WO2001018890A1 - Chargeable electrochemical cell - Google Patents

Chargeable electrochemical cell Download PDF

Info

Publication number
WO2001018890A1
WO2001018890A1 PCT/IL2000/000528 IL0000528W WO0118890A1 WO 2001018890 A1 WO2001018890 A1 WO 2001018890A1 IL 0000528 W IL0000528 W IL 0000528W WO 0118890 A1 WO0118890 A1 WO 0118890A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
cell according
cell
active material
flexible
Prior art date
Application number
PCT/IL2000/000528
Other languages
English (en)
French (fr)
Inventor
Vladimir Kliatzkin
Original Assignee
Unibat Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unibat Ltd. filed Critical Unibat Ltd.
Priority to EP00956761A priority Critical patent/EP1238437A4/en
Priority to AU68623/00A priority patent/AU6862300A/en
Priority to JP2001522612A priority patent/JP2003509818A/ja
Publication of WO2001018890A1 publication Critical patent/WO2001018890A1/en

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • HELECTRICITY
    • H01ELECTRIC 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/24Alkaline accumulators
    • H01M10/28Construction or manufacture
    • HELECTRICITY
    • H01ELECTRIC 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
    • H01M4/70Carriers or collectors characterised by shape or form
    • H01M4/76Containers for holding the active material, e.g. tubes, capsules
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/102Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105Pouches or flexible bags
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/449Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463Separators, membranes or diaphragms characterised by their shape
    • H01M50/466U-shaped, bag-shaped or folded
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • H01M10/12Construction or manufacture
    • HELECTRICITY
    • H01ELECTRIC 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
    • H01M2004/021Physical characteristics, e.g. porosity, surface area
    • HELECTRICITY
    • H01ELECTRIC 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
    • H01M4/663Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50Current conducting connections for cells or batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00Primary cells; Manufacture thereof
    • H01M6/04Cells with aqueous electrolyte
    • H01M6/06Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/10Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with wound or folded electrodes
    • 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to a flexible design for accumulators, fuel cells and electrolyzers based on super light and super strong conductive and msulative materials in the form of special woven fabrics
  • This design can withstand very heavy overloads (property weight) at high accelerations of up to 50,000 g
  • insulation and cell materials which can be provided in a monolithic design
  • This kind of design can withstand accelerations of up to 55,000 g, i e , known products including artillery shells
  • the large decrease (10-50 times) in distance between electrodes in lead-acid accumulators with the resulting decrease in internal resistance of the accumulator (principal part of internal accumulator resistance) creates an element with high electrical efficiency
  • the active material used permits realization of deep charge-discharge cycles - twice that of accumulators with semi-rigid electrodes- and realized capacity of accumulator at multicycle work
  • a specific electrode material layout permits using pairs of electrode materials with dendnte problems
  • metals also have high active surface areas.
  • a specific surface area of special electrodes such as porous electrodes or slurry or powder electrodes, is advantageous and may be used with or without a catalytic plate.
  • Some electrode pairs such as zinc - silver, also have dendrite problems. As a result, dendrite induced short circuits limit the number of cycles during the life of a rechargeable battery.
  • An object of this invention is to decrease the weight and increase the strength of accumulator, fuel cell and electrolyzer electrodes.
  • a design using carbon paper is described in U.S. Patent 4,894,355 which proposes to decrease the active surface area by cutting the ends of the fibers which consist of a carbon paper/polytetraflouroethylene composition.
  • the main load of design takes carbon carrier material - paper, and conductivity parameters, determines thickness and span of electrode.
  • One object of this invention is to combine in one unit conductivity or insulation parameters with a high strength/low weight ratio.
  • Active and/or catalytic materials may be used in plate (catalytic fuel cell or electrolyser) or in friable form (accumulator). Friable materials permit a better use of the chemically active material without weakening the electrode's structure.
  • the efficiency of the electrodes is increased as a result of enhanced intergranular contact induced by an external or internal spring or spring-like element and/or by the battery's outer casing. The invention unifies these parameters and as a result there is a decrease in weight per discharged energy.
  • the battery cell comprises an external or internal flexible envelope or flat layer in which a flat, electrically conductive, flexible wire or fabric grid is embedded in a matrix of granular or powder particles of an active material.
