USH578H - Electrolyte additive for lithium rechargeable organic electrolyte battery - Google Patents
Electrolyte additive for lithium rechargeable organic electrolyte battery Download PDFInfo
- Publication number
- USH578H USH578H US07/153,611 US15361188A USH578H US H578 H USH578 H US H578H US 15361188 A US15361188 A US 15361188A US H578 H USH578 H US H578H
- Authority
- US
- United States
- Prior art keywords
- lithium
- electrolyte battery
- lithium rechargeable
- battery according
- organic electrolyte
- 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.)
- Abandoned
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
- H01M10/056—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
-
- 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
- the invention relates in general to a rechargeable lithium organic electrolyte battery and in particular to an electrolyte additive for such a battery that provides overcharge protection.
- a rechargeable lithium organic electrolyte battery includes a lithium anode, a cathode including compounds such as titanium disulfide, molybdenum oxide, molybdenum sulfide, vanadium oxide, vanadium sulfide, chromium oxide, etc and an electrolyte solution including an inorganic lithium salt such as lithium hexafluoroarsenate, lithium perchlorate, etc in organic solvents such as tetrahydrofuran, 2-methyl tetrahydrofuran, etc.
- lithium organic electrolyte batteries One of the common problems of most lithium organic electrolyte batteries is the oxidation of the solvent during the overcharging of these cells resulting in the degradation of electrolyte solutions. It has been suggested that the oxidation of organic solvents during the overcharging operation could be prevented by using lithium iodide as an electrolyte additive. Thus, during the overcharging operations, lithium iodide would be preferentially oxidized first to lithium tri-iodide and eventually to iodine at lower potentials than the solvent oxidation potential and thus would prevent the oxidation of the solvent.
- the general objective of this invention is to provide overcharge protection for a lithium rechargeable organic electrolyte battery.
- a more particular object of the invention is to effectively use an electrolyte additive to provide overcharge protection for such a battery.
- lithium tri-iodide In the presence of excess lithium iodide, the liberated iodine complexes with lithium iodide to form lithium tri-iodide because of the high equilibrium constant of 10 7 and thus does not react with the tetrahydrofuran solvent. Lithium tri-iodide is stable in these solutions and will react with lithium metal to regenerate lithium iodide that will then provide overcharge protection in the following cycles. The use of excess lithium iodide will thus provide overcharge protection in rechargeable lithium-organic electrolyte cells and increase the cycle life of these cells.
- the organic electrolyte will contain a sufficient amount of lithium iodide additive so that during the overcharging operations all of the lithium iodide is not oxidized to iodine and there is always an excess of lithium iodide present in the solution to combine with the liberated iodine to form stable lithium tri-iodide.
- lithium iodide in tetrahydrofuran solutions is in excess of 1.0 molar and thus enough of lithium iodide can be added to the electrolyte to satisfy the condition that there always be an excess of lithium iodide present to complex with any iodine formed during the overcharging operations. Further, lithium tri-iodide will react with lithium metal to regenerate lithium iodide and restore the cell to its original configuration and be available to provide overcharge protection during the following cycles.
- the invention is also applicable to lithium-organic electrolyte primary cells.
- the invention is applicable to all ambient temperature lithium-organic electrolyte batteries.
Landscapes
- 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)
Abstract
A large excess of lithium iodide in solution is used as an electrolyte adive to provide overcharge protection for a lithium rechargeable organic electrolyte battery.
Description
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 royalty thereon.
The invention relates in general to a rechargeable lithium organic electrolyte battery and in particular to an electrolyte additive for such a battery that provides overcharge protection.
Rechargeable lithium-organic electrolyte batteries are being developed to provide low cost, high energy density power sources for communication, night vision and various other army applications. Typically, a rechargeable lithium organic electrolyte battery includes a lithium anode, a cathode including compounds such as titanium disulfide, molybdenum oxide, molybdenum sulfide, vanadium oxide, vanadium sulfide, chromium oxide, etc and an electrolyte solution including an inorganic lithium salt such as lithium hexafluoroarsenate, lithium perchlorate, etc in organic solvents such as tetrahydrofuran, 2-methyl tetrahydrofuran, etc.
One of the common problems of most lithium organic electrolyte batteries is the oxidation of the solvent during the overcharging of these cells resulting in the degradation of electrolyte solutions. It has been suggested that the oxidation of organic solvents during the overcharging operation could be prevented by using lithium iodide as an electrolyte additive. Thus, during the overcharging operations, lithium iodide would be preferentially oxidized first to lithium tri-iodide and eventually to iodine at lower potentials than the solvent oxidation potential and thus would prevent the oxidation of the solvent. In laboratory experiments however, it was found that the liberated iodine itself reacted with the ethereal solvents such as tetrahydrofuran in the presence of lithium hexafluoroarsenate salt and caused its polymerization rendering this approach infeasible.
The general objective of this invention is to provide overcharge protection for a lithium rechargeable organic electrolyte battery. A more particular object of the invention is to effectively use an electrolyte additive to provide overcharge protection for such a battery.
It has now been found that the aforementioned objects can be attained using a large excess of lithium iodide in the concentration range of about 0.5 to 1.0 molar.
