MXPA06009007A

MXPA06009007A - Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture

Info

Publication number: MXPA06009007A
Application number: MXPA/A/2006/009007A
Authority: MX
Inventors: Bruce D Katz; Yevgeniy S Nimon; Steven J Visco; Jonghe Lutgard C De
Original assignee: Polyplus Battery Company
Priority date: 2004-02-06
Filing date: 2006-08-07
Publication date: 2007-04-10

Abstract

Active metal and active metal intercalation electrode structures and battery cells having ionically conductive protective architecture including an active metal (e.g., lithium) conductive impervious layer separated from the electrode (anode) by a porous separator impregnated with a non-aqueous electrolyte (anolyte). This protective architecture prevents the active metal from deleterious reaction with the environment on the other (cathode) side of the impervious layer, which may include aqueous or non-aqueous liquid electrolytes (catholytes) and/or a variety electrochemically active materials, including liquid, solid and gaseous oxidizers. Safety additives and designs that facilitate manufacture are also provided.

Description

(88) Date of publication of the international search report: 4 May 2006 For two-letter codes and other abbreviations. refer to the "Guidance Notes on Codes and Abbreviations" appearing at the beginning-ning ofeach regular issue of the PCT Gazette.

STRUCTURES OF BATTERY CELLS AND ACTIVE METAL ELECTRODE PROTECTED WITH INTERCHAPTER ARCHITECTURE AQUEOUS BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates generally to active metal electrochemical devices. Particularly, this invention relates to electrochemical structures (e.g., electrodes) of active metal (e.g., alkali metals, such as lithium), intercalation of active metals (e.g., lithium-carbon, carbon) and active metal alloys ( for example, lithium-tin), or alloy metals (for example, tin) and battery cells. The electrode structures have ionically conductive protective architecture that includes a conductive impermeable layer of active metal (eg, lithium) separated from the electrode (anode), by a porous separator impregnated with a non-aqueous electrolyte. This protective architecture prevents the active metal from reacting in a manner detrimental to the environment on the other side (cathode) of the impermeable layer, which may include aqueous liquid, air or organic electrolytes and / or electrochemically active materials.

DESCRIPTION OF THE RELATED TECHNIQUE The low equivalent weight of alkali metals, such as lithium, makes them particularly attractive as a battery electrode component. Lithium provides more energy by volume than traditional battery, nickel and cadmium standards. Unfortunately, rechargeable lithium metal batteries have not yet been successful in the market. The failure of rechargeable lithium metal batteries is largely due to cell cycle problems. In repeated charging and discharging cycles, the lithium "dendrites" gradually develop outside the lithium metal electrode, through the electrolyte, and finally make contact with the positive electrode. This causes an internal short circuit in the battery, rendering the battery unusable after relatively few cycles. During cycling, lithium electrodes can also develop "mossy" deposits that can leave the negative electrode and reduce the capacity of the battery. To address the poor cyclization behavior of lithium in liquid electrolyte systems, some researchers have proposed to coat the electrolyte surface side of the lithium negative electrode with a "protective layer". Said protective layer should conduct lithium ions, but at the same time avoid contact between the surface of the lithium electrode and the bulk electrolyte. Many techniques to apply protective coatings have failed.

Some contemplated lithium metal protective layers are formed in situ by reaction between lithium metal and compounds in the cell electrolyte that make contact with lithium. Most of these films in situ are developed through a controlled chemical reaction after the battery is assembled. Generally, said films have a porous morphology which allows some electrolytes to penetrate the surface of the uncoated lithium metal. In this way, they do not adequately protect the lithium electrode. Various preformed lithium protective layers have been contemplated, for example, the U.S. No. 5,314,765 (issued to Bates on May 24, 1994) discloses an ex situ technique for making a lithium electrode containing a thin layer of ionically powdered lithium phosphorus oxynitride ("LiPON") or related material. LiPON is a single-ion vitreous conductor (conducts lithium ion) that has been studied as a potential electrolyte for lithium microbatteries in the solid state that are fabricated on silicon and used to activate integrated circuits (see U.S. Patent Nos. 5 you. , 597,660, 5,567,210, 5,338,625, and 5,512,147, all issued to Bates et al.). The work in the laboratories of the present applicants has developed technology for the use of vitreous or amorphous protective layers, such as LiPON, in active metal battery electrodes. (See for example, US patents 6,025,094, issued on 02/15/00, 6,402,795, issued on 06/11/02, 6,214,061, issued on 04/10/01 and 6,413,284, issued on 07/02/02, all assigned to PolyPlus Battery Company). Previous attempts to use lithium anodes in aqueous environments relied either on the use of very basic conditions such as the use of concentrated aqueous KOH to reduce the corrosion rate of the Li electrode, or on the use of polymer coatings on the Li electrode to prevent the diffusion of water towards the surface of the Li electrode. However, in all cases, there was a substantial reaction of the alkali metal electrode with water. In this regard, the prior art teaches that the use of aqueous cathodes or electrolytes with Li metal anodes is not possible because the breaking voltage for water is about 1.2 V and a Li / water cell can have a voltage of about 3.0 V. The direct contact between lithium metal and aqueous solutions results in a violent parasitic chemical reaction and corrosion of the lithium electrode with no useful purpose. In this way, the focus of research in the field of lithium metal batteries has been the development of effective non-aqueous electrolyte systems (mainly organic).

BRIEF DESCRIPTION OF THE INVENTION The present invention relates generally to active metal electrochemical devices. In particular, this invention relates to electrochemical structures (e.g., electrodes) of active metal (e.g., alkali metals, such as lithium), intercalation of active metals (e.g., lithium-carbon, carbon) and active metal alloys ( for example, lithium-tin), or alloy metals (for example, tin) and battery cells. The electrochemical structures have an ionically conductive protective architecture that includes a substantially conductive impermeable layer of active metal ions (eg, lithium) separated from the electrode (anode) by a porous separator impregnated with a non-aqueous electrolyte (anolyte). This protective architecture prevents the active metal from reacting in a manner detrimental to the environment on the other side (cathode) of the impermeable layer, which may include aqueous, air or organic liquid electrolytes (catholytes) and / or electrochemically active materials. The spacing layer (interlayer) of the protective architecture prevents harmful reaction between the active metal (e.g., lithium) of the anode and the substantially impermeable layer conducting active metal ions. In this way, the architecture effectively isolates (decouples) the anode / anolyte from the solvent, electrolyte processing and / or cathode environments, including environments that are normally highly corrosive to Li or other active metals, at the same time allowing transportation ionic in and out of these potentially corrosive environments. Various embodiments of the cells and cell structures of the present invention include active metal anode materials, active metal-ion, active metal alloy metal, and active metal intercalation protected with an ionically conductive protective architecture having an analyte not watery These anodes can be combined in battery cells with a variety of possible cathode systems, including water cathodes, air, metal hydride and metal oxide and associated catholyte systems, in particular aqueous catholyte systems. Security additives may also be incorporated into the structures and cells of the present invention for the case where the substantially impermeable layer of the protective architecture (e.g., a glass or glass-ceramic membrane) is fissured or otherwise break and allow the aggressive catholyte to enter and approach the lithium electrode. The non-aqueous interlayer architecture can incorporate a gelling / polymerizing agent which, when in contact with the reactive catholyte, leads to the formation of an impermeable polymer on the lithium surface. For example, the anolyte may include a monomer for a polymer that is insoluble or minimally soluble in water, for example dioxolane (Diox) / polydioxolane, and the catholyte may include a polymerization initiator for the monomer, for example, a protonic acid. In addition, the structures and cells of the present invention can have any suitable shape. An advantageous form facilitating the manufacture is a tubular shape. In one aspect, the invention relates to an electrochemical cell structure. The structure includes an anode composed of an active metal material, active metal-ion, active metal alloy, active metal alloy metal or active metal intercalation. The anode has an ionically conductive protective architecture on its surface. The architecture includes a conducting conductive layer of active metal that has a nonaqueous anolyte and is chemically compatible with the active metal and in contact with the anode, and an ionically conductive layer substantially impermeable chemically compatible with the separating layer and aqueous environments and in contact with the separating layer. The separating layer can be a semipermeable membrane impregnated with an organic anolyte, for example, a microporous polymer impregnated with an anolyte in liquid or gel phase. Said electrochemical structure (electrode) can be paired with a cathode system, including an aqueous cathode system, to form battery cells according to the present invention. The structures and battery cells incorporating the structures of the present invention can have various configurations, including prismatic and cylindrical, and compositions, including active metal ion anodes, intercalation, aqueous cathodes, water, air, metal hydride and metal oxide, and aqueous, organic or ionic liquid catholytes; electrolyte compositions (anolyte and catholyte) to enhance the safety and / or performance of the cells; and manufacturing techniques. These and other features of the invention are further described and exemplified in the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of a cell of electrochemical structure incorporating an ionically conductive protective interlayer architecture in accordance with the present invention; Figure 2 is a schematic illustration of a battery cell incorporating an ionically conductive protective interlayer architecture in accordance with the present invention; Figures 3A-3C illustrate embodiments of battery cells according to the present invention utilizing a protected anode tubular design; Figures 4-7 are graphs of data illustrating the performance of various cells incorporating anodes with an ionically conductive protective barrier architecture in accordance with the present invention; Figure 8 illustrates an experimental cell for testing a variety of Li sheet thicknesses in aqueous electrolytes used to generate the data shown graphically in Figure 7; Figure 9 is a graph of specific energy projections for batteries incorporating anodes with ionically conductive protective interlayer architecture according to the present invention with variable thickness, the gravimetric specific energy value of a cell for a protected anode with a thickness of Li of 3.3 mm, and an illustration of the cell configuration and the parameters used for the calculations; and Figure 10 illustrates a Li / water battery and hydrogen generator for a fuel cell according to one embodiment of the present invention.

