EP0474819A1 - Porous lithium electrode and battery containing the same - Google Patents
Porous lithium electrode and battery containing the sameInfo
- Publication number
- EP0474819A1 EP0474819A1 EP19910906538 EP91906538A EP0474819A1 EP 0474819 A1 EP0474819 A1 EP 0474819A1 EP 19910906538 EP19910906538 EP 19910906538 EP 91906538 A EP91906538 A EP 91906538A EP 0474819 A1 EP0474819 A1 EP 0474819A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- battery
- alloy
- metal
- negative electrode
- 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.)
- Withdrawn
Links
Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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.Battery comprising a negative electrode (5) of lithium or of lithium alloy, a positive electrode (7) and an electrolyte (6) in which the lithium or the lithium alloy of the negative electrode (5) has a density of mass not greater than 75% of standard lithium and not less than 25% of standard lithium, thereby increasing the effective surface area of the lithium or lithium alloy exposed to the electrolyte. The lithium or lithium alloy is preferably deposited by electrolysis on a base material (9) such as a metal foil.
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909007105A GB9007105D0 (en) | 1990-03-29 | 1990-03-29 | A battery |
| GB9007105 | 1990-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0474819A1 true EP0474819A1 (en) | 1992-03-18 |
Family
ID=10673514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19910906538 Withdrawn EP0474819A1 (en) | 1990-03-29 | 1991-03-28 | Porous lithium electrode and battery containing the same |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0474819A1 (en) |
| JP (1) | JPH04507171A (en) |
| CA (1) | CA2056372A1 (en) |
| GB (2) | GB9007105D0 (en) |
| WO (1) | WO1991015034A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL109845A (en) * | 1994-06-01 | 1998-08-16 | Tadiran Ltd | Rechargeable electrochemical cell |
| FR2727246A1 (en) * | 1994-11-17 | 1996-05-24 | Sorapec Lab | Accumulator with porous negative electrode contg. alkali or alkaline earth metal, and porous positive electrode |
| RU2166567C2 (en) * | 1995-09-22 | 2001-05-10 | Сиркюи Фуаль Люксембург Трейдинг С.А.Р.Л. | Process of manufacture of electrically precipitated copper foil and copper foil produced by this process |
| US6432585B1 (en) * | 1997-01-28 | 2002-08-13 | Canon Kabushiki Kaisha | Electrode structural body, rechargeable battery provided with said electrode structural body, and rechargeable battery |
Family Cites Families (7)
| 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 (en) * | 1983-01-14 | 1984-07-24 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| US4780380A (en) * | 1984-06-07 | 1988-10-25 | Standard Oil Company (Indiana) | Porous lithium electrodes and their use in nonaqueous electrochemical cells |
| JPS6463268A (en) * | 1987-09-02 | 1989-03-09 | Kanebo Ltd | Organic electrolytic battery using aluminum-lithium alloyed porous body for negative electrode |
| US4816357A (en) * | 1987-11-25 | 1989-03-28 | Hope Henry F | Intensification of ion exchange in lithium batteries |
| GB8815494D0 (en) * | 1988-06-29 | 1988-08-03 | Univ City | Process for preparation of porous metal |
-
1990
- 1990-03-29 GB GB909007105A patent/GB9007105D0/en active Pending
-
1991
- 1991-03-28 CA CA002056372A patent/CA2056372A1/en not_active Abandoned
- 1991-03-28 JP JP3506349A patent/JPH04507171A/en active Pending
- 1991-03-28 EP EP19910906538 patent/EP0474819A1/en not_active Withdrawn
- 1991-03-28 WO PCT/GB1991/000500 patent/WO1991015034A1/en not_active Ceased
- 1991-03-28 GB GB9106734A patent/GB2242566B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9115034A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1991015034A1 (en) | 1991-10-03 |
| GB2242566B (en) | 1994-01-26 |
| GB9007105D0 (en) | 1990-05-30 |
| CA2056372A1 (en) | 1991-09-30 |
| JPH04507171A (en) | 1992-12-10 |
| GB9106734D0 (en) | 1991-05-15 |
| GB2242566A (en) | 1991-10-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19911128 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB |
|
| 17Q | First examination report despatched |
Effective date: 19931126 |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: JARVIS, CHRISTINE, RUTH Inventor name: NEAT, ROBIN, JOHN 37 LODGE CLOSE Inventor name: RADMALL, PAUL MARSH LODGE MARSH ROAD |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ULTRALIFE BATTERIES (UK) LTD. |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 19951001 |