  • Another envelope is also present containing an electrically conducting wire or fabric grid on which grains or particles of a complementary active metal or compound are positioned.
  • the envelopes are separated by an insulating membrane which is permeable to the ions of a suitable electrolyte.
  • There is also a flexible mechanical spring or electrolyte swelling element that supplies the required pressure to counteract the electrode's volume changes resulting from the chemical reaction in the cell.
  • the active material can be placed in a membrane bag or between sheets.
  • the grains of active material can be fixed in position as distinct units by welding the cover.
  • the present invention provides a means for applying pressure to the external surface of the assembled cell, ensuring close contact between the granular or powder particles and between the particles and the electrode during charging and discharging. This contact is maintained despite significant volume changes of the active material during the reaction.
  • Various pairs of metals or compounds can be used, such as Ag/Zn, Pb/PbO, etc.
  • the electrodes can be fabricated in the form of lengthy ribbons which are then rolled into a spiral configuration.
  • a spring or spring-like means to apply pressure to the external surface of the electrodes and to fabricate the cells in cylindrical form.
  • the spring or spring-like element may be an entirely separate element included in the battery or associated with a swelling separator.
  • the flexibility of the battery cell's walls can function as the spring element.
  • a separate spring element is best suited for flat batteries where ceil wall height is limited.
  • the side walls of the cell are best suited to serve as the spring element when the cell has a cubic, or at least rectangular, shape.
  • Flexible outer cylindrical containers can function as the spring element for cells with helical electrodes.
  • the powder or grains of the active material are preferably in the 5 to 10 micron range, although other sizes can be used.
  • the sheet grids may be made from expanded metals, such as silver (for Ag-Zn element). These are manufactured from expanded metal foil relevant to the active material of the cathode or anode. Conductive fabric thickness is
  • the fabric can be woven from carbon fibers.
  • Conductive materials may be coated with suitable metals, the exact metal depending on the nature of the electrochemical couple in the cell and the environment in which the cell operates.
  • the conducive thread may also be used in combination with non-conductive fibers.
  • a plurality of parallel carbon fibers interwoven with fibers of Kevlar, nylon, polyester, etc. can be used.
  • the configuration may be one in which each carbon fiber constitutes an electrode. It is clear that the carbon fibers must be connected and a conductor lead provided for the current output.
  • a modification of the invention based on the same concept comprises fuel cells in which each membrane bag contains catalyst particles preferably attached to a suitable support.
  • the catalyst may be in the form of ceramic particles coated with an active material, such as Ni, Pt or Cd.
  • a suitable acid can serve as a catalyst in the fuel cell with oxygen and hydrogen reacting to form water and produce electric current. Suitable electrode connections are provided for current uptake. In the case of fuel cells, no external pressure on the cell is required.
  • a catalyst may be directly plated on the carbon fibers increasing the active surface area. Due to the thin elements of the electrochemical cells, the weight to power
  • a high energy, high speed chargeable battery cell can be produced when
  • electrodes According to this invention, electrodes, connection elements and cell
  • walls are made from high-strength, conductive or insulative fibers/fabrics,
  • the conductive part of electrodes may be used as the conductive part of electrodes while for the insulative parts, nylon, polyester, Kevlar or glass fibers can be used.
  • nylon, polyester, Kevlar or glass fibers can be used.
  • insulative material depends on the electrolyte chosen.
  • Parts should be designed to obtain stable electrical contact, resulting
  • Suitable designs can include:
  • Electrodes, insulation elements, spring and outer cell casing made of
  • Electrodes and insulation elements in one unit One piece of fabric
  • the active area per unit weight in this case is 1875 cm 2 /g about 1100 times greater than a solid surface.
  • Additional specifications include conductivity cross-section per span distance, 0.0157 cm 2 /cm, electrical resistance, 0.4 - 0.5 o m * mm 2 , and a permissible stress of 50 kg/mm 2 given a fabric density of 168 g/m 2 i.e. a maximum destroying length of 30 km.
  • lead has a value of 0.122 km, zinc 0.63 km and copper 2.263 km. Therefore, a coated graphite fiber electrode can withstand acceleration 15 times greater than a copper electrode and 300 times greater than a lead electrode for electrodes of equal lengths.
  • Figure 1 is a sectional view of the configuration of an accumulator of the
  • Figure 2 is a sectional view of the design of a Zn-Air accumulator cell or one with Zn - Ag pairs with anodes of the Zn - ZnO, Zn ⁇ AgO or Ag - ZnO slurry type
