US20110200868A1 - THIN-FILM BATTERIES WITH POLYMER AND LiPON ELECTROLYTE LAYERS AND METHOD - Google Patents

THIN-FILM BATTERIES WITH POLYMER AND LiPON ELECTROLYTE LAYERS AND METHOD Download PDF

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US20110200868A1
US20110200868A1 US13/092,542 US201113092542A US2011200868A1 US 20110200868 A1 US20110200868 A1 US 20110200868A1 US 201113092542 A US201113092542 A US 201113092542A US 2011200868 A1 US2011200868 A1 US 2011200868A1
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electrolyte
layer
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lipon
electrolyte layer
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Jody J. Klaassen
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Klaassen Jody J
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Priority to US12/850,078 priority patent/US7939205B2/en
Application filed by Klaassen Jody J filed Critical Klaassen Jody J
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/14Cells with non-aqueous electrolyte
    • H01M6/18Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/187Solid electrolyte characterised by the form
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0088Composites
    • H01M2300/0094Composites in the form of layered products, e.g. coatings
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/661Metal or alloys, e.g. alloy coatings
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49002Electrical device making
    • Y10T29/49108Electric battery cell making
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49002Electrical device making
    • Y10T29/49108Electric battery cell making
    • Y10T29/49112Electric battery cell making including laminating of indefinite length material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/49002Electrical device making
    • Y10T29/49108Electric battery cell making
    • Y10T29/49115Electric battery cell making including coating or impregnating

Abstract

A method and apparatus for making thin-film batteries having composite multi-layered electrolytes with soft electrolyte between hard electrolyte covering the negative and/or positive electrode, and the resulting batteries. In some embodiments, foil-core cathode sheets each having a cathode material (e.g., LiCoO2) covered by a hard electrolyte on both sides, and foil-core anode sheets having an anode material (e.g., lithium metal) covered by a hard electrolyte on both sides, are laminated using a soft (e.g., polymer gel) electrolyte sandwiched between alternating cathode and anode sheets. A hard glass-like electrolyte layer obtains a smooth hard positive-electrode lithium-metal layer upon charging, but when very thin, have randomly spaced pinholes/defects. When the hard layers are formed on both the positive and negative electrodes, one electrode's dendrite-short-causing defects on are not aligned with the other electrode's defects. The soft electrolyte layer both conducts ions across the gap between hard electrolyte layers and fills pinholes.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This invention claims benefit of U.S. Provisional Patent Application 60/699,895 filed Jul. 15, 2005, which is hereby incorporated by reference in its entirety. This is also related to U.S. patent application Ser. No. 10/895,445 entitled “LITHIUM/AIR BATTERIES WITH LiPON AS SEPARATOR AND PROTECTIVE BARRIER AND METHOD” filed Oct. 16, 2003 by J. Klaassen, the inventor of the present application, and to U.S. patent application Ser. No. 11/031,217 entitled “LAYERED BARRIER STRUCTURE HAVING ONE OR MORE DEFINABLE LAYERS AND METHOD” filed Jan. 6, 2005, U.S. patent application Ser. No. 11/______ entitled “THIN-FILM BATTERIES WITH SOFT AND HARD ELECTROLYTE LAYERS AND METHOD” (Attorney docket number 1327.031us1) and U.S. patent application Ser. No. 11/______ entitled “APPARATUS AND METHOD FOR MAKING THIN-FILM BATTERIES WITH SOFT AND HARD ELECTROLYTE LAYERS” (Attorney docket number 1327.031us3), filed on even date herewith, which are all incorporated herein in their entirety by reference.
  • FIELD OF THE INVENTION
  • This invention relates to solid-state energy-storage devices, and more specifically to a method and apparatus for making thin-film (e.g., lithium) battery devices with a soft (e.g., polymer) electrolyte layer, and one or more hard layers (e.g., LiPON) as electrolyte layer(s) and/or protective barrier(s), and the resulting cell(s) and/or battery(s).
  • BACKGROUND OF THE INVENTION
  • Electronics have been incorporated into many portable devices such as computers, mobile phones, tracking systems, scanners, and the like. One drawback to portable devices is the need to include the power supply with the device. Portable devices typically use batteries as power supplies. Batteries must have sufficient capacity to power the device for at least the length of time the device is in use. Sufficient battery capacity can result in a power supply that is quite heavy and/or large compared to the rest of the device. Accordingly, smaller and lighter batteries (i.e., power supplies) with sufficient energy storage are desired. Other energy storage batteries (i.e., power supplies) with sufficient energy storage are desired. Other energy storage devices, such as supercapacitors, and energy conversion devices, such as photovoltaics and fuel cells, are alternatives to batteries for use as power supplies in portable electronics and non-portable electrical applications.
  • Another drawback of conventional batteries is the fact that some are fabricated from potentially toxic materials that may leak and be subject to governmental regulation. Accordingly, it is desired to provide an electrical power source that is safe, solid-state and rechargeable over many charge/discharge life cycles.
  • One type of an energy-storage device is a solid-state, thin-film battery. Examples of thin-film batteries are described in U.S. Pat. Nos. 5,314,765; 5,338,625; 5,445,906; 5,512,147; 5,561,004; 5,567,210; 5,569,520; 5,597,660; 5,612,152; 5,654,084; and 5,705,293, each of which is herein incorporated by reference. U.S. Pat. No. 5,338,625 describes a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or first integrated power source for electronic devices. U.S. Pat. No. 5,445,906 describes a method and system for manufacturing a thin-film battery structure formed with the method that utilizes a plurality of deposition stations at which thin battery component films are built up in sequence upon a web-like substrate as the substrate is automatically moved through the stations.
  • U.S. Pat. No. 6,805,998 entitled “METHOD AND APPARATUS FOR INTEGRATED BATTERY DEVICES” (which is incorporated herein by reference) issued Oct. 19, 2004, by Mark L. Jenson and Jody J. Klaassen (the inventor of the present application), and is assigned to the assignee of the present invention, described a high-speed low-temperature method for depositing thin-film lithium batteries onto a polymer web moving through a series of deposition stations.
  • K. M. Abraham and Z. Jiang, (as described in U.S. Pat. No. 5,510,209, which is incorporated herein by reference) demonstrated a cell with a non-aqueous polymer separator consisting of a film of polyacrylonitrile swollen with a propylene carbonate/ethylene carbonate/LiPF6 electrolyte solution. This organic electrolyte membrane was sandwiched between a lithium metal foil anode and a carbon composite cathode to form the lithitun-air cell. The utilization of the organic electrolyte allowed good performance of the cell in an oxygen or dry air atmosphere.
  • As used herein, the anode of the battery is the positive electrode (which is the anode during battery discharge) and the cathode of the battery is the negative electrode (which is the cathode during battery discharge). (During a charge operation, the positive electrode is the cathode and the negative electrode is the anode, but the anode-cathode terminology herein reflects the discharge portion of the cycle.)
  • U.S. Pat. No. 6,605,237 entitled “Polyphosphazenes as gel polymer electrolytes” (which is incorporated herein by reference), issued to Allcock, et al. on Aug. 12, 2003, and describes co-substituted linear polyphosphazene polymers that could be useful in gel polymer electrolytes, and which have an ion conductivity at room temperature of at least about 10−5 S/cm and comprising (i) a polyphosphazene having controlled ratios of side chains that promote ionic conductivity and hydrophobic, non-conductive side chains that promote mechanical stability, (ii) a small molecule additive, such as propylene carbonate, that influences the ionic conductivity and physical properties of the gel polymer electrolytes, and (iii) a metal salt, such as lithium trifluoromethanesulfonate, that influences the ionic conductivity of the gel polymer electrolytes, and methods of preparing the polyphosphazene polymers and the gel polymer electrolytes. Allcock et al. discuss a system that has been studied extensively for solid-polymer electrolyte (SPE) applications, which is one that is based on poly(organophosphazenes). This class of polymers has yielded excellent candidates for use in SPEs due to the inherent flexibility of the phosphorus-nitrogen backbone and the ease of side group modification via macromolecular substitution-type syntheses. The first poly(organophosphazene) to be used in a phosphazene SPE (solid polymer electrolyte) was poly[bis(2-(2′-methoxyethoxy ethoxy)phosphazene] (hereinafter, MEEP). This polymer was developed in 1983 by Shriver, Allcock and their coworkers (Blonsky, P. M., et al, Journal of the American Chemical Society, 106, 6854 (1983)) and is illustrated in U.S. Pat. No. 6,605,237.
  • Also, the following U.S. Pat. Nos. 7,052,805 (Polymer electrolyte having acidic, basic and elastomeric subunits, published/issued on 2006 May 30); 6,783,897 (Crosslinking agent and crosslinkable solid polymer electrolyte using the same, 2004 Aug. 31); 6,727,024 (Polyalkylene oxide polymer composition for solid polymer electrolytes, 2004 Apr. 27); 6,392,008 (Polyphosphazene polymers, 2002 May 21); 6,369,159 (Antistatic plastic materials containing epihalohydrin polymers, 2002 Apr. 9); 6,214,251 (Polymer electrolyte composition, 2001 Apr. 10); 5,998,559 (Single-ion conducting solid polymer electrolytes, and conductive compositions and batteries made therefrom; 1999 Dec. 7); 5,874,184 (Solid polymer electrolyte, battery and solid-state electric double layer capacitor using the same as well as processes for the manufacture thereof, 1999 Feb. 23); 5,698,664 (Synthesis of polyphosphazenes with controlled molecular weight and polydispersity, 1997 Dec. 16); 5,665,490 (Solid polymer electrolyte, battery and solid-state electric double layer capacitor using the same as well as processes for the manufacture thereof, 1997 Sep. 9); 5,633,098 (Batteries containing single-ion conducting solid polymer electrolytes, 1997 May 27); 5,597,661 (Solid polymer electrolyte, battery and solid-state electric double layer capacitor using the same as well as processes for the manufacture thereof, 1997 Jan. 28); 5,567,783 (Polyphosphazenes bearing crown ether and related podand side groups as solid solvents for ionic conduction, 1996 Oct. 22); 5,562,909 (Phosphazene polyelectrolytes as immunoadjuvants, 1996 Oct. 8); 5,548,060 (Sulfonation of polyphosphazenes, 1996 Aug. 20); 5,414,025 (Method of crosslinking of solid state battery electrolytes by ultraviolet radiation, 1995 May 9); 5,376,478 (Lithium secondary battery of vanadium pentoxide and polyphosphazenes, 1994 Dec. 27); 5,219,679 (Solid electrolytes, 1993 Jun. 15); 5,110,694 (Secondary Li battery incorporating 12-Crown-4 ether, 1992 May 5); 5,102,751 (Plasticizers useful for enhancing ionic conductivity of solid polymer electrolytes, 1992 Apr. 7); 5,061,581 (Novel solid polymer electrolytes, 1991 Oct. 29); 4,656,246 (Polyetheroxy-substituted polyphosphazene purification, 1987 Apr. 7); and 4,523,009, (Polyphosphazene compounds and method of preparation, 1985 Jun. 11), which are all incorporated herein by reference. Each discuss polyphosphazene polymers and/or other polymer electrolytes and/or lithium salts and combinations thereof
  • U.S. patent application Ser. No. 10/895,445 entitled “LITHIUM/ATR BATTERIES WITH LiPON AS SEPARATOR AND PROTECTIVE BARRIER AND METHOD” by the inventor of the present application (which is incorporated herein by reference) describes a method for making lithium batteries including depositing LiPON on a conductive substrate (e.g., a metal such as copper or aluminum) by depositing a chromium adhesion layer on an electrically insulating layer of silicon oxide by vacuum sputter deposition of 50 mu of chromium followed by 500 nm of copper. In some embodiments, a thin film of LiPON (Lithium Phosphorous OxyNitride) is then formed by low-pressure (<10 mtorr) sputter deposition of lithium orthophosphate (Li3PO4) in nitrogen. In some embodiments of the Li-air battery cells, LiPON was deposited over the copper anode current-collector contact to a thickness of 2.5 microns, and a layer of lithium metal was formed onto the copper anode current-collector contact by electroplating through the LiPON layer in a propylene carbonate/LiPF6 electrolyte solution. In some embodiments, the air cathode was a carbon-powder/polyfluoroacrylate-binder coating (Novec-1700) saturated with a propylene carbonate/LiPF6 organic electrolyte solution. In other embodiments, a cathode-current-collector contact layer having carbon granules is deposited, such that atmospheric oxygen could operate as the cathode reactant. This configuration requires providing air access to substantially the entire cathode surface, limiting the ability to densely stack layers for higher electrical capacity (i.e., amp-hours).
  • There is a need for rechargeable lithium-based batteries having improved protection against dendrite formation and with improved density, electrical capacity, rechargeability, and reliability, and smaller volume and lowered cost.
  • BRIEF SUMMARY OF THE INVENTION
  • In some embodiments, the present invention includes a battery having an electrolyte structure that combines a plurality of layers of different electrolytes (e.g., hard-soft-hard). In some embodiments, a thin (0.1 to 1.0 micron) LiPON electrolyte layer serves as a hard coating on the negative electrode preventing the formation of lithium dendrites (especially when paired with a corresponding LiPON electrolyte layer coating on the positive electrode) and/or providing an even (smooth), hard layer of lithium metal on, or as part of, the negative electrode when the battery is charged. In some embodiments, a thin (0.1 to 1.0 micron) LiPON electrolyte on only one electrode (e.g., the negative electrode) may not prevent the formation of lithium dendrites over the long term (e.g., many thousands of discharge-recharge cycles), since the lithium growing through a pinhole may only need to grow about 3 microns or less across the electrolyte to short the battery (i.e., providing a metal electrical conduction path directly from anode to cathode). When LiPON is also used as a coating at the positive electrode (e.g., an electrode that includes LiCoO2) the random locations of the pinholes will not line up (e.g., across the electrolyte from anode to cathode) so lithium would also need to grow sideways in the electrolyte, which doubly ensures that lithium plating at a defect site (which would typically form a dendrite) will not short the battery. In some embodiments, a soft electrolyte layer bridges the gap between the hard electrolyte layer on the negative electrode and the hard electrolyte layer on the positive electrode. At both electrodes, the LiPON layer also provides an improvement in environmental resistance to water vapor and oxygen, especially during manufacture before the battery is completed and otherwise sealed. In some embodiments, the soft electrolyte includes a solid polymer electrolyte (SPE) layer that islocated between and contacts with the LiPON layer on the positive electrode and the LiPON layer on the negative electrode. In some embodiments, the electrolyte structure includes a polymer electrolyte such as PEO-LiX (poly-ethylene oxide lithium-X, where LiX=a metal salt, such as LiPF6, LiBN, LiCF3SO4, CF3SO3Li (lithium trifluoromethanesulfonate, also called triflate), lithium bisperfluoroethanesulfonimide, lithium (Bis) Trifluoromethanesulfonimide, and/or the like, for example). In some embodiments, the electrolyte structure includes a polymer electrolyte such as polyPN-LiX (Polyphosphazene with lithium-X, where LiX=LiPF6, LUBE', LiCF3SO4, and/or the like, for example). In some embodiments, a small-molecule additive, such as propylene carbonate, that influences the ionic conductivity and physical properties of the polymer electrolytes is added to form a gel electrolyte that better fills defects and acts as an adhesive.
  • The present invention provides both a method and an apparatus for making thin-film batteries having composite (e.g., multi-layered) electrolytes with a soft electrolyte layer between hard electrolyte layers covering the negative and/or positive electrodes, and the resulting batteries. In some embodiments, metal-core cathode sheets each having a cathode material (e.g., LiCoO2) deposited on a metal foil, screen, or mesh (e.g., copper, nickel, or stainless steel) or a metal-covered insulator (e.g., a sputtered metal film on a polymer film, a SiO2-covered silicon wafer, or an alumina or sapphire substrate) and is covered by a hard electrolyte (some embodiments form such electrodes on both sides of the substrate), and foil-core anode sheets having a anode material (e.g., lithium metal) deposited on a metal foil (e.g., copper, nickel, or stainless steel) or a metal-covered insulator (e.g., a sputtered metal film on a polymer film, a SiO2-covered silicon wafer, or an alumina or sapphire substrate) and is also covered by a hard electrolyte (some embodiments form such electrodes on both sides of the substrate), and such sheets are laminated using a soft (e.g., polymer gel) electrolyte sandwiched between alternating cathode and anode sheets. In some embodiments, a hard glass-like electrolyte layer obtains a smooth hard positive-electrode lithium-metal layer upon charging, but when such a layer is made very thin, will tend to have randomly spaced pinholes/defects. When the hard layers are formed on both the positive and negative electrodes, one electrode's dendrite-short-causing defects on are not aligned with the other electrode's defects. The soft electrolyte layer conducts ions across the gap between hard electrolyte layers and/or fills pinholes, thin spots, and other defects in the hard electrolyte layers.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1A is a schematic cross-section view of a lithium cell 100 of some embodiments of the invention.
  • FIG. 1B is a schematic cross-section view of a lithium cell 101 of some embodiments of the invention.
  • FIG. 1C is a schematic cross-section view of a lithium cell 102 of some embodiments of the invention.
  • FIG. 2 is a schematic cross-section view of a lithium-battery manufacturing process 200 of some embodiments of the invention.
  • FIG. 3 is a schematic cross-section view of a parallel-connected lithium battery 300 of some embodiments of the invention.
  • FIG. 4 is a schematic cross-section view of a series-connected lithium battery 400 of some embodiments of the invention.
  • FIG. 5A is a schematic cross-section view of a parallel-connected screen-cathode current-collector contact lithium-battery 500 of some embodiments of the invention.
  • FIG. 5B is a schematic cross-section view of a series-connected screen-cathode-current-collector contact lithium-battery 501 of some embodiments of the invention.
  • FIG. 6A is a perspective view of an electrode 600 having a hard-electrolyte-covered current collector with a plating mask 119.
  • FIG. 6B is a perspective view of another electrode 601 having a hard-electrolyte-covered current collector with a plating mask 119.
  • FIG. 6C is a perspective view of a plating system 610.
  • FIGS. 7A, 7B, 7C, 7D, 7E, and 7F are schematic cross-sectional views of the fabrication of an atomic level matrix of copper and copper oxides as cathodes on a substrate of some embodiments of the invention.
  • FIGS. 8A, 8B, 8C, 8D, and 8E are schematic cross-sectional views of the fabrication of an atomic level matrix of copper and copper oxides as cathodes on a copper foil substrate of some embodiments of the invention.
  • FIG. 9 is a schematic cross-section view of a parallel-connected foil-cathode-current-collector contact lithium battery 900 of some embodiments of the invention.
  • FIG. 10A is a schematic cross-section view of an encapsulated surface-mount micro-battery 1000 of some embodiments of the invention.
  • FIG. 10B is a perspective view of an encapsulated surface-mount micro-battery 1000 of some embodiments of the invention.
  • FIG. 11 is a flow chart of a method 1100 for making a battery cell according to some embodiments of the invention.
  • FIG. 12 is a flow chart of a method 1200 for making a stacked battery according to some embodiments of the invention.
  • FIG. 13 is an exploded perspective view of an embodiment of a device as part of a system.
  • FIG. 14 is an exploded perspective view of another embodiment of a device as part of a portable system.
