Source: http://www.google.com/patents/US7781108?dq=oakley+D523,461
Timestamp: 2016-06-30 09:44:41
Document Index: 105070943

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'Application No. 60', 'art 1', 'application No. 2003801061464', 'application No. 04794699', 'Application No. 03809186']

Patent US7781108 - Active metal fuel cells - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsActive metal fuel cells are provided. An active metal fuel cell has a renewable active metal (e.g., lithium) anode and a cathode structure that includes an electronically conductive component (e.g., a porous metal or alloy), an ionically conductive component (e.g., an electrolyte), and a fluid oxidant...http://www.google.com/patents/US7781108?utm_source=gb-gplus-sharePatent US7781108 - Active metal fuel cellsAdvanced Patent SearchPublication numberUS7781108 B2Publication typeGrantApplication numberUS 12/334,116Publication dateAug 24, 2010Priority dateNov 10, 2003Fee statusPaidAlso published asUS7491458, US7998626, US8361664, US8709679, US20050100792, US20090286114, US20100273067, US20110269031, US20140004447, WO2005048385A2, WO2005048385A3Publication number12334116, 334116, US 7781108 B2, US 7781108B2, US-B2-7781108, US7781108 B2, US7781108B2InventorsSteven J. Visco, Yevgeniy S. Nimon, Bruce D. Katz, Lutgard C. De JongheOriginal AssigneePolyplus Battery CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (129), Non-Patent Citations (66), Referenced by (22), Classifications (19), Legal Events (1) External Links: USPTO, USPTO Assignment, EspacenetActive metal fuel cells
US 7781108 B2Abstract
1. A lithium fuel cell, comprising:
an anode comprising solid lithium metal as fuel;
a cathode structure comprising a static electronically conductive component, an ionically conductive component, and a fluid oxidant; and
a lithium ion conductive protective membrane adjacent to the lithium anode, the membrane interposed between the anode and the cathode structure, the membrane isolating the anode from components of the cathode structure;
wherein the ionically conductive component comprises a liquid electrolyte and the fluid oxidant comprises oxygen continuously supplied from the air; and
further comprising lithium dissolved in a solvent on the anode side of the membrane;
wherein the anode is configured such that lithium ions electrically migrate through the membrane to the cathode side during discharge of the fuel cell.
2. The cell of claim 1 wherein the anode is renewable and replaceable.
3. The cell of claim 2 wherein subsequent to cell discharge the renewable anode is supplementarily replaced with a fresh lithium anode.
4. The cell of claim 1 wherein the fluid oxidant further comprises a liquid oxidant.
5. The cell of claim 4 wherein the liquid oxidant comprises an aqueous solution.
6. The cell of claim 4 wherein the liquid oxidant is supplemented by flushing fresh liquid oxidant through the cathode structure.
7. The cell of claim 1 wherein the electrolyte comprises water.
8. The cell of claim 1 wherein the electrolyte comprises an aqueous solution.
9. The cell of claim 1 wherein the electrolyte is flushed through the cathode structure.
10. The cell of claim 9 wherein waste products generated during cell discharge are removed by flushing the electrolyte through the cathode structure.
11. A method of providing continuous electrical power, the method comprising:
i) providing a lithium fuel cell comprising:
wherein the ionically conductive component is a liquid electrolyte and the fluid oxidant comprises oxygen continuously supplied from the air; and
further comprising lithium dissolved in a solvent on the anode side of the membrane, and wherein lithium ions electrically migrate through the membrane to the cathode side during discharge of the fuel cell;
ii) discharging the fuel cell; and
iii) supplementarily adding fresh solid lithium metal fuel for the anode.
12. The method of claim 11, further comprising repeating the discharging and adding until cell operation is no longer desired.
13. The method of claim 11 further comprising supplementarily replacing the electrolyte.
14. The method of claim 13 wherein the supplementarily replacing the electrolyte includes flushing the cathode structure with electrolyte.
