Mist elimination system for electrochemical cells
11228066 · 2022-01-18
Assignee
Inventors
- Ramkumar Krishnan (Scottsdale, AZ, US)
- Joel Hayes (Chandler, AZ, US)
- Scott Klug (Mesa, AZ, US)
- Patrick SAMULESON (Phoenix, AZ, US)
- Craig Trzebny (Phoenix, AZ, US)
Cpc classification
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M50/392
ELECTRICITY
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M50/35
ELECTRICITY
H01M12/08
ELECTRICITY
International classification
H01M50/392
ELECTRICITY
H01M50/35
ELECTRICITY
Abstract
An electrochemical cell includes a mist elimination system that prevents mist from escaping from the cell chamber and conserves moisture within the cell. An exemplary mist elimination system includes a spill prevention device that reduces or prevents an electrolyte from escaping from the cell chamber in the event of an upset, wherein the electrochemical cell is tipped over. A mist elimination system includes a recombination portion that reacts with hydrogen to produce water, that may be reintroduced into the cell chamber. A mist elimination system includes a neutralizer portion that reacts with an electrolyte to bring the pH closer to neutral, as acid/base reaction. A mist elimination system includes a filter that captures mist that may be reintroduced into the cell chamber. A mist elimination system includes a hydrophobic filter on the outer surface to prevent water and other liquids from entering into the mist elimination system.
Claims
1. An electrochemical cell comprising: a cell housing comprising: i) an air chamber; ii) an air chamber air inlet; iii) an air chamber air outlet; iv) an electrolyte chamber, an ionically conductive liquid electrolyte in the electrolyte chamber, wherein a gas space is defined in the electrolyte chamber above the electrolyte and has a cell gas; an oxidant reduction electrode for reducing a gaseous oxidant between the air chamber and the electrolyte chamber, a fuel electrode comprising a metal fuel at least partially within the electrolyte chamber; a mist elimination system configured between the electrolyte chamber and an exhaust vent to separate the cell gas from a mist comprising the ionically conductive liquid electrolyte; wherein the mist elimination system is configured above the volume of ionically conductive liquid electrolyte; the mist elimination system comprising: a spill prevention device; a hydrogen recombination portion, comprising a hydrogen recombination catalyst configured to react with hydrogen gas within the cell gas and form water; a filter body portion comprised of at least one layer of filter media for capturing said mist; a neutralizer portion comprising a neutralizer media configured to react with and neutralize the ionically conductive liquid electrolyte contained within the mist; and wherein the filter body portion contains pores to permit permeation of said cell gas therethrough, wherein the neutralizer portion is configured downstream of the hydrogen recombination portion, the filter body portion, and the spill prevention device.
2. The electrochemical cell of claim 1, wherein the spill prevention device comprising a tortuous path conduit, from an inlet to an outlet, for transferring cell gas therethrough; wherein the tortuous path conduit inlet faces the electrolyte chamber for receiving cell gas.
3. The electrochemical cell of claim 1, wherein the spill prevention device comprises a safety valve.
4. The electrochemical cell of claim 3, wherein the safety valve comprises a ball retained within a conduit having a sealing seat on a downstream side, wherein the ball is pressed against the sealing seat to prevent liquid passage through the safety valve when liquid enters the conduit.
5. The electrochemical cell of claim 1, wherein the filter body portion is formed in a concave shape with an apex directed upwardly in the cell's upright orientation, and body surface extending downwardly from said apex so as to drain absorbed ionically conductive medium back into the electrolyte chamber.
6. The electrochemical cell of claim 1, wherein the water from the reaction of hydrogen with the recombination catalyst is introduced back into the cell through the spill prevention device.
7. The electrochemical cell of claim 1, wherein the hydrogen recombination catalyst is selected from the group consisting of: perovskites, spinels, precious metal based-platinum, palladium, MnO.sub.2, Nickel and a combination thereof.
8. The electrochemical cell of claim 1, wherein the hydrogen recombination portion is configured downstream of the spill prevention device.