  • DETAILED DESCRIPTION OF THE INVENTION
  • Although the following detailed description contains many specifics for the purpose of illustration, a person of ordinary skill in the art will appreciate that many variations and alterations to the following details are within the scope of the invention. Accordingly, the following preferred embodiments of the invention are set forth without any loss of generality to, and without imposing limitations upon the claimed invention.
  • In the following detailed description of the preferred embodiments, reference is made to the accompanying drawings that form a part hereof, and in which are shown by way of illustration specific embodiments in which the invention may be practiced. It is understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.
  • The leading digit(s) of reference numbers appearing in the Figures generally correspond to the Figure number in which that component is first introduced, such that the same reference number is used throughout to refer to an identical component, which appears in multiple Figures. Signals (such as, for example, fluid pressures, fluid flows, or electrical signals that represent such pressures or flows), pipes, tubing or conduits that carry the fluids, wires or other conductors that carry the electrical signals, and connections may be referred to by the same reference number or label, and the actual meaning will be clear from its use in the context of the description.
  • Terminology
  • In this description, the term metal applies both to substantially pure single metallic elements and to alloys or combinations of two or more elements, at least one of which is a metallic element.
  • The term substrate or core generally refers to the physical structure that is the basic work piece that is transformed by various process operations into the desired microelectronic configuration. In some embodiments, substrates include conducting material (such as copper, stainless steel, aluminum and the like), insulating material (such as sapphire, ceramic, or plastic/polymer insulators and the like), semiconducting materials (such as silicon), non-semiconducting, or combinations of semiconducting and non-semiconducting materials. In some, other embodiments, substrates include layered structures, such as a core sheet or piece of material (such as iron-nickel alloy and the like) chosen for its coefficient of thermal expansion (CTE) that more closely matches the CTE of an adjacent structure such as a silicon processor chip. In some such embodiments, such a substrate core is laminated to a sheet of material chosen for electrical and/or thermal conductivity (such as a copper, aluminum alloy and the like), which in turn is covered with a layer of plastic chosen for electrical insulation, stability, and embossing characteristics. An electrolyte is a material that conducts electricity by allowing movement of ions (e.g., lithium ions having a positive charge) while being non-conductive or highly resistive to electron conduction. An electrical cell or battery is a device having an anode and a cathode that are separated by an electrolyte. A dielectric is a material that is non-conducting to electricity, such as, for example, plastic, ceramic, or glass. In some embodiments, a material such as LiPON can act as an electrolyte when a source and sink for lithium are adjacent the LiPON layer, and can also act as a dielectric when placed between two metal layers such as copper or aluminum, which do not form ions that can pass through the LiPON. In some embodiments, devices include an insulating plastic/polymer layer (a dielectric) having wiring traces that carry signals and electrical power horizontally, and vias that carry signals and electrical power vertically between layers of traces.
  • In some embodiments, an anode portion of a thin-film solid-state battery is made (as described in U.S. patent application Ser. No. 10/895,445 discussed above) using a method that includes depositing LiPON on a conductive substrate (e.g., a metal such as copper or aluminum) that is formed by depositing a chromium adhesion layer on an electrically insulating layer of silicon oxide (or on a polymer sheet) using vacuum-sputter deposition of 50 nm of chromium followed by 500 nm of copper. In some embodiments, a thin film of LiPON (Lithium Phosphorous OxyNitride) is then formed by low-pressure (<10 mtorr) sputter deposition of lithium orthophosphate (Li3PO4) in nitrogen, or by sputtering from a LiPON source. In some embodiments LiPON is deposited over the copper anode current-collector contact to a thickness of between 0.1 microns and 2.5 microns. In some embodiments, a layer of lithium metal is formed onto the copper anode current-collector contact by electroplating through the LiPON layer (which was earlier deposited on the copper anode current-collector contact) in a propylene carbonate/LiPF6 organic electrolyte solution. The LiPON acts as a protective layer during fabrication of the battery, and in the assembled battery, it operates as one layer of a multi-layer electrolyte. (In other embodiments, the layer of lithium metal of the anode is formed by an initial charging operation after the battery is assembled.) In some embodiments, a cathode portion of the thin-film solid-state battery is made sputtering LiCoO2 onto a first of metal foil from a LiCoO2 source, over which is deposited a LiPON layer, which in the assembled battery, operates as another layer of the multi-layer electrolyte. In some embodiments, a solid or gel polymer electrolyte is used as a structural connection or adhesive between the two LiPON electrolyte layers, as well as forming an ion-conductive path between the positive and negative electrodes of the battery.
  • It is desirable, in some embodiments, to form a very thin electrolyte. If a single very thin layer of LiPON is used, it tends to have defects (e.g., thin spots or pinholes) and lithium ions will preferentially travel through these paths of least resistance and plate to spike-shaped lithium-metal dendrites that short out the battery. If a single very thin solid or gel polymer electrolyte layer is used, any surface irregularities (e.g., bumps or ridges in the anode or cathode material) will tend to connect through the electrolyte and short the battery. By having two independently formed very thin LiPON (hard) electrolyte component layers, one formed on the battery's anode and another formed on the battery's cathode, any such thin spots or pinholes in one layer will not line up with a thin spot or pinhole in the other layer. The third electrolyte layer (e.g., a soft polymer electrolyte that conducts lithium ions between the two LiPON layers) made of a solid and/or gel polymer electrolyte material does not get shorted out by bumps or other irregularities in either electrode since those irregularities will tend to be coated with LiPON and/or the corresponding spot on the other side will be coated with LiPON. Accordingly, one or more (even all) of the plurality of layers can be made very thin without the danger of having an initial short (from a polymer electrolyte that is too thin allowing the anode and cathode to touch) or a later-developed short (from a pinhole in a LiPON electrolyte layer that allows formation of a lithium-metal dendrite after one or more charge/discharge cycles). Further, the dense, hard, glass-like LiPON layer causes the lithium ions that pass through it to form a lithium-metal layer that is dense and smooth. In other embodiments, one or more other hard and/or glass-like electrolyte layers are used instead of one or more of the LiPON layers.
  • U.S. Pat. No. 6,605,237 entitled “Polyphosphazenes as gel polymer electrolytes” discusses MEEP (poly[bis(2-(2′-methoxyethoxy ethoxy)phosphazene]) and other polymers, which are used in some embodiments of the present invention as structural connector and polymer electrolyte sublayer between two LiPON sublayers. The polyphosphazene (herein called polyPN) used as the connective layer is soft and sticky. Its adhesive properties are what allow the electrode to be and to remain joined. Its softness allows for defect correction and/or for defects to not cause poor battery performance and reliability. In other embodiments, other soft or gel-like ion-conducting polymers are used.
  • U.S. Pat. Nos. 4,523,009, 5,510,209, 5,548,060, 5,562,909, 6,214,251, 6,392,008 6,605,237, and 6,783,897 (which are all incorporated herein by reference) each discuss polyphosphazene polymers and/or other polymer electrolytes and/or various lithium salts and compounds that can be used as, or included in, one or more component layers of an electrolyte in some embodiments of the present invention.
  • The term vertical is defined to mean substantially perpendicular to the major surface of a substrate. Height or depth refers to a distance in a direction perpendicular to the major surface of a substrate.
  • FIG. 1A is a schematic cross-section view of a lithium cell 100 of some embodiments of the invention. In some embodiments, cell 100 includes a first sheet 111 (a cathode or positive-electrode subassembly) having a first metal foil 110 (which acts as a current collector) onto which is deposited a film of cathode material 112, such as, for example, LiCoO2, for example, by sputtering from a LiCoO2 target, and over which is deposited a relatively hard LiPON layer 114 (which acts as a hard-electrolyte current spreader). In some embodiments, cell 100 includes a second sheet 121 (an anode or negative-electrode subassembly) having a second metal foil 120 (which acts as a current collector) onto which is deposited a film of LiPON 124 (which acts as a hard-electrolyte current spreader and as an environmental barrier for lithium that is later plated through this layer), and a layer of lithium 122 (which forms the active portion of the anode or negative-electrode) is plated through the LiPON film 124 (either before or after the entire battery is assembled: if the cathode contains sufficient lithium to start, then the anode lithium layer is formed after assembly by the initial charging of the battery, while if the cathode has little or no lithium to start with, then the anode lithium layer is formed before assembly, e.g., by electroplating in a liquid electrolyte or solution from an external sacrificial lithium-metal electrode). In some embodiments, a sheet or layer of polymer electrolyte 130 is sandwiched between the first sheet 111 and the second sheet 121. In some embodiments, the layer of the polymer electrolyte is deposited onto LiPON layer 114, LiPON layer 124, or a portion of the polymer electrolyte is deposited onto both LiPON layer 114 and LiPON layer 124, and then the first sheet 111 and the second sheet 121 are pressed together or otherwise assembled (in some embodiments, two or more of the sheets are squeezed together between a pair of rollers).
  • In some embodiments, it is the hard-soft-hard combination of electrolyte layers that provide a low-cost, high-quality, high-reliability, highly rechargeable battery system. In some embodiments, the hard layers act as protective barrier layers during manufacture and as current spreader electrolytes that obtain a smooth hard layer of lithium on the anode upon charging. In some embodiments, the hard layers are or include a glass or glass-like electrolyte material (e.g., LiPON). When they are made very thin (in order to increase cell conductivity and reduce cell resistance), these hard layers tend to have randomly spaced pinholes, bumps, or other defects (thicker layers can eliminate many such defects, but will have decreased cell conductivity and increased cell resistance). When the hard layers are formed on both the positive electrode and the corresponding negative electrode, the pinholes and defects of the electrolyte covering one electrode will tend not to be aligned with the pinholes and defects of the electrolyte covering the other electrode. The soft electrolyte layer both conducts ions across the gap between hard layers and tends to fill the pinholes and defects of the hard electrolyte coverings. In some embodiments, the soft electrolyte layer can be a solid or gel polymer electrolyte (these also act as adhesives to hold the cells together and as seals to reduce contamination of the cell from environmental factors and to reduce leakage of the soft electrolyte layer), or can be a liquid electrolyte, optionally infused in a structural element (such as a sponge, screen, or ridges formed of a host solid-polymer (e.g., polyethylene, polypropylene, fluoroethylene or the like) on one or more of the hard electrolyte layers (e.g., by microembossing).
  • In some embodiments, the soft electrolyte layer includes a gel that includes a polyvinylidene difluoride (PVdF), propylene carbonate, and a lithium salt. PVdF is a polymer that does not conduct lithium ions, that is, lithium salts will not dissolve in PVdF. However, PVdF can be swollen with a liquid such as propylene carbonate in which a lithium salt has been dissolved. The gel that results can be used as a soft electrolyte.
  • In some embodiments, the thickness of each of the hard electrolyte layers is one micron or thinner, and the thickness of the soft electrolyte layer is about three microns or thinner. The structure shown in FIG. 1A is also represented in the following Table 1:
  • TABLE 1
    Reference Function or
    Number Property Example Materials
    . . . optionally, more battery layers stacked above . . .
    110 cathode metal foil (e.g., one that does not alloy with Li, such as copper,
    current nickel, stainless steel and the like), metal screen, or metal film on
    collector polymer film or SiO2 layer on Si wafer, (can have electrode formed
    on both sides for battery stack)
    112 cathode LiCoO2 (sputtered or powder-pressed in place), carbon powder,
    material CuO powder (any of the above can be infused with polyPN
    electrolyte material to increase conductivity and lithium transport),
    or
    atomic matrix of copper and copper oxides (which, in some
    embodiments, includes a tapered composition Cu and O structure
    with more copper towards the top and more oxygen towards the
    bottom, e.g., Cu metal gradually mixed to . . . Cu4O . . . Cu2O . . . Cu+O−−. . .
    CuO)
    114 hard LiPON or
    electrolyte other lithium-glass material
    130 soft polyPN with lithium (e.g., LiPF6), or
    electrolyte other polymer (e.g., PEO, polypropylene, etc.) electrolyte material
    124 hard LiPON or
    electrolyte other lithium-glass material
    122 anode Lithium, (can be plated through the hard (e.g., LiPON) layer before
    material or after assembly) (could be zinc with suitable changes to
    electrolytes and cathode material)
    110 anode metal foil (e.g., copper),
    current metal screen, or
    collector metal film on polymer film or SiO2 layer on Si wafer,
    (can have electrode formed on both sides for battery stack)
    . . . optionally, more battery layers stacked below
  • FIG. 1B is a schematic cross-section view of a lithium cell 101 of some embodiments of the invention. In some embodiments, cell 101, which is assembled in an uncharged state, includes a first sheet 111 (a cathode or positive-electrode subassembly) similar to that of FIG. 1A, except that the hard electrolyte 114 extends laterally over first metal foil 110 well beyond the lateral edges of the film of cathode material 112. In some embodiments, the lateral extent of cathode material 112 (such as, for example, LiCoO2, for example) is defined using photoresist and lithographic processes similar to those used for semiconductor integrated circuits (e.g., the cathode material is masked using photoresist, or a hard material such as SiO2 covered by photoresist and etched and the photoresist is removed so that the hard layer (e.g., SiO2) acts as the mask, to define the lateral extent of cathode material 112 (e.g., LiCoO2), and the mask is then removed. The hard electrolyte layer 114 (e.g., LiPON) is deposited on the cathode material 112 as well as onto substrate 110 around the sides of cathode material 112. This sideward extension of the hard LiPON layer 114 acts as a seal to the sides of the lithium in the cathode to protect it from environmental contaminants such as oxygen or water vapor. In some embodiments, cell 101 includes a second sheet 121 (an anode or negative-electrode subassembly similar to that of FIG. 1A, except that no lithium is yet present) having a second metal foil 120 (which acts as a current collector) onto which is deposited a film of LiPON 124 (which acts as a hard-electrolyte current spreader and as an environmental barrier for lithium that is later plated through this layer), and a mask layer 119 around all of the sides of what will be plated lithium layer 122 (see FIG. 1C) that is later plated through the portions of LiPON film 124 not covered by mask 119 (after the entire battery is assembled). (In other embodiments, mask layer 119 is an electrical insulator, such as SiO2, deposited directly on metal foil 120, and photolithographically patterned to expose the metal substrate in the center, and the hard electrolyte layer LiPON film 124 is deposited on top of the mask layer). In some embodiments, the mask material 119 is photoresist and/or an insulator such as SiO2 that have lateral extents that are photolithographically defined. As above, in some embodiments, a layer of soft polymer electrolyte 130 (either a solid polymer electrolyte (SPE) or a gel or liquid polymer electrolyte) (such as polyphosphazene having lithium salts such as LiPF6 to assist lithium conductivity) is sandwiched between the first sheet 111 and the second sheet 121.
  • FIG. 1C is a schematic cross-section view of a lithium cell 102 of some embodiments of the invention. In some embodiments, the lithium metal layer 122 is plated before assembly (a combination of the methods described for FIG. 6C and FIG. 2 below). In other embodiments, a battery 101 (such as shown in FIG. 1B) is assembled before any lithium metal is in the anode assembly 121, and is initially charged by plating lithium from the cathode 112 through electrolyte layers 114, 130, and 124 and onto the anode current collector 120 to form lithium metal layer 122.
  • FIG. 2 is a schematic cross-section view of a lithium-battery manufacturing process 200 of some embodiments of the invention. In some embodiments, one or more double-sided anode sheets 121 are alternated with one or more cathode sheets 111 (wherein an cathode material 112 is deposited on both major faces of foil 110 inside of LiPON layer 114), with a polymer layer 130 placed or formed between each sheet. In some embodiments of anode sheets 121, an anode material 122 is deposited on both major faces of foil 120 inside of (or plated through) LiPON layer 124 (note that, in some embodiments, by this stage, the mask 119 (see FIG. 1B) has been removed from the lateral sides of the anode after lithium metal has been pre-electro-plated through the LiPON not covered by the mask 119 onto current collector 121 using a liquid electrolyte and a lithium sacrificial electrode.
  • In some embodiments, the soft polymer electrolyte layer 130 is spun on as a liquid and then dried. In other embodiments, the soft polymer electrolyte layer 130 is dip coated. In other embodiments, the soft polymer electrolyte layer 130 is cast on. In some embodiments, the soft polymer electrolyte layer 130 is deposited from a liquid source 225, “squeegeed” (by squeegee 221) and/or doctor-bladed (by doctor-blade 222) in place onto both sides of each foil-core double-sided anode sheet 121 (having previously had LiPON layer 124 and anode layer 122 formed thereon), and onto both sides of each foil-core double-sided cathode sheet 111 (having previously had cathode-material layer 112 and LiPON layer 114 formed thereon). In some embodiments, the soft polymer electrolyte layer 130 is deposited by an apparatus that is essentially an offset printing press, wherein a liquid soft polymer electrolyte material and/or solvent mix (“ink”) is printed to the areas to which the soft polymer electrolyte layer 130 is desired.), and the stack is laminated together (“calendared” e.g., by being pressed between rollers 250 (for example, pressed between rubber-coated steel rollers, which, in some embodiments, are heated (e.g., by flowing hot oil inside the rollers)). Note that rollers 250 are schematically shown relative to two central battery layers, where
  • In some embodiments, two or more such resulting stacks are then laminated together in a similar fashion. In other embodiments, all of the alternating layers of a battery device are laminated in a single pressing step.
  • FIG. 3 is a schematic cross-section view of a parallel-connected lithium battery 300 of some embodiments of the invention, resulting from the laminating method of FIG. 2. In some embodiments, the outermost layer 111 and the outermost layer 121 are single sided, having a metal face facing outwards. In other embodiments, all layers 111 are identical one to another (and each is mirror-symmetrical about the center plane of foil 110), and all layers 121 are identical one to another (and each is mirror-symmetrical about the center plane of foil 120). In some embodiments, the edges of layers 111 are electrically connected to one another (for example, soldered, spot-welded or pressed together on the right-hand side) to form external cathode current-collector contact 321, and the edges of layers 121 are electrically connected to one another (for example, soldered, spot-welded or pressed together on the left-hand side) to form external anode current-collector contact 322, thus connecting all the cells in parallel to provide higher output current. In some embodiments, 1- to 30-mA-hour (or more) single cells are thus formed (depending on the area of each cell), and the battery has an amp-hour capacity of about the sum of the parallel cells.
