CA1076645A - Electrochemical cell with clovoborate salt in electrolyte - Google Patents
Electrochemical cell with clovoborate salt in electrolyteInfo
- Publication number
- CA1076645A CA1076645A CA258,520A CA258520A CA1076645A CA 1076645 A CA1076645 A CA 1076645A CA 258520 A CA258520 A CA 258520A CA 1076645 A CA1076645 A CA 1076645A
- Authority
- CA
- Canada
- Prior art keywords
- cells
- electrolyte
- cell
- electrochemical cell
- salt
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
-
- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- 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
Abstract
ABSTRACT
An electrolyte salt containing a clovoborate anion structure when employed in an electrochemical cell comprising an active metal anode and an electrolyte solvent/cathode depolarizer has the characteristics of high potential and current capabilities at low temperatures and resists anode passivation during long time storage even at elevated temperatures.
An electrolyte salt containing a clovoborate anion structure when employed in an electrochemical cell comprising an active metal anode and an electrolyte solvent/cathode depolarizer has the characteristics of high potential and current capabilities at low temperatures and resists anode passivation during long time storage even at elevated temperatures.
Description
107ti~ 5 FIELD OF T}IE I2~VENTION
This invention pertains to electrolytes employed in non-aqueous electrolytic cells and more particularly to celLs utilizing a soluble cathode system in which a fluid oxyhalide or non-metallic oxide or non-metallic halide or mixtures thereof is or are both the electrolyte solvent and the primary active cathode substance.
B~CKGROUND OF THE INVENTION
Electrochemical cells for use as power sources, particularly in con~unction with hearing aids and other medical related devices, are known which employ soluble or liquld cathodes as opposed to the more con-ventional solid cathode cells. In such soluble cathode cells the active cathode material is usually the electrolyte solvent, or one of the co-solvents. During discharge, the solvent or co-solvents are electrochemically reduced on a current collector such as a screen, having applied thereto a mixture of an inert and electrically conductive material such as carbon black, graphite, or other electrical conductors of high surface area, and, pre- ~ ;
ferably, including absorbing and binding agents. The anode for these cells is preferably lithium metal although other active metals above hydrogen in the activity scale or electromotive series including sodium, potassium, rubidium, calcium, magnesium, strontium, barium and cesium may be used either singly or in combination.
Soluble cathode cells based upon the utilization of lithium as the anode active metal and thionyl chloride (SOC12) as both electrolyte solvent and soluble cathode and lithium aluminum chloride (LiAlC14) as the electrolyte salt have been prepared with roughly the dimension of conventional "D~' and "C" size cells, using a convolutely wound structure.
"C" cells were observed to realize /
_/ , b : : ' ' 10~66~5 about 156 watt-hours per pound, about 11.6 watt-hours per cubic inch and up to about 93 watts per pound at about 3 volts potential per cell for freshly prepared cells. These high potentials and capacities make this type of cell particularly useful in devices requiring infrequent replacement of cells such as in heart pacemaker devices. However, several problems exist with this cell which presently militate a~ainst its widespread practical use.
; One deficiency of the cells described above, using LiAlC14 as the electrolyte salt, is that filled or activated cells which have been stored, particularly at elevated temperatures for extended period of time, wlll exhibit an undesirable initiation period or delay time when discharge is attempted. This initiation, or delay time is due to passivation of the lithium anode, that is, formation of an electrically insulating film or layer over the lithium and its severity is dependent upon the conditions of storage. It has been observed that storage at about 72C for about 4 days is sufficient to passivate the lithium anode to the extent that reverse ; polarization of the cell for several minutes may be necessary to sufficiently remove the insulating film or layer and reactivate the anode.
THE INVENTION
It is a feature of the present invention to provide an electrolyte salt as a method for ion transport including a cation of a metal and a clovoborate anion (for nomenclature, see R. Adams, Inorg. Chem. 2, 1087, (1963)). Another feature of the present invention is that the electrolyte ;
salt is sufficiently soluble and stable in a fluid oxyhalide or non-metallic oxide or non-metallic halide and mixtures thereof to function in an electro-chemical cell. Yet another feature of the present invention is that the electrolyte salt, when used in electrochemical , ; -2-1~S7~f~4~
cells, helps reduce capacity losses at low operating tempera-tures, helps reduce passivation of the metal anode, and thus helps reduce the voltage delay associated with start-up after storage at elevated temperatures. It is a further feature of the present invention to provide an electrochemical cell having as electrolyte salt a compound having (a) a cation of a metal and (b) a clovoborate anion with the formula (BmXn) k, where m, n and k are integers, B is boron, and X is selected from the group consisting of H, F Cl, Br, I & OH wherein at least some of the substituents are halides and combinations thereof. The metal clovoborate can be used in combination with an electro-lyte solvent selected from a fluid oxyhalide or non-metallic oxide or non-metallic halide or mixtures thereof. Another ; feature of the invention is a composition of matter including a cation of a metal and a clovoborate anion as an electrolyte salt and a material selected from a fluid oxyhalide or non-metallic oxide or non-metallic halide or mixtures thereof.
