elimination system reacts hydrogen to form water that may be drained back into the electrochemical cell. Gasses produced during normal cell operation, such as for a metal-air cell during self-discharge or cell charge, rise to the surface of the electrolyte as bubbles which burst at the electrolyte surface. The action of the bursting bubble generates a fine mist of electrolyte which will leave the cell with the effluent gas stream. An exemplary mist elimination filter is placed in this gas stream to recapture this electrolyte mist and return it to the liquid electrolyte.
The operational relative humidity ranges, or humidity ranges within the air chamber, may depend on the particular ionically conductive medium, in addition to the temperature of ambient air and the cell, for example. It may be appreciated that aqueous salt electrolytes, e.g., potassium hydroxide, may be characterized as hygroscopic. For example, for a cell comprising an aqueous KOH electrolyte, a relative humidity less than ca. 50% may result in water loss through the oxidant reduction electrode, or air electrode. An ambient relative humidity greater than 80% (or greater than ca. 80%) may result in water uptake into the cell through the oxidant reduction electrode, or air electrode. Water release through the air electrode may occur at greater relative humidity than ca. 50% in an air temperature range of 50 degrees Celsius to 80 degrees Celsius. A relative humidity from 50% (inclusive) to 80% (inclusive), or in a mid-range, may be characterized as neutral. For example, at 70% relatively humidity into the cell, 250 ml of water may be lost at 50 degrees C., and only 15 ml (which is considered negligible in a cell having 8 liters total volume) is lost at 25 degrees C. It should be appreciated that the ranges may also and/or alternatively change depending on the ionically conductive medium and its hygroscopic/hygrophobic characteristics.
A variety of water management techniques are described herein and may be used with the disclosed system. U.S. patent application Ser. No. 15/077,341, to Fluidic Inc., filed on Mar. 22, 2016, entitled Water Management System In Electrochemical Cells with Vapor Return Comprising Air Electrodes describes some other water management systems and techniques and is incorporated, in its entirety, by reference herein.
An exemplary moisture and carbon dioxide management system in accordance with embodiments of this disclosure comprises a scrubber module for removing carbon dioxide, CO2, from the air inflow to the cell. Some exemplary scrubber media, such as soda-lime, requires some moisture to react with the carbon dioxide. The scrubber media may absorb some moisture from the air inflow. This absorbed moisture may be reintroduced to the cell by heating of the scrubber. Heating may be passive heating, wherein heat generated from the cell is used to heat the scrubber, or a dedicated resistive heater element may be used to heat the scrubber.
An exemplary scrubber system operates more effectively when the incoming air to the scrubber is humidified and therefore receiving inflow air to the scrubber after passing through the HEM may improve overall system effectiveness. The scrubber may absorb some of the moisture from the airflow therethrough, and this absorbed moisture may be reintroduced to the cell by heating the scrubber. Heating may be passive heating, wherein heat generated from the cell is used to heat the scrubber, or a dedicated resistive heater element, controlled by the controller, may be used to heat the scrubber. In the case of passive heating, heat from the electrochemical cell may be conducted to the scrubber module and specifically to the scrubber media. Conductive elements may be configured to increase the amount of heating that his conducted to the scrubber media. In the case of active heating, an electrically resistive heating element is configured to heat the scrubber and/or scrubber media. Electrical current generated by the electrochemical cell may be passed through the electrically resistive heating element continuously or it may be turned on and off by a switch that is activated by the control system. Again, the control system may receive input values from one or more sensors that are used to activate the heating of the scrubber heater. In an exemplary embodiment, the electrochemical cell may be configured to run the airflow device even when the electrochemical cell is not operating to produce power, and thereby absorb moisture from the environment in the scrubber media which may be subsequently desorbed, or driven out of the scrubber media and into the electrochemical cell. For example, the control system may subsequently heat the scrubber media to drive off absorbed moisture from the scrubber media.