In the presence of excess lithium iodide, the liberated iodine complexes with lithium iodide to form lithium tri-iodide because of the high equilibrium constant of 107 and thus does not react with the tetrahydrofuran solvent. Lithium tri-iodide is stable in these solutions and will react with lithium metal to regenerate lithium iodide that will then provide overcharge protection in the following cycles. The use of excess lithium iodide will thus provide overcharge protection in rechargeable lithium-organic electrolyte cells and increase the cycle life of these cells.
In a typical cell configuration such as lithium/lithium hexafluoroarsenate-tetrahydrofuran/titanium disulfide, the organic electrolyte will contain a sufficient amount of lithium iodide additive so that during the overcharging operations all of the lithium iodide is not oxidized to iodine and there is always an excess of lithium iodide present in the solution to combine with the liberated iodine to form stable lithium tri-iodide. The solubility of lithium iodide in tetrahydrofuran solutions is in excess of 1.0 molar and thus enough of lithium iodide can be added to the electrolyte to satisfy the condition that there always be an excess of lithium iodide present to complex with any iodine formed during the overcharging operations. Further, lithium tri-iodide will react with lithium metal to regenerate lithium iodide and restore the cell to its original configuration and be available to provide overcharge protection during the following cycles.
The invention is also applicable to lithium-organic electrolyte primary cells. In fact, the invention is applicable to all ambient temperature lithium-organic electrolyte batteries.
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.
Claims (14)
1. In a lithium rechargeable organic electrolyte battery including lithium as the anode, a compound selected from the group consisting of titanium disulfide, molybdenum oxide, molybdenum sulfide, vanadium oxide, vanadium sulfide, and chromium oxide as the cathode, and a solution of an organic lithium salt in an organic solvent as the electrolyte, the improvement of using a large excess of lithium iodide in the solution as an electrolyte additive to provide overcharge protection.
2. A lithium rechargeable organic electrolyte battery according to Claim 1 wherein the large excess of lithium iodide in the solutions is about 0.5 to 1.0 molar.
3. A lithium rechargeable organic electrolyte battery according to claim 2 wherein the cathode is titanium disulfide.
4. A lithium rechargeable organic electrolyte battery according to claim 2 wherein the cathode is molybdenum oxide.
5. A lithium rechargeable organic electrolyte battery according to claim 2 wherein the cathode is molybdenum sulfide.
6. A lithium rechargeable organic electrolyte battery according to cClaim 2 wherein the cathode is vanadium oxide.
7. A lithium rechargeable organic electrolyte battery according to claim 2 wherein the cathode is vanadium sulfide.
8. A lithium rechargeable organic electrolyte battery according to claim 2 wherein the cathode is chromium oxide.
9. A lithium rechargeable organic electrolyte battery according to claim 3 wherein the electrolyte is a solution of lithium hexafluoroarsenate in tetrahydrofuran.
10. A lithium rechargeable organic electrolyte battery according to claim 4 wherein the electrolyte is a solution of lithium hexafluoroarsenate in tetrahydrofuran.
11. A lithium rechargeable organic electrolyte battery according to claim 5 wherein the electrolyte is a solution of lithium
12. A lithium rechargeable organic electrolyte battery according to claim 6 wherein the electrolyte is a solution of lithium hexafluoroarsenate in tetrahydrofuran.
13. A lithium rechargeable organic electrolyte battery according to claim 7 wherein the electrolyte is a solution of lithium hexafluoroarsenate in tetrahydrofuran.
14. A lithium rechargeable organic electrolyte battery according to claim 8 wherein the electrolyte is a solution of lithium hexafluoroarsenate in tetrahydrofuran.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/153,611 USH578H (en) | 1988-02-08 | 1988-02-08 | Electrolyte additive for lithium rechargeable organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/153,611 USH578H (en) | 1988-02-08 | 1988-02-08 | Electrolyte additive for lithium rechargeable organic electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USH578H true USH578H (en) | 1989-02-07 |
Family
ID=22547940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/153,611 Abandoned USH578H (en) | 1988-02-08 | 1988-02-08 | Electrolyte additive for lithium rechargeable organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USH578H (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2682816A1 (en) * | 1991-10-21 | 1993-04-23 | Alsthom Cge Alcatel | Primary or secondary electron generator |
| US6218054B1 (en) | 1991-08-13 | 2001-04-17 | Eveready Battery Company, Inc. | Dioxolane and dimethoxyethane electrolyte solvent system |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4228227A (en) | 1979-08-13 | 1980-10-14 | Honeywell Inc. | Rechargeable electrochemical cell |
-
1988
- 1988-02-08 US US07/153,611 patent/USH578H/en not_active Abandoned
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4228227A (en) | 1979-08-13 | 1980-10-14 | Honeywell Inc. | Rechargeable electrochemical cell |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218054B1 (en) | 1991-08-13 | 2001-04-17 | Eveready Battery Company, Inc. | Dioxolane and dimethoxyethane electrolyte solvent system |
| FR2682816A1 (en) * | 1991-10-21 | 1993-04-23 | Alsthom Cge Alcatel | Primary or secondary electron generator |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| AS | Assignment |
Owner name: UNITED STATES OF AMERICA, THE, AS REPRESENTED BY T Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:BEHL, WISHVENDER K.;CHIN, DER-TAU;REEL/FRAME:005031/0571;SIGNING DATES FROM 19880120 TO 19880127 |