USH1576H - Solid polymer electrolyte having an increased conductivity and solid state cell including the electrolyte - Google Patents

Solid polymer electrolyte having an increased conductivity and solid state cell including the electrolyte Download PDF

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Publication number
USH1576H
USH1576H US08/315,213 US31521394A USH1576H US H1576 H USH1576 H US H1576H US 31521394 A US31521394 A US 31521394A US H1576 H USH1576 H US H1576H
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United States
Prior art keywords
lithium
solid
polymer electrolyte
electrolyte
group
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Abandoned
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US08/315,213
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Charles W. Walker, Jr.
Edward J. Plichta
Wishvender K. Behl
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US Department of Army
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US Department of Army
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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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/185—Cells with non-aqueous electrolyte with solid electrolyte with oxides, hydroxides or oxysalts as solid electrolytes
    • 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

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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)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A solid polymer electrolyte having an increased conductivity is provided luding a solution of at least one lithium salt in at least one polymer host, and wherein said solid polymer electrolyte also includes a dispersion of a lithium ion conducting solid ceramic material. A solid state electrochemical cell including the electrolyte is also provided.

Description

GOVERNMENT INTEREST
The invention described herein may be manufactured, used, and licensed by or for the Government for governmental purposes without the payment to us of any royalties thereon.
FIELD OF INVENTION
The invention relates to solid polymer electrolytes having an increased conductivity for use in solid state polymer electrolyte batteries, and to solid state batteries including the electrolytes.
BACKGROUND OF THE INVENTION
Solid polymer electrolytes (SPEs) containing dissolved metal salts have been proposed as alternatives to liquid electrolytes in electrochemical systems. There are many advantages to using a solid electrolyte, such as the capability for high speed production of thin cells constructed in a bipolar configuration. Further, the polymer electrolyte can act as a mechanical barrier between the anode and cathode thereby eliminating the need for an inert porous separator as well as acting as a binder/adhesive to move and conform to electrode volume changes during cycling. The polymer electrolytes also allow and facilitate the fabrication of cells in any geometric shape and also provide an inherent safety advantage over liquid electrolytes since there is no liquid component in the cell to leak out if the integrity of the sealed cell is broken.
One of the most commonly used polymer electrolytes is based on high molecular weight polyethylene oxide (PEO). An ionically conducting solid polymer electrolyte can be prepared by dissolving PEO and an appropriate salt such as lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium trifluoromethanesulfonate (LiCF3 SO3) or lithium hexafluoroarsenate (LiAsF6) in a suitable volatile solvent such as acetonitrile (CH3 CN). By solution casting, acetonitrile is removed by evaporation, leaving a free standing solid, flexible film of good mechanical strength that contains only PEO with dissolved salt. Such films are ionic conductors.
However, because of the poor ionic conductivity of these polymers of about 10-7 S/cm, these polymers are not practical as electrolytes for electrochemical cells and particularly, rechargeable cells.
