CA2095560C - Highly conductive electrolyte for use in an ambient temperature rechargeable lithium battery and ambient temperature rechargeable lithium battery including said electrolyte - Google Patents
Highly conductive electrolyte for use in an ambient temperature rechargeable lithium battery and ambient temperature rechargeable lithium battery including said electrolyte Download PDFInfo
- Publication number
- CA2095560C CA2095560C CA002095560A CA2095560A CA2095560C CA 2095560 C CA2095560 C CA 2095560C CA 002095560 A CA002095560 A CA 002095560A CA 2095560 A CA2095560 A CA 2095560A CA 2095560 C CA2095560 C CA 2095560C
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- Prior art keywords
- electrolyte
- lithium
- ambient temperature
- lithium battery
- temperature rechargeable
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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
- H01M10/0566—Liquid materials
-
- 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
-
- 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)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A highly conductive electrolyte is provided for use in an ambient temperature rechargeable lithium battery including a lithium intercalating anode and a more positive lithium intercalating cathode. The electrolyte includes a solution of a lithium salt in acetonitrile.
Description
FIELD OF INVENTION
This invention relates in general to ambient tempera-ture, rechargeable, lithium batteries and in particular to the use of highly conductive electrolytes for the lithium batteries.
BACKGROUND OF THE INVENTION
The use of organic electrolytes commonly employed in ambient temperature rechargeable lithium batteries has been hampered by the low conductivities of the electrolytes so that the cells can not be recharged at current densities above about 0.3 mA/cm2 and can not be discharged at current densities above about 3 to 10 mA/cm2.
SUMMARY OF THE INVENTION
The general object of this invention is to provide a high conductivity electrolyte for use in an ambient temperature rechargeable lithium battery. A further aim of the invention is to provide such an electrolyte for use in an ambient temperature rechargeable lithium battery that uses lithium intercalation compounds such as TiS2, WO2, Mo02 and graphite, etc. as anodes instead of lithium metal. A still further aim of the invention is to provide such a battery wherein both the charge and discharge rates are higher than those obtained with conventional electrolytes used in lithium batteries. Another aim of the invention is to provide such a battery that exhibits excellent cycle life.
It has now been found that the aforementioned aims can be attained by providing an electrolyte of 1.5 molar lithium hexafluoroarsenate (LiAsF6) in acetonitrile (AN) for use in a 2i~955G0 battery that includes lithium intercalation compounds such as TiS2, W02, Mo02, VSe2, LiaTiS2, Li2VSe2, lithiated graphite, lithiated carbon, lithiated petroleum coke etc as anodes and a more voltage positive lithium intercalating cathode such as LiCo02 or Li.Ni02.
In lieu of LiAsFg ae the electrolyte salt one may use other lithium salts that dissolve in acetonitrile such as LiA1C14, LiC104, LiBF4, and LiPFg.
As the organic solvent of the electrolyte, it is preferred to use acetonitrile alone, but the invention also contemplates the use of acetonitrile together with other solvents that are not compatible with metallic lithium.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 ie the plot of the conductivities of an elec-trolyte of 1.5 molar LiAsFg in AN.
FTG. 2 shows the discharge curves at current densities of 2 to 20 mA/cm2 for the cell LixTiS2/1.5 M LiAsFg in AN/Li1_xCo02 where X has a value between 0 and 1.
