WO1995015588A1 - Compositions d'electrolyte solide - Google Patents
Compositions d'electrolyte solide Download PDFInfo
- Publication number
- WO1995015588A1 WO1995015588A1 PCT/US1993/011603 US9311603W WO9515588A1 WO 1995015588 A1 WO1995015588 A1 WO 1995015588A1 US 9311603 W US9311603 W US 9311603W WO 9515588 A1 WO9515588 A1 WO 9515588A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solid electrolyte
- ligands
- lithium
- salt
- aprotic solvent
- Prior art date
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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
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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
- H01M10/056—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
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
-
- 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 solid electrolyte compositions and methods of making the compositions.
- Solid electrolyte compositions useful in the manufacture of solid state electrochemical devices are known in the art.
- solid electrolyte compositions comprising a polymeric network interpenetrated by an ionically conducting liquid phase are known.
- Schawb et al. in U.S. Patent 4,792,504, disclose solid polymeric electrolytes comprising a continuous network of crosslinked polyethylene oxide containing an ionic conducting phase which includes a metal salt and a bipolar aprotic solvent.
- the system comprises a two-phase system of a crosslinked polymer network phase which provides the structure for containing an ionic conducting phase in which a liquid complexed with a lithium salt is absorbed or interpenetrated and held as the ionic conducting phase.
- Shackle et al. in U.S. Patent 5,037,712, disclose a solid electrolyte containing radiation curable polysiloxane materials as part of the crosslinked polymer network structure containing the ionically conducting liquid phase.
- the polymer network which provides the basic solid structure for the electrolyte is formed from any number of polyethylinically unsaturated monomers which are polymerized or copolymerized with other monomers by various polymerization mechanisms, including radiation crosslinking.
- the polymeric network structure can be formed from crosslinkable polysiloxanes, crosslinkable polyethylene oxide, various acrylates, epoxy resins, polyacrylonitrile matrix resins as well as other resins appropriate for the properties desired in the solid electrolyte structure.
- the ionically conductive phase typically referred to as the liquid interpenetrating phase, typically comprises propylene carbonate, gamma- butyrolactone, 1,3-dioxolane, tetrahydrofurans, polyethylene glycol dimethyl ethers, glymes, and other materials which are capable of complexing with or solubilizing the desired lithium salt or sodium salt.
- Particular lithium salts, sodium salts and ammonium salts are known in the art, as disclosed in the above referenced patents.
- This invention provides in one aspect a solid electrolyte composition
- a solid electrolyte composition comprising a lithium, sodium or ammonium salt which is coordinated with an appropriate ratio of a ligand component whereby the coordinated ligands are held in coordination with the lithium sodium or ion in sufficient strength to prevent the migration or volatilization of the liquid phase portion of the ligands at conditions under which the solid electrolyte composition is used in electrochemical devices.
- the lithium or sodium salt is coordinated with a molar ratio of ligands appropriate for the positive ion in the salt, for example, for a lithium salt the molar ratio of lithium salt to ligands is generally between about 1:3 and about 1:6 moles of lithium salt to moles of ligands.
- the ligand component includes the crosslinked polymer which provides the continuous network structure of the solid electrolyte wherein the crosslinked polymer comprises compatible sites thereon for coordination with the positive ion in the salt, such as a lithium ion.
- the ligand component comprises an aprotic solvent which is likewise compatible for coordination with the same positive ion in the salt.
- the ligand component of the solid electrolyte generally comprises from about 10% to about 60% by weight of continuous network crosslinked polymer part and from about 40% to about 90% by weight of the aprotic solvent part.
- the solid electrolyte composition according to this invention is formulated around the positive ion of the salt, whereby the appropriate molar ratio of ligands is employed to enable the ligands that are present to fully coordinate with the positive ion in the salt.
- the proper molar ratio of salt to ligands provides a fully complexed and bound (coordinated) ligand component, thereby providing a stable solid electrolyte and preventing liquid phase or aprotic solvent part of the ligand component from migrating or volatilizing from the electrolyte.
- the lithium ion coordinates with appropriate sites on the continuous network of crosslinked polymer, and the lithium component is thereby immobilized by a coordination bonding to the polymer structure.
- the liquid phase or aprotic solvent part such as propylene carbonate, is bound by a coordination attraction to the lithium ion, thereby immobilizing the propylene carbonate.
- Employing the appropriate molar ratios according to the present invention provides a solid electrolyte which is fully coordinated and does not contain excess aprotic solvent which is uncoordinated and available to migrate or volatilize.
- this invention provides a method of making the solid electrolyte described above.
- this invention comprises electrochemical devices containing a solid electrolyte composition in accordance with the above. DETAILED DESCRIPTION OF THE INVENTION
- the present invention provides a different solid electrolyte composition compared to the prior art and further provides a different basis for formulating and constructing the solid electrolyte matrix.
