CA3048680A1 - System and method for metal-air anode renovation - Google Patents
System and method for metal-air anode renovation Download PDFInfo
- Publication number
- CA3048680A1 CA3048680A1 CA3048680A CA3048680A CA3048680A1 CA 3048680 A1 CA3048680 A1 CA 3048680A1 CA 3048680 A CA3048680 A CA 3048680A CA 3048680 A CA3048680 A CA 3048680A CA 3048680 A1 CA3048680 A1 CA 3048680A1
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- CA
- Canada
- Prior art keywords
- cell
- slurry
- metal
- air
- electrolyte
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
- H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/138—Primary casings; Jackets or wrappings adapted for specific cells, e.g. electrochemical cells operating at high temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
- H01M50/691—Arrangements or processes for draining liquids from casings; Cleaning battery or cell casings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
BACKGROUND OF THE INVENTION
[001] During the operation of a metal-air cell, the metallic anode in the cell is consumed and change to oxide form. As is known in the art, in order to resume operation of the cell, the exhausted anode unit is removed from the cell and a new anode unit is inserted. Similarly, the exhausted electrolyte in the cell may be replaced.
SUMMARY OF THE INVENTION
The metal-air cell set further comprises an inflatable element disposed between at least to adjacent metal-air cells, adapted to apply pressure onto the flexible wall, to thereby reduce the volume of the cell.
BRIEF DESCRIPTION OF THE DRAWINGS
DETAILED DESCRIPTION OF THE INVENTION
Tube 1004 may be used for flowing away from case 102 excess fresh electrolyte and slurry or used electrolyte and slurry, as explained below. Inlet 106 may be used to provide fresh electrolyte from a fresh electrolyte container (not shown) into cell case 102. Cell case 102 may contain used electrolyte 120 with used metal granules slurry 122. When removal of used electrolyte and slurry is required, the used electrolyte and the used slurry may be pumped out of cell case 102 by circulating fresh electrolyte via inlet 106 and by allowing the contents of cell case 102 to flow out via tube 1004. At this stage, tube 1002 is closed. Urged flow of fresh electrolyte is pumped into cell case 102, and used electrolyte 220 with used slurry 122 is forced out from cell case 102 via opening 104 and tube 1004. The in-flow of fresh electrolyte via opening 106 may cause turbulent flow inside cell case 102 and crumbles the anode particles, as depicted in Figs. 1A, 1B and 1C, where the content of used slurry 122 in the mixed electrolyte inside cell case 102 gradually reduces until substantially all of the used slurry is removed from cell case 102 and the case is filled with substantially only fresh electrolyte. According to some embodiments, one or more sensors may be used to determine when used slurry 122 and used .. electrolyte 120 have been sufficiently removed from cell case 102. Such sensors may be flow rate sensor, transparency/opacity/ turbidity sensor, viscosity sensor, etc.
Reference is made now to Figs. 2A-2C, which schematically depict three consecutive stages of a process of reloading of fresh electrolyte and fresh slurry into metal-air cell 100, and thus reloading and renovating the anode in the metal air cell/battery, according to some embodiments of the present invention. Fresh electrolyte 220 with suspended fresh metal granules 222 in slurry form may be pumped, circulated or otherwise be urged via supply tube 1002, flowing over the inlet of opening 104, whereby at least some amount of the suspended slurry 222 enters case 102 and sinks in it. Due to the tendency of slurry 222 to sink, the growing volume it gradually occupies inside cell case 102, as seen in Figs. 2A, then 2B and finally 2C, forces corresponding volume of fresh electrolyte 220 to leave cell case 102 and flow via return tube 1004 towards a respective container. Return tube 1004 is also used for receiving the excess amount of electrolyte with slurry that does not flow from supply tube 1002 into cell case 102, in order to direct it to the respective container (not shown). The stage of refilling cell case 102 with fresh electrolyte and fresh metal granules slurry may be stopped based on pre-defined time of circulation or one or more of the following indications ¨
weight of fresh granules that were taken from the container of fresh electrolyte and fresh slurry, conductivity between the slurry particles and the current collector or any other dedicated probe, flow rate sensor, transparency/
opacity/ turbidity sensor, viscosity sensor etc.
compressible wall 310.