  • TABLE 2
    Materials List for FIG. 3 - 1 repeat unit
    Material Thickness
    (microns) Layer Mass (mg/cm2)
    ½ cathode collector foil* 1.5 and up (e.g., 6.25) 4.94
    Nickel seed 0.1 to 0.3 (e.g., 0.3) 0.27
    LiCoO2 0.5 to 10 (e.g., 5.0) 2.80
    LiPON (cathode protect) 0.1 to 2.5 (e.g., 1.0) 0.21
    soft polymer electrolyte and/or “glue” 0.5 to 10 (e.g., 5.0) 0.75
    LiPON (anode protect) 0.1 to 2.5 (e.g., 1.0) 0.21
    Lithium (plated from LiCoO2) about 0.3 times the LiCoO2 0.08
    thickness (e.g., 1.5)
    Copper (or Al, Ni, stainless steel, and 0.1 to 1 (e.g., 0.25) 0.22
    the like) (used as the Li plate surface)
    Anode collector foil 3.0 and up (e.g., 12.5) 9.88
    Copper (or Al, Ni, stainless steel, and 0.1 to 1 (e.g., 0.25) 0.22
    the like) (used as the Li plate surface)
    Lithium (plated from LiCoO2) about 0.3 times the LiCoO2 0.08
    thickness (e.g., 1.5)
    LiPON (anode protect) 0.1 to 2.5 (e.g., 1.0) 0.21
    soft polymer electrolyte and/or “glue” 0.5 to 10 (e.g., 5.0) 0.75
    LiPON (cathode protect) 0.1 to 2.5 (e.g., 1.0) 0.21
    LiCoO2 0.5 to 10.0 (e.g., 5.0) 2.80
    Nickel seed 0.1 to 0.3 (e.g., 0.3) 0.27
    ½ cathode collector foil 1.5 and up (e.g., 6.25) 5.14
    Totals (e.g., 53.1) 28.84
    *In some embodiments, the foils are about 0.5-mils (0.0005 inches = 12.52-microns) thick
  • In some embodiments, the cathode material layers 112 are each about 10 microns thick or more. In some embodiments, 10 microns of LiCoO2 provides about 0.552 mA-hour-per-square-cm per repeat unit 320 at 80% theoretical utilization, and 2.1 mW-hour-per-square-cm at 3.8-volt-discharge voltage. In some embodiments, the charge-storage density is about 104 mA-hour/cubic-cm, and about 19.1 Ahour/kg. In some embodiments, the energy-storage density is about 395 W-hour/liter, and about 72.8 W-hour/kg. In some embodiments, a 10-cm by 6.5-cm by one repeat unit 320 corresponds to 33.6 mA-hour, and about 127 mW-hour. In some embodiments, a final package measuring about 10.8-cm long by 6.5-cm wide by 1.8-cm thick houses three sets of 320 repeat units each, the sets tied in series to deliver 3.75 A-hour discharge from about 12.3 volts to about 9 volts.
  • FIG. 4 is a schematic cross-section view of a series-connected lithium battery 400 of some embodiments of the invention. In the embodiment shown, each sheet 126 has anode material covered with LiPON on one major face (the upper face in FIG. 4) of the foil 125, and cathode material covered with LiPON on the opposite major face (the lower face FIG. 4). In some embodiments, the outermost layers are single sided as shown, having a metal face facing outwards. In other embodiments, all layers 125 are identical one to another, including the outermost layers. In some embodiments, the edge of the top-most layer 125 is electrically connected (for example, on the right-hand side) to form external cathode current-collector contact 421, and the edge of bottom-most layer 126 is electrically connected (for example, on the left-hand side) to form external anode current-collector contact 422, thus connecting all the cells in series. Each repeat unit 420 shows one basic stack layer. Up to one-A-hour or more single cells are thus formed, in some embodiments, depending on the area of each cell.
  • FIG. 5A is a schematic cross-section view of a parallel-connected screen-cathode-current-collector contact lithium-battery 500 of some embodiments of the invention. This embodiment is substantially similar to that of FIG. 3, except that, for the positive electrode, a metal screening or mesh 510 replaces foil 110. In some embodiments, this allows greater contact area to the cathode material 112, which is still completely covered by LiPON layer 114. In some embodiments, metal screening or mesh 510 is formed by selectively etching one or more photo-lithographically-defined areas of a metal foil. In some embodiments, LiCoO2 is sputtered onto the metal screening 510. In other embodiments, a LiCoO2 powder is packed onto the screening 510. In some embodiments, the LiCoO2 (whether deposited by sputtering LiCoO2 or by packing LiCoO2 powder onto the screening 510) is infused with polyPN or other polymer electrolyte material to enhance the ionic conductivity within the cathode. In some embodiments, the screening 510 is initially (before depositing LiCoO2) about 50% open space, and the open space is filled with LiCoO2 and/or polyPN or other ionic-enhancement material.
  • In some embodiments, the metal screening or mesh 510 of all of the layers 511 are electrically connected to one another (for example, on the right-hand side) to form external cathode current-collector contact 521, and the edges of layers 120 are electrically connected to one another (for example, on the left-hand side) to form external anode current-collector contact 522, thus connecting all the cells in parallel. Each repeat unit 520 shows one basic stack layer.
  • TABLE 3
    Materials List for FIG. 5A - 1 repeat unit
    Material Thickness Layer Mass
    (microns) (mg/cm2)
    ½ cathode collector screen/mesh/ 1.5 and up 2.59
    etched foil (e.g., 6.25)
    LiCoO2 (cathode) 8.0 to 40 (e.g., 12.5) 7.00
    LiPON (cathode protection and 0.1 to 2.5 (e.g., 1.0) 0.21
    electrolyte)
    soft polymer electrolyte and/or “glue” 0.5 to 10 (e.g., 5.0) 0.75
    LiPON (anode protection and 0.1 to 2.5 (e.g., 1.0) 0.21
    electrolyte)
    Lithium (plated from LiCoO2) about 0.3 times 0.265
    LiCoO2 thickness
    (e.g., 5.0)
    Copper (or Al, Ni, stainless steel, 0.1 to 1 (e.g., 0.25) 0.22
    and the like) (used as the Li
    plate surface)
    Anode collector foil 3 and up (e.g., 12.5 9.88
    Copper (or Al, Ni, stainless steel, and 0.1 to 1 (e.g., 0.25) 0.22
    thelike) (used as the Li plate surface)
    Lithium (plated from LiCoO2) about 0.3 times 0.265
    LiCoO2 thickness
    (e.g., 5.0)
    LiPON (anode protection and 0.1 to 2.5 (e.g., 1.0) 0.21
    electrolyte)
    soft polymer electrolyte and/or “glue” 0.5 to 10 (e.g., 5.0) 0.75
    LiPON (cathode protection and 0.1 to 2.5 (e.g., 1.0) 0.21
    electrolyte)
    LiCoO2 (cathode) 8.0 to 40 (e.g., 12.5) 7.00
    ½ cathode collector screen/mesh/ 1.5 and up 2.59
    etched foil (e.g., 6.25)
    Totals (e.g., 74.5) 32.37
  • In some embodiments, the cathode material layers include 31.25 microns LiCoO2 in each repeat structure (50% of screen volume) at 80% packing, and 95% electrical utilization corresponds to 1.63 mAhr/cm2/repeat unit, and 6.22 mWhr/cm2/repeat unit at 3.8 V average discharge voltage. In some embodiments, the LiCoO2 is infused with polyPN or other polymer electrolyte material to enhance the ionic conductivity within the cathode. In some embodiments, the charge storage density equals 218 mAhr/cm3; and 50.35 Ahr/kg. In some embodiments, the energy storage density equals 835 Whr/liter, and 192 Whr/kg. In some embodiments, each 10 cm×6.5 cm×1 repeat unit corresponds to 106 mAhr; 404 mWhr. In some embodiments, a final package 10.8 cm×6.5 cm×1.8 cm houses three sets of 80 repeat units each tied in series to deliver 8.5 Ahr in discharge from 12.3 V to 9 V.
  • FIG. 5B is a schematic cross-section view of a series-connected screen-cathode-contact lithium-battery 501 of some embodiments of the invention. This embodiment is substantially similar to that of FIG. 4, except that a metal screening or mesh is laminated to the bottom side of foil 535 (a foil corresponding to foil 110 of FIG. 4), or the bottom side of foil 535 (starting with a foil 110 of FIG. 1A) is selectively etched only part-way through to form a foil top side and a bottom side that has a mesh-like quality. In some embodiments, this allows greater contact area to the cathode material 112, which is still completely covered by LiPON layer 114. In some embodiments, foil-mesh layer 535 is formed by selectively etching a photolithographically-defined areas of a metal foil, but not all the way through. In some embodiments, the outermost layers are single sided as shown, having a metal face facing outwards. In other embodiments, all layers 535 are identical one to another, including the outermost layers (wherein the electrode layers facing outwards are non-functioning). In some embodiments, the edge of the top-most layer 535 is electrically connected (for example, on the right-hand side) to form external cathode current-collector contact 531, and the edge of bottom-most layer 535 is electrically connected (for example, on the left-hand side) to form external anode current-collector contact 532, thus connecting all the cells in series. Each repeat unit 530 shows one basic stack layer.
  • In some embodiments, the thin (0.1 to 1.0 micron) LiPON electrolyte serves as a hard coating at the negative electrode preventing the formation of lithium dendrites. Its use as a coating at the positive electrode (i.e., LiCoO2) doubly ensures that lithium plating at a defect site will not short the battery. At both electrodes, LiPON also provides an improvement in environmental resistance to water vapor and oxygen.
  • In some embodiments, the use of a relatively soft solid polymer electrolyte (SPE) simplifies the construction of cells over a full hard-electrolyte solid-state (e.g., LiPON only as the electrolyte) design. The soft polymer electrolyte functions as an “electrolyte glue” that allows the positive and negative electrodes to be constructed separately and adhered to each other later in the assembly process. In some embodiments, the soft polymer electrolyte is sprayed, squeegeed, or otherwise deposited in liquid form, and later solidified.
  • Without the LiPON coating, some embodiments using a soft polymer electrolyte would need sufficient soft polymer electrolyte thickness to have mechanical rigidity or mechanical strength, which reduces energy density and increases cell resistance. Without the soft polymer electrolyte (“electrolyte glue”), LiPON films would need to be perfect (defect free) over very large areas to achieve high-energy cells. The combination of the two electrolyte material systems eliminates shortcomings of either used alone.
  • Numerous metals can be used as the anode in battery cells of the present invention. One common anode metal is lithium. The lithium must be protected from oxygen and water vapor during manufacturing, assembly, and use of the battery. Zinc is another common anode metal used in some embodiments of the present invention. Zinc is the most electronegative metal that has good stability and corrosion resistance, with the appropriate inhibitor chemistry, in aqueous solutions. Several possible metal-air systems are listed in Table 4 along with a summary of their theoretical characteristics.
  • TABLE 4
    Characteristics of metal-air cells. From “Handbook of Batteries, 3rd Ed.,
    ” David Linden and Thomas B. Reddy, Eds., Table 38.2, McGraw-Hill
    Handbooks, New York, 2002.
    SUMMARY OF OTHER LITHIUM/AIR RESEARCH
    Electro- Theoretical
    chemical specific
    equivalent of Theoretical energy Practical
    Metal metal, cell voltage, Valence (of metal), operating
    anode Ah/g *V change kWh/kg voltage, V
    Li 3.86 3.4 1 13.0 2.4
    Ca 1.34 3.4 2 4.6 2.0
    Mg 2.20 3.1 2 6.8 1.2-1.4
    Al 2.98 2.7 3 8.1 1.1-1.4
    Zn 0.82 1.6 2 1.3 1.0-1.2
    Fe 0.96 1.3 2 1.2 1.0
    *Cell voltage with oxygen cathode
  • Lithium, the lightest alkali metal, has a unique place in battery systems. Its gravimetric electrochemical equivalence of 3.86 amp-hrs/g; is the highest of any metallic anode material. It can be seen from Table 3 that lithium has the highest operational voltage and greatest theoretical specific energy of the metals listed. Using a lithium anode leads to a very light, high energy density battery. The difficulty with lithium technology is providing practical systems that operate in real world conditions. It is possible to construct lithium cells utilizing an aqueous electrolyte, but these cells have limited applicability due to corrosion of the lithium metal anode by water. The lithium anode may also corrode from contact with oxygen. A solution to the rapid corrosion of lithium metal anodes in lithium-air cells includes the use of LiPON as a protective barrier and separator in the structure of an organic-electrolyte lithium cell.
  • In some embodiments, a cell utilizes a LiPON thin film acting as both a portion of the electrolyte structure and a protective barrier against moisture and oxygen corrosion of the lithium metal anode. The structure of thin, flexible, lithium cells lends itself well to high-speed web-deposition processes, as described in U.S. Pat. No. 6,805,998 (which is incorporated herein by reference).
  • In some embodiments, a battery of the present invention (e.g., reference numbers 100, 300, 400, 500, 600 or 900) is incorporated in an electrical device such as a hearing aid, compass, cellular phone, tracking system, scanner, digital camera, portable computer, radio, compact disk player, cassette player, smart card, or other battery-powered device.
  • In some embodiments, the back (outside) of the cathode is exposed (or can be exposed, for example, by removing a protective polymer film layer) to air, such that oxygen acts as a cathode material. In some such embodiments, the air cathode battery is a primary battery that cannot be recharged, while in other embodiments, the air cathode battery is a secondary battery that can be recharged.
  • Other Embodiments Of the Invention
  • One aspect of the invention includes an apparatus including a lithium anode covered by a LiPON electrolyte/protective layer, a lithium-intercalation-material cathode covered by a LiPON electrolyte/protective layer and a polymer electrolyte material sandwiched between the LiPON electrolyte/protective layer that covers the anode and the LiPON electrolyte/protective layer that covers the cathode.
  • In some embodiments, the cathode includes LiCoO2.
  • In some embodiments of the invention, the anode overlays a copper-anode current-collector contact.
  • Another aspect of the invention includes a method including providing an anode substrate having a conductive anode-current-collector contact layer thereon, depositing a LiPON electrolyte/barrier layer over the anode-current-collector contact layer, providing a polymer electrolyte, and providing a cathode substrate having a cathode-current-collector contact layer, depositing a lithium intercalation material on the cathode current-collector contact layer, depositing a LiPON electrolyte/barrier layer over the cathode-current-collector contact layer, and forming a sandwich of the anode substrate and the cathode substrate with the polymer electrolyte therebetween. In some embodiments, a structure is provided having a plurality of anode substrates and a plurality of cathode substrates with polymer electrolyte between each pair of anode and cathode substrates.
  • Another aspect of the invention includes an apparatus that includes a substrate having an anode current-collector contact, a LiPON electrolyte separator deposited on the anode current-collector contact, and a plated layer of lithium anode material between the LiPON and the anode current-collector contact.
  • In some embodiments, the anode current-collector contact includes copper and the substrate includes a polymer.
  • Another aspect of the invention includes an apparatus including a deposition station that deposits LiPON onto an anode current-collector contact, a plating station that plates lithium onto the anode current-collector contact to form an anode substrate, a cathode-deposition station that deposits a cathode material onto a substrate and deposits LiPON onto the cathode material to form a cathode substrate, and an assembly station that assembles the anode substrate to the cathode substrate using a polymer electrolyte material sandwiched between the cathode substrate and the anode substrate.
  • In some embodiments of the invention, the deposition station comprises sputter deposition of LiPON.
  • In some embodiments, the LiPON is deposited onto the anode current-collector contact with a thickness of between about 0.1 microns and about 1 micron. In some embodiments, the anode's LiPON layer is less than 0.1 microns thick. In some embodiments, this LiPON layer is about 0.1 microns. In some embodiments, this LiPON layer is about 0.2 microns. In some embodiments, this LiPON layer is about 0.3 microns. In some embodiments, this LiPON layer is about 0.4 microns. In some embodiments, this LiPON layer is about 0.5 microns. In some embodiments, this LiPON layer is about 0.6 microns. In some embodiments, this LiPON layer is about 0.7 microns. In some embodiments, this LiPON layer is about 0.8 microns. In some embodiments, this LiPON layer is about 0.9 microns. In some embodiments, this LiPON layer is about 1.0 microns. In some embodiments, this LiPON layer is about 1.1 microns. In some embodiments, this LiPON layer is about 1.2 microns. In some embodiments, this LiPON layer is about 1.3 microns. In some embodiments, this LiPON layer is about 1.4 microns. In some embodiments, this LiPON layer is about 1.5 microns. In some embodiments, this LiPON layer is about 1.6 microns. In some embodiments, this LiPON layer is about 1.7 microns. In some embodiments, this LiPON layer is about 1.8 microns. In some embodiments, this LiPON layer is about 1.9 microns. In some embodiments, this LiPON layer is about 2.0 microns. In some embodiments, this LiPON layer is about 2.1 microns. In some embodiments, this LiPON layer is about 2.2 microns. In some embodiments, this LiPON layer is about 2.3 microns. In some embodiments, this LiPON layer is about 2.4 microns. In some embodiments, this LiPON layer is about 2.5 microns. In some embodiments, this LiPON layer is about 2.6 microns. In some embodiments, this LiPON layer is about 2.7 microns. In some embodiments, this LiPON layer is about 2.8 microns. In some embodiments, this LiPON layer is about 2.9 microns. In some embodiments, this LiPON layer is about 3 microns. In some embodiments, this LiPON layer is about 3.5 microns. In some embodiments, this LiPON layer is about 4 microns. In some embodiments, this LiPON layer is about 4.5 microns. In some embodiments, this LiPON layer is about 5 microns. In some embodiments, this LiPON layer is about 5.5 microns. In some embodiments, this LiPON layer is about 6 microns. In some embodiments, this LiPON layer is about 7 microns. In some embodiments, this LiPON layer is about 8 microns. In some embodiments, this LiPON layer is about 7 microns. In some embodiments, this LiPON layer is about 9 microns. In some embodiments, this LiPON layer is about 10 microns. In some embodiments, this LiPON layer is more than 10 microns.
  • In some embodiments, the LiPON is deposited onto the cathode current-collector contact with a thickness of between about 0.1 microns and about 1 micron. In some embodiments, the cathode's LiPON layer is less than 0.1 microns thick. In some embodiments, this LiPON layer is about 0.1 microns. In some embodiments, this LiPON layer is about 0.2 microns. In some embodiments, this LiPON layer is about 0.3 microns. In some embodiments, this LiPON layer is about 0.4 microns. In some embodiments, this LiPON layer is about 0.5 microns. In some embodiments, this LiPON layer is about 0.6 microns. In some embodiments, this LiPON layer is about 0.7 microns. In some embodiments, this LiPON layer is about 0.8 microns. In some embodiments, this LiPON layer is about 0.9 microns. In some embodiments, this LiPON layer is about 1.0 microns. In some embodiments, this LiPON layer is about 1.1 microns. In some embodiments, this LiPON layer is about 1.2 microns. In some embodiments, this LiPON layer is about 1.3 microns. In some embodiments, this LiPON layer is about 1.4 microns. In some embodiments, this LiPON layer is about 1.5 microns. In some embodiments, this LiPON layer is about 1.6 microns. In some embodiments, this LiPON layer is about 1.7 microns. In some embodiments, this LiPON layer is about 1.8 microns. In some embodiments, this LiPON layer is about 1.9 microns. In some embodiments, this LiPON layer is about 2.0 microns. In some embodiments, this LiPON layer is about 2.1 microns. In some embodiments, this LiPON layer is about 2.2 microns. In some embodiments, this LiPON layer is about 2.3 microns. In some embodiments, this LiPON layer is about 2.4 microns. In some embodiments, this LiPON layer is about 2.5 microns. In some embodiments, this LiPON layer is about 2.6 microns. In some embodiments, this LiPON layer is about 2.7 microns. In some embodiments, this LiPON layer is about 2.8 microns. In some embodiments, this LiPON layer is about 2.9 microns. In some embodiments, this LiPON layer is about 3 microns. In some embodiments, this LiPON layer is about 3.5 microns. In some embodiments, this LiPON layer is about 4 microns. In some embodiments, this LiPON layer is about 4.5 microns. In some embodiments, this LiPON layer is about 5 microns. In seine embodiments, this LiPON layer is about 5.5 microns. In some embodiments, this LiPON layer is about 6 microns. In some embodiments, this LiPON layer is about 7 microns. In some embodiments, this LiPON layer is about 8 microns. In some embodiments, this LiPON layer is about 7 microns. In some embodiments, this LiPON layer is about 9 microns. In some embodiments, this LiPON layer is about 10 microns. In some embodiments, this LiPON layer is more than 10 microns.