SUMMARY OF THE INVENTION
The general object of this invention is to provide solid polymer electrolytes having an increased conductivity. A more particular object of the invention is to improve the ionic conductivity of a typical polymer such as PEO with dissolved salt such as LiClO4, LiBF4, LiCF3 SO3 or LiAsF6 so that it can be used as an electrolyte in solid state electrochemical cells.
It has now been found that the aforementioned objects can be attained by incorporating particles of a solid solution of lithium germanium oxide (Li4 GeO4) and lithium vanadium oxide (Li3 VO4) and having the general formula, Li3+x Gex V1-x O4, where 0.2<x<0.8 in the PEO-lithium salt polymer electrolyte.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A solid solution with the composition, Li3.6 Ge0.6 V0.4 O4 is prepared by firing a 2.3 cm pellet of a mixture of 1.33 gms of lithium carbonate, 0.628 gm of germanium oxide and 0.364 gram of vanadium pentoxide that is pressed to a pressure of 6800 kg and placed on a gold foil in a ceramic crucible. The pellet is fired at 600° C. for 20 hours to evolve carbon-dioxide followed by heating to 900° C. for 20 hours. The fired pellet is quenched in air at room temperature and ground to a fine powder and stored in an argon filled dry box having a moisture content of less than 0.5 ppm.
The polymer electrolyte films are prepared by dissolving PEO having an average molecular weight of 4×106, dried at 50° C. under vacuum overnight and LiCF3 SO3 that has been dried at 50° C. under vacuum in molar ratio of 20:1 respectively in acetonitrile that has been distilled under a stream of dry argon with stirring in an argon filled dry box having a moisture content of less than 5 ppm. Ten weight percent of the lithium ion conducting powdered solid material Li3.6 Ge0.6 V0.4 O4 is then added to this solution with vigorous stirring. Films are cast by pouring the solution into flat Teflon dishes. After the solvent is completely evaporated, free-standing films of 50 to 100 μm in thickness are peeled from the dishes. The conductivity of the film is then measured by placing the film between stainless steel blocking electrodes and measuring the conductivities using the AC impedance technique in the 5 Hz to 100 kHz frequency range with an EG&G PAR Model 388 Electrochemical impedance system.
The conductivity of the PEO-LiCF3 SO3 films prepared with only 10 weight percent lithium ion conducting solid ceramic additive, Li3.6 Ge0.6 V0.4 O4 is found to be 10 times higher than the films prepared without the additive at 40° C. The amount of ceramic material additive contained in the polymer electrolyte may be varied between 0 and 100 weight percent.
When the improved solid polymer electrolyte of the invention is included in an electrochemical cell, either primary, or rechargeable, the anode of such a cell might be lithium metal, lithium alloy, LiC6, lithiated graphite, or lithiated petroleum coke. Similarly, the cathode of such a cell might be LiCoO2, Ag2 CrO4, CuO, Bi2 O3, Bi2 Pb2 O5, Cr2 O5, Cr3 O8, MnO2, Ni3 S2, TiS2, FeS2, VSe2, NiS2, CoS2, V6 O13, V2 O5, LiNiO2, LiMnO2, CuF2,(CF)n, CuCl2, AgCl, Crx V1-x S2 where x has a value from 0 to 1.
A particular solid state electrochemical cell according to the invention includes lithium as the anode, LiCoO2 on an aluminum foil current collector as the cathode, and (PEO)20 (LiCF3 SO3) containing 10 weight percent Li3.6 Ge0.6 V0.4 O4 as the solid polymer electrolyte. The cycling conditions include a temperature of 66° C. and a charge and discharge at 0.01 mA cm-2 rate between 4.2-2.4 V. The capacity for cycle 1 is 85.9 mAhg-1 ; for cycle 2 is 74.5 mAhg-1 ; and for cycle 3 is 53.5 mAhg-1.
We wish it to be understood that we do not des0ire to be limited to the exact details of construction shown and described for obvious modifications will occur to a person skilled in the art.