DETAILED DESCRIPTION OF SPECIFIC MODALITIES Detailed reference will now be made to specific modalities of the invention. The examples of the specific modalities are illustrated in the attached drawings. Although 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 encompass alternatives, modifications and equivalents that 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 complete understanding of the present invention. The present invention can be practiced without some or all of the specific details. In other cases, operations of known methods have not been described in detail in order not to unnecessarily confuse the present invention. When used in combination with "comprising", "a method comprising", "a device comprising" or similar language in this specification and in the appended claims, the singular forms "a", "an", and "the "," the "include plural reference unless the context clearly dictates otherwise. Provided that something else is defined, all the technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art to which this invention pertains.

Introduction Active metals are highly reactive under ambient conditions and can benefit from a barrier layer when used as electrodes. They are generally alkali metals (eg, lithium, sodium or potassium), alkaline earth metals (eg, calcium or magnesium), and / or certain transition metals (eg, zinc) and / or alloys of two or more of these. The following active metals may be used: alkali metals (eg, Li, Na, K), alkaline earth metals (eg Ca, Mg, Ba), or binary or ternary alkali metal alloys with Ca, Mg, Sn, Ag , Zn, Bi, Al, Cd, Ga, In. Preferred alloys include lithium-aluminum alloys, lithium-silicon alloys, lithium-tin alloys, lithium-silver alloys, and sodium-lead alloys (e.g., Na4Pb). A preferred active metal electrode is composed of lithium. The low equivalent weight of alkali metals, such as lithium, makes them particularly attractive as a battery electrode component. Lithium provides more energy by volume than traditional battery, nickel and cadmium standards. However, lithium metal or compounds that incorporate lithium with a potential close to that (for example, within about one volt) of lithium metal, such as lithium alloy and lithium-ion anode materials (intercalation of lithium), are highly reactive to many potentially attractive electrolyte and cathode materials. This invention describes the use of a non-aqueous electrolyte interlayer architecture to isolate an active metal (eg, alkali metal, such as lithium), active metal alloy or active metal-ion electrode (typically the anode of a cell battery) of the environment and / or the cathode side of the cell. The architecture includes a conductive spacer layer of active metal ion with a nonaqueous anolyte (ie, electrolyte around the anode), the spacer layer is chemically compatible with the active metal and in contact with the anode, and an ionically conductive layer substantially waterproof chemically compatible with the separating layer and aqueous environments and in contact with the separating layer. The nonaqueous electrolyte interlayer architecture effectively (uncouples) the anode from the environment and / or cathode, including catholyte environments (ie, electrolyte around the cathode), including environments that are normally highly corrosive to Li or other metals active, and at the same time allows ionic transport in and out of these potentially corrosive environments. In this way, a high degree of flexibility is allowed in the other components of an electrochemical device, such as a battery cell, made with the architecture. The isolation of the anode from other components of a battery cell or other electrochemical cell thus allows the use of virtually any solvent, electrolyte and / or cathode material together with the anode. In addition, electrolyte optimization or solvent systems can be performed on the cathode side without impacting the stability and performance of the anode. There are a variety of applications that can benefit from the use of aqueous solutions, including water and electrolytes based on water, air, and other reactive materials to lithium and other active materials, including organic solvents / electrolytes and ionic liquids, on the side of the cathode of the cell with an active metal anode (for example, alkaline, for example, lithium) or active metal intercalation (for example lithium or lithium-ion alloy) in a battery cell. The use of lithium intercalation electrode materials such as lithium-carbon and lithium alloy anodes, rather than lithium metal, for the anode can also provide beneficial characteristics to the battery. In the first place, it allows to achieve a life of prolonged cycle of the battery without the risk of formation of dendrites of lithium metal that can develop from the surface of Li towards the membrane surface causing the deterioration of the membrane. In addition, the use of lithium-carbon and lithium alloy anodes in some embodiments of the present invention instead of lithium metal anode can significantly improve the safety of a battery because it prevents the formation of highly "mossy" lithium. reactive during cycling. The present invention describes an electrode protected from active metal, alloy or intercalation that allows lithium batteries with very high energy density such as those using aqueous electrolytes or other electrolytes that would otherwise react adversely with lithium metal, for example. example. Examples of such high energy battery pairs are lithium-air, lithium-water, lithium-metal hydride, lithium-metal oxide, and lithium-lithium-ion alloy variants thereof. The cells of the invention can incorporate additional components in their electrolytes (analytes and catholytes) to enhance the safety of the cell, and can have a variety of configurations, including flat and tubular / cylindrical.

Nonaqueous interlayer architecture The non-aqueous interlayer architecture of the present invention is provided in an electrochemical cell structure, the structure having an anode composed of a material selected from the group consisting of active metal, active metal-ion, metal alloy active, active metal alloy material, and intercalation of active metal, and an ionically conductive protective architecture on a first surface of the anode. The architecture is composed of an active metal ion conductive separating layer with a nonaqueous anolyte, the separating layer is chemically compatible with the active metal and in contact with the anode, and an ionically conductive layer substantially impermeable chemically compatible with the separating layer and aqueous environments and in contact with the separating layer. The separating layer may include a semipermeable membrane, for example, a microporous polymer, such as those available from Celgard, Inc. Charlotte, North Carolina, impregnated with an organic anolyte. The protective architecture of this invention incorporates a substantially impermeable layer of an active metal ion-conductive glass or glass-ceramic (e.g., a lithium ion conductive glass-ceramic (LIC-GC) having high conductivity of active metal ion. and stability to aggressive electrolytes that react vigorously with the lithium metal for example) such as aqueous electrolytes. Suitable materials are substantially impermeable, ionically conductive and chemically compatible with aqueous electrolytes or other electrolyte (catholyte) and / or cathode materials that would otherwise react adversely with the lithium metal, for example. Said glass or glass-ceramic materials are substantially free of spaces, do not expand and are inherently ion-level conductors. That is, they do not depend on the presence of a liquid electrolyte or other agent for their ionically conductive properties. They also have high ionic conductivity, at least 10"7S / cm, generally at least 10" 6S / cm, for example at least 10"5S / cm at 10" 4S / cm, and as high as 10"3S / cm or more, so that the overall ionic conductivity of the multilayer protective structure is at least 10 ~ 7S / cm and as high as 10"3S / cm or more. The thickness of the layer is preferably about 0.1 to 1000 microns, or when the ionic conductivity of the layer is about 10"7S / cm, about 0.25 to about 1, or when the ionic conductivity of the layer is between about 10. "4 to about 10" 3S / cm, about 10 to 1000 microns, preferably between 1 and 500 microns, and particularly between 10 and 100 microns, for example 20 microns Suitable examples of suitable substantially impermeable lithium ion conductive layers include metal or amorphous metal conductors, such as phosphorus-based glass, oxide-based glass, phosphorus-oxynitride-based glass, sulfur-based glass, oxide / sulfide-based glass, glass based selenide, gallium-based glass, germanium-based glass or boracite glass (as described in DP Button et al., Solid State lonics, Vols. 9-10, Part 1, 585-592 (December 1983); ion conductors of ceramic active metal, 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.SiS2i Li2S.GeS2.Ga2S3l LiO HAI2O3, Na2O-11AI2O3, (Na, Li) 1 + xTi2, xAlx (PO) 3 (0.6 <x < 0.9) and crystallographically related structures , Na3Zr2Si2PO12, Li3Zr2Si2PO12 > Na5ZrP3O12, Na5TiP3O12, Na3Fe2P3O12, Na4NbP3O2, Li5ZrP3O12l Li5T1P3O12, Li3Fe2P3O2 and Li4NbP3O12, and combinations thereof, optionally sintered or melted. Suitable ceramic active metal ion conductors are described, for example, in the US patent. No. 4,985,317 to Adachi er al., Incorporated herein by reference in its entirety and for any purpose.