  • In some embodiments, the plating station performs electroplating at densities of about 0.9 mA/cm2 and voltage of about 40 mV at 0.6 mA between a lithium counterelectrode and the plated lithium of the anode.
  • In some embodiments of the invention, during a precharge of the anode, the lithium is conducted through a liquid propylene carbonate/LiPF6 (or other suitable lithium salt) electrolyte solution and the LiPON barrier/electrolyte layer for the lithium to be wet-bath plated onto the anode connector or conduction layer (e.g., copper foil or a copper layer on an SiO2 or polymer substrate.
  • FIG. 6A is a perspective view of an electrode 600 having a hard-electrolyte-covered current collector with a plating mask 119. In some embodiments, a starting substrate such as 721 shown in FIG. 7B has its metal layer 720 (e.g., copper) photolithographically defined to form patterned metal layer 620 having contact pad 629, used for plating (such as shown in FIG. 6C) and for connecting to the external electrical conductor in the finished battery. In some embodiments, on top of patterned metal layer 620 is a patterned (e.g., photolithographically) hard electrolyte layer 624 (e.g., such as a hard electrolyte layer 124 described in FIG. 1C, but with some of its lateral edges removed). In some embodiments, an optional mask layer 119 is formed and/or patterned over the metal via between the main body of patterned metal layer 620 (which will be plated with lithium through patterned hard electrolyte layer 624 (e.g., LiPON)). In some embodiments, mask 119 prevents lithium from plating on the via, thus leaving sealed the interface between patterned hard electrolyte layer 624 and the metal via (otherwise, water vapor or air could cause the lithium plated in this area to corrode, leaving a gap that could cause more corrosion of the main body of the lithium on patterned metal layer 620. Because the patterned hard electrolyte layer 624 extends laterally beyond the lateral extent of patterned metal layer 620 on the rest of its periphery, no mask is required in those areas, since the lithium will not plate there and the sealed interface between patterned hard electrolyte layer 624 and the underlying non-conductive substrate remains intact and sealed.
  • FIG. 6B is a perspective view of another electrode 601 having a hard-electrolyte-covered current collector with a plating mask 119. In some embodiments such as shown here, the entire substrate surface is metal, so a mask 119 is deposited and/or patterned over the outer periphery of hard electrolyte layer 124 (e.g., LiPON), mask 119 with an interior opening 129 through which lithium will plate through the LiPON layer 124 to most of the central portion of the face of substrate 120 (e.g., a metal foil). In some embodiments, mask 119 is a photoresist layer that is patterned and left in place during plating. In other embodiments, mask 119 is another material (such as deposited SiO2) that is patterned using photoresist, which is then removed. In still other embodiments, mask 119 is a material (such as SiO2) that is deposited directly on the metal substrate 120, and is patterned using photoresist that is then removed before deposition of the hard electrolyte layer 124 (e.g., LiPON), thus preventing lithium from plating around the periphery (i.e., the mask 119 is under the LiPON, in some embodiments).
  • FIG. 6C is a perspective view of a plating system 610. In some embodiments, one or more electrodes 600 and/or electrodes 601 are partially or completely submerged in a liquid electrolyte 606 (e.g., propylene carbonate and/or ethylene carbonate with dissolved LiPF6 or other suitable electrolyte). In some embodiments, a sacrificial block of lithium 605 is kept submerged in the electrolyte 606, and a suitable plating voltage is applied between the lithium block 605 and electrode(s) 600 and/or 601. In some embodiments, the contact pad 629 is kept out of the liquid to prevent lithium from plating there.
  • FIGS. 7A, 7B, 7C, 7D, 7E, and 7F are schematic cross-sectional views of the fabrication (shown as a series 700 of operations) of an atomic level matrix of copper and copper oxides as cathodes on a substrate of some embodiments of the invention. FIG. 7A shows a cross-section view of the starting substrate 710 (e.g., silicon, alumina, stainless steel, aluminum, or polymer, or a composite of different materials). In some embodiments, an aluminum-foil substrate (or other metal that could spontaneously alloy with lithium and thereby degrade performance of the battery) or an insulator or non-conductor (such as silicon or polymer, which does not conduct the electricity from the battery) is coated with copper or nickel (or other metal that conducts electricity and does not readily alloy with lithium and thereby helps maintain performance of the battery).
  • In some embodiments, a cathode starting material contains no lithium (e.g., a copper foil, screening, or insulator coated with a copper conduction layer, then coated with a high-surface area carbon or CuxOx (which has a high volumetric energy density) or other material useful as a lithium-battery electrode, optionally infused with polyPN). In some embodiments, (see FIG. 7B) a metal layer 720 (e.g., copper, nickel, or other suitable metal that does not readily alloy with lithium during charging or discharging of the battery) is deposited (e.g., by sputtering copper with no oxygen) on one or more major faces (e.g., the top and/or bottom surfaces shown in the figures) of a substrate 710 (e.g., a silicon wafer optionally having an SiO2 insulation layer on one or both sides, an alumina or glass wafer, or a polymer film), to form a metal-coated substrate 721. In some embodiments, metal-coated substrate 721 can be used as the current collector base (rather than metal foil 111 or 121) for either the anode or cathode of any of the above-described embodiments.
  • In some embodiments, the starting substrate includes a plurality of metal layers (e.g., aluminum or copper moisture-barrier layers) alternating with a smoothing layer (e.g., spun-on photoresist or polyurethane) between each pair of metal layers to form a barrier stack (e.g., see U.S. patent application Ser. No. 11/031,217 filed Jan. 6, 2005, Attorney Docket: 1327.027US1 entitled “LAYERED BARRIER STRUCTURE HAVING ONE OR MORE DEFINABLE LAYERS AND METHOD”, which is incorporated herein by reference), wherein the top-most metal layer of this stack is a metal that (unlike aluminum) does not readily alloy with lithium during battery charging or discharging (e.g., a metal such as copper). Such a moisture-barrier stack is particularly useful for sealing a substrate that transmits some moisture and/or oxygen over time (e.g., a polymer film substrate such as polyethylene or Kapton™), where the barrier stack.
  • For some embodiments using a lithium-free starting cathode, copper is then is sputtered in a partial O2 atmosphere onto metal-coated substrate 721 (in some embodiments, the concentration of oxygen is increased over time such that the first material deposited is mostly copper, and gradually the material includes more and more oxygen in the copper-copper-oxide matrix) in argon (e.g., forming an atomic-scale mixture of copper, Cu4O in layer 722 (see FIG. 7C), Cu2O in layer 724 (see FIG. 7D), Cu+O and/or CuO in layer 728 (see FIG. 7E), or a succession of the copper substrate 720, then mostly Cu4O in layer 722, then mostly Cu2O in layer 724, then Cu+O−− and then CuO in layer 728 and/or an atomic-scale matrix of copper and copper oxides). In some embodiments, a layer of hard electrolyte 714 (see FIG. 7F), such as LiPON, is deposited across the finished cathode material.
  • FIGS. 8A, 8B, 8C, 8D, and 8E are schematic cross-sectional views of the fabrication (shown as a series 800 of operations) of an atomic level matrix of copper and copper oxides as cathodes on a copper-foil substrate of some embodiments of the invention. In some embodiments, (see FIG. 8A) a copper foil 711 or film is the starting material. In some embodiments, the starting foil is sputtered with argon to clean the surface(s) to be used for cathodes (e.g., the top and/or bottom surfaces shown), then copper is sputtered in a partial O2 atmosphere (in some embodiments, the concentration of oxygen is increased over time such that the first material deposited is mostly copper, and gradually the material includes more and more oxygen in the copper-copper-oxide matrix) in argon (e.g., forming an atomic-scale mixture of copper, Cu4O 722 (see FIG. 8B), Cu2O 724 (see FIG. 5C), Cu+O−− and/or CuO 728 (see FIG. 8D), or a succession of the copper substrate 720, then mostly Cu4O 722, then mostly Cu2O 724, then Cu+O−− and then CuO 728 and/or an atomic-scale matrix of copper and copper oxides). In some embodiments, a layer of hard electrolyte 714 (see FIG. 8E) such as LiPON is deposited across the finished cathode material.
  • In some such embodiments, the copper metal spreads through the copper oxides (which intercalate lithium, in some embodiments), providing better electrical conductivity as the lithium migrates in and out of the cathode. In some embodiments, the anode is precharged by electroplating lithium through the LiPON electrolyte that has been deposited thereon.
  • In other embodiments, one or more copper oxides and/or copper powder are powder-pressed onto a copper substrate or screen (i.e., the cathode conduction layer). In still other embodiments, an ink, having one or more copper oxides and/or copper powder, is printed, sprayed, doctor-bladed, or otherwise deposited on the cathode conduction layer. In some embodiments of the invention, the cathode material is charged with lithium that is conducted through a liquid propylene carbonate/LiPF6 electrolyte solution and the LiPON barrier/electrolyte layer for the lithium to be plated onto/into the cathode material and/or connector or conduction layer.
  • FIG. 9 is a schematic cross-section view of a parallel-connected foil-substrate-cathode-current-collector contact thin-film battery 900 of some embodiments of the invention. Battery 900 includes two cells connected in parallel, where two-sided anode current collector 120 has anode material 122 (e.g., lithium metal) that has been electroplated through hard electrolyte layers 124 (e.g., LiPON) on both sides of central current collector layer 120 (e.g., a metal foil or metal-coated polymer film), as defined by masks 119. In some embodiments, two cathode current collectors 110 each have cathode material 112 (e.g., LiCoO2) deposited and photolithographically patterned and covered with hard electrolyte layers 124 (e.g., LiPON), Pinhole 992 in hard electrolyte layer 124 and/or pinhole 991 in hard electrolyte layer 124 would cause failures of a typical single-layer electrolyte battery, but in the present invention, the pinholes do not align (e.g., vertically in the figure) with one another, and, in some embodiments, are filled with the soft polymer electrolyte 130, which acts to fill such holes and automatically “heal” the battery. Other details of this battery are as described above for FIG. 3.
  • FIG. 10A is a schematic cross-section view of an encapsulated surface-mount single-cell micro-battery device 1000 of some embodiments of the invention (other embodiments use stacks of cells as described above). In some embodiments, a silicon wafer substrate has a plurality of such cells fabricated on it, and is diced apart to form silicon substrate 1011 having a metal current collector 1010 on its surface, which then has cathode material 112 and hard electrolyte layer 114 deposited thereon to form the cathode component. A foil anode component having foil substrate 120, anode metal 122, and hard electrolyte layer 124 is then laminated to the cathode component using a soft polymer electrolyte glue 130. This battery is then connected to a lead frame having cathode connector 1051 and anode connector 1052 and encapsulated in encapsulant material 1050, and the leads formed as gull-wing leads as shown or bent into J-shaped leads that curl under the package. Surface-mount-device 1000 can then be soldered to a circuit board to provide small amounts of battery power to other components on the circuit board (such as real-time clocks or timers, or static random-access memories, RFID circuits, and the like). In other embodiments, a plurality of foil battery cells is used instead and encapsulated to form a surface-mount chip-like battery having higher current and/or higher voltage capabilities.
  • FIG. 10B is a perspective view of the outside of encapsulated surface-mount micro-battery device 1000 (described above in FIG. 10A), of some embodiments of the invention. In some embodiments, a stack of foil battery cells (e.g., such as those described in FIG. 3, FIG. 4, FIG. 5A, and/or FIG. 5B, and, in some embodiments, with or without a silicon wafer substrate) is encapsulated in this form factor to create a surface-mount chip-like battery having higher current and/or higher voltage capabilities.
  • FIG. 11 is a flow chart of a method 1100 for making a battery cell according to some embodiments of the invention. In some embodiments, method 1100 includes providing 1110 a first sheet (e.g., 121) that includes an anode material and a hard electrolyte layer covering the anode material, providing 1112 a second sheet (e.g., 111) having a cathode material and a hard electrolyte layer covering the cathode material, and sandwiching 1114 a soft (e.g., polymer) electrolyte material between the hard electrolyte layer of the first sheet and the hard electrolyte layer of the second sheet. Some embodiments of the method 1100 further include the functions shown in FIG. 12.
  • FIG. 12 is a flow chart of a method 1200 for making a stacked battery according to some embodiments of the invention. In some embodiments, method 1200 includes performing 1210 the method 1100 of FIG. 11, providing 1212 a third sheet that includes an anode material and a hard electrolyte layer covering the anode material, providing a fourth sheet that includes a cathode material and a hard electrolyte layer covering the cathode material, sandwiching 1216 a polymer electrolyte material between the hard electrolyte layer covering the anode material of the third sheet and the hard electrolyte layer covering the cathode material of the fourth sheet, and between the hard electrolyte layer covering the anode material of the first sheet and the hard electrolyte layer covering the cathode material of the fourth sheet.
  • FIG. 13 is a perspective exploded view of information-processing system 1300 (such as a laptop computer) using battery device 1330 (which, in various embodiments, is any one or more of the battery devices described herein). For example, in various exemplary embodiments, information-processing system 1300 embodies a computer, workstation, server, supercomputer, cell phone, automobile, washing machine, multimedia entertainment system, or other device. In some embodiments, packaged circuit 1320 includes a computer processor that is connected to memory 1321, power supply (energy-storage device 1330), input system 1312 (such as a keyboard, mouse, and/or voice-recognition apparatus), input-output system 1313 (such as a CD or DVD read and/or write apparatus), input-output system 1314 (such as a diskette or other magnetic media read/write apparatus), output system 1311 (such as a display, printer, and/or audio output apparatus), wireless communication antenna 1340, and packaged within enclosure having a top shell 1310, middle shell 1315, and bottom shell 1316. In some embodiments, energy-storage device 1330 is deposited (e.g., as vapors forming thin-film layers in a vacuum deposition station) or laminated (as partially assembled electrode films) as thin-film layers directly on and substantially covering one or more surfaces of the enclosure (i.e., top shell 1310, middle shell 1315, and/or bottom shell 1316).
  • FIG. 14 shows an information-processing system 1400 having a similar configuration to that of FIG. 13. In various exemplary embodiments, information-processing system 1400 embodies a pocket computer, personal digital assistant (PDA) or organizer, pager, Blackberry™-type unit, cell phone, GPS system, digital camera, MP3 player-type entertainment system, and/or other device. In some embodiments, packaged circuit 1420 includes a computer processor that is connected to memory 1421, power-supply battery device 1430, input system 1412 (such as a keyboard, joystick, and/or voice-recognition apparatus), input/output system 1414 (such as a portable memory card connection or external interface), output system 1411 (such as a display, printer, and/or audio output apparatus), wireless communication antenna 1440, and packaged within enclosure having a top shell 1410 and bottom shell 1416. In some embodiments, battery device 1430 (which, in various embodiments, is any one or more of the battery devices described herein) is deposited as film layers directly on and substantially covering one or more surfaces of the enclosure (i.e., top shell 1410 and/or bottom shell 1416).
  • In some embodiments, at least one of the hard electrolyte layers is a glass like layer that conducts lithium ions. In some such embodiments, at least one of the hard electrolyte layers includes LiPON. In some embodiments, the first hard electrolyte layer and the second hard electrolyte layer are both LiPON. In some such embodiments, each of the hard electrolyte layers is formed by sputtering from a LiPON source onto substrates having one or more electrode materials. In some such embodiments, each of the hard electrolyte layers is formed by sputtering from a lithium phosphate source in a nitrogen atmosphere onto substrates having one or more electrode materials. In some embodiments, each of the hard electrolyte layers is formed by sputtering from a lithium phosphate source in a nitrogen atmosphere, using an ion-assist voltage, onto substrates having one or more electrode materials.
  • In some embodiments, the soft electrolyte layer includes one or more polymers having a gel-like consistency at room temperatures.
  • In some embodiments, the soft layer includes a polyphosphazene polymer. In some such embodiments, the soft layer includes co-substituted linear polyphosphazene polymers. In some such embodiments, the soft layer includes polyphosphazene polymers having a gel-like consistency at room temperatures. In some such embodiments, the soft layer includes MEEP (poly[bis(2-(2′-methoxyethoxy ethoxy)phosphazene]).
  • In some embodiments, the soft-electrolyte layer is formed by depositing soft-electrolyte material onto the hard-electrolyte layer on the positive electrode, depositing soft-electrolyte material onto the hard-electrolyte layer on the negative electrode, and pressing the soft-electrolyte material on the positive electrode and the soft-electrolyte material on the negative electrode against each other.
  • In some embodiments, the soft layer includes a polymer matrix infused with a liquid and/or gel electrolyte material (e.g., polyPN). In some such embodiments, the polymer matrix is formed by waffle embossing (micro-embossing to leave raised structures, e.g., about 0.1 microns high to about 5 microns high: in some embodiments, about 0.1 microns, about 0.2 microns, about 0.3 microns, about 0.4 microns, about 0.5 microns, about 0.6 microns, about 0.7 microns, about 0.8 microns, about 0.9 microns, about 1.0 microns, about 1.2 microns, about 1.4 microns, about 1.6 microns, about 1.8 microns, about 2.0 microns, about 2.2 microns, about 2.4 microns, about 2.6 microns, about 2.8 microns, about 3.0 microns, about 3.5 microns, about 4 microns, about 4.5 microns, about 5 microns, about 6 microns, about 7 microns, about 8 microns, about 9 microns, or about 10 microns high) a heated polymer material onto at least one of the positive electrode and the negative electrode. In some such embodiments, the waffle embossing forms a pattern of dots. In some such embodiments, the waffle embossing forms a pattern of lines. In some such embodiments, the waffle embossing forms a two-directional/two-dimensional pattern of lines (e.g., in some embodiments, intersecting lines forming squares, triangles, hexagons, and/or the like, while in other embodiments, non-intersecting geometric patterns such as circles, squares, triangles, and/or the like). In other embodiments, a one-directional pattern of lines is microembossed in one direction on the positive electrode and in another direction on the negative electrode.
  • In some embodiments, the soft electrolyte layer includes a thin (e.g., 0.5 to 5.0 microns thick) polymer sponge or screen (e.g., a polypropylene sponge) infused with a liquid and/or gel electrolyte material (e.g., polyPN) and placed between the two hard electrolyte layers.
  • In some such embodiments, the soft-electrolyte layer is formed by depositing a thin soft-electrolyte layer onto the hard electrolyte layer on the positive electrode, depositing a thin soft-electrolyte layer onto the hard electrolyte layer on the negative electrode, and pressing the soft electrolyte layer on the positive electrode and the soft electrolyte layer on the negative electrode against each other. In some such embodiments, at least one of the thin soft-electrolyte layers is formed by doctor blading. In some such embodiments, at least one of the thin met-electrolyte layers is formed by spraying. In some such embodiments, at least one of the thin soft-electrolyte layers is formed by silk-screening. In some such embodiments, at least one of the thin soft-electrolyte layers is formed by printing.