An exemplary scrubber comprises scrubber media that is reversible or irreversible. A reversible scrubber media may be reactivated by heating, for example, wherein the absorbed carbon dioxide is desorbed and driven off from the scrubber media. A reversible scrubber material may be reactivated by heating to about 70° C. or more, or about 90° C. or more. Therefore, a scrubber module that is configured to be heated to drive off absorbed moisture may also be reactivated when comprising a reversible scrubber media. When irreversible scrubber media reacts with the carbon dioxide it is changed chemically and is consumed. Scrubber media, irreversible or reversible, may be purged periodically to regulate the humidity level and in the case of reversible media, to drive off the absorbed carbon dioxide. A purge cycle may be run while a reversible scrubber media is heated to more effectively purge the desorbed carbon dioxide from the system. During a scrubber purge cycle, a flow of air through the scrubber may be reversed, wherein the air flow device, such as a fan, is reversed and therefore pushes air through the cell into the scrubber and out of the air inlet. In addition, the rate of flow of air through the scrubber may be increased, wherein the flow rate is higher, such as at least two times, three times, five times, ten times or more higher than a standard operational flow rate. This may be accomplished by increasing the fan speed, for example. In still another embodiment, a valve enables air to flow through the scrubber and then directly out of the outlet of the system without passing through the cell housing, and/or without passing by the HEM after it exits the scrubber.
A scrubber media may comprise media or material(s) selected from the group of: soda lime, sodium hydroxide, potassium hydroxide, and lithium hydroxide, lithium peroxide, calcium oxide, serpentinite, magnesium silicate, magnesium hydroxide, olivine, molecular sieves, amines, and monoethanolamine, and/or derivatives and/or combinations thereof. Amine scrubber media is reversible whereas soda lime is irreversible.
A scrubber configured to remove carbon dioxide from an air inflow to a metal-air electrochemical cell is described in U.S. patent application Ser. No. 15/077,341, to Fluidic Inc., filed on Mar. 22, 2016, entitled Water Management System In Electrochemical Cells with Vapor Return Comprising Air Electrodes and currently pending; the entirety of which is hereby incorporated by reference herein.
Various portions of the electrochemical cell 100 may be of any suitable structure or composition, including but not limited to being formed from plastic, metal, resin, or combinations thereof. Accordingly, the cell 100 may be assembled in any manner, including being formed from a plurality of elements, being integrally molded, or so on. In various embodiments the cell 100 and/or the housing 110 may include elements or arrangements from one or more of U.S. Pat. Nos. 8,168,337, 8,309,259, 8,491,763, 8,492,052, 8,659,268, 8,877,391, 8,895,197, 8,906,563, 8,911,910, 9,269,996, 9,269,998 and U.S. Patent Application Publication Nos. 20100316935, 20110070506, 20110250512, 20120015264, 20120068667, 20120202127, 20120321969, 20130095393, 20130115523, and 20130115525, each of which are incorporated herein in their entireties by reference.
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The exemplary mist elimination system 80 comprises a hydrogen recombination portion 86, comprising a hydrogen recombination catalyst that reacts with any hydrogen to form water. The catalyst may be configured on a support material such as particles or surfaces of the mist elimination system that are exposed to the gas exiting the cell housing from the anode space. Air may enter in to the mist elimination system through the hydrophobic filter 98 to provide the necessary oxygen for the hydrogen recombination reaction. The hydrophobic filter may prevent or substantially prevent water ingress into the electrochemical cell.
The exemplary mist elimination system comprises a neutralizer portion 90 comprising a neutralizer media 91, such as an acid, configured to neutralize the ionically conductive medium. For example, the ionically conductive medium may comprise a potassium hydroxide solution that is caustic, and a neutralizer may be a solid acid or acid on carbon or some other support material. The neutralizer is configured to reduce any reactive gases that may exhaust from the anode chamber or the chamber containing the ionically conductive medium.
It will be apparent to those skilled in the art that various modifications, combinations and variations can be made in the present disclosure without departing from the spirit or scope of the disclosure. Specific embodiments, features and elements described herein may be modified, and/or combined in any suitable manner. Thus, it is intended that the present disclosure cover the modifications, combinations and variations of this disclosure provided they come within the scope of the appended claims and their equivalents.
This application is a Continuation of U.S. Ser. No. 16/318,513, filed Jan. 17, 2019, which is the U.S. National Phase of PCT/US2017/043489, filed Jul. 24, 2017, which claims priority to Provisional Patent Application Ser. No. 62/365,866, filed Jul. 22, 2016, the subject matter of each of which is incorporated by reference herein in its entirety.
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Number | Date | Country | |
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20210249715 A1 | Aug 2021 | US |
Number | Date | Country | |
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62365866 | Jul 2016 | US |
Number | Date | Country | |
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Parent | 16318513 | US | |
Child | 17245614 | US |