Claims (6)

What is claimed is:
1. A solid polymer electrolyte for use in an electrochemical cell, said polymer electrolyte including a solution of at least one lithium salt in at least one polymer host and wherein said solid polymer electrolyte also includes a solid solution of lithium germanium oxide and lithium vanadium oxide having the general formula Li3+x Gex V1-x O4 where x has a value between 0.2 and 0.8.
2. A solid polymer electrolyte according to claim 1 wherein said lithium salt is selected from the group consisting of lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium hexafluoroarsenate, wherein said polymer host is at least one polymer selected from the group consisting of polyethylene oxide, polyacetylene, poly (alkylthiophene), polyaniline, phenylene, and phenylsulfide, and said lithium ion conducting solid ceramic material is a solid solution of lithium germanium oxide and lithium vanadium oxide having the general formula Li3+x Gex V1-x O4 where x has a value between 0.2 and 0.8.
3. A solid polymer electrolyte according to claim 2 wherein said polymer host is polyethylene oxide, said lithium salt is lithium trifluoromethanesulfonate, and said lithium ion conducting solid ceramic material is Li3.6 Ge0.6 V0.4 O4.
4. A solid state electrochemical cell including lithium metal, lithium metal alloys, and lithium intercalating compounds as the anode, an electrochemically active metallic inorganic compound as the cathode, and a solid solution of at least one lithium salt in at least one polymer host as the electrolyte wherein said solid polymer electrolyte also includes a solid solution of lithium germanium oxide and lithium vanadium oxide having the general formula Li3+x Gex V1-x O4 where X has a value between 0.2 and 0.8.
5. A solid state electrochemical cell including a compound selected from the group consisting of lithium metal, lithium metal alloy, LiC6, lithiated graphite and lithiated petroleum coke as the anode, a compound selected from the group consisting of LiCoO2, Ag2 CrO4, CuO, Bi2 O3, Bi2 Pb2 O5, Cr2 O5, Cr3 O8, MnO2, Ni3 S2, TiS2, FeS2, VSe2, NiS2, CoS2, V6 O13, V2 O5, LiNiO2, LiMnO2, CuF2,(CF)n, CuCl2, AgCl, and Crx V1-x S2 where x has a value of 0 to 1 as the cathode, and a solid solution of at least one lithium salt selected from the group consisting of lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium hexafluoroarsenate in at least one polymer host selected from the group consisting of polyethylene oxide, polyacetylene poly(alkylthiophene), polyaniline, phenylene, and phenylsulfide as the solid polymer electrolyte and wherein said solid polymer electrolyte also includes a dispersion of a lithium ion conducting solid ceramic material including a solid solution of lithium germanium oxide and lithium vanadium oxide having the general formula Li3+x Gex V1-x O4 where x has a value between 0.2 and 0.8.
6. A solid state electrochemical cell according to claim 5 wherein the anode is lithium, the cathode is LiCoO2, the polymer host is polyethylene oxide, the lithium salt is trifluoromethanesulfonate, and the lithium ion conducting solid ceramic material is Li3.6 Ge0.6 V0.4 O4.
US08/315,213 1994-03-07 1994-03-07 Solid polymer electrolyte having an increased conductivity and solid state cell including the electrolyte Abandoned USH1576H (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5695873A (en) * 1995-06-05 1997-12-09 The University Of Dayton Polymer-ceramic composite electrolytes
WO1999039399A1 (en) * 1998-01-30 1999-08-05 Valence Technology, Inc. Polymer electrolytes containing lithiated fillers
US20160226097A1 (en) * 2013-09-27 2016-08-04 Robert Bosch Gmbh Method for manufacturing a lithium cell functional layer
US9926411B1 (en) 2017-03-03 2018-03-27 Blue Current, Inc. Polymerized in-situ hybrid solid ion-conductive compositions
US9972863B2 (en) 2016-07-29 2018-05-15 Blue Current, Inc. Compliant solid-state ionically conductive composite electrolytes and materials
US10457781B2 (en) 2017-03-03 2019-10-29 Blue Current, Inc. Polymerized in-situ hybrid solid ion-conductive compositions
US11394054B2 (en) 2019-12-20 2022-07-19 Blue Current, Inc. Polymer microspheres as binders for composite electrolytes
US11572459B2 (en) 2019-12-20 2023-02-07 Blue Current, Inc. Composite electrolytes with binders
US11581570B2 (en) 2019-01-07 2023-02-14 Blue Current, Inc. Polyurethane hybrid solid ion-conductive compositions
CN116093328A (en) * 2023-03-02 2023-05-09 哈尔滨工业大学 Preparation method of high-magnification silicon-based negative electrode material, preparation method of carbon-free solid-state battery negative electrode piece and application

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US4247499A (en) * 1979-05-18 1981-01-27 General Electric Company Methods of forming a solid ion-conductive electrolyte
US4810599A (en) * 1987-03-27 1989-03-07 Japan Synthetic Rubber Co., Ltd. Structure suitable for solid electrochemical elements
US4990413A (en) * 1989-01-18 1991-02-05 Mhb Joint Venture Composite solid electrolytes and electrochemical devices employing the same
US5011751A (en) * 1988-06-21 1991-04-30 Ricoh Company, Ltd. Electrochemical device
US5085952A (en) * 1987-02-18 1992-02-04 Gould Inc. Solid state cell electrolyte
US5219679A (en) * 1991-01-17 1993-06-15 Eic Laboratories, Inc. Solid electrolytes
US5273847A (en) * 1993-01-19 1993-12-28 The United States Of America As Represented By The Secretary Of The Army Solid state electrolyte for use in a high temperature rechargeable lithium electrochemical cell and high temperature rechargeable lithium electrochemical cell including the solid state electrolyte
US5360686A (en) * 1993-08-20 1994-11-01 The United States Of America As Represented By The National Aeronautics And Space Administration Thin composite solid electrolyte film for lithium batteries