  • In some embodiments, the battery includes a positive electrode that includes a LiCoO2 layer deposited on a copper current-collector layer, about 1 micron of LiPON deposited on the LiCoO2 layer, a layer of between about 1 micron and three microns of polyphosphazene/lithium-salt electrolyte material, and about 1 micron of LiPON on the negative electrode. In some embodiments, the negative electrode includes a copper current collector onto which LiPON is deposited and that is precharged by wet plating lithium onto the copper current collector through the LiPON layer. In some embodiments, the layer of polyphosphazene/lithium-salt electrolyte material is formed by depositing about 1 micron of polyphosphazene/lithium-salt electrolyte material on the LiPON deposited on the positive electrode, depositing about 1 micron of polyphosphazene/lithium-salt electrolyte material on the LiPON on the negative electrode and contacting the polyphosphazene/lithium-salt electrolyte material on the positive electrode to the polyphosphazene/lithium-salt electrolyte material on the negative electrode. In some such embodiments, the contacting includes pressing between rollers.
  • Some embodiments of the invention include an apparatus that includes a battery cell having a positive electrode, a negative electrode, and an electrolyte structure therebetween, wherein the electrolyte structure includes a soft electrolyte layer and at least one hard electrolyte layer.
  • In some embodiments, the electrolyte structure includes a hard electrolyte layer on the negative electrode, and the soft electrolyte layer is sandwiched between the positive electrode and the hard electrolyte layer on the negative electrode. In some such embodiments, the invention omits the hard electrolyte covering on the positive electrode.
  • In some embodiments, the soft electrolyte layer includes a polyphosphazene. In some embodiments, the soft electrolyte layer includes MEEP some embodiments, the soft electrolyte layer also includes a metal salt, such as LiPF6, LiBF4, LiCF3SO4, CF3SO3Li (lithium trifluoromethanesulfonate, also called triflate), lithium bisperfluoroethanesulfonimide, lithium (Bis) Trifluoromethanesulfonimide, or the like or a mixture or two or more such salts, for example.
  • In some embodiments, the electrolyte structure includes a hard electrolyte layer on the positive electrode and a hard electrolyte layer on the negative electrode, and the soft electrolyte layer is sandwiched between the hard electrolyte layer on the positive electrode and the hard electrolyte layer on the negative electrode. In some embodiments, the thicknesses of the hard electrolyte layer on the positive electrode and of the hard electrolyte layer on the negative electrode are each about one micron or less. In some embodiments, the thicknesses of the hard electrolyte layer on the positive electrode and of the hard electrolyte layer on the negative electrode are each about 0.5 microns or less. In some embodiments, the thickness of the soft electrolyte layer is about three microns or less. In some embodiments, the thickness of the soft electrolyte layer is about two microns or less. In some embodiments, the Thickness of the soft electrolyte layer is about one micron or less.
  • In some embodiments, the hard electrolyte layer on the positive electrode includes is substantially the same material as the hard electrolyte layer on the negative electrode. In some embodiments, the hard electrolyte layer on the positive electrode includes is substantially the same thickness as the hard electrolyte layer on the negative electrode.
  • In some embodiments, the hard electrolyte layer on the positive electrode includes LiPON and the hard electrolyte layer on the negative electrode includes LiPON.
  • In some embodiments, the soft electrolyte layer includes a gel.
  • In some embodiments, the soft electrolyte layer includes a gel that includes a polyvinylidene difluoride (PVdF), propylene carbonate, and a lithium salt. PVdF is a polymer that does not conduct lithium ions, that is, lithium salts will not dissolve in PVdF. However, PVdF can be swollen with a liquid such as propylene carbonate in which a lithium salt has been dissolved. The gel that results can be used as a soft electrolyte.
  • Some embodiments further include an encapsulating material surrounding the battery cell, and one or more electrical leads connecting from the battery cell to an exterior of the encapsulating material.
  • Some embodiments further include an electronic device and a housing holding the electrical device, wherein the battery cell is within the housing and supplies power to the electronic device.
  • Some embodiments of the invention include a method that includes providing a positive electrode component, providing a negative electrode component, coating at least the negative electrode component with a hard electrolyte layer, and forming a battery cell using the positive electrode component, the negative electrode component that is coated with the hard electrolyte layer, and a soft electrolyte layer in between.
  • Some embodiments of the method further include coating the positive electrode component with a hard electrolyte layer, wherein an electrolyte structure of the battery cell includes the hard electrolyte layer on the negative electrode, the hard electrolyte layer on the positive electrode, and the soft electrolyte layer which is sandwiched between the hard electrolyte layer on the positive electrode and the hard electrolyte layer on the negative electrode.
  • In some embodiments of the method, the electrolyte structure includes a hard electrolyte layer on the positive electrode and a hard electrolyte layer on the negative electrode, and the soft electrolyte layer is sandwiched between the hard electrolyte layer on the positive electrode and the hard electrolyte layer on the negative electrode.
  • In some embodiments of the method, the hard electrolyte layer on the positive electrode includes LiPON and the hard electrolyte layer on the negative electrode includes LiPON.
  • In some embodiments of the method, the soft electrolyte layer includes a polyphosphazene and a lithium salt. In some embodiments, the soft electrolyte layer includes MEEP and a lithium salt. In some embodiments, the lithium salt includes LiPF6, LiBF4, LiCF3SO4, CF3SO3Li (lithium trifluoromethanesulfonate, also called triflate), lithium bisperfluoroethanesulfonimide, lithium (Bis) Trifluoromethanesulfonimide, or the like or a mixture or two or more such salts, for example.
  • Some embodiments of the invention include an apparatus that includes a positive electrode component coated with a hard electrolyte layer, a negative electrode component coated with a hard electrolyte layer, and electrolyte means for connecting the hard electrolyte layer on the negative electrode component to the hard electrolyte layer on the positive electrode component to form a battery cell.
  • In some embodiments, the means for connecting further includes means for fixing defects in one or more of the hard electrolyte layers.
  • In some embodiments, the hard electrolyte layer on the positive electrode includes LiPON and the hard electrolyte layer on the negative electrode includes LiPON.
  • In some embodiments, the means for connecting includes MEEP. In some embodiments, the means for connecting includes a polyphosphazene and a lithium salt. In some embodiments, the means for connecting includes MEEP and a lithium salt. In some embodiments, the lithium salt includes LiPF6, LiBF4, LiCF3SO4, CF3SO3Li (lithium trifluoromethanesulfonate, also called triflate), lithium bisperfluoroethanesulfonimide, lithium (Bis) Trifluoromethanesulfonimide, or the like or a mixture or two or more such salts, for example.
  • Some embodiments further include an encapsulating material surrounding the battery cell, and one or more electrical leads connecting from the battery cell to an exterior of the encapsulating material.
  • Some embodiments further include an electronic device, wherein the battery cell supplies power to at least a portion of the electronic device.
  • Some embodiments of the invention include an apparatus that includes a first battery cell having a negative electrode, a positive electrode, and an electrolyte structure, wherein the negative electrode includes an anode material and a LiPON layer covering at least a portion of the negative electrode, the positive electrode includes a cathode material and a LiPON layer covering at least a portion of the positive electrode, and the electrolyte structure includes a polymer electrolyte material sandwiched between the LiPON layer of the negative electrode and the LiPON layer of the positive electrode.
  • In some embodiments, the cathode material includes LiCoO2 that is deposited on a positive electrode current-collector material, and the LiPON layer of the positive electrode is deposited on the LiCoO2. In some such embodiments, the positive electrode current-collector contact material includes a metal mesh around which the cathode material is deposited.
  • In some embodiments, the negative electrode includes a negative-electrode current collector made of a metal that does not readily alloy with lithium during a plating operation, and lithium metal is plated onto the negative-electrode current collector through the LiPON layer covering the negative electrode. In some such embodiments, the metal of the negative-electrode current collector includes copper. In some such embodiments, the negative electrode includes a mask layer covers a periphery of the negative-electrode current collector and lithium metal is plated through the LiPON layer covering the negative electrode onto an area of the metal negative-electrode current collector defined by the mask.
  • In some embodiments, the negative electrode includes a current-collector metal layer, and the anode material includes lithium metal deposited on at least one of two major faces of the metal layer that is at least partially covered by the LiPON layer of the negative electrode.
  • In some embodiments, the anode material is deposited on both major faces of the metal layer of the negative electrode, each face at least partially covered by the LiPON layer of the negative electrode.
  • In some embodiments, the positive electrode includes a current-collector metal layer, and the cathode material is deposited on both major faces of the metal layer and is at least partially covered by the LiPON layer.
  • In some embodiments, the negative electrode includes a current-collector metal layer, and the anode material includes lithium metal plated onto both major faces of the negative-electrode current-collector metal layer through the LiPON layer covering the negative electrode.
  • In some embodiments, the negative electrode includes a current-collector contact foil coated with the LiPON layer of the negative electrode, the lithium anode material includes lithium metal plated onto a first major face of the current-collector contact foil through the LiPON layer covering the current-collector contact foil, the lithium cathode material of a second battery cell is deposited onto a second major face of the current-collector contact foil of the negative electrode of the first battery cell, and the LiPON barrier/electrolyte layer covering the cathode material of the second battery cell is then deposited by sputtering.
  • In some embodiments, the positive electrode includes a current-collector foil, the lithium cathode material is deposited onto both major faces of the positive electrode current-collector contact foil, and the LiPON barrier/electrolyte layer covering the positive electrode is then deposited by sputtering.
  • In some embodiments, the positive electrode includes a current-collector contact mesh, the lithium cathode material is deposited onto both major faces of the cathode current-collector contact mesh, and the LiPON barrier/electrolyte layer covering the positive electrode is then deposited by sputtering.
  • Some embodiments of the invention include a method that includes providing a first sheet that includes an anode material and a LiPON barrier/electrolyte layer covering the anode material, providing a second sheet that includes a cathode material that includes lithium and a LiPON banter/electrolyte layer covering the cathode material, and sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the first sheet and the LiPON barrier/electrolyte layer covering the cathode material of the first cathode sheet.
  • Some embodiments of the method further include providing a third sheet that includes an anode material and a LiPON barrier/electrolyte layer covering the anode material, providing a fourth sheet that includes a cathode material that includes lithium and a LiPON barrier/electrolyte layer covering the cathode material, sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the third sheet and the LiPON barrier/electrolyte layer covering the cathode material of the fourth sheet, and sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the first sheet and the LiPON barrier/electrolyte layer covering the cathode material of the fourth sheet.
  • In some embodiments of the method, the anode is deposited as a layer on a copper anode current-collector contact layer through a LiPON layer.
  • In some embodiments of the method, the deposition of a lithium anode is done by electroplating in a propylene carbonate/LiPF6 electrolyte solution.
  • In some embodiments of the method, the first sheet includes a cathode material on a face opposite the anode material and a LiPON barrier/electrolyte layer covering the cathode material, and the second sheet includes an anode material that includes lithium on a face opposite the cathode material and a LiPON barrier/electrolyte layer covering the anode material, wherein the method further includes providing a third sheet that includes an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material on a first face, and an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material on a second face opposite the first face, and sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the first sheet and the LiPON barrier/electrolyte layer covering the cathode material of the third sheet.
  • Some embodiments of the invention include an apparatus that includes a first sheet that includes an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material on a first face of the first sheet, a second sheet that includes a cathode material that includes lithium and a LiPON barrier/electrolyte layer covering the cathode material on a second face of the second sheet, and means for passing ions between the LiPON layer on the first face of the first sheet and the LiPON layer on the second face of the second sheet to form a first battery cell.
  • In some embodiments, the first sheet includes a LiPON layer on a second face of the first sheet, and the apparatus further includes a third sheet that includes an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material on a first face of the third sheet, a fourth sheet that includes a cathode material that includes lithium and a LiPON barrier/electrolyte layer covering the cathode material on a second face of the fourth sheet and a cathode material that includes lithium and a LiPON barrier/electrolyte layer covering the cathode material on a first face of the fourth sheet, means for passing ions between the LiPON layer on the first face of the third sheet and the LiPON layer on the second face of the fourth sheet to form a second battery cell, and means for passing ions between the LiPON layer on the second face of the first sheet and the LiPON layer on the first face of the fourth sheet to form a third battery cell.
  • In some embodiments, the first sheet includes a copper anode current-collector layer, and the anode material includes lithium deposited as a lithium-metal layer on the copper anode current-collector layer through the LiPON layer of the first sheet,
  • In some embodiments, a periphery of the lithium-metal layer is defined by a mask, and the deposition of a lithium anode is done by electroplating in a liquid propylene carbonate/LiPF6 electrolyte solution.
  • In some embodiments, the first sheet includes a cathode material on a second face opposite the anode material on the first face and a LiPON barrier/electrolyte layer covering the cathode material of the first sheet, and the apparatus further includes a third sheet having an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material on a first face of the third sheet, and means for passing ions between the LiPON layer on the second face of the first sheet and the LiPON layer on the first face of the third sheet to form a series-connected pair of battery cells.
  • Some embodiments of the invention include an apparatus that includes a deposition station that deposits a hard electrolyte layer on a negative electrode component, a deposition station that deposits a hard electrolyte layer on a positive electrode component, and a lamination station that laminates the hard electrolyte layer on the negative electrode component to the hard electrolyte layer on the positive electrode component with a soft electrolyte layer therebetween to form a composite electrolyte structure.
  • Some embodiments further include a deposition station that deposits a soft electrolyte layer on the hard electrolyte layer on the negative electrode component. In some embodiments, the soft electrolyte layer includes a polyphosphazene.
  • Some embodiments further include a deposition station that deposits a soft electrolyte layer on the hard electrolyte layer on the negative electrode component, and a deposition station that deposits a soft electrolyte layer on the hard electrolyte layer on the positive electrode component.
  • In some embodiments, the deposition station that deposits the hard electrolyte layer on the positive electrode deposits a material that includes LiPON, the deposition station that deposits the hard electrolyte layer on the negative electrode component deposits a material that includes LiPON, and the deposition station that deposits the soft electrolyte layer deposited on the hard electrolyte layer on the positive electrode component and the deposition station that deposits the soft electrolyte layer on the hard electrolyte layer on the negative electrode deposits a material that includes a polyphosphazene and a lithium salt. In some embodiments, the soft electrolyte layer includes MEEP.
  • In some embodiments, the deposition station that deposits the hard electrolyte layer on the positive electrode deposits a material that includes LiPON and the deposition station that deposits the hard electrolyte layer on the negative electrode deposits a material that includes LiPON.
  • Some embodiments further include a deposition station that deposits a LiCoO2 layer on the positive electrode before the hard electrolyte layer is deposited on the positive electrode component.
  • Some embodiments further include an electroplating station that plates a lithium metal layer on the negative electrode through the hard electrolyte layer after the hard electrolyte layer is deposited on the negative electrode component.
  • Some embodiments further include a patterning station that deposits a photoresist layer and patterns a mask that defines an area on the negative electrode component to which a lithium metal layer can be formed.
  • Some embodiments of the invention include a method that includes providing a positive electrode component, providing a negative electrode component, depositing a hard electrolyte layer on the negative electrode component, depositing a hard electrolyte layer on a positive electrode component, and laminating the hard electrolyte layer on the negative electrode to the hard electrolyte layer on the positive electrode with a soft electrolyte layer therebetween to form a composite electrolyte structure.
  • In some embodiments of the method, the depositing of the hard electrolyte layer on the positive electrode component includes sputtering a LiPON layer, and the depositing of the hard electrolyte layer on the negative electrode component includes sputtering a LiPON layer.
  • In some embodiments of the method, the soft electrolyte layer includes a polyphosphazene and a lithium salt.
  • Some embodiments further include depositing a soft electrolyte layer on the hard electrolyte layer on the negative electrode component, and depositing a soft electrolyte layer on the hard electrolyte layer on a positive electrode component, and wherein the laminating presses the soft electrolyte layer on the hard electrolyte layer on the negative electrode component against the soft electrolyte layer on the hard electrolyte layer on the positive electrode component.
  • In some embodiments, the depositing of the soft electrolyte layer on the hard electrolyte layer on the negative electrode component includes doctor blading.
  • In some embodiments, the depositing of the soft electrolyte layer on the hard electrolyte layer on the negative electrode component includes spraying soft electrolyte material in a liquid form.
  • In some embodiments, the depositing of the soft electrolyte layer on the hard electrolyte layer on the positive electrode component includes spin coating soft electrolyte material in a liquid form.
  • Some embodiments of the invention include an apparatus that includes a source of a positive electrode component, a source of a negative electrode component, means for depositing a hard electrolyte layer on the negative electrode component, means for depositing a hard electrolyte layer on a positive electrode component, and means for laminating the hard electrolyte layer on the negative electrode to the hard electrolyte layer on the positive electrode with a soft electrolyte layer therebetween to form a composite electrolyte structure.
  • Some embodiments further include means for depositing a soft electrolyte layer on the hard electrolyte layer on the negative electrode component, and means for depositing a soft electrolyte layer on the hard electrolyte layer on a positive electrode component, and wherein the means for laminating presses the soft electrolyte layer on the hard electrolyte layer on the negative electrode component against the soft electrolyte layer on the hard electrolyte layer on the positive electrode component.
  • In some embodiments, the hard electrolyte layer deposited on the positive electrode component includes LiPON and the hard electrolyte layer deposited on the negative electrode component includes LiPON.
  • In some embodiments, the soft electrolyte layers include a polyphosphazene and a lithium salt.
  • In some embodiments, the soft electrolyte layers include MEEP.
  • Some embodiments of the invention include an apparatus that includes a battery cell having an anode, a cathode, and an electrolyte structure, wherein the anode includes an anode material that, when the battery cell is charged, includes lithium and a LiPON barrier/electrolyte layer covering at least a portion of the anode, the cathode includes a cathode material that includes lithium and a LiPON barrier/electrolyte layer covering at least a portion of the cathode, and the electrolyte structure includes a polymer electrolyte material sandwiched between the LiPON barrier/electrolyte layer covering the anode and the LiPON barrier/electrolyte layer covering the cathode.
  • In some embodiments of the apparatus, the cathode material includes LiCoO2 deposited on a cathode-current-collector contact material, and then the LiPON barrier/electrolyte layer covering the cathode is deposited.
  • In some embodiments of the apparatus, the cathode material includes LiCoO3 deposited on a cathode-current-collector contact material, and then the LiPON barrier/electrolyte layer covering the cathode is deposited.
  • In some embodiments of the apparatus, the lithium anode material is plated onto a copper anode current-collector contact or current collector through LiPON barrier/electrolyte layer covering the anode.
  • In some embodiments of the apparatus, the anode material is deposited on both major faces of a metal sheet at least partially covered by the LiPON barrier/electrolyte layer.
  • In some embodiments of the apparatus, the cathode material is deposited on both major faces of a metal sheet and is at least partially covered by the LiPON barrier/electrolyte layer.
  • In some embodiments of the apparatus, the cathode current-collector contact material includes a metal mesh around which the cathode material is deposited.
  • In some embodiments of the apparatus, the lithium anode material is plated onto both major faces of an anode current-collector contact foil through LiPON barrier/electrolyte layer covering the anode current-collector contact layer.
  • In some embodiments of the apparatus, the lithium anode material is plated onto a first major face of a current-collector contact foil through LiPON barrier/electrolyte layer covering the current-collector contact foil the lithium cathode material is deposited onto a second major face of the current-collector contact foil, and the LiPON barrier/electrolyte layer covering the cathode is then deposited by sputtering.
  • In some embodiments of the apparatus, the lithium cathode material is deposited onto both major faces of a cathode current-collector contact foil, and the LiPON barrier/electrolyte layer covering the cathode is then deposited by sputtering.