15. The method of claim 11 wherein the fluid oxidant further comprises a liquid oxidant, and the method comprising:
i) providing the lithium fuel cell;
ii) discharging the fuel cell;
iii) supplementarily adding fresh solid lithium metal fuel for the anode;
iv) supplementarily replacing the liquid oxidant;
v) repeating the discharging, adding and replacing until cell operation is no longer desired.
16. The method of claim 15 wherein the supplementarily replacing the liquid oxidant includes flushing the cathode structure with liquid oxidant.
17. The method of claim 15 wherein the liquid oxidant comprises water.
18. The method of claim 15 wherein the liquid oxidant comprises an aqueous solution.
19. A method of removing waste product in the cathode structure of a lithium fuel cell, the method comprising:
ii) discharging the fuel cell, thereby creating waste products in the cathode structure; and
iii) flushing the cathode structure to remove the waste products from the cathode structure.
20. The method of claim 19 wherein the flushing comprises flushing electrolyte through the cathode structure.
21. The method of claim 19 wherein the fluid oxidant comprises a liquid oxidant.
22. The method of claim 21 wherein the flushing comprises flushing liquid oxidant through the cathode structure.
23. The method of claim 22 wherein the liquid oxidant comprises water.
24. The method of claim 23 wherein said liquid oxidant comprises an aqueous solution.
25. The method of claim 19 further comprising repeating the discharging and flushing until cell operation is no longer desired.
This application is a continuation of U.S. patent application Ser. No. 10/825,587 filed Apr. 14, 2004, now U.S. Pat. No. 7,491,458 titled ACTIVE METAL FUEL CELLS (now U.S. Pat. No. 7,491,458; This application claims priority to U.S. Provisional Patent Application No. 60/529,825 filed Dec. 15, 2003, titled ACTIVE METAL FUEL CELLS; and U.S. Provisional Patent Application No. 60/518,948 filed Nov. 10, 2003, titled BI-FUNCTIONALLY COMPATIBLE IONICALLY CONDUCTIVE COMPOSITES FOR ISOLATION OF ACTIVE METAL ELECTRODES IN A VARIETY OF ELECTROCHEMICAL CELLS AND SYSTEMS; the disclosures of which are incorporated herein by reference in their entirety and for all purposes.
When used in combination with “comprising,” “a method comprising,” “a device comprising” or similar language in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural reference unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention belongs.
The active metal anode is renewable in that it is configured for replacement or supplementation of the active metal to provide a fuel supply for continuous operation of the fuel cell for as long as desired. For example, prior to or during operation of the fuel cell, additional lithium, for example, may be added to the anode by contacting the existing lithium of the anode with additional lithium having a bond coat such as a thin layer of Ag, Al, Sn or other suitable Li alloy-forming metal in an inert environment. The new Li/Ag alloys to the old thereby supplementing it or “replacing” it as it is depleted in the fuel cell redox reaction with the cathode oxidant. Alternatively, the active metal fuel of the anode could be continuously supplied to the membrane by virtue of it being dissolved in a suitable solvent, such as, in the case of lithium, hexamethyl phosphoramide (HMPA), ammonia, organic amides, amines, or other suitable solvents.
In a specific embodiment, the protective membrane is composed of at least two components of different materials having different chemical compatibility requirements. By “chemical compatibility” (or “chemically compatible”) it is meant that the referenced material does not react to form a product that is deleterious to fuel cell operation when contacted with one or more other referenced fuel cell components or manufacturing, handling or storage conditions.
A first material component of the composite is ionically conductive, and chemically compatible with an active metal electrode material. Chemical compatibility in this aspect of the invention refers both to a material that is chemically stable and therefore substantially unreactive when contacted with an active metal electrode material. It may also refer to a material that is chemically stable with air, to facilitate storage and handling, and reactive when contacted with an active metal electrode material to produce a product that is chemically stable against the active metal electrode material and has the desirable ionic conductivity (i.e., a first component material). Such a reactive material is sometimes referred to as a “precursor” material.
