WO2005091420A2 - Galvanisches element - Google Patents
Galvanisches element Download PDFInfo
- Publication number
- WO2005091420A2 WO2005091420A2 PCT/EP2005/002932 EP2005002932W WO2005091420A2 WO 2005091420 A2 WO2005091420 A2 WO 2005091420A2 EP 2005002932 W EP2005002932 W EP 2005002932W WO 2005091420 A2 WO2005091420 A2 WO 2005091420A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte
- carbonate
- galvanic element
- negative electrode
- lithium
- Prior art date
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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates to a galvanic element with a negative electrode, which contains lithium as intercalating graphite-like carbon and an organic electrolyte.
- the active electrode materials of such galvanic elements are inorganic compounds which are capable of reversibly storing and removing ions of the most electronegative alkali metal and at the same time the third lightest element lithium.
- Typical examples for the negative electrode are graphite-like carbons, for the positive electrode lithium transition metal oxides such as LiCo0 2 .
- the possible lithium activities result in achievable voltages of up to 4.2 V in the fully charged cell, further increases in the voltages are currently only due to the decomposition voltage of the organically based lithium electrolytes used.
- the combination of high achievable voltages with light materials such as graphite led to the z.
- the highest achievable volumetric and gravimetric energy densities for rechargeable galvanic cells with known intercalation connections are currently capable of reversibly storing and removing ions of the most electronegative alkali metal and at the same time the third lightest element lithium.
- Typical examples for the negative electrode are graphite-like carbons, for the positive electrode lithium transition metal oxides such as Li
- the active electrode materials together with further electrode components such as conductive carbon black and polymeric binders are first applied to the collector electrodes by means of direct coating or lamination and then connected to a precoated polyolefin separator by lamination.
- the resulting bond is characterized by the very good mechanical and electrical contact between all components. Due to the lamination, however, the simultaneous use of metal foils as a collector for the negative and positive electrodes is no longer possible, since then the electrolyte can no longer penetrate sufficiently into the cell laminate during the impregnation.
- a collector foil is usually on the negative side, usually copper, and a current collector, which is perforated and stretched or perforated in any geometry, usually aluminum, on the positive side used.
- An organic lithium electrolyte is generally used in these galvanic elements; the conductive salt is often lithium hexafluorophosphate, which is usually dissolved in a mixture of two carbonates of high and low viscosity or dielectric constant.
- the first carbonate with a high dielectric constant is usually ethylene carbonate, the second dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate. Cycle properties and service life are determined by the formation of an ion-conducting solid cover layer on the electrodes.
- the documents US 5,352,548 and EP 0 582 410 B1 describe electrolyte mixtures consisting of a conductive salt, vinylene carbonate (VC) or a derivative and a low-boiling solvent, the boiling point of which is approximately 150 ° C. and less.
- the amount of the vinylene carbonate or the derivative, which differs from the vinylene carbonate by a methyl or ethyl group or a halogen atom, in the electrolyte is stated to be 20 to 80% by weight.
- the object of the present invention is to provide an organic electrolyte which, due to its special composition, considerably improves the cycle behavior of the element.
- the electrolyte of an element according to the invention contains only diethyl carbonate as the organic aprotic solvent, lithium hexafluorophosphate as the conductive salt and additionally ethylene carbonate and 0.2 to 5% by weight of vinylene carbonate.
- the additive vinylene carbonate is only stable in an electrolyte solution, is usually supplied with stabilizers, and storage at 4 ° C is recommended. Because the additive easily decomposes during formation In order to be able to actively intervene in the formation of the cover layer, the even desired decomposition and the decomposition products that are produced are of great interest, and it is therefore also understandable that only small amounts of additive are required. High levels of vinylene carbonate in the electrolyte can cause significant gassing and cycling problems at higher temperatures.
- the electrolyte preferably contains 0.5 to 1.5% by weight of vinylene carbonate.
- an electrolyte should also be guaranteed in the area of the room temperature and the temperature range below. Therefore, the term solvent is meaningfully to be understood for the functionality of an electrolyte, which also solves this problem for the temperature range mentioned immediately above. This is possible by using only an aprotic solvent in an electrolyte from a 1 molar solution of LiPF 6 , the weight ratio of ethylene carbonate to diethyl carbonate being 3 to 7.
- the carbon-like lithium intercalating material of the negative electrode preferably has a degree of crystallinity of less than 80%.
- the so-called hard carbon is known, a carbon that already differs noticeably from the ideal graphite structure.
- the degree of crystallinity of the active carbon also becomes a variable due to the incorporation of lithium and the volume increases during cycling, which is subject to changes during cell operation.