DESCRIPTION OF THE DRAWING AND THE PREFERRED EMBODIMENT' The electrolyte of 1.5 molar LiAsFg in AN has a conduc-tivity of 0.0501 SCm'1 at 21°C and increases to 0.0692 SCm1 at 61°C. The conductivities of this electrolyte is plotted in FIG. 1 as a function of temperature. These conductivity values are higher than the conductivity of organic electrolytes presently used in ambient temperature rechargeable lithium batteries. ,Unfortunately, this highly conducting electrolyte ~~~9~~60 can not be used in conventional lithium batteries because the lithium anodes react spontaneously with the acetonitrile sol-vent. The highly conducting electrolyte solutions can, however, be used in cells that use lithium intercalation compounds such as TiS2, W02, Mo02, VSe2, Li2TiS2, Li2VSez, lithiated graphite, lithiated carbon, or lithiated petroleum coke as the anode instead of lithium metal and a more voltage positive lithium intercalating cathode such as LiCoOz and LiNi02. The intercalation anodes are chemically stable in acetonitrile solutions unlike lithium metal and allow the fabrication of ambient temperature rechargeable lithium cells that can be charged and discharged at higher rates than the conventional lithium batteries.
A cell is then made using the highly conducting acetonitrile solutions as electrolyte. The cell corresponds to LiXTiS2/1.5 molar LiAsFg - AN/Li~.x Co02 where X has a_value between 0 and 1.
Thin films of titanium disulfide and lithium cobalt oxide are deposited on an aluminum substrate by chemical vapor 2o deposition and sprayed sol gel techniques, respectively. The cell is fabricated and cycled in a glove box. The cell exhibits an open circuit potential of 2.1 volts and can be discharged at current densities up to 20 mA/cm2. The discharge curves at current densities of 2 to 20 mA/cm2 are shown in FIG. 2. The cell can also be charged at a current density of 2 mA/cm2. Both the charge and discharge rates are higher than those obtained with conventional electrolytes used in lithium batteries. The cell also exhibits excellent cycle life and delivers 300 cycles. .
This invention relates in general to ambient tempera-ture, rechargeable, lithium batteries and in particular to the use of highly conductive electrolytes for the lithium batteries.
BACKGROUND OF THE INVENTION
The use of organic electrolytes commonly employed in ambient temperature rechargeable lithium batteries has been hampered by the low conductivities of the electrolytes so that the cells can not be recharged at current densities above about 0.3 mA/cm2 and can not be discharged at current densities above about 3 to 10 mA/cm2.
SUMMARY OF THE INVENTION
The general object of this invention is to provide a high conductivity electrolyte for use in an ambient temperature rechargeable lithium battery. A further aim of the invention is to provide such an electrolyte for use in an ambient temperature rechargeable lithium battery that uses lithium intercalation compounds such as TiS2, WO2, Mo02 and graphite, etc. as anodes instead of lithium metal. A still further aim of the invention is to provide such a battery wherein both the charge and discharge rates are higher than those obtained with conventional electrolytes used in lithium batteries. Another aim of the invention is to provide such a battery that exhibits excellent cycle life.
It has now been found that the aforementioned aims can be attained by providing an electrolyte of 1.5 molar lithium hexafluoroarsenate (LiAsF6) in acetonitrile (AN) for use in a 2i~955G0 battery that includes lithium intercalation compounds such as TiS2, W02, Mo02, VSe2, LiaTiS2, Li2VSe2, lithiated graphite, lithiated carbon, lithiated petroleum coke etc as anodes and a more voltage positive lithium intercalating cathode such as LiCo02 or Li.Ni02.
In lieu of LiAsFg ae the electrolyte salt one may use other lithium salts that dissolve in acetonitrile such as LiA1C14, LiC104, LiBF4, and LiPFg.
As the organic solvent of the electrolyte, it is preferred to use acetonitrile alone, but the invention also contemplates the use of acetonitrile together with other solvents that are not compatible with metallic lithium.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 ie the plot of the conductivities of an elec-trolyte of 1.5 molar LiAsFg in AN.
FTG. 2 shows the discharge curves at current densities of 2 to 20 mA/cm2 for the cell LixTiS2/1.5 M LiAsFg in AN/Li1_xCo02 where X has a value between 0 and 1.