A glass-ceramic material particularly suitable for the substantially impermeable, architecturally protective layer is a lithium ion conductive glass-ceramic having the following composition: Composition% molar P205 26-55% Si02 0-15% Ge02 + Ti02 25-50% in which Ge02 0-50% Ti02 0-50% Zr02 0-10% M203 0 < 10% Al203 0-15% Ga203 0-15% Li2Q 3-25% containing a predominant crystalline phase composed of Li1 + X (M, Al, Ga) x (Ge? -yTiy) 2-x (PO4) 3 where X < 0.8 and 0 < And < 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 Li1 + x + yQxTi2-xSiyP3-yQ12 where 0 < X < 0.4 and 0 < And < 0.6, and where Q is Al or Ga. Glass-ceramics are obtained by melting raw materials in a molten material, casting the molten material in a glass and subjecting the glass to thermal treatment. Such materials are available from OHARA Corporation, Japan and are further described in the U.S.A. Nos. 5,702,995, 6,030,909, 6,315,881 and 6,485,622, incorporated herein by reference. Said substantially conductive lithium ion conductive layers and techniques for their manufacture and incorporation into battery cells are described in the provisional patent application of E.U.A. No. 60 / 418,899, filed on October 15, 2002, entitled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ANODES AND ELECTROLYTES, its patent application of E.U.A. corresponding No. 10 / 686,189 (Proxy Case No. PLUSP027), filed on October 14, 2003, and entitled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ANODES, patent application of E.U.A. No. 10/731, 771 (Proxy Case No. PLUSP027X1), filed on December 5, 2003, and entitled IONICALLY CONDUCTIVE COMPOSITES FOR PROTECTION OF ACTIVE METAL ANODES, and patent application of E.U.A. No. 10 / 772,228 (Case of Attorney No. PLUSP039), filed on February 3, 2004, and entitled IONICALLY CONDUCTIVE MEMBRANES FOR PROTECTION OF ACTIVE METAL ANODES AND BATTERY CELLS. These applications are hereby incorporated by reference in their entirety and for any purpose. A critical limitation in the use of these highly conductive glasses and glass-ceramics in lithium batteries (or other active metal or intercalation of active metal) is their reactivity to lithium metal or compounds that incorporate lithium with a potential close to that (by example, within about one volt) of the lithium metal. The non-aqueous electrolyte layer of the present invention isolates the lithium electrode (for example) from the reaction with the glass or glass-ceramic membrane. The non-aqueous interlayer may have a semipermeable membrane, such as a microporous Celgard separator, to prevent mechanical contact of the lithium electrode with the glass or glass-ceramic membrane. The membrane is impregnated with organic liquid electrolyte (anolyte) with solvents such as ethylene carbonate (EC), propylene carbonate (PC), 1,2-dimethoxy ethane (DME), 1,3-dioxolane (DIOX), or various ethers, glimes, lactoses, sulfones, sulfolane, or mixtures thereof. Also or alternatively, it may have a polymeric electrolyte, a gel-type electrolyte, or a combination thereof. Important criteria are that the lithium electrode is stable in the non-aqueous anolyte, the non-aqueous anolyte is sufficiently conductive for Li + ions, the lithium electrode does not make contact directly with the glass or glass-ceramic membrane, and the complete assembly allows lithium ions to pass through the glass or glass-ceramic membrane. Referring to Figure 1, a specific embodiment of the present invention is illustrated and described. Figure 1 shows a non-scale illustration of an electrochemical cell structure 100 having an active metal anode, active metal-ion, active metal alloy metal, or active metal intercalation material 102 and an architecture Ionically Conductive Protector 104. The protective architecture 104 has an active metal ion conductive separator layer 106 with a nonaqueous anolyte (sometimes also referred to as a transfer electrolyte) on an anode surface 102 and a substantially impermeable ionically conductive layer 108. in contact with the separating layer 106. The separating layer 106 is chemically compatible with the active metal and the substantially impermeable layer 108 is chemically compatible with the separating layer 106 and aqueous environments. The structure 100 may optionally include a current collector 110, composed of a suitable conductive metal that does not alloy with or intercalate with the active metal. When the active metal is lithium, a suitable current collector material is copper. The current collector 110 can also serve to seal the anode of the environment to avoid harmful reaction of the active metal with air or ambient humidity. The separating layer 106 is composed of a semipermeable membrane impregnated with an organic anolyte. For example, the semipermeable membrane may be a microporous polymer, such as is available from Celgard, Inc. The organic anolyte may be in the liquid or gel phase. For example, the anolyte may include a solvent selected from the group consisting of organic carbonates, ethers, lactones, sulfones, etc. and combinations thereof, such as EC, PC, DEC, DMC, EMC, 1, 2-DME or higher glymes, THF, 2MeTHF, sulfolane, and combinations thereof. 1,3-dioxolane can also be used as an anolyte solvent, particularly but not necessarily when it is used to enhance the safety of a cell incorporating the structure, as described below. When the anolyte is in the gel phase, it is possible to add gelling agents such as polyvinylidene fluoride (PVdF) compounds, hexafluoropropylene-vinylidene fluoride (PVdf-HFP) copolymers, polyacrylonitrile compounds, crosslinked polyether compounds, compounds of polyalkylene oxide, polyethylene oxide compounds, and combinations and the like to gel the solvents. Of course, suitable anolytes will also include active metal salts, such as, in the case of lithium, for example, LiPF6, LiBF4, LiAsFe, LSS? 3CF3 or LiN (SO2C2F5) 2. An example of a suitable separating layer is 1 M LiPF6 dissolved in propylene carbonate and impregnated in a microporous polymeric Celgard membrane. There are a number of advantages of a protective architecture in accordance with the present invention. In particular, cell structures incorporating said architecture can be manufactured relatively easily. In one example, the lithium metal is simply placed against a microporous separator impregnated with liquid electrolyte or in organic gel and with the separator adjacent to an active glass ion / glass-ceramic ion conductor. An additional advantage of the non-aqueous interlayer is obtained when ceramic glasses are used. When the amorphous glasses of the type described by the aforementioned OHARA Corp. patents are treated with heat, the glass is devitrified, leading to the formation of a glass-ceramic. However, this heat treatment can lead to the formation of surface roughness which can be difficult to coat using vapor deposition of an inorganic protective interlayer such as LiPON, Cu3N, etc. The use of a non-aqueous liquid (or gel) electrolyte interlayer would easily cover said rough surface by normal liquid flow, thus eliminating the need for surface polishing, etc. In this sense, techniques such as "level drop" can be used (as described by Sony Corporation and Shott Glass (T. Kessler, H.

Wegener, T. Togawa, M. Hayashi, and T. Kakizaki, "Large Microsheet Glass for 40-in. Class PALC Displays," 1997, FMC2-3, downloaded from the Shott Glass website; http://www.schott.com/english, incorporated herein by reference) to form thin layers of glass (20 to 100 microns), and these glasses heat treated to form glass-ceramics.

Battery Cells The non-aqueous interlayer architecture is usefully adopted in battery cells. For example, the electrochemical structure 100 of Figure 1 can be paired with a cathode system 120 to form a cell 200, as illustrated in Figure 2. The cathode system 120 includes an electronically conductive component, an ionically conductive component. conductor, and an electrochemically active component. The cathode system 120 can have any desired composition and, because of the insulation provided by the protective architecture, is not limited by the anode or anolyte composition. In particular, the cathode system can incorporate components that would otherwise be highly reactive with the anode active metal, such as aqueous materials, including water, aqueous catholytes and air, metal hydride electrodes and metal oxide electrodes. In one embodiment, a Celgard separator is placed against one side of the thin glass-ceramic, followed by a liquid or non-aqueous gel electrolyte, and subsequently a lithium electrode. On the other side of the glass-ceramic membrane, an aggressive solvent, such as an aqueous electrolyte, can be used. In this way, for example, an economic Li / water or Li / air cell can be built. The cells according to the present invention can have very high specific capacities and energies. For example, cells with capacities of more than 5, more than 10, more than 100 or even more than 500 mAh / cm2 are possible. As described further in the following examples, a capacity of about 650 mAh / cm2 has been demonstrated for a Li / water test cell according to the present invention having a Li anode of approximately 3.35 mm in thickness. Based on this performance, the projections indicate very high specific energies for Li / air cells according to the present invention. For example, a specific unpacked energy of approximately 3400 Wh / I (4100 Wh / kg) and a specific energy packaged, assuming 70% packet load, of approximately 1000 Wh / I (1200 Wh / kg) for a Li cell / air with a Li anode of 3.3 mm thickness, a laminate thickness of 6 mm and an area of 45 cm2.