- carbon blacks which naturally have a high degree of disorder, are often added to the electrode to improve conductivity. Natural graphites also display disorder due to their formation, but are at least as an active component in electrodes of great interest in terms of costs.
- VC vinylene carbonate
- PS propane sultone
- This additive is not only able to stabilize VC, but also cyclohexylbenzene (CHB), which is used as a so-called overloading additive. If a galvanic element of this type is overloaded without voltage limitation, such an additive prevents the cell from igniting. If too little CHB is added to the electrolyte, the cell still cycles well, but the additive does not apply when overcharging. If you add too much CHB, the overcharge mechanism takes effect, but at the expense of good cycle behavior.
- CHB cyclohexylbenzene
- the electrolyte according to the invention therefore additionally contains up to five percent by weight of CHB, which are stabilized by one to two percent by weight of PS.
- CHB cycle behavior (capacity as a function of the number of cycles) of cells with (upper curve A) and without (lower curve B) vinylene carbonate as an additive.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004014629A DE102004014629A1 (de) | 2004-03-19 | 2004-03-19 | Galvanisches Element |
DE102004014629.2 | 2004-03-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005091420A2 true WO2005091420A2 (de) | 2005-09-29 |
WO2005091420A3 WO2005091420A3 (de) | 2007-04-12 |
Family
ID=34962402
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/002932 WO2005091420A2 (de) | 2004-03-19 | 2005-03-18 | Galvanisches element |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE102004014629A1 (de) |
WO (1) | WO2005091420A2 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102007024394A1 (de) | 2007-05-25 | 2008-11-27 | Robert Bosch Gmbh | Elektrochemischer Energiespeicher |
DE102011084009A1 (de) | 2011-10-05 | 2013-04-11 | Varta Microbattery Gmbh | Lithium-Ionen-Zellen mit verbesserten Eigenschaften |
DE102013201254A1 (de) | 2013-01-28 | 2014-07-31 | Robert Bosch Gmbh | Batterie und Verfahren zur Herstellung derselben |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0582410A1 (de) * | 1992-07-27 | 1994-02-09 | Sanyo Electric Co., Limited. | Sekundärbatterie |
US5626981A (en) * | 1994-04-22 | 1997-05-06 | Saft | Rechargeable lithium electrochemical cell |
EP0980108A1 (de) * | 1998-08-13 | 2000-02-16 | Wilson Greatbatch Limited | Nichtwässrige organische Elektrolyten zur Entladung von ladbaren elektrochemischen Zellen bei niedriger Temperatur |
US6350546B1 (en) * | 1998-01-20 | 2002-02-26 | Wilson Greatbatch Ltd. | Sulfate additives for nonaqueous electrolyte rechargeable cells |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0746047A1 (de) * | 1995-06-01 | 1996-12-04 | Toray Industries, Inc. | Ein amorphes Kohlenstoffmaterial, eine Elektrode und Akkumulateur |
DE19955944A1 (de) * | 1999-11-19 | 2001-07-19 | Merck Patent Gmbh | Verfahren zur Herstellung von Vinylencarbonat und dessen Verwendung |
DE10014089A1 (de) * | 2000-03-22 | 2001-09-27 | Siemens Ag | Verfahren zur automatischen Zuordnung eines Netzwerkplanungsprozesses zu mindestens einem Rechner |
JP4695748B2 (ja) * | 2000-10-12 | 2011-06-08 | パナソニック株式会社 | 非水系電池用電解液および非水系二次電池 |
DE10139409A1 (de) * | 2001-08-17 | 2003-02-27 | Merck Patent Gmbh | Polymerelektrolyte und deren Verwendung in galvanischen Zellen |
-
2004
- 2004-03-19 DE DE102004014629A patent/DE102004014629A1/de not_active Withdrawn
-
2005
- 2005-03-18 WO PCT/EP2005/002932 patent/WO2005091420A2/de active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0582410A1 (de) * | 1992-07-27 | 1994-02-09 | Sanyo Electric Co., Limited. | Sekundärbatterie |
US5626981A (en) * | 1994-04-22 | 1997-05-06 | Saft | Rechargeable lithium electrochemical cell |
US6350546B1 (en) * | 1998-01-20 | 2002-02-26 | Wilson Greatbatch Ltd. | Sulfate additives for nonaqueous electrolyte rechargeable cells |
EP0980108A1 (de) * | 1998-08-13 | 2000-02-16 | Wilson Greatbatch Limited | Nichtwässrige organische Elektrolyten zur Entladung von ladbaren elektrochemischen Zellen bei niedriger Temperatur |
Also Published As
Publication number | Publication date |
---|---|
DE102004014629A1 (de) | 2005-10-06 |
WO2005091420A3 (de) | 2007-04-12 |
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