DESCRIPTION OF THE DRAWING AND THE PREFERRED EMBODIMENT' The electrolyte of 1.5 molar LiAsFg in AN has a conduc-tivity of 0.0501 SCm'1 at 21°C and increases to 0.0692 SCm1 at 61°C. The conductivities of this electrolyte is plotted in FIG. 1 as a function of temperature. These conductivity values are higher than the conductivity of organic electrolytes presently used in ambient temperature rechargeable lithium batteries. ,Unfortunately, this highly conducting electrolyte ~~~9~~60 can not be used in conventional lithium batteries because the lithium anodes react spontaneously with the acetonitrile sol-vent. The highly conducting electrolyte solutions can, however, be used in cells that use lithium intercalation compounds such as TiS2, W02, Mo02, VSe2, Li2TiS2, Li2VSez, lithiated graphite, lithiated carbon, or lithiated petroleum coke as the anode instead of lithium metal and a more voltage positive lithium intercalating cathode such as LiCoOz and LiNi02. The intercalation anodes are chemically stable in acetonitrile solutions unlike lithium metal and allow the fabrication of ambient temperature rechargeable lithium cells that can be charged and discharged at higher rates than the conventional lithium batteries.
A cell is then made using the highly conducting acetonitrile solutions as electrolyte. The cell corresponds to LiXTiS2/1.5 molar LiAsFg - AN/Li~.x Co02 where X has a_value between 0 and 1.
Thin films of titanium disulfide and lithium cobalt oxide are deposited on an aluminum substrate by chemical vapor 2o deposition and sprayed sol gel techniques, respectively. The cell is fabricated and cycled in a glove box. The cell exhibits an open circuit potential of 2.1 volts and can be discharged at current densities up to 20 mA/cm2. The discharge curves at current densities of 2 to 20 mA/cm2 are shown in FIG. 2. The cell can also be charged at a current density of 2 mA/cm2. Both the charge and discharge rates are higher than those obtained with conventional electrolytes used in lithium batteries. The cell also exhibits excellent cycle life and delivers 300 cycles. .
~?09~J6O
We wish it to be understood that we do not desire to be limited to the exact details of construction shown and described for obvious modifications will occur to a person skilled in the art.
We wish it to be understood that we do not desire to be limited to the exact details of construction shown and described for obvious modifications will occur to a person skilled in the art.
4 .
Claims (13)
1. A highly conductive electrolyte for use in an ambient temperature rechargeable lithium battery including a lithium intercalcating anode selected from the group consisting of TiS2, WO2, MoO2, VSe2, Li2TiS2, Li2VSe2, lithiated graphite, lithiated carbon, and lithiated petroleum coke, and a lithium intercalating cathode selected from the group consisting of LiCoO2 and LiNiO2, said electrolyte having a solution of a 1.5 molar concentration of a lithium salt in acetonitrile, wherein the lithium salt is selected from the group consisting of LiAsF 2, LiAlCl 4, LiC10 4, LiBF4, and LiPF6.
2. A highly conductive electrolyte according to claim 1 wherein the lithium salt is LiAsF 6.
3. A highly conductive electrolyte according to claim 1 wherein the lithium salt is LiAlCl 4.
4. A highly conductive electrolyte according to claim 1 wherein the electrolyte salt is LiC10 4.
5. A highly conductive electrolyte according to claim 1 wherein the electrolyte salt is LiBF4.
6. A highly conductive electrolyte according to claim 1 wherein the electrolyte salt is LiPF6.
7. A highly conductive electrolyte according to claim 2 wherein the electrolyte is a solution of about 1.5 molar LiAsF6 in acetonitrile.
8. An ambient temperature rechargeable lithium battery system comprising a lithium intercalating anode selected from the group consisting of TiS2, WO2, MoO2, VSe2, Li2TiS2, Li2VSe2, lithiated graphite, lithiated carbon, and lithiated petroleum coke, a lithium intercalating cathode selected from the group consisting of LiCoO2 and LiNiO2 and a solution of a 1.5 molar concentration of a lithium salt in acetonitrile as the electrolyte wherein the lithium salt in the electrolyte solution is selected from the group consisting of LiA1C1 4, LiC1O4, LiBF9, LiAsF6, and LiPF6.