- Solid electrolyte compositions have typically been constructed by forming a crosslinked polymer network into which is absorbed or interpenetrated a liquid phase typically comprising an aprotic solvent which contains a lithium, sodium or ammonium salt in concentrations generally up to the solubility limit of the aprotic solvent.
- the objective generally was to have the network polymer structure contain as much aprotic solvent and ionic salt as possible. It has generally been accepted that the more aprotic solvent liquid phase contained in the polymer network structure the better conductivity and capacity the solid electrolyte will exhibit.
- the solid electrolyte composition is formulated based on the lithium or sodium ion of the salt present in the electrolyte composition.
- the appropriate ratios and proportions of network structure polymer and the aprotic solvent component can be used to assure the full coordination between the positive ion of the total amount of ligand present so that the resulting solid electrolyte composition does not contain uncoordinated aprotic solvent which can migrate and/or volatilize.
- the total ligand portion of the electrolyte composition includes the network structure crosslinked polymer, to the extent that it has active sites thereon which are compatible for coordination with the positive ion of the salt, and includes the aprotic solvent, which is also compatible for coordination with the positive ion.
- the ligand molar ratio for a lithium salt in the solid electrolyte composition should be no more than about 1:6 moles of lithium salt to moles of total ligands.
- the ratio for a lithium salt will be in the range of about 1:3 to about 1:6 moles of lithium salt to moles of ligand, more preferably the range will be between about 1:4 and about 1:6.
- the ratio will also be generally from about 1:4 to about 1:6.
- the actual ratios employed in a particular electrolyte composition will depend on the particular salt used and will depend on the available sites on each ligand part which is available for coordination with the positive ion.
- the molar ratios in this regard are not direct stoichiometric ratios but are to some extent empirical ratios which can vary depending on the degree of coordination desired and the availability of compatible coordination sites per mole of network polymer or per mole of aprotic solvent. In this regard it is not necessary or desirable that every compatible coordination site on a polymer chain or an aprotic solvent molecule actually be coordinated with the positive ion. In general, if at least an average of one site per molecule is available for coordination with the positive ion, the desired degree of stability of the solid electrolyte composition will be achieved.
- the ligand component of the solid electrolyte composition of this invention it is in general acceptable if the ligand component comprises up to about 60% by weight of a continuous network crosslinked polymer with the remaining portion of the ligand component comprising an aprotic solvent. Also in general, it is desirable to have at least about 10% of the ligand component being the continuous network crosslinked polymer in order to provide sufficient structural aspect of the solid electrolyte composition. More preferably, the ligand component can comprise between about 15% and about 40% by weight of continuous network crosslinked polymer and between about 60% and 85% by weight aprotic solvent. A most preferred ligand component comprises between about 20% about 30% by weight continuous network crosslinked polymer and between about 70% and about 80% by weight aprotic solvent.
- the ligand component can contain other additives and materials which are not incompatible with the solid electrolyte composition structure and which do not interfere with the coordination of the ligands or the retention of the aprotic solvent in the electrolyte composition in accordance with the teachings of this invention. It has generally been understood in the prior art that increased amounts of aprotic solvent, such as propylene carbonate, in a solid electrolyte composition was desirable for providing increased conductivity. However, it has now been found that the lower ratios of the aprotic solvent to the network polymer provide a solid electrolyte having acceptable conductivity plus has improved structural and stability properties over those electrolyte compositions having higher ratios aprotic solvent. Similarly, the lower ratios of ligand component to the metal salt, as employed in the solid electrolyte compositions of this invention, still provide acceptable conductivity and provide superior structural and stability properties.
- aprotic solvent such as propylene carbonate
- the solid electrolyte compositions according to the present invention can be prepared by any appropriate method known in the related art.
- the network polymer can first be formed by crosslinking, then the crosslinked polymer interpenetrated with the mixture of aprotic solvent and metal.
- the aprotic solvent, salt and the monomers which are the precursors of the network crosslinked polymer can be mixed, then the network polymer crosslinked by an appropriate curing mechanism, i.e., catalytically, by radiation curing and the like.
- an appropriate curing mechanism i.e., catalytically, by radiation curing and the like.
- the solid electrolyte composition formed above can be used, for example, in a cathode structure comprising an 80 micron thick layer of a composition comprising 45% by weight V 6 O 13 together with 10% carbon and 45% by weight of the above electrolyte composition.
- Example 2 The above materials were mixed at 75 °C until solution was completed. It was then coated onto a previously prepared radiation cured cathode prepared as in Example 1. The thickness of the electrolyte was 50 microns. A piece of lithium metal foil was then placed on the electrolyte layer. The lithium was smoothed by a 2" diameter steel roller to insure intimate contact between the electrolyte and lithium.