  • Figure 3 is a sectional view of a spiral design for an electrode couple.
  • Figure 4 illustrates a parallel or serial connection between cells.
  • Figure 5 illustrates a multicell, one-piece design of a special fabric.
  • Figure 6 illustrates multi-electrodes and multicells made from one piece of special fabric.
  • FIG. 1 is a sectional view of an example of a unit cell of fabric with central coaxially displaced conductive fabric elements.
  • Electrode conductive element 1 (cathode or anode) is a woven carbon fiber fabric. In this case, the fibers do not need special treatment to increase their microsurface.
  • Electrode housing 6 has a flat piece of conductive fabric 1 inserted into electrical insulation bag 5 filled with a zinc, lead or silver oxide slurry 2 on both sides of conductive element 1.
  • the electrode bag 6 and both layers of slurry 2 are pressed together by a spring and intake are in separate insulation chamber 5 made from electrolyte permeable insulating fabrics which represents an accumulator element.
  • FIG. 2 is a sectional view of a design of a unit cell of fabric. Electrode conductor 1 (cathode or anode) is woven from carbon fibers. Again, the fibers do not require special treatment to increase their surface area.
  • Electrode conductor 1 is made from a zinc, lead or silver oxide slurry 2.
  • Electrode bag 1 can be provided with lattice or diagonal seams 7 to prevent agglomeration of the slurry powder into a single piece. This helps to ensure an adequate powder distribution on the electrode surface.
  • the electrode bag and both intakes are in separate insulation chambers 3 made of electrolyte permeable insulating fabrics. The insulation chambers may be changed and divided into pieces of
  • the sewing threads may be made of insulating material.
  • a couple of these insulated electrodes (cathode and anode) have one
  • pair or set of electrode pairs may be held under pressure by spring elements 8
  • the electrode couple is located in a common shell 4 and constitutes a
  • Shell 4 may be produced from flexible or rigid plastic materials like
  • polyethylene polypropylene, polyurethane or PVC. This material may be
  • electrode ends 6 may be used for the electrical connection of the cell.
  • the shape of the electrode and its position in a battery cell may vary.
  • Electrolyte may be stored permanently in shell 4 or supplied periodically by special welding tubes.
  • Figure 3 is a sectional view of a spiral design for electrodes.
  • a pair of flexible electrodes 1 and 2 of the form shown in Figs. 1 or 2 are rolled into shaping a spiral and inserted into an elastic sleeve 3, the latter serving as a spring element
  • the rolled spiral with spring elements is inserted into outer housing 4.
  • the swelling separator and outer housing may also serve as the spring elements.
  • Figure 4 illustrates a connection 3 between cells 1 and 2 with the cells connected serially or in parallel.
  • Some electrode bags which are meant to be connected can be made from a single piece of conductive fabric. In such a case, all conventional connecting parts are excluded, decreasing accumulator weight and complexity and increasing reliability.
  • Figure 5 illustrates a one piece multi-electrode design which consists of a special fiber combination with a trim conductivity and insulation fiber or group of fibers, for use as electrode insulation or connecting elements.
  • This trim may be different for weft and warp, for different accumulator designs, or because of weave problems.
  • the one-piece multi-electrode design includes a conductive part of electrode 1 made from conductive fibers and an insulative part 2 made of insulative fibers. Conductive parts of fabrics may also be used in conjunction with cross conductive thread stripes, which can connect electrode parts.
  • connection may be preliminarily plated and welded.
  • the trim of conductive parts does not determine what kind of electrode (cathode or anode) may be connected and what type of connection, parallel or series, should be used.
  • a one piece multi-electrode fabric is a common element that permits different designs and electrical configurations of accumulators, fuel cells, or electrolyzers.
  • the fabric can be coated on one side with PVC, polyethylene, polypropylene or polyurethane, for welding with other layers of the design, and outer shell formation. In such a case, the conductive fibers must be first treated to permit adhesion to the coating material.
  • Figure 6 illustrates a design that can be realized with a multi-electrode one piece fabric.
  • This design is an example of a slurry electrode accumulator with serial connection of separate cells.
  • the design consists of two one-piece multi-electrode units 1 , separated by an electrolyte permeable fabric 2 that can be sewn or welded separately from the electrode design piece.
  • the welding seams position is in a form that provides insulation of separate cells formation with intake and outlet channels if a flow electrolyte system is used and permeability of outer space.
  • Electrode particle diameter 0.005-0.01mm
  • Silver electrode thickness 0.8 mm
  • Zinc electrode thickness 0.92 mm
  • Zinc electrode thickness 0.92 mm
  • Electrode particle diameter 0.005-0.01mm
  • Zinc electrode thickness 0.92 mm