  • In some embodiments of the apparatus, the lithium cathode material is deposited onto both major faces of a cathode current-collector contact mesh, and the LiPON barrier/electrolyte layer covering the cathode is then deposited by sputtering.
  • In some embodiments, another aspect of the invention includes a method that includes providing a first sheet that includes an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material, providing a second sheet that includes a cathode material that includes lithium and a LiPON barrier/electrolyte layer covering the cathode material, and sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the first sheet and the LiPON barrier/electrolyte layer covering the cathode material of the second sheet.
  • Some embodiments of the method further include providing a third sheet that includes an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material, providing a fourth sheet that includes a cathode material that includes lithium and a LiPON barrier/electrolyte layer covering the cathode material, sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the third sheet and the LiPON barrier/electrolyte layer covering the cathode material of the fourth sheet, and sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the first sheet and the LiPON barrier/electrolyte layer covering the cathode material of the fourth sheet.
  • In some embodiments of the method, the anode is deposited as a layer on a copper anode current-collector contact layer through a LiPON layer.
  • In some embodiments of the method, the deposition of a lithium anode is done by electroplating in a propylene carbonate/LiPF6 electrolyte solution.
  • In some embodiments of the method, the first sheet includes a cathode material on a face opposite the anode material and a LiPON barrier/electrolyte layer covering the cathode material, and the second sheet includes an anode material that includes lithium on a face opposite the cathode material on the second sheet and a LiPON barrier/electrolyte layer covering the anode material, and the method further includes providing a third sheet that includes an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material on a first face, and an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material on a second face opposite the first face, and sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the first sheet and the LiPON barrier/electrolyte layer covering the cathode material of the third sheet.
  • In some embodiments, another aspect of the invention includes an apparatus that includes a first sheet that includes an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material, a second sheet that includes a cathode material that includes lithium and a LiPON barrier/electrolyte layer covering the cathode material, and means for sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the first sheet and the LiPON barrier/electrolyte layer covering the cathode material of the second sheet.
  • Some embodiments of this apparatus include a third sheet that includes an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material, a fourth sheet that includes a cathode material that includes lithium and a LiPON barrier/electrolyte layer covering the cathode material, means for sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the third sheet and the LiPON barrier/electrolyte layer covering the cathode material of the fourth sheet, and means for sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the first sheet and the LiPON barrier/electrolyte layer covering the cathode material of the fourth sheet.
  • In some embodiments, the first sheet includes a cathode material on a face opposite the anode material and a LiPON barrier/electrolyte layer covering the cathode material, and the second sheet includes an anode material that includes lithium on a face opposite the cathode material and a LiPON barrier/electrolyte layer covering the anode material, and the apparatus further includes a third sheet that includes an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material on a first face, and an anode material that includes lithium and a LiPON barrier/electrolyte layer covering the anode material on a second face opposite the first face, and means for sandwiching a polymer electrolyte material between the LiPON barrier/electrolyte layer covering the anode material of the first sheet and the LiPON barrier/electrolyte layer covering the cathode material of the third sheet.
  • It is to be understood that the above description is intended to be illustrative, and not restrictive. Although numerous characteristics and advantages of various embodiments as described herein have been set forth in the foregoing description, together with details of the structure and function of various embodiments, many other embodiments and changes to details will be apparent to those of skill in the art upon reviewing the above description. The scope of the invention should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. In the appended claims, the terms “including” and “in which” are used as the plain-English equivalents of the respective terms “comprising” and “wherein,” respectively. Moreover, the terms “first,” “second,” and “third,” etc., are used merely as labels, and are not intended to impose numerical requirements on their objects.

Claims (22)

1-31. (canceled)
32. A method of forming a battery cell having a composite electrolyte structure comprising:
a) providing a positive electrode component;
b) providing a negative electrode component;
c) depositing a first electrolyte layer having randomly spaced defects therein on the negative electrode component;
d) depositing a second electrolyte layer having randomly spaced defects therein on a positive electrode component;
e) providing a third electrolyte material that comprises a polymer or a gel that is soft compared to the first and second electrolyte layers;
f) laminating the first electrolyte layer on the negative electrode to the second electrolyte layer on the positive electrode using a the third soft electrolyte material to at least partially fill and fix the defects in at least one of the first and second electrolyte layers to form a the composite electrolyte structure of a the battery cell;
wherein the third electrolyte layer is applied as a liquid and then dried.
33. The method of claim 1, wherein the third electrolyte layer is applied as a dip coating.
34. The method of claim 1, wherein the third electrolyte layer is spun on.
35. The method of claim 1, wherein the third electrolyte layer is cast on.
36. The method of claim 1, wherein the third electrolyte layer is deposited from a liquid source and squeegeed and/or doctor-bladed in place.
37. The method of claim 1, wherein the third electrolyte layer is printed to areas to which the third electrolyte is desired.
38. The method of claim 1, wherein the first and second electrolyte layers are LiPON.
39. The method of claim 7, wherein the third electrolyte layer comprises polyvinylidene difluoride, propylene carbonate, and a lithium salt.
40. The method of claim 7, wherein the third electrolyte layer comprises MEEP.
41. The method of claim 7, wherein the third electrolyte layer comprises a polyphosphazene and a lithium salt.
42. A battery cell having a negative electrode, a positive electrode, and an electrolyte structure, wherein
a) the negative electrode includes a first electrolyte layer covering at least a portion of the negative electrode and having randomly spaced defects;
b) the positive electrode includes a cathode material and a second electrolyte layer covering at least a portion of the positive electrode and having randomly spaced defects; and
c) the electrolyte structure includes a third electrolyte material that comprises a polymer or a gel that is soft compared to the first and second electrolyte layers sandwiched between the first electrolyte of the negative electrode and the second electrolyte layer of the positive electrode;
wherein the randomly spaced defects in the first and second electrolyte layers are at least partially filled by the third soft electrolyte material and wherein the third soft electrolyte layer fixes defects in at least one of the first and second electrolyte layers.
43. The battery cell of claim 11 wherein the positive electrode current-collector material includes a metal mesh around which the cathode material is deposited.
44. The battery cell of claim 11, wherein the negative electrode includes a negative-electrode current collector made of a metal that does not readily alloy with lithium during a plating operation, and lithium metal is plated onto the negative-electrode current collector through the first electrolyte layer covering the negative electrode.
45. The battery cell of claim 11, wherein the negative electrode includes a mask layer that covers a periphery of the negative-electrode current collector and lithium metal is plated through the first electrolyte layer covering the negative electrode onto an area of the metal negative-electrode current collector defined by the mask.
46. The battery cell of claim 11, wherein: the negative electrode includes a current-collector metal layer and an anode material, and the anode material includes lithium metal deposited on at least one of two major faces of the metal layer, which is at least partially covered by the first electrolyte layer of the negative electrode.
47. The battery cell of claim 11, wherein: the anode material is deposited on both major faces of the metal layer of the negative electrode, each face at least partially covered by the first electrolyte layer of the negative electrode.
48. The battery cell of claim 11, wherein: the positive electrode includes a current-collector metal layer, and the cathode material is deposited on both major faces of the metal layer and is at least partially covered by the second electrolyte layer.
49. The battery cell of claim 11, wherein: the negative electrode includes a current-collector metal layer and an anode material, and the anode material includes lithium metal plated onto both major faces of the negative-electrode current-collector metal layer through the first electrolyte layer covering the negative electrode.
50. The battery cell of claim 11, further comprising: an encapsulating material surrounding the battery cell; and one or more electrical leads connecting from the battery cell to an exterior of the encapsulating material.
51. The battery cell of claim 11, further comprising: an electronic device; and a housing holding the electronic device, wherein the battery cell is within the housing and supplies power to the electronic device.
52. The battery cell of claim 11, wherein: the positive electrode comprises oxides of copper.
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US12/850,078 US7939205B2 (en) 2005-07-15 2010-08-04 Thin-film batteries with polymer and LiPON electrolyte layers and method
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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060222954A1 (en) * 1999-11-23 2006-10-05 Skotheim Terje A Lithium anodes for electrochemical cells
US20100129699A1 (en) * 2006-12-04 2010-05-27 Mikhaylik Yuriy V Separation of electrolytes
US20110014524A1 (en) * 1999-11-23 2011-01-20 Sion Power Corporation Protection of anodes for electrochemical cells
US20110294015A1 (en) * 2010-05-25 2011-12-01 Robert Bosch Gmbh Method and Apparatus for Production of a Thin-Film Battery
US20120058380A1 (en) * 2011-11-09 2012-03-08 Sakti3, Inc. Monolithically integrated thin-film solid state lithium battery device having multiple layers of lithium electrochemical cells
US8338034B2 (en) 2006-03-22 2012-12-25 Sion Power Corporation Electrode protection in both aqueous and non-aqueous electrochemical cells, including rechargeable lithium batteries
US20130130085A1 (en) * 2010-07-22 2013-05-23 University Of Central Florida Research Foundation, Inc. Alkali metal-cathode solution battery
WO2013134114A2 (en) * 2012-03-04 2013-09-12 Indiana University Research And Technology Center Method and apparatus for extracting energy and metal from seawater electrodes
US8936870B2 (en) 2011-10-13 2015-01-20 Sion Power Corporation Electrode structure and method for making the same
US9005311B2 (en) 2012-11-02 2015-04-14 Sion Power Corporation Electrode active surface pretreatment
WO2015054040A1 (en) 2013-10-07 2015-04-16 Scherson Daniel Electrochemical method and apparatus for forming a vacuum in a sealed enclosure
CN105051954A (en) * 2013-03-15 2015-11-11 苹果公司 Thin film encapsulation battery systems
US9548492B2 (en) 2011-06-17 2017-01-17 Sion Power Corporation Plating technique for electrode
US9570775B2 (en) 2013-03-15 2017-02-14 Apple Inc. Thin film transfer battery systems
US9601751B2 (en) 2013-03-15 2017-03-21 Apple Inc. Annealing method for thin film electrodes
US9711770B2 (en) 2012-11-27 2017-07-18 Apple Inc. Laminar battery system
WO2017165338A1 (en) * 2016-03-21 2017-09-28 Scherson Daniel Electrochemical method and apparatus for consuming gases
US9899661B2 (en) 2013-03-13 2018-02-20 Apple Inc. Method to improve LiCoO2 morphology in thin film batteries
US10033029B2 (en) 2012-11-27 2018-07-24 Apple Inc. Battery with increased energy density and method of manufacturing the same
US10141600B2 (en) 2013-03-15 2018-11-27 Apple Inc. Thin film pattern layer battery systems

Families Citing this family (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7776478B2 (en) 2005-07-15 2010-08-17 Cymbet Corporation Thin-film batteries with polymer and LiPON electrolyte layers and method
KR101387855B1 (en) * 2005-07-15 2014-04-22 사임베트 코퍼레이션 Thin-film batteries with soft and hard electrolyte layers and method
KR100686848B1 (en) * 2005-10-11 2007-02-16 삼성에스디아이 주식회사 Lithium rechargeable battery
JP5274035B2 (en) * 2007-03-27 2013-08-28 三洋電機株式会社 Fuel cell
US7923144B2 (en) * 2007-03-31 2011-04-12 Tesla Motors, Inc. Tunable frangible battery pack system
US8021496B2 (en) 2007-05-16 2011-09-20 Fmc Corporation Stabilized lithium metal powder for Li-ion application, composition and process
TW200919803A (en) * 2007-06-07 2009-05-01 Koninkl Philips Electronics Nv Solid-state battery and method for manufacturing of such a solid-state battery
US7830646B2 (en) * 2007-09-25 2010-11-09 Ioxus, Inc. Multi electrode series connected arrangement supercapacitor
WO2009108184A1 (en) * 2008-02-25 2009-09-03 Midwest Research Institute Homogeneous, dual layer, solid state, thin film deposition for structural and/or electrochemical characteristics
DE102008023571A1 (en) * 2008-05-03 2009-11-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Thin housing film for electrochemical elements
US20090279230A1 (en) * 2008-05-08 2009-11-12 Renewable Energy Development, Inc. Electrode structure for the manufacture of an electric double layer capacitor
US8906534B2 (en) * 2008-05-28 2014-12-09 Taiwan Semiconductor Manufacturing Company, Ltd. Stacked multi-cell battery concept
KR101503458B1 (en) * 2008-06-25 2015-03-18 삼성전자주식회사 The flexibility is improved rechargeable battery
US8411413B2 (en) * 2008-08-28 2013-04-02 Ioxus, Inc. High voltage EDLC cell and method for the manufacture thereof
US8638211B2 (en) * 2009-04-30 2014-01-28 Icontrol Networks, Inc. Configurable controller and interface for home SMA, phone and multimedia
US8450012B2 (en) 2009-05-27 2013-05-28 Amprius, Inc. Interconnected hollow nanostructures containing high capacity active materials for use in rechargeable batteries
US20100330419A1 (en) * 2009-06-02 2010-12-30 Yi Cui Electrospinning to fabricate battery electrodes
US20110135810A1 (en) * 2009-12-03 2011-06-09 Marina Yakovleva Finely deposited lithium metal powder
US9013155B2 (en) * 2010-01-09 2015-04-21 Dais Analytic Corporation Energy storage devices including a solid multilayer electrolyte
CN102804303B (en) * 2010-01-09 2015-09-09 戴斯分析公司 Energy storage device comprising a multilayer solid electrolyte
US9500555B2 (en) * 2010-01-19 2016-11-22 Clark Robert Gunness Method and system for leak detection in roofing and waterproofing membranes
US8735003B2 (en) 2010-06-16 2014-05-27 Alliance For Sustainable Energy, Llc Lithium-ion batteries having conformal solid electrolyte layers
US20110318651A1 (en) * 2010-06-24 2011-12-29 Basf Se Thermoelectric generator
CN102456927B (en) * 2010-10-30 2014-05-28 比亚迪股份有限公司 Method for manufacturing lithium ion battery
JP5634372B2 (en) * 2010-11-04 2014-12-03 三菱電機株式会社 Power storage device cell
JP5614646B2 (en) * 2010-11-15 2014-10-29 独立行政法人産業技術総合研究所 Electrode thin film, all-solid lithium battery, and a method of manufacturing the electrode for a thin film
US9853325B2 (en) 2011-06-29 2017-12-26 Space Charge, LLC Rugged, gel-free, lithium-free, high energy density solid-state electrochemical energy storage devices
US9331501B2 (en) 2011-08-17 2016-05-03 Cymbet Corporation Multi-cell thin film microbattery array
DE102011053782A1 (en) * 2011-09-20 2013-03-21 Deutsches Zentrum für Luft- und Raumfahrt e.V. Lithium air battery for supply of electrical power to electrically operated vehicle, has oxygen electrode element with porous structure located on cathode contact element and staying in contact with one separator element of twin anode
DE102012200862A1 (en) * 2012-01-23 2013-07-25 Robert Bosch Gmbh Battery manufacturing by spin coating
US9771661B2 (en) 2012-02-06 2017-09-26 Honeywell International Inc. Methods for producing a high temperature oxidation resistant MCrAlX coating on superalloy substrates
KR20150016210A (en) 2012-03-01 2015-02-11 엑셀라트론 솔리드 스테이트 엘엘씨 High Capacity Solid State Composite Cathode, Solid State Composite Separator, Solid-State Rechargeable Lithium Battery and Methods of Making Same
US9099252B2 (en) * 2012-05-18 2015-08-04 Nokia Technologies Oy Apparatus and associated methods
US10084168B2 (en) 2012-10-09 2018-09-25 Johnson Battery Technologies, Inc. Solid-state battery separators and methods of fabrication
EP2907190B1 (en) * 2012-10-15 2017-12-06 Cymbet Corporation Thin film batteries comprising a glass or ceramic substrate
US9735450B2 (en) 2012-10-18 2017-08-15 Ambri Inc. Electrochemical energy storage devices
US9312522B2 (en) 2012-10-18 2016-04-12 Ambri Inc. Electrochemical energy storage devices
US9419463B2 (en) 2012-11-29 2016-08-16 Cymbet Corporation Thin film microbattery charge and output control
US9362546B1 (en) 2013-01-07 2016-06-07 Quantumscape Corporation Thin film lithium conducting powder material deposition from flux
US9520618B2 (en) 2013-02-12 2016-12-13 Ambri Inc. Electrochemical energy storage devices
US9368285B1 (en) * 2013-02-27 2016-06-14 Amazon Technologies, Inc. Power cell embedded in enclosure
US10270139B1 (en) 2013-03-14 2019-04-23 Ambri Inc. Systems and methods for recycling electrochemical energy storage devices
US9923208B2 (en) * 2013-05-10 2018-03-20 Nanyang Technological University Electrolyte membrane for liquid anode cell battery
US9502737B2 (en) 2013-05-23 2016-11-22 Ambri Inc. Voltage-enhanced energy storage devices
US9859565B2 (en) * 2013-06-28 2018-01-02 Intel Corporation Ultrafast reliable silicon enabled battery and associated methods
US20150099188A1 (en) * 2013-10-07 2015-04-09 Quantumscape Corporation Garnet materials for li secondary batteries and methods of making and using garnet materials
US9343736B2 (en) 2014-03-31 2016-05-17 Battelle Memorial Institute Lithium compensation for full cell operation
FR3023418B1 (en) * 2014-07-01 2016-07-15 I-Ten fully solid battery comprising an electrolyte material crosslinked solid polymer
FR3023417B1 (en) * 2014-07-01 2016-07-15 I-Ten fully solid battery comprising a solid electrolyte and a layer of solid polymer material
TW201622229A (en) * 2014-08-28 2016-06-16 Applied Materials Inc Special mask to increase LiPON ionic conductivity and TFB fabrication yield
JP2016058250A (en) * 2014-09-10 2016-04-21 セイコーエプソン株式会社 Electrode body for lithium battery and lithium battery
US9799919B2 (en) * 2014-11-28 2017-10-24 Toyota Motor Engineering & Manufacturing North America, Inc. In-situ magnesium-metal generated rechargeable magnesium battery
KR20160075233A (en) * 2014-12-19 2016-06-29 삼성전자주식회사 Composite electrolyte, and lithium battery comprising electrolyte
US20160211547A1 (en) * 2015-01-15 2016-07-21 Google Inc. Hybrid Rechargeable Battery
US10087540B2 (en) 2015-02-17 2018-10-02 Honeywell International Inc. Surface modifiers for ionic liquid aluminum electroplating solutions, processes for electroplating aluminum therefrom, and methods for producing an aluminum coating using the same
US10008739B2 (en) 2015-02-23 2018-06-26 Front Edge Technology, Inc. Solid-state lithium battery with electrolyte
US10181800B1 (en) 2015-03-02 2019-01-15 Ambri Inc. Power conversion systems for energy storage devices
US9905370B2 (en) * 2015-03-05 2018-02-27 Tuqiang Chen Energy storage electrodes and devices
JP2018518797A (en) 2015-04-16 2018-07-12 クアンタムスケイプ コーポレイション The method for producing a high-density solid electrolyte using a setter plates and which for a solid electrolyte prepared
US9893385B1 (en) 2015-04-23 2018-02-13 Ambri Inc. Battery management systems for energy storage devices
KR20160131806A (en) * 2015-05-08 2016-11-16 삼성에스디아이 주식회사 Lithium batteries
JP6233372B2 (en) * 2015-09-14 2017-11-22 トヨタ自動車株式会社 Method for manufacturing an all-solid-state cell
AU2016365310A1 (en) * 2015-12-03 2018-06-14 Research Foundation Of The City University Of New York Method for producing a lithium film
US9966630B2 (en) 2016-01-27 2018-05-08 Quantumscape Corporation Annealed garnet electrolyte separators
WO2018022983A1 (en) * 2016-07-29 2018-02-01 Massachusetts Institute Of Technology A li-ion thin film microbattery and method of fabricating the same
CN106784970B (en) * 2016-12-21 2019-04-19 惠州金源精密自动化设备有限公司 A kind of soft-package battery molded package machine
US10177427B2 (en) 2017-02-10 2019-01-08 General Electric Company Electrochemical cell for use in high temperature metal-air battery
US10347937B2 (en) 2017-06-23 2019-07-09 Quantumscape Corporation Lithium-stuffed garnet electrolytes with secondary phase inclusions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE36843E (en) * 1993-06-21 2000-08-29 Micron Technology, Inc. Polymer-lithium batteries and improved methods for manufacturing batteries
US6420071B1 (en) * 2000-03-21 2002-07-16 Midwest Research Institute Method for improving the durability of ion insertion materials
US6465121B1 (en) * 2000-08-30 2002-10-15 Lev M. Dawson Method for distributing electrolyte in batteries
US7776478B2 (en) * 2005-07-15 2010-08-17 Cymbet Corporation Thin-film batteries with polymer and LiPON electrolyte layers and method

Family Cites Families (230)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419487A (en) 1966-01-24 1968-12-31 Dow Corning Method of growing thin film semiconductors using an electron beam
US4207119A (en) 1978-06-02 1980-06-10 Eastman Kodak Company Polycrystalline thin film CdS/CdTe photovoltaic cell
JPS5850417B2 (en) 1979-07-31 1983-11-10 Fujitsu Ltd
US4333808A (en) 1979-10-30 1982-06-08 International Business Machines Corporation Method for manufacture of ultra-thin film capacitor
JPS6239550B2 (en) 1980-02-19 1987-08-24 Sharp Kk
US4299890A (en) 1980-06-18 1981-11-10 Duracell International Inc. Solid state cell
US4353160A (en) 1980-11-24 1982-10-12 Spire Corporation Solar cell junction processing system
JPH0334662B2 (en) 1980-12-26 1991-05-23 Hitachi Seisakusho Kk
EP0078404B1 (en) 1981-10-29 1992-04-01 Motorola Energy Systems Inc. Electric energy storage devices
US4435445A (en) 1982-05-13 1984-03-06 Energy Conversion Devices, Inc. Photo-assisted CVD
JPH0460355B2 (en) 1982-06-11 1992-09-25 Hitachi Ltd
US4520039A (en) 1982-09-23 1985-05-28 Sovonics Solar Systems Compositionally varied materials and method for synthesizing the materials
US4440108A (en) 1982-09-24 1984-04-03 Spire Corporation Ion beam coating apparatus
US4684848A (en) 1983-09-26 1987-08-04 Kaufman & Robinson, Inc. Broad-beam electron source
DE3404326C1 (en) 1984-02-08 1985-02-14 Thomson Brandt Gmbh Video recorder with reduction of the image crosstalk
CA1257165A (en) 1984-02-08 1989-07-11 Paul Epstein Infusion system having plural fluid input ports and at least one patient output port
JPH06101335B2 (en) 1984-11-26 1994-12-12 株式会社日立製作所 All-solid-state lithium battery
US4633129A (en) 1985-04-30 1986-12-30 International Business Machines Corporation Hollow cathode
FR2581483B1 (en) 1985-05-03 1990-07-13 Balkanski Minko solid battery integrable and method of realization
FR2593968B1 (en) 1986-02-04 1994-12-09 Accumulateurs Fixes An activatable battery embodying the couple Li / SO2 Cl2
US4862032A (en) 1986-10-20 1989-08-29 Kaufman Harold R End-Hall ion source
US4740431A (en) 1986-12-22 1988-04-26 Spice Corporation Integrated solar cell and battery
US5126031A (en) 1987-03-02 1992-06-30 Gordon Arnold Z Coprecipitated hydrogels in pressure tolerant gas diffusion electrodes
CA1332324C (en) 1987-03-30 1994-10-11 Jun Shioya Method for producing thin film of oxide superconductor
US4832463A (en) 1987-09-08 1989-05-23 Tufts University Thin film ion conducting coating
US5098737A (en) 1988-04-18 1992-03-24 Board Of Regents The University Of Texas System Amorphic diamond material produced by laser plasma deposition
FR2631955B1 (en) 1988-05-25 1990-08-10 Accumulateurs Fixes Method of preparing a compound containing derived vanadium oxide for thermal battery cathode
FR2638764B1 (en) 1988-11-04 1993-05-07 Centre Nat Rech Scient composite element comprising a layered chalcogenide or titanium oxychalcogenure, usable in particular as a positive electrode in an electrochemical cell in thin layers
DE68913736T2 (en) 1988-12-16 1994-06-30 Otsuka Kagaku Kk Battery with completely solid secondary cells.
