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WO1991015034A1 - Electrode en lithium poreux et batterie comportant une telle electrode - Google Patents

Electrode en lithium poreux et batterie comportant une telle electrode Download PDF

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Publication number
WO1991015034A1
WO1991015034A1 PCT/GB1991/000500 GB9100500W WO9115034A1 WO 1991015034 A1 WO1991015034 A1 WO 1991015034A1 GB 9100500 W GB9100500 W GB 9100500W WO 9115034 A1 WO9115034 A1 WO 9115034A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
battery
metal
alloy
lithium metal
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/GB1991/000500
Other languages
English (en)
Inventor
Paul Radmall
Robin John Neat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dowty Electronic Components Ltd
Original Assignee
Dowty Electronic Components 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 Dowty Electronic Components Ltd filed Critical Dowty Electronic Components Ltd
Publication of WO1991015034A1 publication Critical patent/WO1991015034A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to a battery, and a lithium metal or lithium alloy negative electrode with an increased electrochemically active surface area for use in a battery.
  • the lithium metal or lithium alloy material used has a bulk density of that of standard lithium i.e. 534 kg/m 3 , and exhibits the same no -porous characteristics as lithium. This means the surface area available for electrochemical interaction within the battery is defined by the external area of the electrode exposed to the electrolyte. Hence in the industry there is a tendency towards using negative electrodes which are extremely thin sheets of lithium, and therefore have little strength. Disclosure of the Invention
  • the present invention is concerned with providing a battery having a lithium metal or lithium alloy negative electrode which has an increased electro ⁇ hemically active surface area.
  • a battery in accordance with the present invention, includes a negative electrode of lithium metal or lithium alloy, a positive electrode, and an electrolyte wherein the lithium metal or lithium alloy of the negative electrode has a bulk density no greater than 75% that of standard lithium and no less than 25% that of standard lithium, thereby to increase the effective surface area of lithium metal or lithium alloy exposed to the electrolyte.
  • the lithium alloys which may be used as the negative electrode of a battery made in accordance with the present invention are substantially lithium metal and therefore have a density substantially the same as lithium metal.
  • Standard lithium has a bulk density of 534 kg/m 3 , therefore the bulk density range for the lithium metal or lithium alloy of the negative electrode in a battery made in accordance with the present invention is between 400.5 kg/m 3 and 133.5 kg/m 3 . It should also be noted that standard lithium is a substantially solid body of material and includes no porous structure, i.e. contains substantially no free space in its interior.
  • the bulk density of lithium metal or lithium alloy is decreased to the relevant level by increasing the porosity of the material. In effect this means increasing the free space available within lithium metal or lithium alloy.
  • a mass of lithium weighing 534 kg will occupy the following space: lm 3 at standard bulk density (534 kg/m 3 ), 1.33m 3 at 75% standard bulk density (400.5 kg/m 3 ), 4m 3 at 25% standard bulk density (213.6 kg/m 3 ).
  • the amount of internal surface area created by the reduction in bulk density is clearly dependent upon the way the volume of free space required to reduce the bulk density is distributed throughout the body of the lithium metal or lithium alloy.
  • the lithium metal or lithium alloy of the negative electrode is formed on a base material by electro-deposition.
  • the electro-deposition process may comprise any standard electro-deposition process further details of which can be obtained from the technical literature.
  • the co-pending patent application No. 9005337.2 discloses a suitable lithium electro-deposition process and is incorporated herein by reference.
  • the lithium metal or lithium alloy is preferably deposited from a solution which comprises Lithium Hexafluoroarsenate (LiAsF ⁇ ) dissolved in a solvent.
  • Lithium Chloride (LiCl) or Lithium Hexafluorophosphate (LiPF ⁇ ) may be used.
  • the electro-deposition process is carried out with a current density in the range 5-15 A/cm 2 .
  • the lithium metal or lithium alloy is electro- deposited on a base material comprising a metal foil such as nickel foil, or a conductive organic material or a polymer material such as a loaded polymer.
  • the electrolytic solution of the electro- deposition bath may be partially trapped in pockets within the lithium metal or lithium alloy so formed, and can be mixed to a composition such that it will assist the operation of the battery in which it is used, i.e. act as an electrolyte itself in combination with the battery electrolyte.
  • a battery made in accordance with the present invention may be a primary battery or a secondary battery.
  • a battery made in accordance with the present invention may include a liquid or a solid electrolyte material, or a mixture of the two, for example, a liquid supported in a solid.
  • Figure 1 shows a schematic view of a solid state battery made in accordance with the present invention
  • Figure 2 shows a cross-section through the material of the core of the battery of Figure 1.
  • a solid state lithium battery made in accordance with the present invention comprises a core member 1, a casing 2 made of non-porous water resistant material which completely encapsulates the core member 1 of the battery and maintains said core member 1 dry, a positive terminal 3 which extends through the casing 2 and enables the core member 1 of the battery to be connected to a device, and a negative terminal 4 which extends through the casing 2 and enables the core member 1 of the battery to be connected to a device.
  • the core member 1 of the battery comprises the following layers.
  • a first layer 5 of lithium metal has a bulk density of between 400.5 kg/m 3 and 133.5 kg/m 3 and forms the negative electrode of the battery.
  • This layer is formed on a base material 9, for example nickel foil, by electro- deposition in a bath comprising a solution of lithium salt such as lithium hexafluoroarsenate (LiAsF 6 ) or lithium chloride (LiCl) or lithium hexafluorophosphate (liPF ⁇ ) or a mixture of these salts in a solvent.
  • a current density between 5-15 A/cm z is used.
  • the base material 9 is connected to the negative terminal 4 of the battery.
  • a second layer 6 comprises solid electrolyte material, for example, polyethylene Oxide (PEO) containing a mixture of propylene carbonate (PC) and ethylene carbonate (EC) and having dispersed therein a lithium salt, for example, lithium perchlorate (LiC10 4 ) .
  • PEO polyethylene Oxide
  • PC propylene carbonate
  • EC ethylene carbonate
  • LiC10 4 lithium perchlorate
  • a third layer 7 comprises electrochemically active material such as manganese dioxide (MnO-*,), dispersed in a polymeric material, such as the electrolyte of the battery. This third layer forms the positive terminal of the battery and is connected to the positive terminal 4.
  • electrochemically active material such as manganese dioxide (MnO-*,)
  • a fourth layer 8 comprises the current collector of the battery.
  • These layers in the core 1 of the battery constitute an electrochemical cell that provide the battery with the necessary electrochemical driving force.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Batterie comprenant une électrode négative (5) de lithium ou en alliage de lithium, une électrode positive (7) et un électrolyte (6) dans lequel le lithium ou l'alliage de lithium de l'électrode négative (5) possède une densité de masse non supérieure aux 75 % du lithium standard et non inférieure aux 25 % de lithium standard, pour, de ce fait, augmenter la surface efficace du lithium ou de l'alliage de lithium exposée à l'électrolyte. Le lithium ou l'alliage de lithium est, de préférence, déposé par électrolyse sur une matière de base (9) comme une feuille métallique.
PCT/GB1991/000500 1990-03-29 1991-03-28 Electrode en lithium poreux et batterie comportant une telle electrode Ceased WO1991015034A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9007105.1 1990-03-29
GB909007105A GB9007105D0 (en) 1990-03-29 1990-03-29 A battery