A second layer of the protective composite may be composed of a material that is substantially impervious, ionically conductive and chemically compatible with the first material or precursor and the cathode structure, such as glassy or amorphous metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors. Such suitable materials are substantially gap-free, non-swellable and are inherently ionically conductive. That is, they do not depend on the presence of a liquid electrolyte or other agent for their ionically conductive properties. Glassy or amorphous metal ion conductors, such as a phosphorus-based glass, oxide-based glass, phosphorus-oxynitride-based glass, sulpher-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium-based glass; ceramic active metal ion conductors, such as lithium beta-alumina, sodium beta-alumina, Li superionic conductor (LISICON), Na superionic conductor (NASICON), and the like; or glass-ceramic active metal ion conductors. Specific examples include LiPON, Li3PO4.Li2S.SiS2, Li2S.GeS2.Ga2S3, Li2O.11Al2O3, Na2O.11Al2O3, (Na, Li)1+xTi2−xAlx(PO4)3 (0.6≦x≦0.9) and crystallographically related structures, Na3Zr2Si2PO12, Li3Zr2Si2PO12, Na5ZrP3O12, Na5TiP3O12, Na3Fe2P3O12, Na4NbP3O12, Li5ZrP3O12, Li5TiP3O12, Li3Fe2P3O12 and Li4NbP3O12, and combinations thereof, optionally sintered or melted, may be used. Suitable ceramic ion active metal ion conductors are described, for example, in U.S. Pat. No. 4,985,317 to Adachi et al., incorporated by reference herein in its entirety and for all purposes.
Composition mol % P2O5 26-55% SiO2 0-15% GeO2 + TiO2 25-50% in which GeO2 0-50% TiO2 0-50% ZrO2 0-10% M2O3 0 < 10% Al2O3 0-15% Ga2O3 0-15% Li2O 3-25% and containing a predominant crystalline phase composed of Li1+x(M,Al,Ga)x(Ge1−yTiy)2−x(PO4)3 where X≦0.8 and 0≦Y≦1.0 and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/or and Li1+x+yQxTi2−xSiyP3−yO12 where 0<X≦0.4 and 0<Y≦0.6, and where Q is Al or Ga. The glass-ceramics are obtained by melting raw materials to a melt, casting the melt to a glass and subjecting the glass to a heat treatment. Such materials are available from OHARA Corporation, Japan and are further described in U.S. Pat. Nos. 5,702,995, 6,030,909, 6,315,881 and 6,485,622, incorporated herein by reference.
Such compositions, components and methods for their fabrication are described in U.S. Provisional Patent Application No. 60/418,899, filed Oct. 15, 2002, titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ANODES AND ELECTROLYTES, its corresponding U.S. patent application Ser. No. 10/686,189, filed Oct. 14, 2003, and titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ANODES, which is now U.S. Pat. No. 7,282,296, issued on Oct. 16, 2007; U.S. patent application Ser. No. 10/731,771, filed Dec. 5, 2003, and titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ANODES, which is now U.S. Pat. No. 7,282,302, issued on Oct. 16, 2007; and U.S. patent application Ser. No. 10/772,228, filed Feb. 3, 2004, and titled IONICALLY CONDUCTIVE MEMBRANES FOR PROTECTION OF ACTIVE METAL ANODES AND BATTERY CELLS, which is now U.S. Pat. No. 7,390,591, issued on Jun. 24, 2008. These applications are incorporated by reference herein in their entirety for all purposes.
2(b). 2Li+PbI2=2 LiI+Pb (reaction to form Li-ion conductor/metal composite).