DE69033286D1 (en) 1989-02-15 1999-10-21 Hitachi Ltd Method and apparatus for forming a film
US5220516A (en) * 1989-02-21 1993-06-15 International Business Machines Corp. Asynchronous staging of objects between computer systems in cooperative processing systems
EP0390692A3 (en) 1989-03-29 1991-10-02 Teruaki Katsube Method of forming thin film, apparatus for forming thin film and sensor
US5022930A (en) 1989-06-20 1991-06-11 Photon Energy, Inc. Thin film photovoltaic panel and method
EP0410627A1 (en) 1989-07-27 1991-01-30 Kabushiki Kaisha Toshiba Oxide film with preferred crystal orientation, method of manufacturing the same, and magneto-optical recording medium
US5601652A (en) 1989-08-03 1997-02-11 United Technologies Corporation Apparatus for applying ceramic coatings
US5051274A (en) 1989-09-11 1991-09-24 Tufts University Ion-beam based deposition of coatings for electrochromic devices
US5189550A (en) 1989-09-11 1993-02-23 Tufts University Ion-beam based deposition of coatings for electrochromic devices
JP2713481B2 (en) 1989-12-04 1998-02-16 株式会社日立製作所 Multi-film forming method and a multi-thin-film forming apparatus according to an ion beam sputtering
US5192947A (en) 1990-02-02 1993-03-09 Simon Neustein Credit card pager apparatus
US5061581A (en) 1990-02-07 1991-10-29 Sri International Novel solid polymer electrolytes
JPH03234016A (en) 1990-02-09 1991-10-18 Isuzu Motors Ltd Electric double layer capacitor
US5202196A (en) 1990-04-26 1993-04-13 Lianxiang Wang High capacity colloidal storage battery, a collodial electrolyte used in it, and the processes for producing them
US5151848A (en) 1990-08-24 1992-09-29 The United States Of America As Represented By The Secretary Of The Air Force Supercapacitor
GB2248852A (en) 1990-10-16 1992-04-22 Secr Defence Vapour deposition
FR2672713B1 (en) 1991-02-13 1995-05-05 Inst Nat Polytech Grenoble
US5180645A (en) 1991-03-01 1993-01-19 Motorola, Inc. Integral solid state embedded power supply
US5166009A (en) 1991-03-28 1992-11-24 The United States Of America As Represented By The Secretary Of The Navy Mixed polymer electrolyte and mixed polymer electrolyte battery
CA2065581C (en) 1991-04-22 2002-03-12 Andal Corp. Plasma enhancement apparatus and method for physical vapor deposition
SE468305B (en) 1991-04-24 1992-12-14 Moelnlycke Ab Foerfarande and apparatus PROGRAM TO paafoera particles PAA a loepande web
US5171413A (en) 1991-09-16 1992-12-15 Tufts University Methods for manufacturing solid state ionic devices
US5482611A (en) 1991-09-30 1996-01-09 Helmer; John C. Physical vapor deposition employing ion extraction from a plasma
US5203944A (en) * 1991-10-10 1993-04-20 Prinz Fritz B Method for fabrication of three-dimensional articles by thermal spray deposition using masks as support structures
JP3118037B2 (en) 1991-10-28 2000-12-18 キヤノン株式会社 The deposited film forming method and a deposited film forming apparatus
US5261968A (en) 1992-01-13 1993-11-16 Photon Energy, Inc. Photovoltaic cell and method
US5494762A (en) 1992-01-16 1996-02-27 Nippondenso Co., Ltd. Non-aqueous electrolyte lithium secondary cell
US5248349A (en) 1992-05-12 1993-09-28 Solar Cells, Inc. Process for making photovoltaic devices and resultant product
US6741178B1 (en) 1992-06-17 2004-05-25 Micron Technology, Inc Electrically powered postage stamp or mailing or shipping label operative with radio frequency (RF) communication
DE4345610B4 (en) 1992-06-17 2013-01-03 Micron Technology Inc. A method for manufacturing a radio frequency identification device (RFID)
US5776278A (en) 1992-06-17 1998-07-07 Micron Communications, Inc. Method of manufacturing an enclosed transceiver
US5338625A (en) 1992-07-29 1994-08-16 Martin Marietta Energy Systems, Inc. Thin film battery and method for making same
US5426561A (en) 1992-09-29 1995-06-20 The United States Of America As Represented By The United States National Aeronautics And Space Administration High energy density and high power density ultracapacitors and supercapacitors
US5414025A (en) 1992-09-30 1995-05-09 The Penn State Research Foundation Method of crosslinking of solid state battery electrolytes by ultraviolet radiation
US5273837A (en) 1992-12-23 1993-12-28 Corning Incorporated Solid electrolyte fuel cells
US5863337A (en) 1993-02-16 1999-01-26 Ppg Industries, Inc. Apparatus for coating a moving glass substrate
TW271490B (en) 1993-05-05 1996-03-01 Varian Associates
US5501175A (en) 1993-07-02 1996-03-26 Sumitomo Electric Industries, Ltd. Process for preparing high crystallinity oxide thin film
US5433096A (en) 1993-08-26 1995-07-18 Strattec Security Corporation Key assembly for vehicle ignition locks
DE4331216A1 (en) 1993-09-15 1995-03-16 Sel Alcatel Ag Mobile telephone
US5314765A (en) 1993-10-14 1994-05-24 Martin Marietta Energy Systems, Inc. Protective lithium ion conducting ceramic coating for lithium metal anodes and associate method
US5558953A (en) 1993-10-21 1996-09-24 Matsushita Electric Industrial Co., Ltd. Electrocrystallized lithuim metal, method for producing the same, and lithium secondary battery
US5714404A (en) 1993-11-18 1998-02-03 Regents Of The University Of California Fabrication of polycrystalline thin films by pulsed laser processing
US5985485A (en) 1993-11-19 1999-11-16 Ovshinsky; Stanford R. Solid state battery having a disordered hydrogenated carbon negative electrode
US5387482A (en) 1993-11-26 1995-02-07 Motorola, Inc. Multilayered electrolyte and electrochemical cells used same
US5549989A (en) 1993-12-20 1996-08-27 Motorola, Inc. Electrochemical capacitor having a proton conducting solid electrolyte
JP3571785B2 (en) 1993-12-28 2004-09-29 キヤノン株式会社 Deposited film forming method and a deposited film forming apparatus
US5569520A (en) 1994-01-12 1996-10-29 Martin Marietta Energy Systems, Inc. Rechargeable lithium battery for use in applications requiring a low to high power output
US5648187A (en) 1994-02-16 1997-07-15 Moltech Corporation Stabilized anode for lithium-polymer batteries
US5426005A (en) 1994-02-18 1995-06-20 Motorola, Inc. Interpenetrating polymer network electrolytes and electrochemical cells using same
US5561004A (en) 1994-02-25 1996-10-01 Bates; John B. Packaging material for thin film lithium batteries
US5914507A (en) 1994-05-11 1999-06-22 Regents Of The University Of Minnesota PZT microdevice
US5411592A (en) 1994-06-06 1995-05-02 Ovonic Battery Company, Inc. Apparatus for deposition of thin-film, solid state batteries
US5445126A (en) 1994-06-24 1995-08-29 Eaton Corporation Accelerator pedal calibration and fault detection
US5654111A (en) 1994-06-28 1997-08-05 Sony Corporation Electronic device having a battery and a battery therefor
US5393572A (en) 1994-07-11 1995-02-28 Southwest Research Institute Ion beam assisted method of producing a diamond like carbon coating
US5654084A (en) 1994-07-22 1997-08-05 Martin Marietta Energy Systems, Inc. Protective coatings for sensitive materials
US5529671A (en) 1994-07-27 1996-06-25 Litton Systems, Inc. Apparatus and method for ion beam polishing and for in-situ ellipsometric deposition of ion beam films
US5503948A (en) * 1994-08-02 1996-04-02 Microelectronics And Computer Technology Corporation Thin cell electrochemical battery system; and method of interconnecting multiple thin cells
US5445906A (en) 1994-08-03 1995-08-29 Martin Marietta Energy Systems, Inc. Method and system for constructing a rechargeable battery and battery structures formed with the method
US5528222A (en) 1994-09-09 1996-06-18 International Business Machines Corporation Radio frequency circuit and memory in thin flexible package
US5830331A (en) 1994-09-23 1998-11-03 Seagate Technology, Inc. Apparatus and method for sputtering carbon
US5585999A (en) 1994-09-30 1996-12-17 The United States Of America As Represented By The Secretary Of The Air Force Supercapacitor electrochemical cell
US5621607A (en) 1994-10-07 1997-04-15 Maxwell Laboratories, Inc. High performance double layer capacitors including aluminum carbon composite electrodes
US5695885A (en) 1994-10-14 1997-12-09 Texas Instruments Incorporated External battery and photoyoltaic battery charger
US5425966A (en) 1994-10-27 1995-06-20 Wayne State University Process for coating with single source precursors
US5523179A (en) 1994-11-23 1996-06-04 Polyplus Battery Company Rechargeable positive electrode
US5686201A (en) 1994-11-23 1997-11-11 Polyplus Battery Company, Inc. Rechargeable positive electrodes
US6025094A (en) 1994-11-23 2000-02-15 Polyplus Battery Company, Inc. Protective coatings for negative electrodes
US6955866B2 (en) 1998-09-03 2005-10-18 Polyplus Battery Company Coated lithium electrodes
US5582623A (en) 1994-11-23 1996-12-10 Polyplus Battery Company, Inc. Methods of fabricating rechargeable positive electrodes
US5814420A (en) 1994-11-23 1998-09-29 Polyplus Battery Company, Inc. Rechargeable positive electrodes
US6017651A (en) 1994-11-23 2000-01-25 Polyplus Battery Company, Inc. Methods and reagents for enhancing the cycling efficiency of lithium polymer batteries
US5510209A (en) 1995-01-05 1996-04-23 Eic Laboratories, Inc. Solid polymer electrolyte-based oxygen batteries
NL1000139C2 (en) 1995-04-13 1996-10-15 Od & Me Bv Magnetron sputtering system.