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4247499A (en) * 1979-05-18 1981-01-27 General Electric Company Methods of forming a solid ion-conductive electrolyte
US5085952A (en) * 1987-02-18 1992-02-04 Gould Inc. Solid state cell electrolyte
US4810599A (en) * 1987-03-27 1989-03-07 Japan Synthetic Rubber Co., Ltd. Structure suitable for solid electrochemical elements
US5011751A (en) * 1988-06-21 1991-04-30 Ricoh Company, Ltd. Electrochemical device
US4990413A (en) * 1989-01-18 1991-02-05 Mhb Joint Venture Composite solid electrolytes and electrochemical devices employing the same
US5219679A (en) * 1991-01-17 1993-06-15 Eic Laboratories, Inc. Solid electrolytes
US5273847A (en) * 1993-01-19 1993-12-28 The United States Of America As Represented By The Secretary Of The Army Solid state electrolyte for use in a high temperature rechargeable lithium electrochemical cell and high temperature rechargeable lithium electrochemical cell including the solid state electrolyte
US5360686A (en) * 1993-08-20 1994-11-01 The United States Of America As Represented By The National Aeronautics And Space Administration Thin composite solid electrolyte film for lithium batteries

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5695873A (en) * 1995-06-05 1997-12-09 The University Of Dayton Polymer-ceramic composite electrolytes
WO1999039399A1 (en) * 1998-01-30 1999-08-05 Valence Technology, Inc. Polymer electrolytes containing lithiated fillers
US20160226097A1 (en) * 2013-09-27 2016-08-04 Robert Bosch Gmbh Method for manufacturing a lithium cell functional layer
US11355750B2 (en) 2016-07-29 2022-06-07 Blue Current, Inc. Compliant solid-state ionically conductive composite materials and method for making same
US9972863B2 (en) 2016-07-29 2018-05-15 Blue Current, Inc. Compliant solid-state ionically conductive composite electrolytes and materials
US9972838B2 (en) 2016-07-29 2018-05-15 Blue Current, Inc. Solid-state ionically conductive composite electrodes
US10797314B2 (en) 2016-07-29 2020-10-06 Blue Current, Inc. Compliant solid-state ionically conductive composite materials and method for making same
US10457781B2 (en) 2017-03-03 2019-10-29 Blue Current, Inc. Polymerized in-situ hybrid solid ion-conductive compositions
US10174173B2 (en) 2017-03-03 2019-01-08 Blue Current, Inc. Polymerized in-situ hybrid solid ion-conductive compositions
US10079404B1 (en) 2017-03-03 2018-09-18 Blue Current, Inc. Polymerized in-situ hybrid solid ion-conductive compositions
US9926411B1 (en) 2017-03-03 2018-03-27 Blue Current, Inc. Polymerized in-situ hybrid solid ion-conductive compositions
US11581570B2 (en) 2019-01-07 2023-02-14 Blue Current, Inc. Polyurethane hybrid solid ion-conductive compositions
US11394054B2 (en) 2019-12-20 2022-07-19 Blue Current, Inc. Polymer microspheres as binders for composite electrolytes
US11572459B2 (en) 2019-12-20 2023-02-07 Blue Current, Inc. Composite electrolytes with binders
US11667772B2 (en) 2019-12-20 2023-06-06 Blue Current, Inc. Composite electrolytes with binders
CN116093328A (en) * 2023-03-02 2023-05-09 哈尔滨工业大学 Preparation method of high-magnification silicon-based negative electrode material, preparation method of carbon-free solid-state battery negative electrode piece and application
CN116093328B (en) * 2023-03-02 2023-09-22 哈尔滨工业大学 Preparation method of high-magnification silicon-based negative electrode material, preparation method of carbon-free solid-state battery negative electrode piece and application

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