Also, an approach may be used where a first material and second material are coated with another material such as a transient and/or wetting layer. For example, an OHARA glass ceramic plate is coated with a LiPON layer, followed by a thin silver (Ag) coating. When lithium is evaporated onto this structure, the Ag is converted to Ag—Li and diffuses, at least in part, into the greater mass of deposited lithium, and a protected lithium electrode is created. The thin Ag coating prevents the hot (vapor phase) lithium from contacting and adversely reaction with the LiPON first material layer. After deposition, the solid phase lithium is stable against the LiPON. A multitude of such transient/wetting (e.g., Al, Sn or other Li alloy-forming metal) and first layer material combinations can be used to achieve the desired result.
In addition to protection of the first layer material against reaction with Li, a Li alloy-forming metal film can serve two more purposes. In some cases after formation the first layer material the vacuum needs to be broken in order to transfer this material through the ambient or dry room atmosphere to the other chamber for Li deposition. The metal film can protect the first layer against reaction with components of this atmosphere. In addition, the Li alloy-forming metal can serve as a bonding layer for reaction bonding of Li to the first layer material. When lithium is deposited onto this structure, the Ag is converted to Ag—Li and diffuses, at least in part, into the greater mass of deposited lithium.
In addition to the protective composite laminates described above, a protective membrane in accordance with the present invention may alternatively be a functionally graded layer, as shown in FIG. 1B. Through the use of appropriate deposition technology such as RF sputter deposition, electron beam deposition, thermal spray deposition, and or plasma spray deposition, it is possible to use multiple sources to lay down a graded film. In this way, the discrete interface between layers of distinct composition and functional character is replaced by a gradual transition of from one layer to the other. The result, as with the discrete layer composites described above, is a bi-functionally compatible ionically conductive composite 120 stable on one side 114 to lithium or other active metal, and on the other side 116 substantially impervious and stable to the cathode/electrolyte, other battery cell components and preferably to ambient conditions. In this embodiment, the proportion of the first material to the second material in the composite may vary widely based on ionic conductivity and mechanical strength issues, for example. In many, but not all, embodiments the second material will dominate. For example, suitable ratios of first to second materials may be 1-1000 or 1-500, for example about 1 to 200 where the second material has greater strength and ionic conductivity than the first (e.g., 2000 Å of LiPON and 20-30 microns of OHARA glass-ceramic). The transition between materials may occur over any (e.g., relatively short, long or intermediate) distance in the composite. To form a protected anode, lithium is then bonded to the graded membrane on the first component material (stable to active metal) side of the graded composite protective layer, for example as described in U.S. patent application Ser. No. 10/686,189, filed Oct. 14, 2003, and titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ANODES, which is now U.S. Pat. No. 7,282,296, issued on Oct. 16, 2007; U.S. patent application Ser. No. 10/731,771, filed Dec. 5, 2003, and titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ANODES, which is now U.S. Pat. No. 7,282,302, issued on Oct. 16, 2007; and U.S. patent application Ser. No. 10/772,228, filed Feb. 3, 2004, and titled IONICALLY CONDUCTIVE MEMBRANES FOR PROTECTION OF ACTIVE METAL ANODES AND BATTERY CELLS, which is now U.S. Pat. No. 7,390,591, issued on Jun. 24, 2008, previously incorporated by reference herein.
As the fuel cell operates to generate electricity, the lithium metal of the renewable anode is consumed. The metal is then supplemented with fresh lithium metal, as required, to provide continuous operation for as long as desired. For example, prior to or during operation of the fuel cell, additional lithium may be added to the anode by contacting the existing lithium of the anode with additional lithium having a bond coat, such as a thin layer of Ag or other suitable alloying metal, in an inert environment. The Ag layer reacts with the surface of the existing Li forming Li—Ag alloy. The Li—Al alloy layer serves as a strong reaction bond between the additional Li and the existing lithium. The new Li/Ag alloys to the old thereby supplementing it or “replacing” it as it is depleted in the fuel cell redox reaction with the cathode oxidant. In this way, the renewable lithium anode can be replaced or supplemented through the use of a thin bonding foil such as Ag, Al, or Sn foil, as shown in the figure, as it is depleted.
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