CA1131306A - Tetrafluoroborate additive for high drain rate lithium cells - Google Patents
Tetrafluoroborate additive for high drain rate lithium cellsInfo
- Publication number
- CA1131306A CA1131306A CA335,955A CA335955A CA1131306A CA 1131306 A CA1131306 A CA 1131306A CA 335955 A CA335955 A CA 335955A CA 1131306 A CA1131306 A CA 1131306A
- Authority
- CA
- Canada
- Prior art keywords
- electrolyte
- lithium
- cell
- dissolved
- methylformate
- 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.)
- Expired
Links
- -1 Tetrafluoroborate Chemical compound 0.000 title claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 22
- 239000000654 additive Substances 0.000 title claims abstract description 13
- 230000000996 additive effect Effects 0.000 title claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011591 potassium Substances 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 27
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical group COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052788 barium Inorganic materials 0.000 abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052790 beryllium Inorganic materials 0.000 abstract description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052792 caesium Inorganic materials 0.000 abstract description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- 229910052701 rubidium Inorganic materials 0.000 abstract description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011345 viscous material Substances 0.000 description 3
- 210000003850 cellular structure Anatomy 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910020261 KBF4 Inorganic materials 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
ADDITIVE FOR HIGH DRAIN RATE LITHIUM CELLS
Abstract An improved high drain rate lithium cell is provided. The improvement is the use of an additive to stabilize the cell. The additive is a minor portion of a tetrafluoroborate salt of sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, barium, aluminum or mixtures thereof.
Abstract An improved high drain rate lithium cell is provided. The improvement is the use of an additive to stabilize the cell. The additive is a minor portion of a tetrafluoroborate salt of sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, barium, aluminum or mixtures thereof.
Description
30~
ADDITrVE FOR HIGH DRAIN RATE LITHIl~l CELLS
Backgrou~d of the Invention 1. Field of the Invention This invention relates to an additive for non-aqueous elec-trolyte of a high rate lithium electrochemical cell. More particularly, r it relates to the use of certain alkali metal tetrafluoroborates as additives for sta~ilizing ehe cell.
L
ADDITrVE FOR HIGH DRAIN RATE LITHIl~l CELLS
Backgrou~d of the Invention 1. Field of the Invention This invention relates to an additive for non-aqueous elec-trolyte of a high rate lithium electrochemical cell. More particularly, r it relates to the use of certain alkali metal tetrafluoroborates as additives for sta~ilizing ehe cell.
L
2. Prior Art It has been known for some time that high rate drain cells having anodes of lithium and electrolyte of solvent and solute are not stable, particularly at high temperatures.
The instability probIem is three fold. First, there is a short discharge life after storage due to apparent chemical changes in the electrolyte; secondly, there is a pressure build-up because of detrimental side reactions in the electrolyte; and thirdly, there are cell degradation reactions among cell components. Yet these same unstable electrolyte systems for lithi~m batteries produce extremely high energy due to high conductivity of the solute in the solvent.
In lithium cells, cell degradation reactions can be manifested in various ways: crust formation on the anode, eg., with SOC12 solutions;
gas formation and cell rupture, eg., with lithium hexafluoroarsenate in methylformate, and polymerization of solvent, eg., in THF solutions.
- In all three type degradations, the reaction leads to decreased perform-ance, if not complete failure, of the cell. When using non-aqueou~
solvents in the electrolyte, both gassing and formation of viscous, if not solid, reaction products near the anode are of maJor concern; stable or stablized electrolyte has to be used in lithium cells.
11;~1;~0~
There are many applications, eg., watch, camera, etc., for which batteries must be constructed in a shape requiring high conductivity to permit efficient and economical utilization of the chemicals. Design limitations require utilization of highly conductive electrolytes. Ho~ever, conditions of use require electrolytes capable of long term storage.
In United States Patent 3,887,397, issued June 3, 1975, to Robert J~ Horning, it is disclosed that in lithium cells having a highly conductive methylformate/lithium hexafluoroarsenate electrolyte, the addition of small amounts of lithium tetrafluoroborate will significantly improve the stability of the cell. Thus by using lithium tetrafluoroborate as a stabilizer, Horning succeeded in practically eliminating the gassing reaction between lithium and the specific electrolyte.
However, no mention is made in the patent of any other tetra-fluoroborate which could be utilized or of any ability to control non-gassing reactions causing deposition of reddish-brown viscous products on and near the lithium. Such viscous deposits will hinder the performance of the anode after prolonged storage andior at higher rates by slowing ionic mobility near the anode.
It is the objective of this invention to provide a method of stabilizing non-aqueous lithium batteries in terms of reducing chemical interactions between the electrolyte and cell components.
A more particular object of this invention is to provide stabilizing additives for high rate lithium cells so that gassing and other reaction product formations are not observed.
Summary of the Invention It has been discovered that the stability of high rate batteries which contain a lithium anode, an electrolyte having a solvent and solute and a cathode will be significantly improved by the addition to the electrolyte of a minor portion of a tetrafluoroborate salt of sodium, potassium, or mixtures thereof dissolved in said electrolyte, wherein the amount of tetrafluoroborate salt ranges from 0.05 to 0.1 molar.
~,~
~S 3~3~)~
Detailed ~escription of the Invention The cathode can be any cathodic material which i8 inert to the electrolyte, among these are V205, Ag2CrO4, (CF)n, ~nO2, CuS and others which are known to those skilled in the art. As stated above, this invention relates basically to stabilizing of the electrolyte and anode, hence, does not require any particular cathode for use.
The solvents of the electrolyte used in the current invention are those which are known for use in high rate cells. Examples include methylformate, gamma butyrolactone, 1,2 - dimethoxyethane and 1,3 -dioxolane, and mixtures thereof.
The solutes which are dissolved in the solvents to form the electrolyte are also known to those skilled in the art. Examples include the hexafluoroarsenates, the trifluoromethylsulfonates and the perchlorates. It is preferred that the salt of these cations be the lithium salt.
The additive is a tetrafluoroborate salt of sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, barium, aluminum or mixtures thereof. The sodium and potassium salts are preferred.
The amount of the tetrafluoroborate salt which should be employed varies depending upon the stability desired. Normally, the amount of tetrafluoroborate salt will range from approximately 0.05 molar to as much as 0.8 molar in the electrolyte. A more preferred range is about from 0.05 to 0.1 molar percent.
The current inventors have found that the use of these tetra-fluoroborate salts not only stops the gas reaction but also decreases and practically eliminates~the non-gassing side reactions`. For,example, in the case of lithium hexafluoroarsenate in methylformate with lithium tetrafluoroborate or no additives, these side reactions produce a reddish-brown viscous product that clings to the lithium. This product will effect the high rate performance of cells by both slowing ionic bility near the anode. The current inventors have found that even in
The instability probIem is three fold. First, there is a short discharge life after storage due to apparent chemical changes in the electrolyte; secondly, there is a pressure build-up because of detrimental side reactions in the electrolyte; and thirdly, there are cell degradation reactions among cell components. Yet these same unstable electrolyte systems for lithi~m batteries produce extremely high energy due to high conductivity of the solute in the solvent.
In lithium cells, cell degradation reactions can be manifested in various ways: crust formation on the anode, eg., with SOC12 solutions;
gas formation and cell rupture, eg., with lithium hexafluoroarsenate in methylformate, and polymerization of solvent, eg., in THF solutions.
- In all three type degradations, the reaction leads to decreased perform-ance, if not complete failure, of the cell. When using non-aqueou~
solvents in the electrolyte, both gassing and formation of viscous, if not solid, reaction products near the anode are of maJor concern; stable or stablized electrolyte has to be used in lithium cells.
11;~1;~0~
There are many applications, eg., watch, camera, etc., for which batteries must be constructed in a shape requiring high conductivity to permit efficient and economical utilization of the chemicals. Design limitations require utilization of highly conductive electrolytes. Ho~ever, conditions of use require electrolytes capable of long term storage.
In United States Patent 3,887,397, issued June 3, 1975, to Robert J~ Horning, it is disclosed that in lithium cells having a highly conductive methylformate/lithium hexafluoroarsenate electrolyte, the addition of small amounts of lithium tetrafluoroborate will significantly improve the stability of the cell. Thus by using lithium tetrafluoroborate as a stabilizer, Horning succeeded in practically eliminating the gassing reaction between lithium and the specific electrolyte.
However, no mention is made in the patent of any other tetra-fluoroborate which could be utilized or of any ability to control non-gassing reactions causing deposition of reddish-brown viscous products on and near the lithium. Such viscous deposits will hinder the performance of the anode after prolonged storage andior at higher rates by slowing ionic mobility near the anode.
It is the objective of this invention to provide a method of stabilizing non-aqueous lithium batteries in terms of reducing chemical interactions between the electrolyte and cell components.
A more particular object of this invention is to provide stabilizing additives for high rate lithium cells so that gassing and other reaction product formations are not observed.
Summary of the Invention It has been discovered that the stability of high rate batteries which contain a lithium anode, an electrolyte having a solvent and solute and a cathode will be significantly improved by the addition to the electrolyte of a minor portion of a tetrafluoroborate salt of sodium, potassium, or mixtures thereof dissolved in said electrolyte, wherein the amount of tetrafluoroborate salt ranges from 0.05 to 0.1 molar.
~,~
~S 3~3~)~
Detailed ~escription of the Invention The cathode can be any cathodic material which i8 inert to the electrolyte, among these are V205, Ag2CrO4, (CF)n, ~nO2, CuS and others which are known to those skilled in the art. As stated above, this invention relates basically to stabilizing of the electrolyte and anode, hence, does not require any particular cathode for use.
The solvents of the electrolyte used in the current invention are those which are known for use in high rate cells. Examples include methylformate, gamma butyrolactone, 1,2 - dimethoxyethane and 1,3 -dioxolane, and mixtures thereof.
The solutes which are dissolved in the solvents to form the electrolyte are also known to those skilled in the art. Examples include the hexafluoroarsenates, the trifluoromethylsulfonates and the perchlorates. It is preferred that the salt of these cations be the lithium salt.
The additive is a tetrafluoroborate salt of sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, barium, aluminum or mixtures thereof. The sodium and potassium salts are preferred.
The amount of the tetrafluoroborate salt which should be employed varies depending upon the stability desired. Normally, the amount of tetrafluoroborate salt will range from approximately 0.05 molar to as much as 0.8 molar in the electrolyte. A more preferred range is about from 0.05 to 0.1 molar percent.
The current inventors have found that the use of these tetra-fluoroborate salts not only stops the gas reaction but also decreases and practically eliminates~the non-gassing side reactions`. For,example, in the case of lithium hexafluoroarsenate in methylformate with lithium tetrafluoroborate or no additives, these side reactions produce a reddish-brown viscous product that clings to the lithium. This product will effect the high rate performance of cells by both slowing ionic bility near the anode. The current inventors have found that even in
3~
highly reactive llthlu~ hexsfluoroarsenate in methylformate electrolyte, the elimination of the ~de reaction is increased if one uses the tetra-fluoroborate salt of sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, barium, aluminum or mixtures thereof.
EX~MPLE 1 Strips of lithium were placed in four heavy glass tubes each having a different electrolyte solution. The tubes were part of an apparatus used to measure the gassing and observe corrosion on the lithium. The apparatus consisted of a heavy glass tube (Fischer and Porter Co., Aerosol Reaction Vessel, No. 110-205) connected to an Bourdon gauge (-30 to 150 inches mercury, U.S. Gauge No. 5060). The seal between the gas vessel and tube leading to the gauge was made with a stainless steel adapter plug fitted with a silicone rubber ~0~! ring.
The sealed apparatus was placed into an oven at 165F and monitored daily for gassing and for impurity formation on the lithium.
The experiments were continued until there was a significant increase in the pressure within the test tubes of 1 to 1-1/2 atmospheres of pressure over the pressure of equilibrium at 165F or until they extended over a period of time in which a significant difference could be seen in the additives.
In all the tests the solvent was methylformate and the solute was 2.0 molar LiAsF6. The electrolyte differed only by additive. The results were as foll~ws:
Hours Until Visual Significant Inspection Additive Pressure Build IT~ Of Lithium None 787 Substantial Amount of Viscous Material O.IM LiBF4 984* Large Amount of Viscous Material 0.1~ NaBF 984* Substantially Free of
highly reactive llthlu~ hexsfluoroarsenate in methylformate electrolyte, the elimination of the ~de reaction is increased if one uses the tetra-fluoroborate salt of sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, barium, aluminum or mixtures thereof.
EX~MPLE 1 Strips of lithium were placed in four heavy glass tubes each having a different electrolyte solution. The tubes were part of an apparatus used to measure the gassing and observe corrosion on the lithium. The apparatus consisted of a heavy glass tube (Fischer and Porter Co., Aerosol Reaction Vessel, No. 110-205) connected to an Bourdon gauge (-30 to 150 inches mercury, U.S. Gauge No. 5060). The seal between the gas vessel and tube leading to the gauge was made with a stainless steel adapter plug fitted with a silicone rubber ~0~! ring.
The sealed apparatus was placed into an oven at 165F and monitored daily for gassing and for impurity formation on the lithium.
The experiments were continued until there was a significant increase in the pressure within the test tubes of 1 to 1-1/2 atmospheres of pressure over the pressure of equilibrium at 165F or until they extended over a period of time in which a significant difference could be seen in the additives.
In all the tests the solvent was methylformate and the solute was 2.0 molar LiAsF6. The electrolyte differed only by additive. The results were as foll~ws:
Hours Until Visual Significant Inspection Additive Pressure Build IT~ Of Lithium None 787 Substantial Amount of Viscous Material O.IM LiBF4 984* Large Amount of Viscous Material 0.1~ NaBF 984* Substantially Free of
4 Viscous Material O.1~ KBF4 984* Substantially Free of Viscous ~aterial * ~he test was deliberately terminated at this point.
Claims (6)
1. An improvement in an electrochemical cell having a lithium anode, a non-aqueous electrolyte comprised of a solvent and solute and a cathode, the improvement comprises having as an additive a minor portion of a tetra-fluoroborate salt of sodium, potassium, or mixtures thereof dissolved in said electrolyte, wherein the amount of tetrafluoroborate salt ranges from 0.05 to 0.1 molar.
2. The cell of claim 1 wherein the electrolyte is methylformate, gamma-butyrolactone, 1,2-dimethyoxyethane, 1,3-dioxolane or mixtures thereof.
3. The cell of claim 1 wherein the solvent is methylformate.
4. The cell of claim 1 wherein the solute is lithium hexafluoro-arsenate, lithium trifluoromethylsulfonate or lithium perchlorate.
5. In a current producing cell having a lithium anode, an electrolyte of methylformate having lithium hexafluoroarsenate dissolved therein and a cathode, the improvement comprising having a minor portion of sodium tetra-fluoroborate dissolved in said electrolyte, wherein the amount of tetrafluoro-borate salt ranges from 0.05 to 0.1 molar.
6. In a current producing cell having a lithium anode, an electrolyte of methylformate having lithium hexafluoroarsenate dissolved therein and a cathode, the improvement comprising having a minor portion of potassium tetrafluoroborate dissolved in said electrolyte, wherein the amount of tetrafluoroborate salt ranges from 0.05 to 0.1 molar.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US94542578A | 1978-09-25 | 1978-09-25 | |
| US945,425 | 1978-09-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1131306A true CA1131306A (en) | 1982-09-07 |
Family
ID=25483067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA335,955A Expired CA1131306A (en) | 1978-09-25 | 1979-09-19 | Tetrafluoroborate additive for high drain rate lithium cells |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5546298A (en) |
| CA (1) | CA1131306A (en) |
| DE (1) | DE2938461A1 (en) |
| DK (1) | DK398079A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4279972A (en) * | 1979-08-27 | 1981-07-21 | Duracell International Inc. | Non-aqueous electrolyte cell |
| JPS5996667A (en) * | 1982-11-25 | 1984-06-04 | Nippon Telegr & Teleph Corp <Ntt> | Electrolyte for lithium battery |
-
1979
- 1979-09-19 CA CA335,955A patent/CA1131306A/en not_active Expired
- 1979-09-22 DE DE19792938461 patent/DE2938461A1/en not_active Withdrawn
- 1979-09-24 DK DK398079A patent/DK398079A/en unknown
- 1979-09-25 JP JP12309579A patent/JPS5546298A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DK398079A (en) | 1980-03-26 |
| JPS5546298A (en) | 1980-03-31 |
| DE2938461A1 (en) | 1980-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3947289A (en) | Mixed solvents for high and low temperature organic electrolyte batteries | |
| US3907597A (en) | Nonaqueous cell having an electrolyte containing sulfolane or an alkyl-substituted derivative thereof | |
| US4139680A (en) | Method for preventing dendritic growth in secondary cells | |
| US3993501A (en) | Nonaqueous electrochemical cell | |
| US3423242A (en) | Electric current-producing cell with anhydrous organic liquid electrolyte | |
| US4160070A (en) | Additive for high drain rate lithium cells | |
| US4056663A (en) | Performance in an organic electrolyte | |
| US4218523A (en) | Nonaqueous electrochemical cell | |
| US3493433A (en) | Electrodeposition of alkali metals from nonaqueous solvents | |
| US5589295A (en) | Thin film polymeric gel electrolytes | |
| EP0111214A2 (en) | Nonaqueous cell and a method for treating an active metal anode of a nonaqueous cell | |
| IE50677B1 (en) | Non-aqueous li/mno2 cell | |
| US3279952A (en) | Electric current-producing cell having acetic anhydride electrolyte solvent | |
| US4177329A (en) | Electrolyte salts for non aqueous electrochemical cells | |
| US4444855A (en) | Non-aqueous electrochemical cell | |
| US4195122A (en) | Additive for high drain rate lithium cells | |
| US4216279A (en) | Manganese dioxide fluoride-containing cathodes for solid electrolyte cells | |
| US4277545A (en) | Nonaqueous cell | |
| CA1131306A (en) | Tetrafluoroborate additive for high drain rate lithium cells | |
| US4400453A (en) | Non-aqueous electrochemical cell | |
| Jasinski | A summary of patents on organic electrolyte batteries | |
| CA1043866A (en) | Nonaqueous cell having an electrolyte containing crotonitrile | |
| US3887397A (en) | Highly conductive stable electrolyte for lithium batteries | |
| US4439503A (en) | Metal-organic liquid depolarizer electrochemical cell | |
| US4327159A (en) | Non-aqueous electrochemical cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19990907 |