These and various other features of the invention as well as many specific advantages will be more fully apparent from a detailed consideration of the remainder of this disclosure and the drawings, s According to the above features, from a broad aspect, the present invention provides an electrochemical cell includ-ing a metal anode, a cathode, and as electrolyte salt a salt including a metal cationand a clovoborate anion.
~RI~F DESCRIPTION OF THE DR~WINGS
Figure 1 is a test cell structure including a lithium anode, thionyl chloride electrolyte solvent/cathode depolarizer and clovoborate electrolyte salt system, ~,~, J
.;
1(~766~S
Figures 2 and 3 show polarization data for the clovoborate electrolyte salt C size cells having different separators shortly after filling, on discharge at room temperature, Figure 4 is a discharge curve of prior art cells using LiAlC14 as the electrolyte salt under low temperature .
conditions after high temperature storage - 3a -:1~
17f~i4S
Figure 5 is a discharge curve of cells using the clovoborate electrolyte salt of the invention under the same conditions as the prior art cells shown in figure 4; and Figure 6 is a schematic drawing of a clovoborate structure.
DETAILED DFSCRIPTION OF THE INVENTION
Generally speaking, the present invention relates to an electro-lyte salt containing a clovoborate anion whose closed caged structure is illustrated in Figure 6 and a metal as the cation. The metal of the cation is selected from the metals Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba in Groups IA and IIA of the Periodic Table. This metal usually though not necessarily is the same as the metal of the anode of the electrical system in which the electrolyte is a component. Therefore in high energy density cells currently available the preferred metals would include lithium (Li), sodium (Na), potassium (K), magnesium (Mg), and calcium (Ca). The clovoborate anion has the general formula (B X ) k where B is the element boron and m, n and k are integers and X can be selected from a wide range of elements and groups of elements which may also include organic groups alone or in combination. This wide range of possibilities may be attributed essentially to the structure of the clovoborate anion which because of its caged struc-ture is stable and resistant to degradation. The substituent groups on the caged boron structure may control, to some extent, the usefulness of the salt as an electrolyte salt. As examples of ~everal clovoborate salts useful in electrochemical cells and the like, X in the above formula is preferably selected from the halogens (F, Cl, Br and I) but can also be H or OH prefer-ably in combination with halogen or halogens. The halogenated form of the clovoborate anion appears to provide more advantageous results than the hydride form because where X
.
" .
~' , - . .
is hydrogen rather than a halogen, the B-X bond appears less stable, but -all nevertheless embody the concepts of the invention. With the halogen and hydrogen forms of the clovoborate anion ~ust mentioned, the preferable forms would be those in which m and n of the above formula are integers selected from the group of 6-20 for M and 6-18 for n. Most preferably m and n are both 6, 9, 10, 11 or 12. Generally both m and n are the same, but in some cases they may differ because of cage linkups. The integer k may range from 1-4 but preferably is 2. As a single embodiment a presently preferred compositlon is where X is chlorine and m and n are both 10. This composition is quite useful as an electrolyte salt in electrochemical cells.
In particular, the composition is especially useful when u~ed as an elec-trolyte salt in an electrochemical cell containing a metal anode such as lithium and an electrolyte solvent cathode depolarizer material such as thionyl chloride. When the composition is used in an electrochemical cell, it is presently preferred that the metal of the cation be the same as the active metal of the anode in order to help prevent, among other things, the formation of extraneous salts upon electrical discharge. Thus, for example, `' when a lithium anode is used, it is preferred that the composition used as i the electrolyte salt includes a cation of lithium.
Use of an electrolyte salt embodying the concepts of the inven-tion in an electrochemical cell having a lithium anode and thionyl chloride electrolyte solvent/soluble cathode depolarizer provides a cell capable of operating under heavy load conditions at low temperatures with minimal start-up delay even after extended periods of storage at elevated temperatures.
The preferred concentration of electrolyte salt in a thionyl chloride electrolyte solvent/cathode depolarizer is such .
.