Cathode Systems As mentioned above, the cathode system 120 of a battery cell according to the present invention can have any desired composition and, due to the isolation provided by the protective architecture, is not limited by the anode or anolyte composition . In particular, the cathode system can incorporate components which would otherwise be highly reactive with the anode active metal, such as aqueous materials, including water, aqueous solutions and air, metal hydride electrodes and metal oxide electrodes. The battery cells of the present invention may include, without limitation, water, aqueous solutions, air electrodes and metal hydride electrodes, such as those described in copending application No. 10 / 772,157 entitled ACTIVE METAL / AGUEOUS ELECTROCHEMICAL CELLS AND SYSTEMS, incorporated herein by reference and for any purpose, and metal oxide electrodes, as used for example in conventional Li-ion cells. The effective isolation between the anode and cathode achieved through the protective barrier architecture of the present invention also allows a high degree of flexibility in the choice of catholyte systems, in particular aqueous systems, but also non-aqueous systems. Because the protected anode is completely decoupled from the catholyte, so that the compatibility of the catholyte with the anode is no longer a problem, solvents and salts can be used which are not kinetically stable to Li. For cells using water as an electrochemically active cathode material, an electronically conductive porous support structure can provide the electronically conductive component of the cathode system. An aqueous electrolyte (catholyte) provides ion carriers for the transport (conductivity) of Li ions and anions that combine with Li. The electrochemically active component (water) and the ionically conductive component (aqueous catholyte) will be mixed as a single solution, although they are elements conceptually separated from the battery cell. Suitable catholytes for the Li / water battery cell of the invention include any aqueous electrolyte with suitable ionic conductivity. Suitable electrolytes can be acids, for example, strong acids such as HCl, H2SO4, H3P0 or weak acids such as acetic acid / Li acetate; basic, for example LiOH; neutral, for example, seawater, LiCI, LiBr, Lil; or amphoteric, for example NH4CI, NH4Br, etc. The convenience of seawater as an electrolyte allows a battery cell for marine applications with a very high energy density. Before use, the cell structure is composed of the protected anode and an electronically conductive porous support structure (electronically conductive component of the cathode). When necessary, the cell is completed by immersing it in seawater which provides the electrochemically active and ionically conductive components. Because the latter components are provided by seawater in the environment, they do not need to be transported as part of the battery cell before use (and therefore do not need to be included in the cell's energy density calculation) ). Said cell is referred to as an "open" cell because the reaction products on the cathode side are not contained. Therefore, said cell is a primary cell.

Secondary Li / water cells according to the invention are also possible. As indicated above, said cells are referred to as "closed" cells because the reaction products on the side of the cathode are contained on the cathode side of the cell to be available to recharge the anode by moving the Li ions back towards the Protective membrane when the appropriate recharge potential is applied to the cell.

As mentioned above and as described below, in another embodiment of the invention, the ionomers coated in the electronically conductive porous catalytic support reduce or eliminate the need for ionic conductivity in the electrochemically active material. The electrochemical reaction that occurs in a Li / water cell is a redox reaction in which the electrochemically active cathode material is reduced. In a Li / water cell, the electronically conductive catalytic support facilitates the redox reaction. As indicated previously, although not for this limited, in a Li / water cell, it is believed that the reaction of the cell is: Li + H2O = LiOH +1/2 H2 It is believed that the reactions of meaia ceide at the anode and cathode are: Anode: Li = Li + + e "Cathode: e" + H2O = OH "+ 1/2 H2 Accordingly, the catalyst for the Li / water cathode promotes the transfer of electrons to water, generating hydrogen and ion hydroxide. and common for this reaction is nickel metal, precious metals such as Pt, Pd, Ru, Au, etc. will also work but are more expensive, also considered within the scope of Li (or other active metal) / water batteries. invention are batteries with a protected Li anode and an aqueous electrolyte composed of gaseous oxidants and / or water-soluble solids that can be used as cathode active materials (electrochemically active component) .The use of water-soluble compounds, which are oxidants stronger than water can significantly increase the battery power in some applications compared to the lithium / water battery, where during the discharge reaction of the cell, the evolution of Electrochemical hydrogen on the surface of the cathode. Examples of such gaseous oxidants are O2, SO2 and N02 Also, metal nitrites in particular NaNO2 and KNO2 and metal sulphites such as Na2SO3 and K2SO3 are stronger oxidants than water and can easily be dissolved in large concentrations. Another class of water-soluble inorganic oxidants are lithium, sodium and potassium peroxides, as well as H2O2 hydrogen peroxide.

The use of hydrogen peroxide as an oxidant can be especially beneficial. There are at least two ways to use hydrogen peroxide in a battery cell in accordance with the present invention. First, the chemical decomposition of hydrogen peroxide on the cathode surface leads to the production of oxygen gas, which can be used as an active cathode material. The second, which perhaps is the most effective way, is based on the direct electroreduction of hydrogen peroxide on the surface of the cathode. In principle, hydrogen peroxide can be reduced from both basic and acidic solutions. The highest energy density can be achieved for a battery that uses the reduction of hydrogen peroxide from acid solutions. In this case a cell with a Li anode generates E ° = 4.82 V (for standard conditions) compared to E ° = 3.05 V for a Li / water coupling. However, due to the very high reactivity of both acids and hydrogen peroxide with unprotected Li, said cell can be implemented only for the Li protected anode as in accordance with the present invention. For cells that use air as an electrochemically active cathode material, the electrochemically active component with air from this cell includes moisture to provide water for the electrochemical reaction. The cells have an electronically conductive support structure connected to the anode to allow electron transfer to reduce the active cathode material with air. The electronically conductive support structure is generally porous to allow the flow of fluid (air) and either catalytic or treated with a catalyst to catalyze the reduction of the cathode active material. An aqueous electrolyte with suitable ionic conductivity or an ionomer is also in contact with the electronically conductive support structure to allow the transport of ions within the electronically conductive support structure to complete the redox reaction. The cathode-air system includes an electronically conductive component (for example, a porous electronic conductor), an ionically conductive component with at least one aqueous constituent and air as an electrochemically active component. It can be any electrode with suitable air, including those conventionally used in metal (for example Zn) / air or low temperature fuel cells (for example PEM) batteries. Air cathodes used in metal / air batteries, particularly in Zn / air batteries, are described in many sources including "Handbook of Batteries" (Linden and TB Reddy, McGraw-Hill, NY, Third Edition) and are usually composed of several layers including an air diffusion membrane, a hydrophobic Teflon layer, a catalyst layer, and an electronically conductive metal / current collector component, such as a Ni screen. The catalyst layer also includes an ionically conductive / electrolyte component which may be aqueous and / or ionomeric. A typical aqueous electrolyte is composed of KOH dissolved in water. A typical ionomeric electrolyte is composed of a polymer conductor of Li hydrated ion (water) as a polymer film of perfluorosulfonic acid (for example Du Pont NAFION) The air diffusion membrane adjusts the air flow (oxygen). The hydrophobic layer prevents the penetration of the cell electrolyte into the air diffusion membrane. This layer usually contains carbon and Teflon particles. The catalyst layer usually contains carbon with a high surface area and a catalyst for acceleration of the oxygen gas. Metal oxides, for example MnO2 are used as catalysts for the reduction of oxygen in most commercial cathodes. Alternative catalysts include metal macrocycles such as cobalt phthalocyanine and highly dispersed precious metals such as platinum and platinum / ruthenium alloys. Since the air electrode structure is chemically isolated from the active metal electrode, the chemical composition of the electrode with air is not restricted by the potential reactivity with the active anode material. This can allow the design of better performing air electrodes using materials that would normally attack unprotected metal electrodes. Another type of active / aqueous metal battery cell incorporating a protected anode and a cathode system with an aqueous component in accordance with the present invention is a lithium (or other active metal) / metal hydride battery. For example, lithium anodes protected with a non-aqueous interlayer architecture as described herein can be discharged and charged in suitable aqueous solutions as electrolytes in a lithium / metal hydride battery. Suitable electrolytes offer a source of protons. Examples include aqueous solutions of halide acids or acid salts, including chloride or bromide acids or salts, for example HCl, HBr, NH 4 Cl or NH 4 Br. In addition to the aqueous, air, etcetera systems noted above, better performance can be achieved with cathode systems incorporating conventional Li-ion battery cathode and electrolytes such as metal oxide cathodes (eg LixCo02, LixN02, Li Ni02, LixMN20 and LiFeP0) and the binary, tertiary or multicomponent mixtures of alkyl carbonates or their mixtures with ethers as solvents for a metal salt of Li (for example LiPF6, LiAsF6 or LiBF); or Li metal battery cathodes (eg elemental sulfur or polysulfide) and electrolytes composed of organic carbonates, ethers, glimes, lactose, sulfones, sulfolane and combinations thereof, such as EC, PC, DEC, DMC, EMC, 1, 2-DME, THF, 2MeTHF, and combinations thereof as described, for example, in U.S. Patent No. 6,376,123, incorporated herein by reference. Furthermore, the catholyte solution may be composed of only low viscosity solvents, such as ethers such as 1,2-dimethoxy ethane (DME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,3-dioxolane (DIOX), 4- methyldioxolane (4-MeDIOX) or organic carbonates such as Dimethylcarbonate (DMC), ethylmethylcarbonate (EMC), diethylcarbonate (DEC), or mixtures thereof. In addition, super low viscosity ester solvents or co-solvents such as methyl formate and methyl acetate that are very reactive to unprotected Li can be used. As those skilled in the art know, the ionic conductivity and diffusion rates are inversely proportional to the viscosity such that all other things being equal, the performance of the battery improves as the viscosity of the solvent decreases. The use of such catholyte solvent systems significantly improves the performance of the battery, particularly discharge and charge characteristics at low temperatures. Ionic liquids can also be used in catholytes of the present invention. Ionic liquids are organic salts with melting points under 100 degrees, often even lower at room temperature. The most common ionic liquids are imidazolium and pyridinium derivatives, but phosphonium or tetraalkylammonium compounds are also known. Ionic liquids have the desirable attributes of high ionic conductivity, high thermal stability, non-measurable vapor pressure and non-flammability. Representative ionic liquids are 1-ethyl-3-methylimidazolium tosylate (EMIM-Ts), butyl-3-methylimidazolium 1-octyl sulfate (BMIM-OctS04), 1-ethyl-3-methylimidazolium hexafluorophosphate, and tetrafluoroborate 1- hexyl-3-methylimidazolium. Although there has been a substantial interest in ionic liquids for electrochemical applications such as capacitors and batteries, they are unstable to metallic lithium and lithiated carbon. However, protected lithium anodes such as those described in this invention are isolated from direct chemical reaction and consequently lithium metal batteries using ionic liquids are possible as an embodiment of the present invention. Such batteries must be particularly stable at elevated temperatures.