- the cells produced by the above example were tested and found to produce batteries with high power performance.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
Electrolyte solide possédant des ligands à solvant et des ligands à polymère coordonnés avec des ions métal et présentant une stabilité et une résistance améliorées contre la volatisation et la migration des constituants de phase liquide. L'électrolyte solide comprend un sel de métal servant à produire un ion métal coordonné avec un rapport molaire de ligands approprié à l'ion métal. En ce qui concerne l'ion de lithium, le rapport se situe entre environ 1:3 et environ 1:6 de moles de sel de lithium par rapport aux moles de ligands, les ligands étant constitués d'environ 10 % à environ 60 % en poids d'un polymère réticulé à réseau structurel et d'environ 40 % à environ 90 % en poids de solvant exempt de protons.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/943,885 US5229225A (en) | 1992-09-11 | 1992-09-11 | Solid electrolyte composition |
AU51291/93A AU5129193A (en) | 1992-09-11 | 1993-09-15 | Solid electrolyte composition |
PCT/US1993/008732 WO1995008196A1 (fr) | 1992-09-11 | 1993-09-15 | Composition d'electrolyte solide |
PCT/US1993/011603 WO1995015588A1 (fr) | 1992-09-11 | 1993-12-02 | Compositions d'electrolyte solide |
AU57324/94A AU5732494A (en) | 1992-09-11 | 1993-12-02 | Solid electrolyte composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/943,885 US5229225A (en) | 1992-09-11 | 1992-09-11 | Solid electrolyte composition |
PCT/US1993/011603 WO1995015588A1 (fr) | 1992-09-11 | 1993-12-02 | Compositions d'electrolyte solide |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995015588A1 true WO1995015588A1 (fr) | 1995-06-08 |
Family
ID=26787144
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1993/011603 WO1995015588A1 (fr) | 1992-09-11 | 1993-12-02 | Compositions d'electrolyte solide |
Country Status (1)
Country | Link |
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WO (1) | WO1995015588A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014062898A1 (fr) * | 2012-10-19 | 2014-04-24 | The University Of North Carolina At Chapel Hill | Polymères conducteurs ioniques et mélanges de polymères pour batteries à alcalinométallique-ion |
US9540312B2 (en) | 2015-02-03 | 2017-01-10 | Blue Current, Inc. | Non-flammable electrolyte composition including carbonate-terminated perfluoropolymer and phosphate-terminated or phosphonate-terminated perfluoropolymer and battery using same |
US9755273B2 (en) | 2013-04-01 | 2017-09-05 | The University Of North Carolina At Chapel Hill | Ion conducting fluoropolymer carbonates for alkali metal ion batteries |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4792504A (en) * | 1987-09-18 | 1988-12-20 | Mhb Joint Venture | Liquid containing polymer networks as solid electrolytes |
EP0318161A1 (fr) * | 1987-10-30 | 1989-05-31 | Mhb Joint Venture | Méthodes de fabrication de réseaux polymères interpénétrés, demi-piles anodiques et demi-piles cathodiques et leur application dans des piles électrochimiques |
US5229225A (en) * | 1992-09-11 | 1993-07-20 | Valence Technology, Inc. | Solid electrolyte composition |
-
1993
- 1993-12-02 WO PCT/US1993/011603 patent/WO1995015588A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4792504A (en) * | 1987-09-18 | 1988-12-20 | Mhb Joint Venture | Liquid containing polymer networks as solid electrolytes |
EP0318161A1 (fr) * | 1987-10-30 | 1989-05-31 | Mhb Joint Venture | Méthodes de fabrication de réseaux polymères interpénétrés, demi-piles anodiques et demi-piles cathodiques et leur application dans des piles électrochimiques |
US5229225A (en) * | 1992-09-11 | 1993-07-20 | Valence Technology, Inc. | Solid electrolyte composition |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014062898A1 (fr) * | 2012-10-19 | 2014-04-24 | The University Of North Carolina At Chapel Hill | Polymères conducteurs ioniques et mélanges de polymères pour batteries à alcalinométallique-ion |
US9748604B2 (en) | 2012-10-19 | 2017-08-29 | The University Of North Carolina At Chapel Hill | Ion conducting polymers and polymer blends for alkali metal ion batteries |
US9755273B2 (en) | 2013-04-01 | 2017-09-05 | The University Of North Carolina At Chapel Hill | Ion conducting fluoropolymer carbonates for alkali metal ion batteries |
US9540312B2 (en) | 2015-02-03 | 2017-01-10 | Blue Current, Inc. | Non-flammable electrolyte composition including carbonate-terminated perfluoropolymer and phosphate-terminated or phosphonate-terminated perfluoropolymer and battery using same |
US10077231B2 (en) | 2015-02-03 | 2018-09-18 | Blue Current, Inc. | Functionalized fluoropolymers and electrolyte compositions |
US10227288B2 (en) | 2015-02-03 | 2019-03-12 | Blue Current, Inc. | Functionalized fluoropolymers and electrolyte compositions |
US10308587B2 (en) | 2015-02-03 | 2019-06-04 | Blue Current, Inc. | Functionalized fluoropolymers and electrolyte compositions |
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