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inert Electrodes (AREA)
  • Secondary Cells (AREA)
  • Hybrid Cells (AREA)
  • Cell Separators (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
PCT/IL2000/000528 1999-09-09 2000-09-04 Chargeable electrochemical cell WO2001018890A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP00956761A EP1238437A4 (en) 1999-09-09 2000-09-04 CHARGEABLE ELECTROCHEMICAL CELL
AU68623/00A AU6862300A (en) 1999-09-09 2000-09-04 Chargeable electrochemical cell
JP2001522612A JP2003509818A (ja) 1999-09-09 2000-09-04 充電可能な電気化学セル

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL131842 1999-09-09
IL131842A IL131842A (en) 1999-09-09 1999-09-09 Chargeable electrochemical cell

Publications (1)

Publication Number Publication Date
WO2001018890A1 true WO2001018890A1 (en) 2001-03-15

Family

ID=11073238

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IL2000/000528 WO2001018890A1 (en) 1999-09-09 2000-09-04 Chargeable electrochemical cell

Country Status (8)

Country Link
EP (1) EP1238437A4 (zh)
JP (1) JP2003509818A (zh)
KR (1) KR100861098B1 (zh)
CN (1) CN100449821C (zh)
AU (1) AU6862300A (zh)
IL (1) IL131842A (zh)
RU (1) RU2264004C2 (zh)
WO (1) WO2001018890A1 (zh)

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Publication number Priority date Publication date Assignee Title
WO2010050484A1 (ja) * 2008-10-27 2010-05-06 日産自動車株式会社 蓄電デバイス用複合電極、その製造方法及び蓄電デバイス
KR101821428B1 (ko) * 2009-12-24 2018-01-23 아크액티브 리미티드 납축전지 구조의 개선
JP5397436B2 (ja) * 2010-11-18 2014-01-22 日産自動車株式会社 二次電池
KR101255242B1 (ko) * 2011-04-15 2013-04-16 삼성에스디아이 주식회사 전기화학전지
CZ2011405A3 (cs) * 2011-07-01 2013-01-09 He3Da S.R.O. Lithiový akumulátor
US8535851B1 (en) 2012-06-19 2013-09-17 ZAF Energy Systems, Incorporated Metal-air battery and gas impermeable anodic conductive matrix

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US829643A (en) * 1905-12-22 1906-08-28 Harriet S Ford Storage battery.
US4160068A (en) * 1978-11-21 1979-07-03 Ford Motor Company Storage battery
US5480742A (en) * 1993-05-13 1996-01-02 Erez; Mordechai Electrochemical cell including compressed, unbonded, electrode granules and liquid electrolyte
US5580676A (en) * 1993-08-17 1996-12-03 Sony Corporation Rectangular battery

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JPS5592270A (en) * 1978-12-28 1980-07-12 Nippon Supingu Kk Steel material cutting position adjusting device
US4215186A (en) * 1979-02-26 1980-07-29 Jaeger Ben E Battery plate separator and battery containing the same
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US829643A (en) * 1905-12-22 1906-08-28 Harriet S Ford Storage battery.
US4160068A (en) * 1978-11-21 1979-07-03 Ford Motor Company Storage battery
US5480742A (en) * 1993-05-13 1996-01-02 Erez; Mordechai Electrochemical cell including compressed, unbonded, electrode granules and liquid electrolyte
US5580676A (en) * 1993-08-17 1996-12-03 Sony Corporation Rectangular battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1238437A4 *

Also Published As

Publication number Publication date
KR100861098B1 (ko) 2008-09-30
KR20020059392A (ko) 2002-07-12
IL131842A (en) 2007-03-08
EP1238437A1 (en) 2002-09-11
RU2264004C2 (ru) 2005-11-10
IL131842A0 (en) 2001-03-19
EP1238437A4 (en) 2006-10-04
JP2003509818A (ja) 2003-03-11
AU6862300A (en) 2001-04-10
CN1373909A (zh) 2002-10-09
CN100449821C (zh) 2009-01-07

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