9. An ambient temperature rechargeable lithium battery system according to claim 8 wherein the lithium intercalating anode is Li2TiS2.
10. An ambient temperature rechargeable lithium battery system according to claim 8 wherein the lithium intercalating cathode is LiCoO2.
11. An ambient temperature rechargeable lithium battery system according to claim 8 wherein the lithium intercalating cathode is LiNiO2.
12. An ambient temperature rechargeable lithium battery system according to claim 8 wherein the lithium salt in the electrolyte solution is LiAsF6.
13. An ambient temperature rechargeable lithium battery system including TiS2 as the anode, LiCoO2 and the cathode, and a solution of about 1.5 molar LiAsF6 in acetonitrile as the electrolyte.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/945,039 | 1992-09-15 | ||
| US07/945,039 US5300376A (en) | 1992-09-15 | 1992-09-15 | Highly conductive electrolyte for use in an ambient temperature rechargeable lithium battery and ambient temperature rechargeable lithium battery including said electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2095560A1 CA2095560A1 (en) | 1994-03-16 |
| CA2095560C true CA2095560C (en) | 2000-07-04 |
Family
ID=25482520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002095560A Expired - Fee Related CA2095560C (en) | 1992-09-15 | 1993-05-05 | Highly conductive electrolyte for use in an ambient temperature rechargeable lithium battery and ambient temperature rechargeable lithium battery including said electrolyte |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5300376A (en) |
| CA (1) | CA2095560C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5478671A (en) * | 1992-04-24 | 1995-12-26 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
| US5618640A (en) * | 1993-10-22 | 1997-04-08 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
| US5849429A (en) * | 1996-10-23 | 1998-12-15 | Samsung Display Devices Co., Ltd. | Purification process for lithium battery electrolytes |
| US20040072055A1 (en) * | 2000-04-14 | 2004-04-15 | Getz Matthew George | Graphite article useful as a fuel cell component substrate |
| US6645657B2 (en) * | 2001-05-03 | 2003-11-11 | Fuelcell Energy, Inc. | Sol-gel coated cathode side hardware for carbonate fuel cells |
| JP4836371B2 (en) * | 2001-09-13 | 2011-12-14 | パナソニック株式会社 | Positive electrode active material and non-aqueous electrolyte secondary battery including the same |
| US9391325B2 (en) * | 2002-03-01 | 2016-07-12 | Panasonic Corporation | Positive electrode active material, production method thereof and non-aqueous electrolyte secondary battery |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE213557C (en) * | ||||
| JPS54125443A (en) * | 1978-03-22 | 1979-09-28 | Toshiba Ray O Vac | Organic solvent cell |
| US4882244A (en) * | 1987-04-02 | 1989-11-21 | The University Of Michigan-Ann Arbor | Battery containing a metal anode and an electrolyte providing high rates of metal electrolysis at near ambient temperatures |
| EP0390185B1 (en) * | 1989-03-30 | 1994-06-22 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| JP3052314B2 (en) * | 1989-08-31 | 2000-06-12 | 三菱化学株式会社 | Lithium battery |
| US5102751A (en) * | 1990-02-07 | 1992-04-07 | Sri International | Plasticizers useful for enhancing ionic conductivity of solid polymer electrolytes |
| JP2914388B2 (en) * | 1990-04-17 | 1999-06-28 | 株式会社ユアサコーポレーション | Polymer solid electrolyte |
-
1992
- 1992-09-15 US US07/945,039 patent/US5300376A/en not_active Expired - Fee Related
-
1993
- 1993-05-05 CA CA002095560A patent/CA2095560C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2095560A1 (en) | 1994-03-16 |
| US5300376A (en) | 1994-04-05 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |