Source: http://www.google.fr/patents/US9362538
Timestamp: 2018-01-19 12:06:02
Document Index: 369352066

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'Application No. 60', 'art 1', 'art 1', 'application No. 2', 'application No. 2', 'application No. 2', 'application No. 2003801061464', 'application No. 200480037293', 'application No. 200480037293', 'application No. 200480037293', 'application No. 200480042697', 'application No. 200480042697', 'application No. 200480042697', 'application No. 200910174918', 'application No. 03809186', 'application No. 03809186', 'application No. 03809186', 'application No. 03809186', 'application No. 04794655', 'application No. 04794699', 'application No. 04794699', 'application No. 04794699', 'application no. 2004', 'application No. 2006', 'application No. 2006', 'application No. 2006', 'application No. 2006', 'application No. 2006', 'application No. 2006', 'application No. 2014', 'application No. 10', 'application No. 10', 'application No. 10', 'application No. 10', 'application No. 10', 'application No. 2005', 'application No. 2006', 'application No. 2013', 'application No. 9', 'application No. 9', 'application No. 097122683']

Brevet US9362538 - Advanced lithium ion batteries based on solid state protected lithium electrodes - Google Brevets
Disclosed are ionically conductive membranes for protection of active metal anodes and methods for their fabrication. The membranes may be incorporated in active metal negative electrode (anode) structures and battery cells. In accordance with the invention, the membrane has the desired properties of...http://www.google.fr/patents/US9362538?utm_source=gb-gplus-shareBrevet US9362538 - Advanced lithium ion batteries based on solid state protected lithium electrodes
Numéro de publication US9362538 B2
Numéro de demande US 14/292,699
Autre référence de publication US7838144, US8114171, US8778522, US20080057386, US20090297935, US20110039144, US20120094188, US20130164628, US20140272524
Numéro de publication 14292699, 292699, US 9362538 B2, US 9362538B2, US-B2-9362538, US9362538 B2, US9362538B2
Inventeurs Steven J. Visco, Yevgeniy S. Nimon, Bruce D. Katz
Citations de brevets (267), Citations hors brevets (213), Référencé par (1), Classifications (28)
US 9362538 B2
an anode and a lithium ion cathode comprising a lithium ion intercalation compound;
wherein the anode is an electrochemical device component comprising:
an active metal lithium electrode having a first surface and a second surface; and
a composite protective membrane on the first surface of the electrode, the composite protective membrane being ionically conductive and chemically compatible with the active metal lithium on a side in contact with the active metal electrode, and substantially impervious, ionically conductive and chemically compatible with active metal lithium corrosive environments on the other side, the membrane comprising a substantially impervious sintered ceramic or glass-ceramic layer having a thickness between 10 and 1000 microns;
wherein the ionic conductivity of the membrane is at least 10-7 S/cm;
a current collector on the second surface of the active metal electrode; and
wherein the device component can be handled or stored in normal ambient atmospheric conditions without degradation prior to incorporation into an electrochemical device.
2. The battery cell of claim 1, wherein the active metal electrode is lithium metal.
3. The battery cell of claim 1, wherein the active metal electrode comprises a lithium alloy.
4. The battery cell of claim 1, wherein ceramic is a sintered ceramic.
5. The battery cell of claim 1, wherein ceramic is a glass-ceramic.
6. The battery cell of claim 1, further comprising a liquid electrolyte disposed between and in contact with the cathode and the protective membrane.
7. The battery cell of claim 1, wherein the composite protective membrane further comprises a lithium ion conductive material interlayer in direct contact with the active lithium metal electrode and the substantially impervious layer, the interlayer chemically compatible with the impervious layer and the active lithium metal electrode.
8. The battery cell of claim 7, wherein the interlayer thickness is in the range of 0.1 to 5 microns.
9. The battery cell of claim 7, wherein the interlayer thickness is in the range of 0.2 to 1 micron.
10. The battery cell of claim 7, wherein the interlayer is a lithium ion conducting glass.
11. The battery cell of claim 7, wherein the interlayer comprises LiPON.
12. The battery cell of claim 7, wherein the interlayer is a layer of LiPON.
13. The battery cell of claim 7, wherein the interlayer comprises a material selected from the group consisting of lithium nitride, lithium phosphide, and lithium iodide.
14. The battery cell of claim 7, wherein the interlayer comprises a material selected from the group consisting of Li3N, LI, and Li3P.
15. The battery cell of claim 7, wherein the interlayer comprises the reaction product of a precursor material layer with lithium metal.
16. The battery cell of claim 15, wherein the precursor material is selected from the group consisting of copper nitride, tin nitride, zinc nitride, iron nitride, cobalt nitride, aluminum nitride and silicon nitride.
17. The battery cell of claim 15, wherein the precursor material comprises red phosphorous.
18. The battery cell of claim 15, wherein the precursor material comprises I2.
19. The battery cell of claim 1, wherein the lithium ion intercalation cathode is a 4V cathode.
20. The battery cell of claim 1, wherein the lithium ion intercalation cathode is a 5V cathode.
21. The battery cell of claim 1, wherein the lithium ion intercalation compound is a metal oxide or a metal sulfide.
22. The battery cell of claim 1, wherein the lithium ion intercalation compound is a metal oxide.
23. The battery cell of claim 1, wherein the intercalation compound comprises a transition metal selected from the group consisting of Co, Ni, Mn, Fe, V, Mo, Cu, Ti and Cr.
24. The battery cell of claim 1 wherein the intercalation compound comprises a transition metal selected from the group consisting Co, Ni, Mn and Fe.
25. The battery cell of claim 1 wherein the intercalation compound is selected from the group consisting of LixCoO2, LixNiO2, LixMn2O4 and LiFePO4.
26. The battery cell of claim 1 wherein the intercalation compound is unlithiated.
27. The battery cell of claim 1, further comprising a liquid electrolyte disposed between and in contact with the cathode and the protective membrane, and not in contact with the active lithium metal electrode.
28. The battery cell of claim 27, wherein the liquid electrolyte comprises a solvent selected from the group consisting of organic carbonate, ether, and ester.
29. The battery cell of claim 27, wherein the liquid electrolyte comprises at least one solvent or salt that is chemically incompatible with the active lithium metal electrode.
30. The battery cell of claim 29, wherein the liquid electrolyte comprises a the salt that is an ionic liquid.
31. The battery cell of claim 30, wherein the ionic liquid is selected from the group consisting of imidazolium, pyridinium, phosphonium and tetralkylammonium compounds.
32. The battery cell of claim 1, further comprising a gel electrolyte disposed between and in contact with the cathode and the protective membrane, and not in contact with the active lithium metal electrode.
33. The battery cell of claim 1, wherein the cathode lithium ion intercalation compound is a lithium metal oxide.
34. The battery cell of claim 1, wherein the cathode lithium ion intercalation compound is selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide and lithium iron phosphate.
35. The battery cell of claim 1, wherein the cathode lithium ion intercalation compound is unlithiated.
36. The battery cell of claim 35, wherein the cathode lithium ion intercalation compound is a metal oxide or a metal sulfide.
This application is a continuation of U.S. patent application Ser. No. 13/708,540, filed Dec. 7, 2012, titled PROTECTED LITHIUM ELECTRODES BASED ON SINTERED CERAMIC OR GLASS CERAMIC MEMBRANES, now U.S. Pat. No. 8,778,522, issued Jul. 15, 2014; which is a continuation of U.S. patent application Ser. No. 13/336,459, filed Dec. 23, 2011, titled SOLID STATE BATTERY, now abandoned; which is a continuation of U.S. patent application Ser. No. 12/907,819, filed Oct. 19, 2010, titled IN SITU FORMED IONICALLY CONDUCTIVE MEMBRANES FOR PROTECTION OF ACTIVE METAL ANODES AND BATTERY CELLS, now U.S. Pat. No. 8,114,171, issued Feb. 14, 2012; which is a continuation of U.S. patent application Ser. No. 12/475,403, filed May 29, 2009, titled PROTECTIVE COMPOSITE BATTERY SEPARATOR AND ELECTROCHEMICAL DEVICE COMPONENT WITH RED PHOSPHORUS, now U.S. Pat. No. 7,838,144, issued Nov. 23, 2010; which is a continuation of U.S. patent application Ser. No. 11/824,574, filed Jun. 29, 2007, titled IONICALLY CONDUCTIVE MEMBRANES FOR PROTECTION OF ACTIVE METAL ANODES AND BATTERY CELLS, now abandoned; which is a continuation of U.S. patent application Ser. No. 10/772,228, filed Feb. 3, 2004, titled IONICALLY CONDUCTIVE MEMBRANES FOR PROTECTION OF ACTIVE METAL ANODES AND BATTERY CELLS, now U.S. Pat. No. 7,390,591, issued Jun. 24, 2008; which is a continuation-in-part of U.S. patent application Ser. No. 10/731,771 filed Dec. 5, 2003, titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ANODES, now U.S. Pat. No. 7,282,302, issued Oct. 16, 2007; which is a continuation-in-part of U.S. patent application Ser. No. 10/686,189 filed Oct. 14, 2003, titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ANODES, now U.S. Pat. No. 7,282,296, issued Oct. 16, 2007; which claims priority to U.S. Provisional Patent Application No. 60/418,899 filed Oct. 15, 2002, titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ANODES AND ELECTROLYSES.
This application also claims priority through prior application Ser. No. 10/772,228 in its chain of priority to U.S. Provisional Patent Application No. 60/511,710 filed Oct. 14, 2003, titled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ELECTRODES IN CORROSIVE ENVIRONMENTS and U.S. Provisional Patent Application No. 60/518,948 filed Nov. 10, 2003, titled BI-FUNCTIONALLY COMPATIBLE IONICALLY COMPOSITES FOR ISOLATION OF ACTIVE METAL ELECTRODES IN A VARIETY OF ELECTROCHEMICAL CELLS AND SYSTEMS.
The low equivalent weight of alkali metals, such as lithium, renders them particularly attractive as a battery electrode component. Lithium provides greater energy per volume than the traditional battery standards, nickel and cadmium. Unfortunately, no rechargeable lithium metal batteries have yet succeeded in the market place.
Work in the present applicants' laboratories has developed technology for the use of glassy or amorphous protective layers, such as LiPON, in active metal battery electrodes. (See, for example, U.S. Pat. No. 6,025,094, issued Feb. 15, 2000, U.S. Pat. No. 6,402,795, issued Jun. 11, 2002, U.S. Pat. No. 6,214,061, issued Apr. 10, 2001 and U.S. Pat. No. 6,413,284, issued Jul. 2, 2002, all assigned to PolyPlus Battery Company). Despite this progress, alternative protective layers and structures, that could also enhance active metal, particularly lithium metal, battery performance, continue to be sought. In particular, protective layers that combine the characteristics of high ionic conductivity and chemical stability to materials and conditions on either side of the protective layer are desired.
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 environments normally corrosive to the active metal of the anode, including glassy or amorphous metal ion conductors, such as a phosphorus-based glass, oxide-based glass, phosphorus-oxynitride-based glass, sulfur-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium-based glass or boracite glass (such as are described D. P. Button et al., Solid State Ionics, Vols. 9-10, Part 1, 585-592 (December 1983); 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. 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.
In solid state embodiments, a suitable second layer may include a polymer component to enhance its properties. For example, a glass-ceramic active metal ion conductor, like the glass-ceramic materials described above, may also be combined with polymer electrolytes to form flexible composite sheets of material which may be used as second layer of the protective composite. One important example of such a flexible composite material has been developed by OHARA Corp. (Japan). It is composed of particles of a Li-ion conducting glass-ceramic material, such as described above, and a solid polymer electrolyte based on PEO-Li salt complexes. OHARA Corp. manufactures this material in the form of sheet with a thickness of about 50 microns that renders it flexible while maintaining its high ionic conductivity. Because of its relatively high ionic conductivity (better than 4*40−5 S/cm at room temperature in the case of the OHARA product) and stability toward metallic Li, this type of composite electrolyte can be used at room temperature or elevated temperatures in fully solid-state cells.
FIGS. 2A and B are schematic illustrations of ionically conductive protective membrane battery separators in accordance with the present invention.
Reference will now be made in detail to specific embodiments of the invention. Examples of the specific embodiments are illustrated in the accompanying drawings. While the invention will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the invention to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be practiced without some or all of these specific details. In other instances, well known process operations have not been described in detail so as not to unnecessarily obscure the present invention.
As noted above, the first material may also be a precursor material which is chemically compatible with an active metal 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 layer material). Examples of suitable precursor materials include metal nitrides, red phosphorus, nitrogen and phosphorus containing organics (e.g., amines, phosphines, borazine (B3N3H6), triazine (C3N3H3)) and halides. Some specific examples include P (red phosphorus), Cu3N, SnNx, Zn3N2, FeNx, CoNx, aluminum nitride (AlN), silicon nitride (Si3N4) and I2, Br2, Cl2 and F2. Such precursor materials can subsequently react with active metal (e.g., Li) to form Li metal salts, such as the lithium nitrides, phosphides and halides described above. In some instances, these first layer material precursors may also be chemically stable in air (including moisture and other materials normally present in ambient atmosphere), thus facilitating handling and fabrication. Examples include metal nitrides, for example Cu3N.
Adjacent to the first material or precursor layer 202 is a second layer 204 that is substantially impervious, ionically conductive and chemically compatible with the first material or precursor, including glassy or amorphous metal ion conductors, such as a phosphorus-based glass, oxide-based glass, phosphorus-oxynitride-based glass, sulfur-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium-based glass or boracite glass (such as are described D. P. Button et al., Solid State Ionics, Vols. 9-10, Part 1, 585-592 (December 1983); 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. 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.
A second layer 306 of the protective composite is composed of a substantially impervious, ionically conductive and chemically compatible with the first material or precursor, including glassy or amorphous metal ion conductors, such as a phosphorus-based glass, oxide-based glass, phosphorus-oxynitride-based glass, sulfur-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium-based glass or boracite 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. 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. Suitable glass-ceramic ion active metal ion conductors are described, for example, in U.S. Pat. Nos. 5,702,995, 6,030,909, 6,315,881 and 6,485,622, previously incorporated herein by reference and are available from OHARA Corporation, Japan.
With regard to the fabrication methods described above it is important to note that commercial lithium foils are typically extruded and have numerous surface defects due to this process, many of which have deep recesses that would be unreachable by line-of-sight deposition techniques such as RF sputter deposition, thermal and E-beam evaporation, etc. Another issue is that active metals such as lithium may be reactive to the thin-film deposition environment leading to further deterioration of the surface during the coating process. This typically leads to gaps and holes in a membrane deposited onto the surface of an active metal electrode. However, by inverting the process, this problem is avoided; lithium is deposited on the protective membrane rather than the protective membrane being deposited on lithium. Glass and glass-ceramic membranes can be made quite smooth either by melt-casting techniques, cut and polish methods, or a variety of known methods leading to smooth surfaces (lithium is a soft metal that cannot be polished). Single or multiple smooth, gap-free membranes may then be deposited onto the smooth surface. After deposition is complete, active metal can be deposited onto the smooth surface by evaporation, resulting is a active meta/protective membrane interface that is smooth and gap-free. Alternatively, a transient bonding layer such as Ag can be deposited onto the protective membrane such that extruded lithium foil can be joined to the membrane by pressing the foil against the Ag layer.
Approximately 0.75 microns of LiPON was RF sputter-deposited onto copper foil samples in a MRC 8671 Sputter Deposition system. Some of the copper foil samples were coated with an additional layer of Cu3N (approximately 0.9 microns) by RF Magnetron sputtering of a copper target in a nitrogen environment. One LiPON/Cu sample was transferred to a vacuum evaporator, and approximately 3 to 7 microns of lithium metal was evaporated directly onto the LiPON surface. Another Cu3N/LiPON/Cu sample was coated with a similar thickness of lithium. The impedance for the unprotected LiPON/Cu sample is shown in FIG. 7A; the evaporation of lithium onto the LiPON surface led to a dramatic rise in the resistance of the sample, which is undesirable for electrochemical devices. The beneficial effects of the protective Cu3N film can be seen in FIG. 7B; the impedance is dramatically lower in this case.
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Classification internationale H01M10/0562, H01M10/0565, H01M10/0525, H01M10/056, H01M6/18, H01M2/16, H01M2/14
Classification coopérative H01M2/1673, Y10T29/49108, Y10T29/49115, H01M2300/0094, H01M6/182, H01M10/0525, Y02E60/122, H01M10/056, H01M2/145, H01M10/0562, H01M2300/0065, H01M6/188, H01M2300/008, H01M10/0565, H01M6/181, H01M6/185, H01M6/187, H01M6/18, H01M2/16, H01M2300/0071, Y02P70/54