~07664S
that the conductivity lies within a useful range. A preferred embodiment would be a precentage ranging between about 10 wt. % to about 25 wt. ~ of the total weight of the electrolyte salt and cathode depolarizer combi-nation. The presently most preferred concentration is about 12 wt. %
electrolyte salt. At 20C, the conductivity of pure SOC12 is 3.5 x 10 9 ohm 1 cm 1, Thus the ratio of SOC12 to the electrolyte salt would be such that the conductivity of the preferred electrolyte solution would thus be in the range of 4.0 x 10 9 to 1.0 x 10 1 ohm 1 cm 1 at 20C.
In thionyl type cells with lithium anodes, specific presently preferred salts known and characterized in the chemicsl literature include Li B Cl Li BlOBrlO' Li2BloIlo~ Li2B12C112, Li2 12 12 2 12 12 Li2B6Br6, and Li2B12Br8F4. Less preferred salts include Li2BgC18H, Li2BgBr6H3,
This invention pertains to electrolytes employed in non-aqueous electrolytic cells and more particularly to celLs utilizing a soluble cathode system in which a fluid oxyhalide or non-metallic oxide or non-metallic halide or mixtures thereof is or are both the electrolyte solvent and the primary active cathode substance.
B~CKGROUND OF THE INVENTION
Electrochemical cells for use as power sources, particularly in con~unction with hearing aids and other medical related devices, are known which employ soluble or liquld cathodes as opposed to the more con-ventional solid cathode cells. In such soluble cathode cells the active cathode material is usually the electrolyte solvent, or one of the co-solvents. During discharge, the solvent or co-solvents are electrochemically reduced on a current collector such as a screen, having applied thereto a mixture of an inert and electrically conductive material such as carbon black, graphite, or other electrical conductors of high surface area, and, pre- ~ ;
ferably, including absorbing and binding agents. The anode for these cells is preferably lithium metal although other active metals above hydrogen in the activity scale or electromotive series including sodium, potassium, rubidium, calcium, magnesium, strontium, barium and cesium may be used either singly or in combination.
Soluble cathode cells based upon the utilization of lithium as the anode active metal and thionyl chloride (SOC12) as both electrolyte solvent and soluble cathode and lithium aluminum chloride (LiAlC14) as the electrolyte salt have been prepared with roughly the dimension of conventional "D~' and "C" size cells, using a convolutely wound structure.
"C" cells were observed to realize /
_/ , b : : ' ' 10~66~5 about 156 watt-hours per pound, about 11.6 watt-hours per cubic inch and up to about 93 watts per pound at about 3 volts potential per cell for freshly prepared cells. These high potentials and capacities make this type of cell particularly useful in devices requiring infrequent replacement of cells such as in heart pacemaker devices. However, several problems exist with this cell which presently militate a~ainst its widespread practical use.
; One deficiency of the cells described above, using LiAlC14 as the electrolyte salt, is that filled or activated cells which have been stored, particularly at elevated temperatures for extended period of time, wlll exhibit an undesirable initiation period or delay time when discharge is attempted. This initiation, or delay time is due to passivation of the lithium anode, that is, formation of an electrically insulating film or layer over the lithium and its severity is dependent upon the conditions of storage. It has been observed that storage at about 72C for about 4 days is sufficient to passivate the lithium anode to the extent that reverse ; polarization of the cell for several minutes may be necessary to sufficiently remove the insulating film or layer and reactivate the anode.
THE INVENTION
It is a feature of the present invention to provide an electrolyte salt as a method for ion transport including a cation of a metal and a clovoborate anion (for nomenclature, see R. Adams, Inorg. Chem. 2, 1087, (1963)). Another feature of the present invention is that the electrolyte ;
salt is sufficiently soluble and stable in a fluid oxyhalide or non-metallic oxide or non-metallic halide and mixtures thereof to function in an electro-chemical cell. Yet another feature of the present invention is that the electrolyte salt, when used in electrochemical , ; -2-1~S7~f~4~
cells, helps reduce capacity losses at low operating tempera-tures, helps reduce passivation of the metal anode, and thus helps reduce the voltage delay associated with start-up after storage at elevated temperatures. It is a further feature of the present invention to provide an electrochemical cell having as electrolyte salt a compound having (a) a cation of a metal and (b) a clovoborate anion with the formula (BmXn) k, where m, n and k are integers, B is boron, and X is selected from the group consisting of H, F Cl, Br, I & OH wherein at least some of the substituents are halides and combinations thereof. The metal clovoborate can be used in combination with an electro-lyte solvent selected from a fluid oxyhalide or non-metallic oxide or non-metallic halide or mixtures thereof. Another ; feature of the invention is a composition of matter including a cation of a metal and a clovoborate anion as an electrolyte salt and a material selected from a fluid oxyhalide or non-metallic oxide or non-metallic halide or mixtures thereof.