US5872080A (en) 1995-04-19 1999-02-16 The Regents Of The University Of California High temperature superconducting thick films
US5695873A (en) 1995-06-05 1997-12-09 The University Of Dayton Polymer-ceramic composite electrolytes
US5501924A (en) 1995-06-07 1996-03-26 Eveready Battery Company, Inc. Alkaline cell having a cathode including a tin dioxide additive
US5622652A (en) 1995-06-07 1997-04-22 Img Group Limited Electrically-conductive liquid for directly printing an electrical circuit component onto a substrate, and a method for making such a liquid
US5599644A (en) 1995-06-07 1997-02-04 Eveready Battery Company, Inc. Cathodes for electrochemical cells having additives
US5569564A (en) 1995-06-07 1996-10-29 Eveready Battery Company, Inc. Alkaline cell having a cathode including a titanate additive
US5626976A (en) 1995-07-24 1997-05-06 Motorola, Inc. Flexible energy storage device with integral charging unit
GB2305075A (en) 1995-09-05 1997-03-26 Ibm Radio Frequency Tag for Electronic Apparatus
US6608464B1 (en) 1995-12-11 2003-08-19 The Johns Hopkins University Integrated power source layered with thin film rechargeable batteries, charger, and charge-control
US5644207A (en) 1995-12-11 1997-07-01 The Johns Hopkins University Integrated power source
TW330341B (en) 1996-01-19 1998-04-21 Murada Seisakusho Kk Metallic thin film and method of manufacturing the same and surface acoustic wave device using the metallic thin film and the same thereof
FR2746934B1 (en) 1996-03-27 1998-05-07 Saint Gobain Vitrage electrochemical device
US5925483A (en) 1996-05-06 1999-07-20 Kejha; Joseph B. Multi-layer polymeric electrolytes for electrochemical devices
US6001715A (en) 1996-06-26 1999-12-14 The United States Of America As Represented By The Secretary Of The Navy Non-thermal process for annealing crystalline materials
US5849426A (en) 1996-09-20 1998-12-15 Motorola, Inc. Hybrid energy storage system
JP3111909B2 (en) 1996-09-27 2000-11-27 松下電器産業株式会社 Mobile telephone
GB2318127B (en) 1996-10-10 2001-03-07 Gen Vacuum Equipment Ltd A vacuum process and apparatus for depositing lithium/lithium nitride coating on flexiible moving web
US5932284A (en) 1996-10-11 1999-08-03 Kimberly-Clark Worldwide, Inc. Method of applying adhesive to an edge of moving web
US5853916A (en) 1996-10-28 1998-12-29 Motorola, Inc. Multi-layered polymeric gel electrolyte and electrochemical cell using same
US5978207A (en) 1996-10-30 1999-11-02 The Research Foundation Of The State University Of New York Thin film capacitor
JP3303694B2 (en) 1996-12-17 2002-07-22 三菱電機株式会社 A lithium ion secondary battery and a manufacturing method thereof
US5842118A (en) 1996-12-18 1998-11-24 Micron Communications, Inc. Communication system including diversity antenna queuing
TW399029B (en) 1996-12-25 2000-07-21 Sony Corp Graphite powder suitable for negative electrode material of lithium ion secondary batteries
US5705293A (en) 1997-01-09 1998-01-06 Lockheed Martin Energy Research Corporation Solid state thin film battery having a high temperature lithium alloy anode
AU719341B2 (en) 1997-01-22 2000-05-04 De Nora Elettrodi S.P.A. Method of forming robust metal, metal oxide, and metal alloy layers on ion-conductive polymer membranes
US5935727A (en) 1997-04-10 1999-08-10 The Dow Chemical Company Solid oxide fuel cells
US6599580B2 (en) 1997-05-01 2003-07-29 Wilson Greatbatch Ltd. Method for improving electrical conductivity of a metal oxide layer on a substrate utilizing high energy beam mixing
JPH1131520A (en) 1997-05-13 1999-02-02 Mazda Motor Corp Solid high molecular type fuel cell
US6042687A (en) 1997-06-30 2000-03-28 Lam Research Corporation Method and apparatus for improving etch and deposition uniformity in plasma semiconductor processing
US6238813B1 (en) 1997-07-25 2001-05-29 Cardiac Pacemakers, Inc. Battery system for implantable medical device
US6086962A (en) 1997-07-25 2000-07-11 Diamonex, Incorporated Method for deposition of diamond-like carbon and silicon-doped diamond-like carbon coatings from a hall-current ion source
US6056857A (en) 1997-08-13 2000-05-02 Praxair S.T. Technology, Inc. Cryogenic annealing of sputtering targets
US5982284A (en) 1997-09-19 1999-11-09 Avery Dennison Corporation Tag or label with laminated thin, flat, flexible device
US6110620A (en) 1997-09-30 2000-08-29 Eveready Battery Company, Inc. Controlled crystallite size electrode
US6982132B1 (en) 1997-10-15 2006-01-03 Trustees Of Tufts College Rechargeable thin film battery and method for making the same
US6094292A (en) 1997-10-15 2000-07-25 Trustees Of Tufts College Electrochromic window with high reflectivity modulation
US6136165A (en) 1997-11-26 2000-10-24 Cvc Products, Inc. Apparatus for inductively-coupled-plasma-enhanced ionized physical-vapor deposition
US6222117B1 (en) 1998-01-05 2001-04-24 Canon Kabushiki Kaisha Photovoltaic device, manufacturing method of photovoltaic device, photovoltaic device integrated with building material and power-generating apparatus
US6402795B1 (en) 1998-02-18 2002-06-11 Polyplus Battery Company, Inc. Plating metal negative electrodes under protective coatings
US6072801A (en) 1998-02-19 2000-06-06 Micron Technology, Inc. Method of addressing messages, method of establishing wireless communications, and communications system
US6203944B1 (en) 1998-03-26 2001-03-20 3M Innovative Properties Company Electrode for a lithium battery
JP4379925B2 (en) 1998-04-21 2009-12-09 ソニー株式会社 Graphite powder suitable for a negative electrode material of a lithium ion secondary battery
JP4092669B2 (en) * 1998-04-27 2008-05-28 ソニー株式会社 Solid electrolyte secondary battery
US6147354A (en) 1998-07-02 2000-11-14 Maishev; Yuri Universal cold-cathode type ion source with closed-loop electron drifting and adjustable ionization gap
US6002208A (en) 1998-07-02 1999-12-14 Advanced Ion Technology, Inc. Universal cold-cathode type ion source with closed-loop electron drifting and adjustable ion-emitting slit
JP3257516B2 (en) 1998-07-23 2002-02-18 日本電気株式会社 Stacked electrolyte and a battery using the
US6264709B1 (en) 1998-08-21 2001-07-24 Korea Institute Of Science And Tech. Method for making electrical and electronic devices with vertically integrated and interconnected thin-film type battery
US6133159A (en) 1998-08-27 2000-10-17 Micron Technology, Inc. Methods for preparing ruthenium oxide films
US6181545B1 (en) 1998-09-24 2001-01-30 Telcordia Technologies, Inc. Supercapacitor structure
US6130507A (en) 1998-09-28 2000-10-10 Advanced Ion Technology, Inc Cold-cathode ion source with propagation of ions in the electron drift plane
US7297441B2 (en) * 1998-10-23 2007-11-20 Sony Corporation Nonaqueous-electrolyte secondary battery
US6395043B1 (en) 1998-11-25 2002-05-28 Timer Technologies, Llc Printing electrochemical cells with in-line cured electrolyte
US6163260A (en) 1998-12-10 2000-12-19 Intermec Ip Corp. Linerless label tracking system
US6866901B2 (en) 1999-10-25 2005-03-15 Vitex Systems, Inc. Method for edge sealing barrier films
JP2000188113A (en) 1998-12-24 2000-07-04 Torai Onitsukusu Kk Totally solid lithium ion battery and its manufacture
US6153067A (en) 1998-12-30 2000-11-28 Advanced Ion Technology, Inc. Method for combined treatment of an object with an ion beam and a magnetron plasma with a combined magnetron-plasma and ion-beam source
US6037717A (en) 1999-01-04 2000-03-14 Advanced Ion Technology, Inc. Cold-cathode ion source with a controlled position of ion beam
US6236061B1 (en) 1999-01-08 2001-05-22 Lakshaman Mahinda Walpita Semiconductor crystallization on composite polymer substrates
EP1039552B1 (en) 1999-02-25 2010-05-12 Kaneka Corporation Thin-film photoelectric conversion device and sputtering-deposition method
US6280875B1 (en) 1999-03-24 2001-08-28 Teledyne Technologies Incorporated Rechargeable battery structure with metal substrate
JP2000285929A (en) 1999-03-31 2000-10-13 Sony Corp Solid electrolyte battery
US6168884B1 (en) 1999-04-02 2001-01-02 Lockheed Martin Energy Research Corporation Battery with an in-situ activation plated lithium anode
US6261693B1 (en) 1999-05-03 2001-07-17 Guardian Industries Corporation Highly tetrahedral amorphous carbon coating on glass
US6413676B1 (en) 1999-06-28 2002-07-02 Lithium Power Technologies, Inc. Lithium ion polymer electrolytes
US6181237B1 (en) 1999-08-17 2001-01-30 Lucent Technologies Inc. Method and apparatus for generating pressure based alerting signals
US6391664B1 (en) 1999-09-29 2002-05-21 Advanced Micro Devices, Inc. Selectively activatable solar cells for integrated circuit analysis
DE19948742C1 (en) 1999-10-09 2000-12-28 Dornier Gmbh Electrochemical capacitor used e.g. in telecommunications consists of single cell(s) with electrodes formed of an electrically conducting or semiconducting nano-structured film
DE19949605A1 (en) 1999-10-15 2001-04-19 Bosch Gmbh Robert Acceleration sensor for car air bag control has micromachined stop bars prevents misfunction due to perpendicular acceleration
US6413285B1 (en) 1999-11-01 2002-07-02 Polyplus Battery Company Layered arrangements of lithium electrodes
US6399489B1 (en) 1999-11-01 2002-06-04 Applied Materials, Inc. Barrier layer deposition using HDP-CVD
US6327909B1 (en) 1999-11-30 2001-12-11 Xerox Corporation Bistable mechanical sensors capable of threshold detection and automatic elimination of excessively high amplitude data
US6576365B1 (en) 1999-12-06 2003-06-10 E.C.R. - Electro Chemical Research Ltd. Ultra-thin electrochemical energy storage devices
US6475854B2 (en) 1999-12-30 2002-11-05 Applied Materials, Inc. Method of forming metal electrodes
KR100515571B1 (en) * 2000-02-08 2005-09-20 주식회사 엘지화학 Stacked electrochemical cell
US6281795B1 (en) 2000-02-08 2001-08-28 Moore North America, Inc. RFID or EAS label mount with double sided tape
AU5289001A (en) 2000-03-02 2001-09-12 Microchips Inc Microfabricated devices for the storage and selective exposure of chemicals and devices
EP1275168A2 (en) 2000-03-24 2003-01-15 Cymbet Corporation Method and apparatus for integrated-battery devices
US6645656B1 (en) 2000-03-24 2003-11-11 University Of Houston Thin film solid oxide fuel cell and method for forming
WO2001093363A2 (en) * 2000-05-26 2001-12-06 Covalent Associates, Inc. Non-flammable electrolytes
IL153121D0 (en) 2000-06-02 2003-06-24 Stanford Res Inst Int Polymer composition
US6749648B1 (en) * 2000-06-19 2004-06-15 Nanagram Corporation Lithium metal oxides
US6432577B1 (en) 2000-06-29 2002-08-13 Sandia Corporation Apparatus and method for fabricating a microbattery
US6402796B1 (en) 2000-08-07 2002-06-11 Excellatron Solid State, Llc Method of producing a thin film battery
US20020110733A1 (en) 2000-08-07 2002-08-15 Johnson Lonnie G. Systems and methods for producing multilayer thin film energy storage devices
FR2818808B1 (en) 2000-12-22 2006-07-14 Commissariat Energie Atomique Fuel cell for powering electronic devices, including laptops
US6558836B1 (en) 2001-02-08 2003-05-06 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Structure of thin-film lithium microbatteries
US7075436B2 (en) 2001-02-12 2006-07-11 Symbol Technologies, Inc. Method, system, and apparatus for binary traversal of a tag population
US7094500B2 (en) * 2001-04-24 2006-08-22 Matsushita Electric Industrial Co., Ltd. Secondary battery
US20030007894A1 (en) 2001-04-27 2003-01-09 Genoptix Methods and apparatus for use of optical forces for identification, characterization and/or sorting of particles
US6991662B2 (en) 2001-09-10 2006-01-31 Polyplus Battery Company Encapsulated alloy electrodes
FR2831318B1 (en) 2001-10-22 2006-06-09 Commissariat Energie Atomique Energy storage device has fast charge in the form of thin films
FR2831331B1 (en) 2001-10-22 2004-11-19 Commissariat Energie Atomique Method for producing a microbattery
FR2831327B1 (en) 2001-10-22 2004-06-25 Commissariat Energie Atomique micro or nano-electronic component comprising a source of energy and means for protecting the energy source
FR2832549B1 (en) 2001-11-16 2004-05-28 Commissariat Energie Atomique Fuel cell has high surface area and low volume and process for its manufacturing
US6897164B2 (en) 2002-02-14 2005-05-24 3M Innovative Properties Company Aperture masks for circuit fabrication
US6821348B2 (en) 2002-02-14 2004-11-23 3M Innovative Properties Company In-line deposition processes for circuit fabrication
US20030151118A1 (en) 2002-02-14 2003-08-14 3M Innovative Properties Company Aperture masks for circuit fabrication
US20030171984A1 (en) 2002-03-06 2003-09-11 Wodka Joseph F. Customization of promotional material through use of programmable radio frequency identification technology
FR2838870B1 (en) 2002-04-23 2004-05-28 Commissariat Energie Atomique Element stack base fuel limiting the crossing of the electrolyte with methanol
US6610971B1 (en) 2002-05-07 2003-08-26 The United States Of America As Represented By The Secretary Of The Navy Ship self-defense missile weapon system
US6818356B1 (en) 2002-07-09 2004-11-16 Oak Ridge Micro-Energy, Inc. Thin film battery and electrolyte therefor
US6770176B2 (en) * 2002-08-02 2004-08-03 Itn Energy Systems. Inc. Apparatus and method for fracture absorption layer
CA2502438C (en) 2002-10-15 2011-11-29 Polyplus Battery Company Ionically conductive composites for protection of active metal anodes
US7072697B2 (en) 2002-10-22 2006-07-04 Nokia Corporation Method and device for transponder aided wake-up of a low power radio device by a wake-up event
JP4135469B2 (en) * 2002-10-30 2008-08-20 日産自動車株式会社 Polymer battery, the battery pack and the vehicle
US7135979B2 (en) 2002-11-14 2006-11-14 Brady Worldwide, Inc. In-mold radio frequency identification device label
KR100682883B1 (en) 2002-11-27 2007-02-15 삼성전자주식회사 Solid electrolyte and battery employing the same
US6906436B2 (en) 2003-01-02 2005-06-14 Cymbet Corporation Solid state activity-activated battery device and method
US7603144B2 (en) 2003-01-02 2009-10-13 Cymbet Corporation Active wireless tagging system on peel and stick substrate
US7294209B2 (en) 2003-01-02 2007-11-13 Cymbet Corporation Apparatus and method for depositing material onto a substrate using a roll-to-roll mask
US20040131760A1 (en) 2003-01-02 2004-07-08 Stuart Shakespeare Apparatus and method for depositing material onto multiple independently moving substrates in a chamber
JP2005044663A (en) 2003-07-23 2005-02-17 Sony Corp Solid electrolyte, lithium ion battery, and its manufacturing method
US20050079418A1 (en) 2003-10-14 2005-04-14 3M Innovative Properties Company In-line deposition processes for thin film battery fabrication
FR2860925A1 (en) 2003-10-14 2005-04-15 Commissariat Energie Atomique Microbattery includes a first electrode and electrolyte comprising a material with a tetrahedral structure with a central atom of phosphorus, boron, silicon, sulfur, molybdenum, vanadium or germanium
US7211351B2 (en) 2003-10-16 2007-05-01 Cymbet Corporation Lithium/air batteries with LiPON as separator and protective barrier and method
FR2862436B1 (en) 2003-11-14 2006-02-10 Commissariat Energie Atomique Micro-lithium battery provided with a protective casing and method for manufacturing such a micro-battery
FR2862437B1 (en) 2003-11-14 2006-02-10 Commissariat Energie Atomique Method of manufacturing a micro-lithium battery
US7691536B2 (en) * 2004-02-20 2010-04-06 Excellatron Solid State, Llc Lithium oxygen batteries and method of producing same
WO2005086979A2 (en) 2004-03-11 2005-09-22 Oleinick Energy, Llc Photovoltaic-embedded surface
US7129844B2 (en) 2004-07-29 2006-10-31 Hewlett-Packard Development Company, L.P. Remote communications devices, wireless communications systems, remote communications device operable methods, and retail monitoring methods
FR2874128B1 (en) 2004-08-03 2006-10-13 Commissariat Energie Atomique Microbattery with through connections and method of making such a microbattery
FR2880197B1 (en) 2004-12-23 2007-02-02 Commissariat Energie Atomique Electrolyte structure for microbattery
US7727293B2 (en) 2005-02-25 2010-06-01 SOCIéTé BIC Hydrogen generating fuel cell cartridges
KR101387855B1 (en) * 2005-07-15 2014-04-22 사임베트 코퍼레이션 Thin-film batteries with soft and hard electrolyte layers and method
US20070012244A1 (en) 2005-07-15 2007-01-18 Cymbet Corporation Apparatus and method for making thin-film batteries with soft and hard electrolyte layers
JP6111828B2 (en) 2013-04-30 2017-04-12 ウシオ電機株式会社 Heat treatment apparatus
JP6196178B2 (en) 2014-03-18 2017-09-13 東洋ゴム工業株式会社 Method for producing an acid gas-containing gas treating separation membrane, and acid gas containing gas treating separation membrane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE36843E (en) * 1993-06-21 2000-08-29 Micron Technology, Inc. Polymer-lithium batteries and improved methods for manufacturing batteries
US6420071B1 (en) * 2000-03-21 2002-07-16 Midwest Research Institute Method for improving the durability of ion insertion materials
US6465121B1 (en) * 2000-08-30 2002-10-15 Lev M. Dawson Method for distributing electrolyte in batteries
US7776478B2 (en) * 2005-07-15 2010-08-17 Cymbet Corporation Thin-film batteries with polymer and LiPON electrolyte layers and method

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8623557B2 (en) 1999-11-23 2014-01-07 Sion Power Corporation Lithium anodes for electrochemical cells
US20080014501A1 (en) * 1999-11-23 2008-01-17 Skotheim Terje A Lithium anodes for electrochemical cells
US9397342B2 (en) 1999-11-23 2016-07-19 Sion Power Corporation Lithium anodes for electrochemical cells
US20110014524A1 (en) * 1999-11-23 2011-01-20 Sion Power Corporation Protection of anodes for electrochemical cells
US20110159376A1 (en) * 1999-11-23 2011-06-30 Sion Power Corporation Protection of anodes for electrochemical cells
US9065149B2 (en) 1999-11-23 2015-06-23 Sion Power Corporation Lithium anodes for electrochemical cells
US10069146B2 (en) 1999-11-23 2018-09-04 Sion Power Corporation Lithium anodes for electrochemical cells
US20060222954A1 (en) * 1999-11-23 2006-10-05 Skotheim Terje A Lithium anodes for electrochemical cells
US8415054B2 (en) 1999-11-23 2013-04-09 Sion Power Corporation Lithium anodes for electrochemical cells
US8753771B2 (en) 1999-11-23 2014-06-17 Sion Power Corporation Lithium anodes for electrochemical cells
US8728661B2 (en) 1999-11-23 2014-05-20 Sion Power Corporation Lithium anodes for electrochemical cells
US9653735B2 (en) 1999-11-23 2017-05-16 Sion Power Corporation Lithium anodes for electrochemical cells
US8338034B2 (en) 2006-03-22 2012-12-25 Sion Power Corporation Electrode protection in both aqueous and non-aqueous electrochemical cells, including rechargeable lithium batteries
US8603680B2 (en) 2006-03-22 2013-12-10 Sion Power Corporation Electrode protection in both aqueous and non-aqueous electrochemical cells, including rechargeable lithium batteries
US9040201B2 (en) 2006-03-22 2015-05-26 Sion Power Corporation Electrode protection in both aqueous and non-aqueous electrochemical cells, including rechargeable lithium batteries
US20100129699A1 (en) * 2006-12-04 2010-05-27 Mikhaylik Yuriy V Separation of electrolytes
US8617748B2 (en) 2006-12-04 2013-12-31 Sion Power Corporation Separation of electrolytes
US20110294015A1 (en) * 2010-05-25 2011-12-01 Robert Bosch Gmbh Method and Apparatus for Production of a Thin-Film Battery
US9941507B2 (en) * 2010-05-25 2018-04-10 Robert Bosch Gmbh Method and apparatus for production of a thin-film battery
US20130130085A1 (en) * 2010-07-22 2013-05-23 University Of Central Florida Research Foundation, Inc. Alkali metal-cathode solution battery
US8883339B2 (en) * 2010-07-22 2014-11-11 University Of Central Florida Research Foundation, Inc. Alkali metal-cathode solution battery
US9548492B2 (en) 2011-06-17 2017-01-17 Sion Power Corporation Plating technique for electrode
US9040197B2 (en) 2011-10-13 2015-05-26 Sion Power Corporation Electrode structure and method for making the same
US8936870B2 (en) 2011-10-13 2015-01-20 Sion Power Corporation Electrode structure and method for making the same
US20120058380A1 (en) * 2011-11-09 2012-03-08 Sakti3, Inc. Monolithically integrated thin-film solid state lithium battery device having multiple layers of lithium electrochemical cells
WO2013134114A3 (en) * 2012-03-04 2014-06-12 Indiana University Research And Technology Center Method and apparatus for extracting energy and metal from seawater electrodes
WO2013134114A2 (en) * 2012-03-04 2013-09-12 Indiana University Research And Technology Center Method and apparatus for extracting energy and metal from seawater electrodes
US9005311B2 (en) 2012-11-02 2015-04-14 Sion Power Corporation Electrode active surface pretreatment
US9711770B2 (en) 2012-11-27 2017-07-18 Apple Inc. Laminar battery system
US10033029B2 (en) 2012-11-27 2018-07-24 Apple Inc. Battery with increased energy density and method of manufacturing the same
US9899661B2 (en) 2013-03-13 2018-02-20 Apple Inc. Method to improve LiCoO2 morphology in thin film batteries
US9570775B2 (en) 2013-03-15 2017-02-14 Apple Inc. Thin film transfer battery systems
US10141600B2 (en) 2013-03-15 2018-11-27 Apple Inc. Thin film pattern layer battery systems
US9887403B2 (en) 2013-03-15 2018-02-06 Apple Inc. Thin film encapsulation battery systems
US9601751B2 (en) 2013-03-15 2017-03-21 Apple Inc. Annealing method for thin film electrodes
CN105051954A (en) * 2013-03-15 2015-11-11 苹果公司 Thin film encapsulation battery systems
WO2015054040A1 (en) 2013-10-07 2015-04-16 Scherson Daniel Electrochemical method and apparatus for forming a vacuum in a sealed enclosure
US9863055B2 (en) 2013-10-07 2018-01-09 Daniel A. Scherson Electrochemical method and apparatus for forming a vacuum in a sealed enclosure
WO2017165338A1 (en) * 2016-03-21 2017-09-28 Scherson Daniel Electrochemical method and apparatus for consuming gases

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