Separator wall 304 may be made, as is known in the art, for separating between electrolyte and slurry residing in space 303 and air cathode 340 located on the outer side of separator wall 304, allowing only electrolyte and thus electrical flow through it. On the other side of air cathode 340, porous support wall 306 may be disposed. Porous wall 306 may be made of material that provides sufficient mechanical support for air cathode 340 and for separator wall 304, to be able to stand against pressures developing in cell 300. Porous support wall 306 may further be made of material that may enable passage of gas through it, for example in order to provide air to cathode 340.
Current collector 320 may be disposed inside space 303. Current collector 320 may be made of metal or other material with high conductivity and may be formed as wire mesh with mesh holes big enough to allow free flow of electrolyte and slurry through the holes back and forth, while enabling adjoining of metal granules in a slurry onto current collector 320, as explained hereinbelow, according to some embodiments of the present invention. Cell case 302 may be equipped with internal pressure control means 302B, which may be any kind of pressure relief and/or control enabling setting the required level of pressure inside cell case 300 when, for example, the volume of the cell case and / or the volume of the electrolyte and slurry in the cell case changes. For example, if the internal volume of cell case 300 decreases due to, for example, external pressure EP that is exerted on flexible wall 310, that pushes it inwardly so that the movement of wall 310 to position 310A wall and as a result the inner space 303 is decreased.
According to some embodiments, pressure maintaining means, such as pressure control means 302B, may cause the pressure built inside cell case 302 to rise to a defined level.
The rising pressure and the decreasing volume may cause certain amount of the electrolyte to be squeezed from the slurry, thereby raising the relative content of fresh slurry in the electrolyte. Further, at least some of the slurry may be adjoined onto current collector 320, and in general, reducing the distances between granules of metal in the slurry and thereby reducing the overall electrical resistance in a current path from current collector 320 towards cathode 340 via electrolyte and slurry in space 303.
Another method of controlling the amount of pressure required is to measure the conductivity between the current collector and the cathode or additional electrode (not shown) inserted in the slurry space 303.
According to some embodiments, the pressure EP exerted on flexible wall 310 induces same pressure inside space 303. If required, the resultant pressure in space 303 may be controlled to be equal, to not exceed or to be lower than, a predefined pressure level. The pressure inside space 303 may be controlled and/or measured by pressure regulator/pressure gauge 302B, as is known in the art.
Cells 400A, 400B, 400C, etc., may be positioned side-by-side-by-side with respect to each other in at least two different arrangements: anode-to-anode (or cathode-to-cathode), and anode-to-cathode.
Cell set 400 of Fig. 4 is schematically arranged in an anode-to-anode (ATA) arrangement. Cells 400A-400C are presented in an empty stage, containing very little or none electrolyte and slurry.
On the other side of air cathode 440, porous support wall 406 may be disposed. Porous wall 406 may be made of material that provides sufficient mechanical support for air cathode 440 and for separator wall 404, to be able to stand against pressures developing in cell 400A / 400B / 400C. Porous support wall 406 may further be made of material that may enable passage of gas through it, for example in order to provide air to cathode 440. Current collector 420 may be disposed inside space 403. Current collector 420 may be made of metal or other material with high electrical conductivity and may be formed as wire mesh with mesh holes big enough to allow free flow of electrolyte and suspended slurry through the holes back and forth, while enabling adjoining of metal granules in a slurry onto current collector 420, as explained hereinbelow, according to some embodiments of the present invention.
According to some embodiments, current collector 420 may be made of a flexible sheet of metal placed adjacent to the flexible wall 410, allowing external pressure EP to compact the slurry inside volume 403
water, or by pressurized gas, e.g. air.
In cell set 500, between the cells of at least some of the pairs having with cells having their cathode sides next to each other, gas supply and counter force support means 470 may be disposed. Such means may comprise an inflatable balloon having certain level of porosity on its envelope. The material of which the balloon is made is selected to be able to stand the level of pressure it should provide in order to provide counter-force to be exerted onto porous wall 406, for example when main pressure is provided by balloon 450. Further, balloon 470 may be designed to release through its porous envelope, gas with oxygen, such as air, at a rate that is sufficient for enriching the air in air cathodes 440 with sufficient oxygen.
substantive change between cell set 550 and cell set 500 is in that cells 400A ¨ 400C are filled with fresh electrolyte and fresh metal granules slurry. Cell set 550 is shown in a configuration that is suitable for applying pressure onto flexible walls of the cells by means of pressure providing means 450, applying counter pressure onto the porous support walls by counter force and gas supply means 475, to enable enriching relative amount of metal granules in the electrolyte in the cells, as described above.
Second inflatable element 660 may have in its face closer to support wall of cell 600C a plurality of small vent holes adapted to release air in a defined rate when second inflatable element 660 is inflated to provide pressure onto flexible wall, thereby providing fresh air to the cathode of cell 600C.
Claims (20)
circulating electrolyte through the cell to evacuate used slurry from the cell;
circulating electrolyte with fresh slurry into the cell and allowing sedimentation of the fresh slurry inside the cell to form an anode; and compacting the slurry to reduce the gaps between its particles.
porous wall disposed at the cathode outer face of the cell and defining first outer face of the cell;
air cathode layer adjacent the porous wall;
separator wall disposed on the inner face of the air cathode layer;
cell space volume to contain electrolyte and metal granules slurry;
current collector layer to form an anode, made of current conductive material disposed in the space; and flexible wall defining a second outer face of the cell, wherein the flexible wall is adapted to be pushed towards inside of the cell subject to pressure applied to its outer face, thereby to reduce the volume of the space.
opening in the cell space volume to allow circulating flow of fluid to evacuate used slurry from the cell; and opening in the cell space volume to allow flow of electrolyte with metal granules slurry to flow into the cell space volume.
plurality of metal-air cells, each comprising at least:
porous wall disposed at the cathode outer face of the cell and defining first outer face of the cell;
air cathode layer adjacent the porous wall;
separator wall disposed on the inner face of the air cathode layer;
cell space volume to contain electrolyte and metal granules slurry;
current collector layer to form an anode, made of current conductive material disposed in the space; and flexible wall defining a second outer face of the cell, wherein the flexible wall is adapted to be pushed towards inside of the cell subject to pressure applied to its outer face, thereby to reduce the volume of the space an inflatable element disposed between at least two adjacent metal-air cells, adapted to apply pressure onto the flexible wall, thereby to reduce the volume of the cell.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15/396,841 | 2017-01-03 | ||
| US15/396,841 US10581061B2 (en) | 2017-01-03 | 2017-01-03 | System and method for metal-air anode renovation |
| PCT/IL2017/051407 WO2018127905A1 (en) | 2017-01-03 | 2017-12-31 | System and method for metal-air anode renovation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA3048680A1 true CA3048680A1 (en) | 2018-07-12 |
Family
ID=62712099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA3048680A Pending CA3048680A1 (en) | 2017-01-03 | 2017-12-31 | System and method for metal-air anode renovation |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US10581061B2 (en) |
| EP (1) | EP3566260B1 (en) |
| CN (1) | CN110383576B (en) |
| CA (1) | CA3048680A1 (en) |
| ES (1) | ES2955164T3 (en) |
| IL (1) | IL267651B2 (en) |
| WO (1) | WO2018127905A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11894544B2 (en) | 2017-01-03 | 2024-02-06 | Phinergy Ltd. | System and method for metal-air anode renovation |
| ES2974225T3 (en) * | 2018-08-22 | 2024-06-26 | Alumapower Corp | Rapid electrolyte refueling system for aerial drones |
| CN110224108B (en) * | 2019-06-13 | 2022-07-12 | 安徽浩瀚星宇新能源科技有限公司 | Rolling processing device of pole piece for processing lithium ion battery |
| IL319199A (en) * | 2022-08-25 | 2025-04-01 | Phinergy Ltd | Anode formation in metal-air cells |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3759748A (en) * | 1970-04-06 | 1973-09-18 | Leesona Corp | Electrically recharged metal air cell |
| CH533366A (en) * | 1970-06-09 | 1973-01-31 | Battelle Memorial Institute | Process for the production of electrical energy by electrochemical oxidation of zinc and generator for its implementation |
| US3847671A (en) | 1973-04-13 | 1974-11-12 | Electromedia | Hydraulically-refuelable metal-gas depolarized battery system |
| US4389466A (en) | 1981-06-03 | 1983-06-21 | The United States Of America As Represented By The United States Department Of Energy | Rapidly refuelable fuel cell |
| US4491624A (en) | 1982-09-30 | 1985-01-01 | Synectics, Inc. | Metal-air electrochemical cell |
| US4911993A (en) * | 1988-02-01 | 1990-03-27 | Eltech Systems Corporation | Bipolar, filter-press, consumable metal anode battery |
| IL100903A (en) * | 1992-02-10 | 1995-06-29 | Pecherer Eugeny | Zinc anode for batteries with improved performance |
| US5434020A (en) * | 1993-11-15 | 1995-07-18 | The Regents Of The University Of California | Continuous-feed electrochemical cell with nonpacking particulate electrode |
| US5849427A (en) | 1993-12-02 | 1998-12-15 | Lawrence Berkeley Laboratory | Hydraulically refueled battery employing a packed bed metal particle electrode |
| US5952117A (en) | 1996-10-24 | 1999-09-14 | Metallic Power, Inc. | Method and apparatus for refueling an electrochemical power source |
| US6127061A (en) * | 1999-01-26 | 2000-10-03 | High-Density Energy, Inc. | Catalytic air cathode for air-metal batteries |
| US6296958B1 (en) | 2000-03-08 | 2001-10-02 | Metallic Power, Inc. | Refuelable electrochemical power source capable of being maintained in a substantially constant full condition and method of using the same |
| US6558825B1 (en) * | 2000-05-12 | 2003-05-06 | Reveo, Inc. | Fuel containment and recycling system |
| WO2003103072A2 (en) * | 2002-05-31 | 2003-12-11 | Evionyx, Inc | Metal air cell incorporating easily refuelable electrodes |
| CN100403594C (en) * | 2005-04-28 | 2008-07-16 | 中国科学技术大学 | Injection type zinc-air battery device |
| JP5050065B2 (en) * | 2010-02-05 | 2012-10-17 | 株式会社日立製作所 | Metal-air secondary battery |
| US20160111705A1 (en) * | 2012-08-01 | 2016-04-21 | Sharp Laboratories of America (SLA), Inc. | Metal-Air Battery with Expandable Anode |
| US9666919B1 (en) | 2013-06-03 | 2017-05-30 | Wendell D. Brown | Refuelable electrochemical battery |
| CN105680081B (en) * | 2014-11-17 | 2018-02-09 | 北京好风光储能技术有限公司 | A kind of lithium flow battery discharger |
| WO2017110880A1 (en) | 2015-12-21 | 2017-06-29 | Sharp Kabushiki Kaisha | Metal-air battery with expandable anode |
-
2017
- 2017-01-03 US US15/396,841 patent/US10581061B2/en active Active
- 2017-12-31 WO PCT/IL2017/051407 patent/WO2018127905A1/en not_active Ceased
- 2017-12-31 CN CN201780087862.4A patent/CN110383576B/en active Active
- 2017-12-31 ES ES17890038T patent/ES2955164T3/en active Active
- 2017-12-31 CA CA3048680A patent/CA3048680A1/en active Pending
- 2017-12-31 EP EP17890038.7A patent/EP3566260B1/en active Active
- 2017-12-31 IL IL267651A patent/IL267651B2/en unknown
-
2020
- 2020-01-28 US US16/774,632 patent/US11171320B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018127905A1 (en) | 2018-07-12 |
| CN110383576A (en) | 2019-10-25 |
| US10581061B2 (en) | 2020-03-03 |
| IL267651B2 (en) | 2023-04-01 |
| EP3566260A1 (en) | 2019-11-13 |
| EP3566260B1 (en) | 2023-07-12 |
| US11171320B2 (en) | 2021-11-09 |
| EP3566260A4 (en) | 2020-08-12 |
| IL267651B (en) | 2022-12-01 |
| US20180191044A1 (en) | 2018-07-05 |
| IL267651A (en) | 2019-08-29 |
| ES2955164T3 (en) | 2023-11-29 |
| CN110383576B (en) | 2023-04-18 |
| US20200243837A1 (en) | 2020-07-30 |
| EP3566260C0 (en) | 2023-07-12 |
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