These and various other features of the invention as well as many specific advantages will be more fully apparent from a detailed consideration of the remainder of this disclosure and the drawings, s According to the above features, from a broad aspect, the present invention provides an electrochemical cell includ-ing a metal anode, a cathode, and as electrolyte salt a salt including a metal cationand a clovoborate anion.
~RI~F DESCRIPTION OF THE DR~WINGS
Figure 1 is a test cell structure including a lithium anode, thionyl chloride electrolyte solvent/cathode depolarizer and clovoborate electrolyte salt system, ~,~, J
.;
1(~766~S
Figures 2 and 3 show polarization data for the clovoborate electrolyte salt C size cells having different separators shortly after filling, on discharge at room temperature, Figure 4 is a discharge curve of prior art cells using LiAlC14 as the electrolyte salt under low temperature .
conditions after high temperature storage - 3a -:1~
17f~i4S
Figure 5 is a discharge curve of cells using the clovoborate electrolyte salt of the invention under the same conditions as the prior art cells shown in figure 4; and Figure 6 is a schematic drawing of a clovoborate structure.
DETAILED DFSCRIPTION OF THE INVENTION
Generally speaking, the present invention relates to an electro-lyte salt containing a clovoborate anion whose closed caged structure is illustrated in Figure 6 and a metal as the cation. The metal of the cation is selected from the metals Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba in Groups IA and IIA of the Periodic Table. This metal usually though not necessarily is the same as the metal of the anode of the electrical system in which the electrolyte is a component. Therefore in high energy density cells currently available the preferred metals would include lithium (Li), sodium (Na), potassium (K), magnesium (Mg), and calcium (Ca). The clovoborate anion has the general formula (B X ) k where B is the element boron and m, n and k are integers and X can be selected from a wide range of elements and groups of elements which may also include organic groups alone or in combination. This wide range of possibilities may be attributed essentially to the structure of the clovoborate anion which because of its caged struc-ture is stable and resistant to degradation. The substituent groups on the caged boron structure may control, to some extent, the usefulness of the salt as an electrolyte salt. As examples of ~everal clovoborate salts useful in electrochemical cells and the like, X in the above formula is preferably selected from the halogens (F, Cl, Br and I) but can also be H or OH prefer-ably in combination with halogen or halogens. The halogenated form of the clovoborate anion appears to provide more advantageous results than the hydride form because where X
.
" .
~' , - . .
is hydrogen rather than a halogen, the B-X bond appears less stable, but -all nevertheless embody the concepts of the invention. With the halogen and hydrogen forms of the clovoborate anion ~ust mentioned, the preferable forms would be those in which m and n of the above formula are integers selected from the group of 6-20 for M and 6-18 for n. Most preferably m and n are both 6, 9, 10, 11 or 12. Generally both m and n are the same, but in some cases they may differ because of cage linkups. The integer k may range from 1-4 but preferably is 2. As a single embodiment a presently preferred compositlon is where X is chlorine and m and n are both 10. This composition is quite useful as an electrolyte salt in electrochemical cells.
In particular, the composition is especially useful when u~ed as an elec-trolyte salt in an electrochemical cell containing a metal anode such as lithium and an electrolyte solvent cathode depolarizer material such as thionyl chloride. When the composition is used in an electrochemical cell, it is presently preferred that the metal of the cation be the same as the active metal of the anode in order to help prevent, among other things, the formation of extraneous salts upon electrical discharge. Thus, for example, `' when a lithium anode is used, it is preferred that the composition used as i the electrolyte salt includes a cation of lithium.
Use of an electrolyte salt embodying the concepts of the inven-tion in an electrochemical cell having a lithium anode and thionyl chloride electrolyte solvent/soluble cathode depolarizer provides a cell capable of operating under heavy load conditions at low temperatures with minimal start-up delay even after extended periods of storage at elevated temperatures.
The preferred concentration of electrolyte salt in a thionyl chloride electrolyte solvent/cathode depolarizer is such .
.
~07664S
that the conductivity lies within a useful range. A preferred embodiment would be a precentage ranging between about 10 wt. % to about 25 wt. ~ of the total weight of the electrolyte salt and cathode depolarizer combi-nation. The presently most preferred concentration is about 12 wt. %
electrolyte salt. At 20C, the conductivity of pure SOC12 is 3.5 x 10 9 ohm 1 cm 1, Thus the ratio of SOC12 to the electrolyte salt would be such that the conductivity of the preferred electrolyte solution would thus be in the range of 4.0 x 10 9 to 1.0 x 10 1 ohm 1 cm 1 at 20C.
In thionyl type cells with lithium anodes, specific presently preferred salts known and characterized in the chemicsl literature include Li B Cl Li BlOBrlO' Li2BloIlo~ Li2B12C112, Li2 12 12 2 12 12 Li2B6Br6, and Li2B12Br8F4. Less preferred salts include Li2BgC18H, Li2BgBr6H3,
2 11 9 2 2 12 8F4~ Li2B12H7Fs~ and Li2B12H6F6 and Li B F OH
The electrolyte salts of the present invention are also useful in electrochemical cells utilizing a solvent selected from a fluid oxyhalide, or non-metallic oxide or non-metallic halide and mixtures thereof such as phosphorous oxychloride (POC13), selenium oxychloride (SeOC12), sulfur di-' oxide (S02), sulfur trioxide (S03), vanadium oxytrichloride VOC13, chromyl i chloride (CrO2C12), sulfuric oxychloride (S02C12), Nitryl chloride (N02Cl), nitrosyl chloride (NOCl), nitrogen dioxide (N02), sulfur monochloride (S2C12) ; and sulfur monobromide (S2Br2). Each of the above can be used together with thionyl chloride (SOC12) as electrolyte solvent/cathode depolarizer or separately. Cosolvents or solvents other than SOC12 may also be electro-chemically reduced on the cathode, but this reduction will not occur at the same potential as that for SOC12. Cosolvents will thus alter the energy ~ density of such cells, either lowering .~ :
~ `
1~766~S
lt or raising it dependlng upon the solvent or cosolyent chosen, Howeyer, co-solvents may be necessary or useful in improving high and low temperature characteristics of the cell or in modifying properties of the system.
Fluid oxyhalldes such as phosphorous oxychloride (pOC13)~ fluid non-metallic oxides or fluid non-metallic halides or mixtures thereof may entirely replace thionyl chloride, SOC12, for the purposes of the pxesent invention even though the disc~large voltage may be generally lower.
Halogenated clovoborate anion and, in particular, the anion having the formula BloCllo are generally prepared by the halogenation of the hydride form of the corresponding anion having the formula (BnHn) , The preparation o the clovoborate anion BloHlo has been discussed by Hawthorne and Muetterties and their co-workers in a series of articles appearing in J, ~m.
Chem. Soc. 81, 5519 (1959); 84, 1056 (1962); 84, 1057 (1962), The formation , . , =
o~ B12H12 was reported and discussed by Ellis, Gaines and Schaeffer (J, Am. Chem. Soc. 85, 3885 (1963), by Miller, Miller, and Muetterties (idem.) and by ~dams, Siedle, and Grant (Inorg. Chem, 3~ 461 (1964), BloHlo and ~12H12 ls disclosed by Muetterties and co-wor~ers in Inorg.
Chem. 3, 159 (1964), Examples o the halogenated anions include (Bl2Xl2) , (BloXlo) , and (B6Br6) (observation by W.R, Hertler in article by Klanberg, Muetterties, Inorg. Chem. 5, 1955 (1966 )) where X is a halogen i.e. fluorine?
chlorine, bromine oX iodlne, The anions having n=6, 10? 12 are more resistant to de~radati~n as a result of more st~ble bonding and thus ~re pre~erred ~or purpoaes of the present invention.
, , ~ ~
1076~45 Figure 6 shows the ca~yed structure of the stable Blo clovoborate anion with the boron atoms depicted and numbered.
The caged structure remains substantially the same with other constituents including halogens replacing some or all of the original hydrogens.
The cells utilizing the novel electrolyte according to this invention are constructed with cathode current collectors of acetylene black with a Teflon binder applied to a nickel screen.
Teflon is a trademark registered by E.I. du Pont De Nemours Company, Wilmington, Delaware, U.S.A. After treating the screen to insure proper adherence of the acetylene black, the cells are assembled. Typical cells can be constructed in the "C" and "D" configurations using flat lithium metal anodes and separators of borosilicate glass fibers. The cathode current collectors for cell of the "C" configuration should preferably measure about 8 l/2" x 1 1/2" and each contain from 1 to 1.6 grams of acetylene black applied to the nickel screen. The anode, separator, and cathode current collector strip assembly are then convolutely wound for insertion into a container for the cell.
Because of the various properties discovered in cells using the novel electrolyte of this invention several test cells are used to determine more precisely those properties Thus, test cells of standard D size are utilized in testing the low temperature capabilities of the cells after extending high temperature storage while cells of the standard C size are used in ambient temperature start-up characteristics determinations.
Both sizes are constructed as above with the C size cells having Teflon cases and rubber seals and the D cells having metal cases and glass seals. Cell size, does not ho~ever affect cell per-formance except for total capacity.
'I'he invention will be more fully described by the followir,g examples, wherein EXAMPI,E 1 describes the preparation of 1,i2BloCllo as an example of the halogenated salts of this invention, EXAMPI,E 2 describes the preparation and handling of an electrolyte containing -the Li2BloCllo dissolved in thionyl chloride for utilization in electrochemical energy generating cells. EXAMPI,E 2 additionally shows the stable nature of the salt when dissolved in the thionyl chloride. It is postulated that the salt is substantially soluble and ionically dissociates in the thionyl chloride through formation of a com-plex between the anion and the SOC12. The anion is the active principle of this invention, and is also believed to be the agent which helps prevent the passivation of the lithium anode.
EXAMPLE 3 describes the preparation of the C size cells according to this invention (the D size cells are prepared in basically the same manner) and the initial discharge character-,~ istics of the C cells, EXAMPLE 3 demons~rates that the electro-lyte of the present invention when added to the aforementioned cell functions both as a useful electr~lyte and as a soluble cathode or depolarizer.
EXAMPLE 4 demonstrates the low temperature characteristics of the D cell using the novel electrolyte of this invention as compared to the performance of prior art cells, EXAMPLE 5 demonstrates, in tabular form, the discharge characteristics of the cells according to this invention and : those of the prior art after prolonged periods of storage at 72 C, EXAMPLE S demonstrates that the start-up delay for cells according to the present invention is bhorter and less severe than cells using LiAlC14 as the dissolved conductive species for the : _9_ 107~64s electrolyte.
It is understood that the attached examples are merely exemplary and that all art recognized equivalents of the materials may be utilized and that such interchangeable utiliza-tion of equivalents is intended to be within the scope of this invention.
It may be further noted, that the invention may be practiced with other metal anodes. In such circumstances, the specific active metal salts of such active metals with the halogenated clovoborate anions preferably may be substituted, but the lithium salts may also be used.
~rhe preparation of novel electrolytically conductive lithium halogenated clovoborate salts is exemplified by the pre-paration of Li2BloCllo:
The anion BloCllo is prepared starting with decaborane, B1oH14. About 5 grams of BloH14 (41 millimoles) are dissolved in about~ 30 ml. of anhydrous benzene in a 200 ml round bottom flask. In a separate vessel about 14.5 ml of 20 distilled triethylamine (104 mm) and about 35 ml of anhydrous benzene are mixed. The mixture is then added slowly to the flask containing the solution of decaborane and the total mixture is refluxed for about 16 to about 24 hours. After this time, a white solid separated whose composition is (NEt3H)2BloHlo, i.e. the bistriethylammonium salt of the anion BloHlo . The procedure to this point is described by M.F. Hawthorne and A.R. Pitochelli (J. Am. Chem. Soc. 81, 5519, (1959)).
The BloHlo anion is then chlorinated in aqueous solution and the~ BloHlo is transformed to BloCllo by the following pro-cedure which differs from the one described by Muetteries et al , . .
- : , - - ,. :
107~45 (Inorganic Chem. 3, 159, (1964)) in that higher concentrations in the order of 2.5 x 10 M and the sodium salt are used in place of the ammonium salt and lower concentrations in the reference in the order of 4.3 x 10 4 M.
About 6.45 grams (40 mm) of (NEt3H)2BloHlo are dissolved in a solution of about 3.52 grams of NaOH (88 mm, a 10~ excess) in about 60 ml of water. The released triethyl amine is removed first by using a separatory funnel, then by using the funnel and washing the solution with several 30 ml portions of benzene. The remaining solution is then ad~usted to about pH
5 using acetic acid, and diluted to about 160 ml with water. Chlorine gas is then slowly introduced into the agitated solution. After about 12 to 15 hours, excess chlorine is removed by boiling from the resultant deep green solution. An aqueous solution of about 12.3 ml of triethylamine (88 mm) in a slight excess of 6 m hydrochloric acid is then added to the reaction vessel. The slightly soluble salt (NEt3H)2BloCllo is precipitated and is then filtered and washéd to remove sodium chloride, sodium acetate, hydro-chloric acid and water.
The lithium salt is then prepared and purified by the following method:
About 2.11 grams of lithium hydroxide (88 mm) are dissolved in 50 ml of water. About 26.7 grams (40 mm) of(NEt3H)2BlOCl10 are then introduced and dissolved. The released triethylamine is extracted with about three 50 ml portions of benzene. The aqueous solution i8 then acidified with con-centrated hydrochloric acid while agitating. The remaining amine precipitates and is filtered to substantially remove it from the solution. The solution is ; then made basic again with a slight excess of solid LiOH. About 4.2 grams (100 mm) of lithium chloride are :, , ., then dissolved ln the basic solution and the solution is mixed with about 50 ml of tetrahydrofuran in a separatory funnel. The lighter phase then con-tains essentially all of the desired product, along with some water and lithium chloride. This phase is mixed with one gram of solid lithium chloride. The salt removes most of the water from the ethereal solution, forming a heavier aqueous phase which is removed. The process is repeated until solid lithium chloride remains after mixing and standing. The lighter phase after separa-tion from all solids and droplets of aqueous phase is then transferred to a 100 ml flask which includes a small fractionating column leaving an azeo-tropic mixture of THF and water with the dissolved desired product. Frac-tional distillation of the mixture results in the removal of the wet azeo-trope of the THF and water at a temperature of 64C, rendering the solution gradually drier. Crystals of the product form as the liquid distilled from the flask is replaced with dry tetrahydrofuran. These are filtered and washed with dry tetrahydrofuran, then dried at about 1~0C (available oven temperature) for about 48 hours. The resulting Li2BlQCllo crystals are checked for purity by infrared spectroscopy.
The preparation of electrolyte including thionyl chloride soluble cathode material:
A solution is prepared by dissolving about 3 grams of Li2BloCllo in about 12 ml distilled thionyl chloride, refluxing in a glass vessel with strips of freshly cut lithium for about 2 hours, then adding distilled thionyl chloride to a total volume of about 25 ml. The resulting mixture is deep violet in color and contains no precipitate. The bistriethylammonium salts of substituted clovoborate anions are only :
'~
1~766~S
slightly soluble in water and may be easily recovered by precipitation. A sample of this amine salt is prepared in water from the original L,i2BloCllo and another from a hydrolized aliquot of the solution Li2BloCllo in thionyl chloride. The two samples produced substantially identical infrared spectra, demonstrating that no harmful substitution or alternation of the anion occurs during reflux in SOC12 with lithium metal present. After hydrolysis, the solution of Li2BloClo in water was colorless, suggesting that the color is produced by a complex formation between the anion and SOC12.
Figure 1 is a cross sectional view of the electro-chemical test cell assembly used for testing the electrochemical generator of this invention. The test cells having C and D
cell size configuration are substantially alike with the C cells being described as follows and the D cells differing by having metal cases and glass seals instead of the Teflon casing and rubber seals used in the C size test cell:
The assembly as shown in Figure 1 consists of an aluminum cell holder 2 holding the cell elements consisting of Teflon cell body 3 and Teflon cover 4 enclosing and sealing via "0" ring 6 of neoprene and helically wound electrode stack 5. The electrode stack S consists of cathode collector sheet 8 of nickel expanded metal mesh and lithium ribbon 9 separated from each other by separator mats 7. The electrode stack is con-volutely wound. The dimensions are selected so that the wound stack assembly 5 has the approximate dimensions of a commercial C cell, i.e. 0.90 inches in diameter and 1.75 inches in height.
As the electrolyte and the anode are air-sensitive the cell and its elements are sealed from the external environment by the "O" ring 6 and electrode septums 15 for cathode terminal 12 and anode terminal 13 respectively which reach the exterior of the cell through the insulating screws 14. The terminals are connected via cathode lead 10 and anode lead 11 respectively to the cathode and anode elements 8 and 9.
The electrolyte is lntroduced into the cell via electrolyte fill port 16 through the self-sealing neoprene septum 18 and about 25 ml of the electrolyte are used to fill the cell.
The test cell i8 provided with a lithium reference electrode 17, similar to the feed throughs 14, to monitor electrode polarization. The anode 9 in the test cell contains about 6 ampere hours of lithium.
The open circuit potential of the Li/SOC12 cells of both the prior art and this invention is about 3.62 - 0.05 volts.
When the electrolyte according to EXAMPLE 2 is introduced into the above described cell having glass fiber separators between the anode 9 and the cathode collector 8 such cells show the polarization potentials under loads as in Figure 2. When polypropylene separators are substituted for the glass fiber separators such cells exhibit the polarization potentials at the different loads as shown in Figure 3.
Low temperature characteristics of cells using the novel electro-lyte of this invention as compared to prior art cells:
All of the cells used were of standard D size and stored for either 1 month or 4 weeks at 72C. The cells were cooled to -30C for two hours prior to discharge.
~¦ Prior art cells using LiAlC14 as the electrolyte ' . :~- . , . : - .
~076645 performed as depicted in Figure 4 at various constant current loads. The e]ectrolyte consists of about 1 Molar LiAlC14 in SOC12 as the only solvent.