Safety additives As a safety measure, the non-aqueous interlayer architecture can incorporate a gelling / polymerizing agent which, when in contact with the reactive electrolyte (for example water), leads to the formation of an impermeable polymer on the surface of the anode (for example lithium). This security measure is used for the case where the substantially impermeable layer of the protective architecture (a glass or glass-ceramic membrane) breaks or disintegrates and allows the entrance of the aggressive catholyte and approaches the lithium electrode, increasing the possibility of a violent reaction between the Li anode and the aqueous catholyte. Said reaction can be avoided by providing in the anolyte a monomer for a polymer which is insoluble or minimally soluble in water, for example diolxane (Diox) (for example in an amount of about 5-20% by volume) and in the catholyte a polymerization initiator for the monomer, for example a protonic acid. A dioxyl-based anolyte can be composed of organic carbonates (EC, PC, DEC, DMC, EMC), ethers (1,2-DME, THF, 2MeTHF, 1,3-dioxolane and others) and mixtures thereof. The anolyte comprising dioloxane as a main solvent (for example 50-100% by volume) and Li salts, in particular LiAsF6, LiBF4, LiS03CF3, LiN (S02C2F5) 2 > It is especially attractive. Diox is a good passivating agent for the Li surface and good cycling data for Li metals have been achieved from Diox-based electrolytes (see for example US Patent 5,506,068). In addition to its compatibility with the Li metal, Diox in combination with the ionic salts mentioned above forms highly conductive electrolytes. A corresponding aqueous catholyte contains a polymerization initiator for Diox that produces a polymerization product of Diox (polydioxolane) that is not or is minimally soluble in water. If the membrane disintegrates, the catholyte containing the dissolved initiator comes into direct contact with the dioxyl-based anolyte and the polymerization of Diox occurs at the Li-anode surface. Polidioxolane, which is a polymerization product of Diox, has high strength, so the cell closes. Additionally, the formed polydioxolane layer functions as a barrier preventing the reaction between the Li surface and the aqueous catholyte. Diox can be polymerized with protonic acids dissolved in the catholyte. Also, water-soluble Lewis acids, in particular the benzezoyl cation, can help this purpose. Thus, improvement in cycling and safety is achieved through the use of a dioxolane-based anolyte (Diox) and a catholyte containing a polymerization initiator for Diox.

Active metal ion and alloy anodes The invention relates to batteries and other electrochemical structures having anodes composed of active metals, as described above. A preferred active metal electrode is composed of lithium (Li). Anolytes suitable to these structures and cells are described above. The invention also relates to electrochemical structures having active metal ion (for example lithium-carbon) or active metal alloy (for example Li-Sn) anodes. Some structures may initially have unloaded active metal ion interlayer materials (eg carbon) or alloy metals (eg tin (Sn)) that are subsequently charged with active metal or active metal ions. Although the invention can be applied to a variety of active metals, it is described here mainly with reference to lithium, as an example. Coal materials commonly used in conventional lithium ion cells, particularly petroleum coke and mesocarbon microbead carbons, can be used as anode materials in Li-ion aqueous battery cells. Lithium alloys comprising one or more of the metals selected from the group including Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and Si, preferably Al, Sn or Si, can also be used as anode materials for such a battery. In a particular embodiment the anode comprises Li, Cu and Sn. Anolyte for such structures can incorporate support salts, for example LiPF6, LiBF4, LiAsF6, LiCl04, LiS03CF3, LN (CF3S02) 2 or LN (S02C2F5) 2 dissolved in binary or ternary mixtures of non-aqueous solvents, for example EC, PC, DEC, DMC, EMC, MA, MF, commonly used in conventional Li cells. Gel-polymer electrolytes, for example electrolytes comprising one of the salts mentioned above, a polymeric binder such as PVdF, copolymer PCdF-HFP, PAN or PEO or PEO and a plasticizer (solvent) such as EC, PC, DEC, DMC, EMC , THF, 2MeTHF, 1, 2-DME and their mixtures can also be used. For batteries that use these anodes, a suitable cathode structure can be added to the electrochemical structure on the other side of the protective architecture. The architecture allows Li-type cells that use a series of exotic cathodes such as water, air, metal hydrides and metal oxides. For aqueous Li-ion battery cells, for example, aqueous catholyte can be basic, acid or neutral and contains lithium cations. An example of a suitable aqueous catholyte is 2 M LiCl, 1 M HCl. During the first charging of the battery with a lithium-carbon lithium alloy anode, lithium cations are transported from the catholyte through the protective architecture (including the anolyte) to the anode surface where the interleaving process takes place. as in conventional lithium ion cells. In one embodiment, the anode is chemically or electrochemically lithiated ex-situ prior to assembly of the cell.

Cell Designs Electrochemical structures and battery cells in accordance with the present invention can have any suitable geometry. For example, flat geometries can be achieved by stacking flat layers of the various components of the structures or cells (anode, interlayer, cathode, etc.) in accordance with known battery cell manufacturing techniques that are readily adaptable to the present! given the description of the cell structure or components that are provided here. These stacked layers can be configured as prismatic structures or cells. Alternatively, the use of tubular glass or glass / ceramic electrolytes with a non-aqueous interlayer architecture allows the construction of anodes with high surface area with low seal area. In contrast to the flat plate design where the seal length increases with the cell surface area, the tubular construction uses an end seal where the length of the tube can be increased to trigger the surface area while the seal area does not vary. This allows the construction of Li / water and Li / air cells with large surface area that should have corresponding high power density. The use of a non-aqueous interlayer architecture in accordance with the present invention facilitates construction. An open end (with a seal) or glass with a closed end or glass / ceramic (ie solid electrolyte conductive substantially metal active ion) tube is partially filled with a non-aqueous organic electrolyte (anolyte or transfer electrolyte) as shown in FIG. described above, for example as it is typically used in primary lithium batteries. A lithium metal rod surrounded by some type of physical separator (for example a semi-permeable polymer film such as Celgard, Tonin, polypropylene mesh, etc.) having a current collector is inserted into the tube. A simple epoxy seal, glass to metal seal, or other appropriate seal is used to physically isolate lithium from the environment. The protected anode can then be inserted into a cylindrical air electrode to make a cylindrical cell, as shown in Figure 3A. Or a set of anodes can be inserted into a prismatic air electrode, as shown in Figure 3B. This technology can also be used to generate Li / water, Li / metal hydride or Li / metal oxide cells by replacing the air electrode with suitable aqueous cathode, metal hydride or metal oxide systems, as described here above. In addition to the use of lithium metal bars or wires (in capillary tubes), this invention can also be used to isolate a rechargeable L × CX anode from aqueous or corrosive environments. In this case, suitable anolyte solvents (transfer electrolyte) are used in the tubular anode to form a passive film in the lithiated carbon electrode. This will allow the construction of Li-ion cells of high surface area using a number of exotic cathodes such as air, water, metal hydrides or metal oxides, for example as shown in Figure 3C.

EXAMPLES The following examples provide details illustrating advantageous properties of Li metal battery cells and aqueous ion Li in accordance with the present invention. These examples are provided to exemplify and more clearly illustrate aspects of the present invention and in no way are intended to be restrictive.