9. The electrochemical cell of claim 1, wherein the neutralizer media comprises an acid component.
10. The electrochemical cell of claim 1, wherein the neutralizer media comprises an acid component selected from the group consisting of: citric, oxalic, carboxylic, sulfamic, benzoic, boric, sulfuric, hydrochloric, and nitric acid.
11. The electrochemical cell of claim 1, wherein the neutralizer media comprises a solid acid.
12. The electrochemical cell of claim 1, wherein the mist elimination system further comprises a hydrophobic filter configured downstream of the neutralizer portion on an exhaust end of the mist elimination system.
13. The electrochemical cell of claim 12, wherein the hydrophobic filter comprises a fluoropolymer filter media.
14. The electrochemical cell of claim 12, wherein the hydrophobic filter comprises an expanded microporous fluoropolymer filter media.
15. The electrochemical cell of claim 1, wherein the mist elimination system comprises a first mist elimination stack and a second mist elimination stack, wherein each of the first mist elimination stack and the second mist elimination stack comprises: the hydrogen recombination portion, the filter body portion, and the neutralizer portion, wherein each filter body portion contains pores to permit permeation of said cell gas therethrough, wherein each neutralizer portion is configured downstream of the hydrogen recombination portion and the filter body portion in their respective stack, and wherein the second mist elimination stack is stacked over the first mist elimination stack.
16. The electrochemical cell according to claim 1, wherein the spill prevention device comprises a safety valve comprising: a ball retained within a conduit; a sealing seat on a downstream side of said conduit, wherein the ball is pressed against the sealing seat to prevent liquid passage through the safety valve when liquid enters the conduit; and wherein the mist elimination system further comprises: a hydrophobic filter, wherein the hydrophobic filter is configured on an exhaust end of the mist elimination system; and wherein the hydrophobic filter is configured downstream of the neutralizer portion and is on an exterior of a mist elimination system.
17. The electrochemical cell of claim 1, wherein the mist elimination system comprises a stack comprising the hydrogen recombination portion, the filter body portion, and the neutralizer portion.
18. The electrochemical cell of claim 1, wherein the fuel electrode is positioned apart from the oxidant reduction electrode, thereby defining a gap, and wherein said ionically conductive liquid electrolyte is in the gap.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) 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.
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DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS
(12) 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 disclosure.
(13) 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.
(14) 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.
(15) An exemplary mist elimination system in accordance with embodiments of this disclosure is configured to control the loss of liquid ionically conductive medium, such as an electrolyte, from the electrochemical cell, which may be in the form of a mist or cell gas or vapor. A mist elimination system may comprise a safety vent, baffle or valve, a filter, a hydrogen recombination catalyst, a neutralizer and a hydrophobic filter or any combination thereof, for example. An exemplary mist elimination system in accordance with embodiments of this disclosure prevents or substantially prevents leaks of a liquid ionically conductive medium, or electrolyte in the event of an upset of the cell, and conserves moisture by draining captured moisture as well as chemically formed water, back into the cell.
(16) In an exemplary embodiment, a mist elimination system comprises a spill prevention device, such as a safety vent, baffle or valve, to prevent or substantially prevent liquid from leaking from the cell in the event of an upset. In an exemplary embodiment, a safety valve includes a spherical stop that is free to move within a conduit having a sealing seat on at least the downstream side of the valve, whereby if the cell is upset, the liquid medium therein will flow into the conduit and force the spherical stop against the spherical seat and thereby plug and stop (or substantially stop) the flow of liquid from the cell. Under normal operation however, air flows around the spherical stop to vent the cell. In another exemplary embodiment, a vent having a tortuous path conduit prevents or substantially prevents liquid electrolyte from directly leaking out of the cell and into the filter. The safety vent may comprise a conduit that spirals or otherwise traverses to prevent (or substantially prevent) and reduce any hydrostatic head on the filter and remainder of the mist elimination system in the event of an upset, wherein the cell falls and liquid electrolyte is in direct contact with the safety vent. In an embodiment, an exemplary mist elimination system, or a spill prevention device of a mist elimination system, may be closed and sealed during shipping, such as by being plugged or otherwise covered and sealed. A pressure relief valve may be configured to release pressure from within the cell during shipping as well as during operation and may be configured to open when the pressure within the cell exceeds a threshold value.
(17) An exemplary mist elimination system in accordance with embodiments of this disclosure comprises a filter, which may be configured downstream of the safety vent and may comprise a non-woven or woven filter media, or membrane. In an exemplary embodiment, the filter is a concave filter as described in U.S. Pat. No. 9,269,998, to Fluidic Inc., issued on Feb. 23, 2016 and entitled Concave Gas Vent For Electrochemical Cell; the entirety of which is incorporated by reference herein. An exemplary filter comprises a filter body portion comprised of at least one layer so as to absorb a portion of the ionically conductive liquid or mist. The body portion is formed in a concave shape with an apex positioned towards the top of the cell in its upright orientation, and with body surfaces extending downwardly from said apex so as to drain absorbed ionically conductive medium back into the interior chamber. The body portion contains pores so as to permit permeation of the gas therethrough. The filter may be highly efficient at removing mist and vapor that passes through the safety vent, such as more than about 80% efficient, more than about 90% efficient, more than about 95% efficient, more than about 99% efficient and any range between and including the efficiency values provided.
(18) In an embodiment, the filter layer may be at least partially hydrophobic which may facilitate coalescence and liquid droplet drainage as discussed previously. As a non-limiting example, the filter layer may comprise a polypropylene felt. Such a material may be a non-uniform mat of random fibers formed by needle punching, in accordance with terms known in the textile arts. In various embodiments, the filter material may be in felt shape (i.e. flexible) or may be sintered to form a rigid porous layer, or be an arrangement of these materials. The filter layer 85 may comprise any suitable material. Non-limiting examples of such material include, but are not limited to: polypropylene, polyethylene, polyesters, fluoropolymers, acrylonitrile butadiene styrene (ABS), and Noryl (i.e. modified polyphenylene ether), combinations and derivatives thereof. In some embodiments, at least a portion of the material may be modified by surface treatments (e.g. modifying the hydrophobicity/hydrophilicity). In some embodiments the filter may comprise porous metal foams, including but not limited to comprising metals such as steel, stainless steel, bronze, and copper, and may in some embodiments be coated with a metal layer such as nickel and its alloys.
(19) An exemplary mist elimination system in accordance with embodiments of this disclosure comprises a hydrogen recombination portion comprising a recombination catalyst that reacts with hydrogen/oxygen that may be formed from self-discharging or overcharging of the cell. The hydrogen recombination catalyst may be any suitable catalyst that will react with hydrogen to form water in the presence of oxygen, or other support media. Exemplary recombination catalyst includes, but is not limited to, perovskites, spinels, precious metal based-platinum, palladium etc., MnO.sub.2, nickel or a combination of these. An exemplary recombination portion may be configured downstream of the spill prevention device and the filter to protect the recombination catalyst from direct exposure to the electrolyte liquid.
(20) An exemplary mist elimination system in accordance with embodiments of this disclosure comprises a neutralizer that reacts with any liquid ionically conductive medium in the gas that passes through the mist elimination system. Neutralize, as used herein, means to react the liquid ionically conductive medium, in mist or gas phase, with a neutralization media, produce products of the reaction that are near neutral pH, such as to between 4 and 10, and more preferably between 5 and 9, and even more preferably between 6 and 8, in some embodiments. For example, neutralization media comprising an acid may be used to react with any caustic electrolyte, such as potassium hydroxide, KOH. A neutralizer may comprise a solid acid, or an acid supported on carbon or other support media. An acid may be coated onto a carbon or other support material, for example. A neutralizer may be configured with granulated or powder neutralizer media and may be in the form of a packed bed. The neutralizer may be configured in a neutralizer module that is replaceable, as the neutralizer media will be consumed in the reaction with the ionically conductive media, and therefore require replenishment. An exemplary neutralizer portion may be configured downstream of the spill prevention device, the filter and the recombination portion. An exemplary neutralizer may comprise one or more of the following acids: citric, oaxalic, carboxylic, sulfamic, benzoic, boric, sulfuric, hydrochloric, and nitric acid.
(21) An exemplary mist elimination system in accordance with embodiments of this disclosure comprises a hydrophobic filter that may be configured at the exit of the mist elimination system, to both keep any liquid from escaping the cell through the hydrophobic filter and to prevent or substantially prevent water from getting into the cell from the environment. A hydrophobic filter may comprise a fluoropolymer, such as a microporous fluoropolymer membrane, an expanded fluoropolymer membrane such as expanded polytetrafluoroethylene (PTFE) membrane, a polymer membrane, foam, woven media or non-woven media and the like. A microporous media or membrane may have a mean flow pore size, as measured by a Coulter porometer and/or according to ASTM F 316, Standard Test Methods for Pore Size Characteristics of Membrane Filters by Bubble Point and Mean Flow Pore Test, that is less than about 5 um, less than about 2 um, or less than 1 um. These membranes may be inherently hydrophobic or may comprise a hydrophobic coating that reduces the surface energy of the media to prevent or substantially prevent liquid water wet-out.
(22) A mist elimination system in accordance with embodiments of this disclosure may comprise multiple layers of one or more elements including the vent baffle or valve, a filter, a hydrogen recombination catalyst, a neutralizer and a hydrophobic filter, to ensure mist elimination and in some cases to provide a factor of safety. For example, two or more layers of hydrophobic filter media may be incorporated into the mist elimination module. In another embodiment, that entire composite stack, or portion thereof is replicated in a separate layer.
(23) 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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(25) Although in the illustrated embodiment of
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(28) The mist eliminator system comprises a spill prevention device 82, a safety vent 83, that is in communication with the interior chamber 122 of the cell housing 110, and therefore exposed to the ionically conductive medium 124 and/or gas space there above. The exemplary safety vent comprises a tortuous path conduit 99 that will slow the transfer of any liquid electrolyte to the downstream portions of the mist eliminator system. A tortuous path conduit may be a relatively small conduit that spirals or traverses back and forth to create an extended conduit length between the interior opening 95 and the exterior opening 96.
(29) A filter 85 is configured downstream of the safety vent and may be a concave shaped filter that will drain absorbed ionically conductive medium back into the anode chamber, as described in U.S. Pat. No. 9,269,998, Concave Gas Vent For Electrochemical Cell, to Fluidic Inc., the entirety of which is incorporated by reference herein.
(30) The exemplary mist elimination system comprises a hydrogen recombination portion 86, with a hydrogen recombination catalyst 87 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 to provide the oxygen used for the hydrogen recombination reaction. A parasitic corrosion reaction at the metal anode, or water reduction reaction, may occur in the cell corresponding to the equation Zn+2H.sub.2O->Zn(OH).sub.2+H.sub.2, or similar reaction depending on the type of metal used in a metal-air cell. While such hydrogen gas may be in a much smaller quantity than the evolved oxygen, it may be appreciated that the presence of hydrogen within the cell 100 is generally undesirable. In addition, it is desirable to react the hydrogen gas out of the exhaust stream from the electrochemical cell, both to prevent (or substantially prevent) egress of hydrogen from the cell and to regenerate the water lost during the corrosion reaction and return it to the cell.
(31) The exemplary mist elimination system comprises a neutralizer portion 90 comprising a neutralizer media 91, such as an acid component 92, 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 combined with a support material, such as acid incorporated into and/or carbon. The neutralizer is configured to eliminate any reactive electrolyte that may exhaust from the anode chamber or the chamber containing the ionically conductive medium that is not captured by the mist filter material 85. A neutralizer may comprise an absorbent that will absorb and entrain or absorb and react with the ionically conductive media, such as silica, or a molecular sieve. The neutralizer may also comprise a reactive material such as a solid acid or base or a liquid acid or base entrained in a porous media such as activated carbon. If the ionically conductive media is a base, such as potassium hydroxide, the neutralizer may comprise one or more of the following acids: citric, oaxalic, carboxylic, sulfamic, benzoic, boric, sulfuric, hydrochloric, and nitric acid.
(32) The mist elimination system 80 shown in
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(38) 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.