Pouched metal-air battery cells

Information

  • Patent Grant
  • 11367914
  • Patent Number
    11,367,914
  • Date Filed
    Friday, November 5, 2021
    2 years ago
  • Date Issued
    Tuesday, June 21, 2022
    2 years ago
Abstract
A metal air battery cell has a sealed pouch defined by a metallocene film and a gas and liquid impermeable flexible layer, and an electrochemical cell contained within the pouch. The metallocene film and gas and liquid impermeable flexible layer are sealed to each other and around the electrochemical cell.
Description
TECHNICAL FIELD

This disclosure relates to metal-air batteries and electrodes therein.


BACKGROUND

Electrochemical devices, such as batteries and fuel cells, typically incorporate an electrolyte source to provide the anions or cations necessary to produce an electrochemical reaction. Batteries and fuel cells operate on the electrochemical reaction of hydrogen-air, metal-air, metal-halide, metal-hydride, metal-intercalation compounds, or other materials capable of electrochemical reaction.


Metal-air batteries (or metal-oxygen batteries) with aqueous and non-aqueous electrolytes have attracted industry interest for many years as these reactors can have high energy densities and be relatively inexpensive to produce. Sizes can range from the small to power hearing aids or cameras to the large to power vehicles.


A unique property of metal-oxygen batteries compared to other batteries is that the cathode active material (i.e., oxygen) is typically not stored in the battery. When the battery is exposed to the environment, oxygen enters the cell through an oxygen diffusion membrane and porous air electrode and is reduced at the surface of a catalytic air electrode, forming peroxide ions and/or oxide ions in non-aqueous electrolytes or hydroxide anions in aqueous electrolytes. As an example, a mass of metal can form a porous anode that is saturated with an electrolyte. During discharge, oxygen reacts at a cathode to form hydroxyl ions that migrate into the metal-electrolyte to form a metal hydroxide, releasing electrons to travel to a cathode. The metal hydroxide decays into metal oxide and the resulting water returns to the electrolyte. The water and hydroxyls from the anode are recycled at the cathode, so the water is not consumed. The reverse process can also occur. During charge, electrons react with the metal oxide to reform the metal, releasing hydroxyl ions that migrate to the cathode. The hydroxyl ions are then oxidized to oxygen gas and water.


SUMMARY

A metal air battery cell has an electrode assembly including an air electrode, a negative electrode, a separator in contact with and disposed between the electrodes, and a sealed pouch that envelops the electrode assembly and contains an electrolyte therein. The pouch is defined by a gas permeable hydrophobic flexible layer in contact with the air electrode, and a gas and liquid impermeable flexible layer in contact with the negative electrode. The metal air battery cell further has a metallocene film in contact with and completely covering the gas permeable hydrophobic flexible layer such that the gas permeable hydrophobic flexible layer is between the metallocene film and air electrode.


A metal air battery cell has an electrode assembly including an air electrode and a gas permeable hydrophobic flexible layer in contact with the air electrode, a negative electrode, a separator in contact with and disposed between the electrodes, and a sealed pouch that envelops the electrode assembly and contains an electrolyte therein. The pouch is defined by a metallocene film that is in contact with the electrodes and completely covers the gas permeable hydrophobic flexible layer such that the gas permeable hydrophobic flexible layer is between the metallocene film and air electrode.


A metal air battery cell has an electrode assembly including two air electrodes and two gas permeable hydrophobic flexible layers, a negative electrode disposed between the air electrodes, at least one separator in contact with and disposed between the air electrodes and negative electrode, and a sealed pouch that envelops the electrode assembly and contains an electrolyte therein. The pouch is defined by a metallocene film in contact with the air electrodes such that the metallocene film is in contact with and completely covers the two gas permeable hydrophobic flexible layers, and each of the gas permeable hydrophobic flexible layers is between the metallocene film and one of the air electrodes.


A metal air battery cell has a sealed pouch defined by a metallocene film and a gas and liquid impermeable flexible layer, and an electrochemical cell contained within the pouch. The metallocene film and gas and liquid impermeable flexible layer are sealed to each other and around the electrochemical cell.