EXAMPLE 1 Li cell / sea water A series of experiments was conducted in which the commercial ionic conductive glass / ceramic of OHARA Corporation was used as a membrane separating the aqueous catholyte and the non-aqueous anolyte. The cell structure was Li / non-aqueous electrolyte / glass-ceramic / aqueous electrolyte / Pt. A thin sheet of lithium from Chemetall Foote Corporation with a thickness of 125 microns was used as the anode. The glass / ceramic plates were in the range of 0.3 to 0.48 mm in thickness. The glass-ceramic plate was placed inside an electrochemical cell by using two O-rings such that the glass-ceramic plate was exposed to an aqueous environment on one side and a non-aqueous environment on the other side. In this case, the aqueous electrolyte comprised an artificial seawater prepared with 35 ppt of "Instant Ocean" from Aquarium Systems, Inc. The conductivity of the seawater was determined as 4.5 10"2 S / cm.A microporous Celgard separator placed on the other side of the glass-ceramic was filled with non-aqueous electrolyte comprised of 1 M LiPF6 dissolved in propylene carbonate The charge volume of the nonaqueous electrolyte was 0.25 ml per 1 cm2 of Li electrode surface, a platinum counter electrode completely immersed in the Marine water catholyte was used to facilitate the reduction of hydrogen when the battery circuit was completed.An Ag / AgCI reference electrode was used to control the Li anode potential in the cell.Measured values were recalculated in powers on the scale of Standard Hydrogen Electrode (SHE) An open circuit potential (OCP) of 3.05 volts corresponding closely to the potential thermodynamic difference between Li / Li + and H2 / H + in water was observed (figure 4). When the circuit was closed, the hydrogen evolution was immediately seen at the Pt electrode, which indicated anode and cathode electrode reactions in cell 2Li = 2Li + 2e and 2H + + 2e "= H2.The potential-time curve for the anodic dissolution of Li at a discharge rate of 0.3 mA / cm2 is presented in figure 2. The results indicate an operating cell with a stable discharge voltage It should be emphasized that in all experiments using a Li anode in contact direct with seawater the use of Li was very poor, and such batteries could not be used at all and moderate current densities similar to those used in this example due to the extremely high corrosion rate of Li in seawater (about 19 A / cm2).

EXAMPLE 2 Li / air cell The cell structure was similar to that in the previous example, but instead of a Pt electrode completely immersed in the electrolyte, this experimental cell had an air electrode made for commercial Zn / air batteries. An aqueous electrolyte used was 1 M LiOH. An anode of Li and a non-aqueous electrolyte were the same as described in the previous example. An open circuit potential of 3.2 V was observed for this cell. Figure 5 shows the discharge-time voltage curve at a discharge speed of 0.3 mA / cm2. The cell exhibited discharge voltage of 2.8-2.9 V for more than 14 hours. This result shows that a good performance can be achieved for Li / air cells with solid electrolyte membrane that separates aqueous catholyte and non-aqueous anolyte.

EXAMPLE 3 Li ion cell In these experiments the commercial ionic conductive glass-ceramic of OHARA Corporation was used as a membrane separating the aqueous catholyte and the non-aqueous anolyte. The cell structure was carbon / non-aqueous electrolyte / glass-ceramic plate / aqueous electrolyte / Pt. A commercial carbon electrode on copper substrate comprising a synthetic graphite similar to carbon electrodes commonly used in lithium ion batteries was used as an anode. The thickness of the glass-ceramic plate was 0.3 mm. The glass-ceramic plate was placed in an electrochemical cell by using two O-rings such that the glass-ceramic plate was exposed to an aqueous environment on one side and a non-aqueous environment on the other side. The aqueous electrolyte comprised 2 M LiCl and 1 M HCl. Two layers of microporous Celgard separator placed on the other side of the glass-ceramic were filled with non-aqueous electrolyte comprised of 1 M LiPF6 dissolved in the mixture of ethylene carbonate and dimethyl carbonate (1: 1 by volume). A reference electrode of lithium wire was placed between two layers of Celgard separator to control the potential of the carbon anode during the keyboard. A platinum mesh completely in the 2 M solution, 9 M, 1 M HCl was used as the cell cathode. An Ag / AgCI reference electrode placed in the aqueous electrolyte was used to control the potential of the carbon electrode and voltage drop in the glass-ceramic plate, as well as potential of the Pt cathode during cycling. An open circuit voltage (OCV) around one volt was observed for this cell. The voltage difference of 3.2 volts between the reference electrode Li and the Ag / AgCI reference electrode closely corresponding to the thermodynamic value was observed. The cell was charged at 0.1 mA / cm2 until the potential of 5 mV carbon electrode vs. Li reference electrode and then at 0.05 mA / cm2 using the same cutting potential. The discharge velocity was 0.1 mA / cm2 and the discharge cutoff potential for the carbon anode was 1.8 V versus Li reference electrode. The data in Figure 6 show that the cell with intercalated carbon anode and aqueous electrolyte containing Li cations can work in reverse. This is the first known example wherein the aqueous solution has been used in a Li-ion cell instead of solid lithiated oxide cathode as a source of Li ions to charge the carbon anode.

EXAMPLE 4 Performance of Thick Li Anode Protected Glass-Ceramic in Aqueous Electrolyte An experimental Li / water cell to test a variety of thin sheet thicknesses of Li in aqueous electrolytes was designed. The cell, shown in FIG. 8, contains an anode compartment with a protected Li-thin anode of 2.0 cm2 active area on Cu substrate. Li electrode with a thickness of about 3.3-3.5 mm were manufactured from a Li metal rod. The manufacturing process involved extruding and winding the Li bar followed by pressure static of the resulting thin sheet on the surface of the Ni gauze current connector with a hydraulic press. A die with a polypropylene body was used for the pressure operation to avoid the chemical reaction with the thin lithium sheet. A glass-ceramic membrane with a thickness of about 50 microns was placed inside the electrochemical cell by using O-rings such that the glass-ceramic membrane was exposed to an aqueous environment (catholyte) on one side and a non-aqueous environment ( anolyte on the other side). The anolyte provided a liquid interlayer between the anode and the surface of the glass-ceramic membrane. The cell was filled with 4 M aqueous NH4CI catholic, which allowed the cathode to be regulated during storage and discharge of the cell. A microporous Celgard separator placed on the other side of the glass-ceramic membrane was filled with nonaqueous anolyte comprised of 1 M LCIO dissolved in propylene carbonate. The anode compartment was sealed against an aqueous solution such that only the protective glass-ceramic membrane was exposed to an aqueous environment, a reference electrode and a metal screen counter electrode. The cell body made from the borosilicate glass was filled with 100 ml of the catholyte. A Ti screen counter electrode was used as a cathode to facilitate the evolution of hydrogen (water reduction) during the anodic dissolution of Li. An Ag / AgCI reference electrode placed next to the surface of the protective glass membrane was used to control the potential of the Li anode during discharge. Measured values were recalculated into potentials on the standard hydrogen electrode (SHE) scale. The cell was equipped with a vent to release hydrogen gas generated at the cathode. The time-potential curve for continuous discharge of these cells is shown in Figure 7. The cell exhibited a very large discharge for almost 1400 hrs at a closed-circuit voltage of approximately 2.7-2.9 V. The value of discharge capacity achieved It was very large, around 650 mAh / cm2. More than 3.35 mm of Li were moved through the Li-anode / aqueous electrolyte interface without destruction of the protective glass-ceramic membrane 50 μm thick. The thickness of the thin sheet of Li used in this experiment was on the 3.35-3.40 mm scale. Postmortem analysis of the unloaded Li anode confirmed that the total amount of Li was removed from the Ni current collector at the end of the cell discharge. This shows that the efficiency in columns for the discharge of the protected Li anode is close to 100%. The Li discharge capacity achieved was used to project the performance of Li / Air prismatic batteries. In Figure 9, specific energy projections for batteries with a varied thickness of protected Li and cell specific gravimetric energy value for a glass protected anode with a thickness of Li of 3.3 mm are shown. This figure also illustrates the cell configuration and shows the parameters used for the calculations. The cell dimensions corresponded to the area of a business card (about 45 cm2) and about 6 mm in thickness (including 3.3 mm Li-anode). This generates a very large projected capacity of 90 Wh. As can be seen from Figure 9, the experimentally achieved discharge capacity of glass protected anode allows the construction of Li / Air battery with exceptional high performance characteristics.

Alternative mode, Li / aqua battery and hydrogen generator for fuel cell The use of protective architecture in active metal electrodes in accordance with the present invention allows the construction of active metal / water batteries that have minimal corrosion currents, described above. The Li / water battery has a very high theoretical energy density of 8450 Wh / kg. The cell reaction is Li + H2O = LiOH + 1/2 H2. Although the hydrogen produced by the cell reaction is typically lost, in this embodiment of the present invention it is used to provide fuel for a fuel cell at room temperature. The hydrogen produced can either be fed directly to the fuel cell or can be used to recharge a metal hydride alloy for later use in a fuel cell. For about one company, Millenium Cell «http://www.millenniumcell.com./news/tech.html» makes use of the reaction of sodium borohydride with water to produce hydrogen. However, this reaction requires the use of a catalyst and the energy produced from the chemical reaction NaBH4 and water is lost as heat.

NaCH4 + 2 H20? 4 H H2 + NaB02 When combined with the fuel cell reaction, H2 + 02 = H20, the complete cell reaction is considered: NaBH4 + 202 - 2 H20 + NaB02 The energy density for this system can be calculated from the equivalent weight of the NaBH4 reagent. The gravimetric capacity of NaBH4 is 2820 mAh / g; since the cell voltage is around 1, the specific energy of this system is 2820 Wh / kg. If one calculates the energy density based on the final product NaB02, the energy density is lower, around 1620 Wh / kg. In the case of the Li / water cell, the generation of hydrogen proceeds by a believed electrochemical reaction described by: Li + H2O = LiOH + 1/2 H2 In this case, the energy of the chemical reaction is converted to electrical energy in a 3 volt cell, by the conversion of hydrogen to water in a fuel cell, followed by the conversion of hydrogen to water in a fuel cell, giving a global cell reaction believed and described: Li + 1/2 H2O + 1/4 O2 = LiOH where all the chemical energy is theoretically converted into electrical energy. The energy density based on the lithium anode is 3830 mAh / g at a cell potential of about 3 volts which is 11,500 Wh / kg (4 times higher than NaBH 4). If one includes the weight of the water necessary for the reaction, the energy density is then 5030 Wh / kg. If the energy density is based on the weight of the LiOH discharge product, it is then 3500 Wh / kg, or twice the energy density of the NaB02 system. This can be compared to previous concepts where the reaction of lithium metal with water to produce hydrogen has also been considered. In that scenario the energy density is decreased by a factor of three, since most of the energy in the Li / H20 reaction is wasted as heat, and the energy density is based on a cell potential for the H2 / coupling 02 (as opposed to 3 for Li / H20) that in practice is less than one. In this embodiment of the present invention, illustrated in Figure 10, the production of hydrogen can also be carefully controlled by charging through the Li / water battery, the Li / water battery has a long shelf life due to the protective membrane and the hydrogen that leaves the cell is already humidified for use in the fuel cell H2 / air.

Conclusions Although the above invention has been described in some detail for the purpose of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the invention.

In particular, although the invention is previously described with reference to a lithium metal, alloy or intercalating anode, the anode can also be composed of any active metal, in particular, other alkmetals, such as sodium. It should be noted that there are many alternative ways of implementing both the method and compositions of the present invention.

Accordingly, the present embodiments should be considered as illustrative and not restrictive and the invention is not limited by the details given herein. All references cited herein are incorporated by reference for all purposes.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - An electrochemical cell structure, comprising: an anode comprising a material selected from the group consisting of active metal, active metal-ion, active metal-alloy metal, and active metal intercalation metal; and an ionically conductive protective architecture on a first surface of the anode, the architecture comprising, an active metal ion conductive separating layer comprising a nonaqueous anolyte, the separating layer chemically compatible with the active metal, and in contact with the anode, and an ionically conductive substantially waterproof layer chemically compatible with the separator layer and aqueous environments; and in contact with the separating layer.

2. The structure according to claim 1, further characterized in that the separating layer comprises a semipermeable membrane impregnated with a non-aqueous anolyte.

3. The structure according to claim 2, further characterized in that the semipermeable membrane is a microporous polymer.

4. The structure according to claim 3, further characterized in that the anolyte is in the liquid phase.

5. - The structure according to claim 4, further characterized in that the anolyte comprises a solvent selected from the group consisting of organic carbonates, ethers, esters, formates, lactones, sulfones, sulfolane and combinations thereof.

6. The structure according to claim 5, further characterized in that the anolyte comprises a solvent of the selected group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1, 2-DME or higher glymes, sulfolane , methyl formate, methyl acetate and combinations thereof and a support salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiCIO4, LiSO3CF3, LiN (CF3S02) 2 and LiN (SO2C2F5) 2.

7. The structure according to claim 6, further characterized in that the anolyte further comprises 1,3-dioxolane.

8. The structure according to claim 3, further characterized in that the anolyte is in the gel phase.

9. The structure according to claim 8, further characterized in that the anolyte comprises a gelling agent selected from the group consisting of PVdF, copolymer of PVdF-HFP, PAN, and PEO and mixtures thereof; a plasticizer selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1, 2-DME and mixtures thereof; and Li salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiCl04, LiS03CF3, LiN (CF3S02) 2 and LiN (S02C2F5) 2.

10. - The structure according to any of the preceding claims, further characterized in that the substantially impermeable ionically conductive layer comprises a material selected from the group consisting of vitreous or amorphous active metal ion conductors, ceramic active metal ion conductors, and ion conductors of active metal / glass ceramic.

11. The structure according to any of the preceding claims, further characterized in that the active metal is lithium.

12. The structure according to any of the preceding claims, further characterized in that the substantially impermeable ionically conductive layer is an ion-conducting glass / ceramic having the following composition: P205 26-55% mol, Si02 0-15% in mol, Ge02 + Ti02 25-50% in mol where Ge02 0-50% in mol, Ti02 0-50% in mol, Zr02 0-10% in mol, M203 0 < 10% in mol, Al203 0-15% in mol, Ga203 0-15% in mol, Li20 3-25% in mol and containing a predominant crystalline phase composed of L¡? +? (M, AI, Ga) x (Ge? -yTiy) 2-x (P04) 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 Li1 + x + yQxTi2.xSiyP3-y012 where 0 < X < 0.4 and 0 < And < 0.6, and where Q is Al or Ga.

13. The structure according to any of the preceding claims, further characterized in that the substantially impermeable ionically conductive layer has an ionic conductivity of at least 10"5S / cm

14. The structure according to any of the preceding claims, further characterized in that the nonaqueous electrolyte separating layer has a conductivity. ionic at least 10"5S / cm.

15. The structure according to any of the preceding claims, further characterized in that the anode comprises an active metal.

16. The structure according to any of the preceding claims, further characterized in that the anode comprises active metal-ions.

17. The structure according to any of the preceding claims, further characterized in that the anode comprises an active metal alloy metal.

18. The structure according to claim 17, further characterized in that the metal of active metal alloy is selected from the group consisting of Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and Sb

19. The structure according to any of the preceding claims, further characterized in that the anode comprises active metal intercalation material.

20. - The structure according to claim 19, further characterized in that the active metal intercalation material comprises carbon.

21.- A battery cell, comprising: an active metal anode; a cathode structure; and an ionically conductive protective architecture on a first surface of the anode, the architecture comprises, an active metal ion conductive separating layer comprising a nonaqueous anolyte, the separating layer chemically compatible with the active metal, and in contact with the anode, and an ionically conductive substantially impermeable layer chemically compatible with the separator layer and the cathode structure, and in contact with the cathode structure.

22. The cell according to claim 21, further characterized in that the separating layer comprises a semipermeable membrane impregnated with a non-aqueous anolyte.

23. The cell according to claim 22, further characterized in that the semipermeable membrane is a microporous polymer.

24. The cell according to claim 23, further characterized in that the anolyte is in the liquid phase.

25. The cell according to claim 24, further characterized in that the anolyte comprises a solvent selected from the group consisting of organic carbonates, ethers, esters, formates, lactones, sulfones, sulfolane and combinations thereof.

26. The cell according to claim 25, further characterized in that the anolyte comprises a solvent selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1, 2-DME or higher glymes, sulfolane , methyl formate, methyl acetate, and combinations thereof and a support salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiCl04, LiS03CF3, LiN (CF3S02) 2 and LiN (S02C2F5) 2.

27. The cell according to claim 26, further characterized in that the anolyte further comprises 1,3-dioxolane.

28. The cell according to claim 23, further characterized in that the anolyte is in the gel phase.

29. The cell according to claim 28, further characterized in that the anolyte comprises a gelling agent selected from the group consisting of PVdF, copolymer of PVdF-HFP, PAN and PEO, and mixtures thereof; a plasticizer selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1, 2-DME and mixtures thereof; and a Li salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiCl4, LiS03CF3, LiN (CF3S02) 2 and LiN (S02C2F5) 2 ..

30.- The cell according to claim 21, further characterized because the substantially impermeable ionically conductive layer comprises a material selected from the group consisting of glassy or amorphous active metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors.

31. The cell according to claim 30, further characterized in that the active metal is lithium.

32. The cell according to claim 31, further characterized in that the ionically conductive substantially impermeable layer is an ion-conductive glass-ceramic having the following composition: P Od 26-55 mol%, Si02 0-15% in mol, Ge02 + Ti02 25-50% by mol where Ge02 0-50% by mol, Ti02 0-50% by mol, Zr02 0-10% by mol, M203 0 < 10% in mol, Al203 0-15% in mol, Ga203 0-15% in mol, Li20 3-25% in mol and containing a predominant crystalline phase composed of Li? + X (M, AI, Ga) x ( Ge? -yTiy) 2-x (P04) 3 where X < 0.8 and 0 < And < 1.0, and wherein M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb and / or Li1 +? + YQxTi2-xSiyP3-y012 where 0 < X < 0.4 and 0 < And < 0.6, and where Q is Al or Ga.

33. The cell according to claim 21, further characterized in that the substantially impermeable ionically conductive layer has an ionic conductivity of at least 10"5S / cm.

The cell according to claim 21, further characterized in that Non-aqueous electrolyte separator layer has an ionic conductivity of at least 10"5S / cm.

35. - The cell according to claim 21, further characterized in that the anode comprises active metal.

36. The cell according to claim 21, further characterized in that the anode comprises active metal-ions.

37. The cell according to claim 21, further characterized in that the anode comprises an active metal alloy metal.

38.- The cell according to claim 37, further characterized in that the metal of active metal alloy is selected from the group consisting of Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and Sb

39. The cell according to claim 21, further characterized in that the anode comprises intercalation material material.

40. The cell according to claim 39, further characterized in that the active metal intercalation material comprises carbon.

41.- The cell according to claim 21, further characterized in that the cathode structure comprises an electronically conductive component, an ionically conductive component, and an electrochemically active component, wherein at least one component of the cathode structure comprises a Aqueous constituent.

42. - The cell according to claim 41, further characterized in that the cathode structure comprises an aqueous electrochemically active component.

43. The cell according to claim 42, further characterized in that the aqueous electrochemically active component is water.

44. The cell according to claim 42, further characterized in that the aqueous electrochemically active component comprises a water-soluble oxidant selected from the group consisting of gaseous, liquid and solid oxidants and combinations thereof.

45. The cell according to claim 44, further characterized in that the water-soluble gaseous oxidants are selected from the group consisting of O2, SO2 and N02, and the water-soluble solid oxidants are selected from the group consisting of NaN02, KN02, Na2S03 and K2S03.

46.- The cell according to claim 44, further characterized in that the water-soluble oxidant is peroxide.

47. The cell according to claim 46, further characterized in that the water-soluble oxidant is hydrogen peroxide.

48. The cell according to claim 41, further characterized in that the ionically conductive component and the electrochemically active component are comprised by an aqueous electrolyte.

49. The cell according to claim 48, further characterized in that the aqueous electrolyte is selected from the group consisting of strong acid solutions, weak acid solutions, basic solutions, neutral solutions, amphoteric solutions, peroxide solutions, and combinations from the same.

50.- The cell according to claim 48, further characterized in that the aqueous electrolyte comprises elements selected from the group consisting of aqueous solutions of HCl, H2SO4, H3P04, acetic acid / Li acetate, LiOH; seawater, LiCI, LiBr, Lil, NH4CI, NH4Br and hydrogen peroxide and combinations thereof.

51. The cell according to claim 50, further characterized in that the aqueous electrolyte is seawater.

52. The cell according to claim 10, further characterized in that the aqueous electrolyte comprises seawater and hydrogen peroxide.

53. The cell according to claim 50, further characterized in that the aqueous electrolyte comprises an acid peroxide solution.

54. The cell according to claim 50, further characterized in that hydrogen peroxide dissolved in aqueous electrolyte flows through the cell.

55. - The cell according to claim 41, further characterized in that the electronically conductive component of the cathode structure is a porous catalytic support.

56.- The cell according to claim 55, further characterized in that the electronically porous catalytic conductive support comprises nickel.

57. The cell according to claim 55, further characterized in that the porous electronically conductive catalytic support is treated with an ionomer.

58. The cell according to claim 42, further characterized in that the electrochemically active material of the cathode structure comprises air.

59. The cell according to claim 58, further characterized in that the air comprises humidity.

60.- The cell according to claim 59, further characterized in that the ionically conductive material comprises an aqueous constituent.

61.- The cell according to claim 60, further characterized in that the ionically conductive material further comprises an ionomer.

62. The cell according to claim 61, further characterized in that the ionically conductive material comprises an acidic or neutral aqueous electrolyte.

63. - The cell according to claim 62, further characterized in that the aqueous electrolyte comprises LiCI.

64.- The cell according to claim 62, further characterized in that the aqueous electrolyte comprises one of NH CI, and HCl.

65.- The cell according to claim 41, further characterized in that the cathode structure comprises an air diffusion membrane, a hydrophobic polymeric layer, an oxygen reduction catalyst, an electrolyte, and an electronically conductive component / collector of current.

66. The cell according to claim 65, further characterized in that the electronically conductive component / current collector comprises a porous nickel material.

67.- The cell according to claim 65, further characterized in that it comprises a separator placed between the protective membrane and the cathode structure.

68.- The cell according to claim 41, further characterized in that the electrochemically active component of the cathode structure comprises a metal hydride alloy.

69. The cell according to claim 68, further characterized in that the ionically conductive component of the cathode structure comprises an aqueous electrolyte.

70. - The cell according to claim 69, further characterized in that the aqueous electrolyte is acidic.

71. The cell according to claim 70, further characterized in that the aqueous electrolyte comprises a halide acid or an acid salt.

72. The cell according to claim 71, further characterized in that the aqueous electrolyte comprises a chloride or a bromide acid or an acid salt.

73. The cell according to claim 72, further characterized in that the aqueous electrolyte comprises one of HCl, HBr, NH4CI and NH4Br.

The cell according to claim 73, further characterized in that the metal hydride alloy comprises an alloy of AB5 and an alloy of AB2.

75.- The cell according to claim 21, further characterized in that the cell is a primary cell.

76.- The cell according to claim 21, further characterized in that the cell is a rechargeable cell.

77.- The cell according to claim 21, further characterized in that the cell has a flat configuration.

78.- The cell according to claim 21, further characterized in that the cell has a tubular configuration.

79. - The cell according to claim 41, further characterized in that the active metal is lithium and the cathode structure comprises an aqueous ionically conductive component and an electrochemically active component of transition metal oxide. 80.- The cell according to claim 79, further characterized in that the transition metal oxide is selected from the group consisting of NiOOH, AgO, iron oxide, lead oxide and manganese oxide. 81. The cell according to claim 21, further characterized in that the anolyte further comprises a monomer for a polymer that is insoluble or minimally insoluble in water and the catholyte comprises a polymerization initiator for the monomer. 82. The cell according to claim 81, further characterized in that the monomer is 1,3-dioxolane. 83. The cell according to claim 82, further characterized in that the polymerization initiator comprises at least one of the group consisting of protonic acid and water-soluble Lewis acids dissolved in the catholyte. 84. The cell according to claim 83, further characterized in that the polymerization initiator comprises a benbenzoyl cation. 85.- A method for providing the closure of an electrochemical cell according to claim 21 in the case of a structural failure comprising providing in the anolyte a monomer for a polymer that is insoluble or minimally soluble in water and in the catholyte a polymerization initiator for the monomer. 86.- The cell according to claim 21, further characterized in that the cathode structure comprises an ionically conductive component. 87. The cell according to claim 86, further characterized in that the ionically conductive component comprises a nonaqueous catholyte. 88. The cell according to claim 87, further characterized in that the catholyte comprises a material selected from the group consisting of organic liquids and ionic liquids. 89. The cell according to claim 88, further characterized in that the catholyte is a solution of a Li salt in an aprotic solvent selected from the group consisting of organic carbonates, ethers, lactones, sulfone esters, formates and combinations of the same. 90.- The cell according to claim 89, further characterized in that the catholyte is selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1, 2-DME and higher glymes, 1,3-dioxolane, sulfolane, methyl formate, methyl acetate, and combinations thereof, and a support salt selected from the group consisting of L-PF6, LiBF4, LiAsF6, LiCl04. LiS03CF3, LiN (CF3S02) 2, LiN (SO2C2F5) 2 and combinations thereof. 91.- The cell according to claim 90, further characterized in that it comprises dissolving a solid, liquid or gaseous oxidant selected from the group consisting of lithium polysulfides, N02, S02, SOCI2. 92. The cell according to claim 87, further characterized in that the catholyte comprises an ionic liquid selected from the group consisting of imidazolium derivatives, pyridinium derivatives, phosphonium compound, and tetraalkylammonium compounds, and combinations thereof. 93. The cell according to claim 92, further characterized in that the ionic liquid is selected from the group consisting of 1-ethyl-3-methylimidazolium tosylate (EMIM-Ts), 1-butyl-3-methylimidazolium sulfate. octyl (BMIM-OctS04), 1-ethyl-3-methylimidazolium hexafluorophosphate, and 1-hexyl-3-methylimidazolium tetrafluoroborate. 94.- A method for manufacturing a battery cell according to claim 21, characterized in that it comprises: providing the following components, an active metal anode; a cathode structure; and an ionically conductive protective architecture on a first surface of the anode, the architecture comprising, an active metal ion conductive separating layer comprising a nonaqueous anolyte, the separating layer chemically compatible with the active metal, and in contact with the anode and an ionically conductive substantially impermeable layer chemically compatible with the separating layer and the cathode structure, and in contact with the cathode structure; and assemble the components. The method according to claim 94, further characterized in that the substantially impermeable ionically conductive layer is tubular. 96.- The cell according to claim 21, further characterized in that the cell has a discharge capacity of more than 10 mAh / cm2. 97.- The cell according to claim 96, further characterized in that the cell has a discharge capacity of more than 100 mAh / cm2. 98.- The cell according to claim 97, further characterized in that the cell has a discharge capacity of more than 500 mAh / cm2. 99.- The cell according to claim 50, further characterized in that the anode has Li with a thickness of about 3.35 mm, the cell is filled with an aqueous electrolyte comprising NH CI and the cell has a discharge capacity of about 650 mAh / cm2. 100.- The cell according to claim 58, further characterized in that the cell has a Li anode with 3.3 mm thickness and an area of 45 cm2 and a specific unpacked energy of around 3400 Wh / I (4100 Wh / kg). 101. The cell according to claim 100, further characterized in that the cell has a packet load at 70%, and a specific packaged energy of about 1000 Wh / I (1200 Wh / kg). 102. The cell according to claim 43, further characterized in that it comprises a fuel cell PEM H2 / 02 to capture hydrogen released from the cathode structure in the redox reaction of the battery cell.