Publications (1)

Publication Number Publication Date
WO1991015034A1 true WO1991015034A1 (fr) 1991-10-03

Family

ID=10673514

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1991/000500 Ceased WO1991015034A1 (fr) 1990-03-29 1991-03-28 Electrode en lithium poreux et batterie comportant une telle electrode

Country Status (5)

Country Link
EP (1) EP0474819A1 (fr)
JP (1) JPH04507171A (fr)
CA (1) CA2056372A1 (fr)
GB (2) GB9007105D0 (fr)
WO (1) WO1991015034A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2727246A1 (fr) * 1994-11-17 1996-05-24 Sorapec Lab Accumulateur a electrodes poreuses a base d'un metal alcalin ou alcalino-terreux et comprenant un electrolyte a l'etat liquide et un electrolyte a l'etat solide

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL109845A (en) * 1994-06-01 1998-08-16 Tadiran Ltd Rechargeable electrochemical cell
RU2166567C2 (ru) * 1995-09-22 2001-05-10 Сиркюи Фуаль Люксембург Трейдинг С.А.Р.Л. Способ изготовления электроосажденной медной фольги и медная фольга, полученная этим способом
EP0855752B1 (fr) * 1997-01-28 2006-11-29 Canon Kabushiki Kaisha Electrode de corps structural, accumulateur pourvu de cet électrode de corps structural et procédé de fabrication d'une telle éléctrode et un tel accumulateur

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0164254A2 (fr) * 1984-06-07 1985-12-11 Amoco Corporation Electrodes poreuses en lithium et leur utilisation dans des cellules électrochimiques non aqueuses
US4816357A (en) * 1987-11-25 1989-03-28 Hope Henry F Intensification of ion exchange in lithium batteries
WO1990000208A1 (fr) * 1988-06-29 1990-01-11 The City University Procede de preparation de metal poreux

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4002492A (en) * 1975-07-01 1977-01-11 Exxon Research And Engineering Company Rechargeable lithium-aluminum anode
GB2087858B (en) * 1980-11-25 1984-08-22 Mizushima Koichi Reduction of so2 in polluted gases high surface area conductors
JPS59128779A (ja) * 1983-01-14 1984-07-24 Sanyo Electric Co Ltd 非水電解液二次電池の製造方法
JPS6463268A (en) * 1987-09-02 1989-03-09 Kanebo Ltd Organic electrolytic battery using aluminum-lithium alloyed porous body for negative electrode

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0164254A2 (fr) * 1984-06-07 1985-12-11 Amoco Corporation Electrodes poreuses en lithium et leur utilisation dans des cellules électrochimiques non aqueuses
US4816357A (en) * 1987-11-25 1989-03-28 Hope Henry F Intensification of ion exchange in lithium batteries
WO1990000208A1 (fr) * 1988-06-29 1990-01-11 The City University Procede de preparation de metal poreux

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Patent Abstracts of Japan, volume 13, no. 272 (E-777), 22 June 1989; & JP-A-01063268 (KANEBO LTD), 9 March 1989 *
Patent Abstracts of Japan, volume 8, no. 256 (E-280), 22 November 1984; & JP-A-59128779 (SANYO DENKI KK) 24 July 1084 see abstract *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2727246A1 (fr) * 1994-11-17 1996-05-24 Sorapec Lab Accumulateur a electrodes poreuses a base d'un metal alcalin ou alcalino-terreux et comprenant un electrolyte a l'etat liquide et un electrolyte a l'etat solide

Also Published As

Publication number Publication date
GB9007105D0 (en) 1990-05-30
CA2056372A1 (fr) 1991-09-30
EP0474819A1 (fr) 1992-03-18
GB2242566A (en) 1991-10-02
GB9106734D0 (en) 1991-05-15
JPH04507171A (ja) 1992-12-10
GB2242566B (en) 1994-01-26

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