A metal air battery cell includes an electrochemical cell and a sealed pouch containing the electrochemical cell. The pouch is defined by a metallocene film that envelops the electrochemical cell.





BRIEF DESCRIPTION OF THE DRAWINGS


FIGS. 1 and 2 are side views, in cross-section, of metal-air pouch cells.



FIG. 3 is a plot of discharge voltage versus time for a metal-air pouch cell with a gas reduction layer.



FIG. 4 is a plot of discharge voltage versus time for a metal-air pouch cell without a gas reduction layer.





DETAILED DESCRIPTION

Embodiments of the present disclosure are described herein. It is to be understood, however, that the disclosed embodiments are merely examples and other embodiments can take various and alternative forms. The figures are not necessarily to scale. Some features could be exaggerated or minimized 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 those of ordinary skill in the art will understand, various features illustrated and described with reference to any one of the figures can be combined with features illustrated in one or more other figures to produce embodiments that are not explicitly illustrated or described. The combinations of features illustrated provide representative embodiments for typical applications. Various combinations and modifications of the features consistent with the teachings of this disclosure, however, could be desired for particular applications or implementations.


Containment of a metal-air battery usually requires complex ridged structures with pressure seals or adhesives to contain moisture, while also allowing the passage of air to the positive electrode. Here, metal-air pouch cells are described that can contain moisture and also allow the access of needed air by, for example, sealing a gas permeable and hydrophobic material to a gas and liquid impermeable material and/or a gas reduction material. The gas permeable and hydrophobic material may allow gas flow to the air electrode or electrodes while deterring the escape of moisture due to its hydrophobic nature. The gas reduction material may limit the gas flow. These materials can be heat sealed, at ends of the pouch, to a gas and liquid impermeable material. Such a pouch may be simple, light weight, thin, easily manufactured, and cost effective, while providing all of the necessary containment functions for a metal-air cell.


Referring to FIG. 1, a metal-air battery cell 10 (e.g., an electrochemically rechargeable battery cell, a primary battery cell, etc.) includes an electrode assembly 12 and a pouch 14. The electrode assembly 12 includes an air electrode (e.g., a bi-directional air electrode) 16, a negative electrode (e.g., zinc electrode) 18, and a separator (or membrane) 20 in contact with and between the air electrode 16 and negative electrode 18.


The pouch 14 includes a gas permeable hydrophobic flexible layer 22 in contact with the side of the air electrode 16 opposite the separator 20, and a gas and liquid impermeable flexible layer 24 in contact with the negative electrode 18 such that the gas permeable hydrophobic flexible layer 22 is not in contact with the negative electrode 18, and the gas and liquid impermeable flexible layer 24 is not in contact with the air electrode 16. The gas permeable hydrophobic flexible layer 22 can be non-sintered polytetrafluoroethylene. It can also be polymeric and chemically inert in the electrolyte environment. The pouch 14 further includes a gas reduction layer 26 in contact with the side of the gas permeable hydrophobic flexible layer 22 opposite the air electrode 16. In other examples, the gas reduction layer 26 is not part of the pouch 14, but instead heat sealed or otherwise bonded to it. The gas reduction layer 26 can be metallocene, have a thickness in the approximate range of 1 to 30 microns, and/or may have a Gurley air permeability of 10,000 to 50,000 seconds or more. Without the gas reduction layer 26, the pouch 14 may have a Gurley air permeability in the range of 100 to 500 Gurley seconds.


The gas permeable hydrophobic flexible layer 22 (or gas reduction layer 26) and the gas and liquid impermeable flexible layer 24 are sealed (e.g., heat sealed) to each other around a perimeter of the pouch 14. A thermoplastic hot melt or other adhesive can further define a seam for the pouch 14. As a result, the pouch 14 envelops the electrode assembly 12 and contains an electrolyte 28 within which the electrode assembly 12 is immersed, in contact with, or wetted. The electrolyte 28 may be acidic, alkaline, or neutral. And, it may be a gel, an ionic liquid, a liquid, or a solid.


Referring to FIG. 2, a metal-air battery cell 110 includes an electrode assembly 112 and a pouch 114. The electrode assembly 112 includes an air electrode 116, a negative electrode 118, and a separator 120 in contact with and between the air electrode 116 and negative electrode 118.


The pouch 114 includes a gas permeable hydrophobic flexible layer 122 in contact with the side of the air electrode 116 opposite the separator 120, and a gas reduction layer 125 in contact with the negative electrode 118 such that the gas permeable hydrophobic flexible layer 122 is not in contact with the negative electrode 118, and the gas reduction layer 125 is not in contact with the air electrode 116. The pouch 114 further includes a gas reduction layer 126 in contact with the side of the gas permeable hydrophobic flexible layer 122 opposite the air electrode 116. The gas reduction layers 125, 126 may be distinct components or portions of one continuous component.


The gas permeable hydrophobic flexible layer 122 (or the gas reduction layer 126) and the gas reduction layer 125 are sealed to each other around a perimeter of the pouch 114. A thermoplastic hot melt or other adhesive can further define a seam for the pouch 114. As a result, the pouch 114 envelops the electrode assembly 112 and contains an electrolyte 128 within which the electrode assembly 112 is immersed, in contact with, or wetted.


Other contemplated pouch configurations include a gas reduction layer or layers in contact with and enveloping two gas permeable hydrophobic flexible layers, which are in contact with sides of two air electrodes opposite the separators. The separators are also in contact with one negative electrode. The gas reduction layer or layers may be distinct components or portions of one continuous component.


Referring to FIGS. 3 and 4, the performance of metal-air pouch cells, of the types contemplated herein, with and without gas reduction layers is noticeably different when tested with a pulse discharge followed by standby current. FIG. 3 shows that the discharge voltage of a metal-air pouch cell with a gas reduction layer remains relatively consistent well past 2,000 hours of operation. FIG. 4 shows that the discharge voltage of a metal-air pouch cell without a gas reduction layer significantly degrades after a mere 70 hours.


While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms encompassed by the claims. The words used in the specification are words of description rather than limitation, and it is understood that various changes can be made without departing from the spirit and scope of the disclosure. As previously described, the features of various embodiments can be combined to form further embodiments of the invention that may not be explicitly described or illustrated. While various embodiments could have been described as providing advantages or being preferred over other embodiments or prior art implementations with respect to one or more desired characteristics, those of ordinary skill in the art recognize that one or more features or characteristics can be compromised to achieve desired overall system attributes, which depend on the specific application and implementation. These attributes can include, but are not limited to cost, strength, durability, life cycle cost, marketability, appearance, packaging, size, serviceability, weight, manufacturability, ease of assembly, etc. As such, embodiments described as less desirable than other embodiments or prior art implementations with respect to one or more characteristics are not outside the scope of the disclosure and can be desirable for particular applications.

Claims
  • 1. A metal air battery cell comprising: an electrode assembly including an air electrode;a negative electrode;a separator in contact with and disposed between the electrodes;a sealed pouch that envelops the electrode assembly and contains an electrolyte therein, wherein the pouch is defined by a gas permeable hydrophobic flexible layer in contact with the air electrode, and a gas and liquid impermeable flexible layer in contact with the negative electrode; anda metallocene film in contact with and completely covering the gas permeable hydrophobic flexible layer such that the gas permeable hydrophobic flexible layer is between the metallocene film and air electrode.
  • 2. The metal air battery cell of claim 1, wherein the metallocene film is in contact with or adhered with the gas permeable hydrophobic flexible layer.
  • 3. The metal air battery cell of claim 1 further comprising a terminal extending from and away at least one of the electrodes, and through the pouch, wherein the gas permeable hydrophobic flexible layer and gas and liquid impermeable flexible layer are each in contact with the terminal and sealed to each other and around the terminal.
  • 4. The metal air battery cell of claim 1, wherein the negative electrode includes zinc.
  • 5. The metal air battery cell of claim 1, wherein the hydrophobic gas diffusion layer includes a non-sintered polytetrafluoroethylene film.
  • 6. The metal air battery cell of claim 1, wherein the hydrophobic gas diffusion layer includes a carbon network.
CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of provisional application No. 63/110,629, filed Nov. 6, 2020, the entire contents of which are incorporated by reference herein.

US Referenced Citations (63)
Number Name Date Kind
2422045 Ruben Jun 1947 A
2593893 King Apr 1952 A
3201281 Solomon Aug 1965 A
3230115 Tamminen Jan 1966 A
3513031 Zaromb May 1970 A
3785868 Devitt Jan 1974 A
4060670 Tamminen Nov 1977 A
4225657 Klein et al. Sep 1980 A
4298666 Taskier Nov 1981 A
5405713 Pecherer et al. Apr 1995 A
5508121 Sawa Apr 1996 A
5626988 Daniel-Ivad et al. May 1997 A
6127061 Shun et al. Oct 2000 A
6395701 Connor et al. May 2002 B1
6447942 Ovshinsky et al. Sep 2002 B1
6660680 Hampden-Smith et al. Dec 2003 B1
6753108 Hampden-Smith et al. Jun 2004 B1
6838504 Webster et al. Jan 2005 B1
6911412 Hampden-Smith et al. Jun 2005 B2
6991754 Hampden-Smith et al. Jan 2006 B2
7066976 Hampden-Smith et al. Jun 2006 B2
7087341 Hampden-Smith et al. Aug 2006 B2
7138354 Hampden-Smith et al. Nov 2006 B2
7141528 Hampden-Smith et al. Nov 2006 B2
7226547 Hampden-Smith et al. Jun 2007 B2
7341674 Trinh et al. Mar 2008 B1
7348096 Schubert et al. Mar 2008 B2
7632605 Guo et al. Dec 2009 B2
7722687 Hampden-Smith et al. May 2010 B2
7824806 Visco et al. Nov 2010 B2
8481187 Zhang et al. Jul 2013 B2
8580704 Lefevre et al. Nov 2013 B2
9133337 Ludvik et al. Sep 2015 B2
9431660 Christensen et al. Aug 2016 B2
9464162 Kron et al. Oct 2016 B2
9564656 Zhamu et al. Feb 2017 B1
9680193 Amendola et al. Jun 2017 B2
9734954 Lai et al. Aug 2017 B2
9819055 Zeine Nov 2017 B2
9905856 Zhamu et al. Feb 2018 B1
9957163 Fan et al. May 2018 B2
10026995 Zhamu et al. Jul 2018 B2
10158121 Zhamu et al. Dec 2018 B2
10211450 Vu et al. Feb 2019 B2
10604854 Dai et al. Mar 2020 B2
20030180609 Yamashita Sep 2003 A1
20090023077 Kato et al. Jan 2009 A1
20090317708 Brandl Dec 2009 A1
20100112454 Visco May 2010 A1
20110059364 Zhang et al. Mar 2011 A1
20120148892 Hoecker Jun 2012 A1
20130084474 Mills Apr 2013 A1
20140072836 Mills Mar 2014 A1
20150118585 Wilkins Apr 2015 A1
20170027168 Heath Feb 2017 A1
20170152359 Yen Jun 2017 A1
20170166716 Yen Jun 2017 A1
20170184543 Posner et al. Jun 2017 A1
20170207484 Zhamu et al. Jul 2017 A1
20180047984 Kang et al. Feb 2018 A1
20190067732 Zhamu et al. Feb 2019 A1
20190221891 Lockett et al. Jul 2019 A1
20190273297 Weisenstein et al. Sep 2019 A1
Foreign Referenced Citations (8)
Number Date Country
101969144 Feb 2011 CN
4014945 Nov 1991 DE
2005100742 Apr 2005 JP
2016081705 May 2016 JP
1020190081377 Jul 2019 KR
20200010873 Jan 2020 KR
19965 Oct 2001 RU
0044405 Aug 2000 WO
Non-Patent Literature Citations (1)
Entry
International Search Report and Written Opinion of the International Searching Authority for International Application No. PCT/US2021/058393, dated Feb. 10, 2022, 8 pgs.
Related Publications (1)
Number Date Country
20220149465 A1 May 2022 US
Provisional Applications (1)
Number Date Country
63110629 Nov 2020 US