The discharge curve ofcell A is taken under a load of about 0.25 amperes.
The discharge curve of cell B is taken under a load of about 1.00 amperes.
As shown in figure 4, cell B required about 0.8 amp-hours, or about 0.8 hours, or 48 minutes before its terminal potential recovered above zero volts. Cell A delayed to about 2.4 volts for several seconds and this delay is not shown in Fig. 4.
In comparison substantially identical cells using the novel electrolyte with 0.4333 N Li2BloCllo in SOC12 only, are discharged after storage of about 72 C for 1 month.
Cell D which discharges at a rate of 1 ampere delayed to about 2.6 volts, but recovered to about 3.3 volts in less than 1 second. Cell C which discharges at a rate of about 0.25 amp did not drop below 3 volts on startup. Figure 5 shows the , 20 above-mentioned cells with the novel clovoborate electrolyte during the rest of their discharge. The discharge curve of cell C shows that this cell which runs at about 0.25 amp realizes about 4.8 amp hours before the output drops to 2 volts. This cell has a running potential above 2.75 volts. In contrast the prior art cell A discharged at this rate realizes only 3.5 amp "
hours to about 2 volts and has a less desirable sloping dis-` charge curve (Figure 4). The cell containing Li2BloCllo functions well at 1 amp in marked contrast to the functioning of cell B
which uses LiAlC14 (Fig. 4).
~07664S
Room temperature discharge characteristics after about 72C storage as compared to prior art cells:
'I'est cells are constructed in the slze C configuration for both the prior art material containing about 1.5 M LiAlC14 in SOC12 only, as the electrolyte and electrolyte solvent re- .
spectively, and the cells utilizing the novel electrolyte of this invention in the concentration of about 0.50 N Li2BloCllo in SOC12 only. All the cells are discharged at about 0.50 amp constant current at room temperature following storage.
The following -tables illustrate advantage of cells utilizing the novel electrolyte of this invention particularly when compared to cells utilizing the electrolyte, LiAlC14, of the prior art. Table 1 shows the recovery time when discharged at ambient temperature for prior art cells when stored at about 72 C for varying lengths of time without any discharge before storage.
Table II shows the prior art cells' recovery time after being discharged at about 0.5 amp constant current for an hour prior to storage at about 72 C.
Table III shows the recovery time for cells using the novel electrolyte containing the clovoborate anion of this invention after discharge for a short period of time shown in Figures 2 & 3 prior to storage which discharge was performed to obtain the polarization curve of Figures 2 & 3.
, ~ -16-. .
~O ~0 ~ n ~ _ ~
0 r r r ::~
o~
tD
o ~ ~ ~3 D~ C') C~` 4 ~ ~ ~ ~
~3 ~ Y ~ g ~:~ ~ ~ g g ~ ~ .
0 e: ~ ~3 ~ ~~ ~3 ~ ~ ~ ~ ~3 ~ ~ cn cncl~ ~ ~ .
~ r~ .
H
u~ c~ cn ~ ~ ~ ~ r o. P~ o ~ .
r~ _, ~I ~ , ~) ~o ~ ~ ~ ~O o O ~ ~_ O o O o ~ tD * ~ (D ~ ~
" ~ ., æ ~ ~ ~ c ~ ,t :' rr ~ ~r ~ ~t- rl ~ SCI O ~3 , ~D W P~ ~1 r w o w ~ 1- :~
. ~ ~o w ~,_ e~ ~ ~
. ~D ~ ~ ~ C ~: ~ ~ W
C ~ O ~ ,_ r~ ~ ~ D. rr n o o ~ On ~n o ~ ~ g ~ ;~
O æ ,~ CO 3~ ~ w O
o r o u~ o ~,o r r~ o w w w w o ~ E~ ~ & Z 3 ~ ' 8 z z g~ 03 ~1-- a ~ w~ r3 ~
8 rr ~. o rr 8 o ~ a ~ ~ 0 O~ r~ 3 . ~ ~ ~
r~ ::
~1 ~ O ~ ~o O W~ r~
I~ O ~ ~n ~3g cn ~n ~ cn ~ C
.. ~ W ~ ~ ~ ~
: Z 3 wo ~ ' o c~
cn r~ c ~r3 r .
.
. .
~.07~6~5 F`rom a comparison between 'I'ables I and II it is evident that discharge prior to storage will improve the time needed for recovery of those cells to 2 volts. ~owever, a comparison between 'I'ables II and III shows that though both are discharged prior to storage the recovery capabilities of`
the cells using the novel electrolyte of this invention are far greater than those of the prior art. In fact, the only cell with LiAlC14 which recovered past 3 volts was cell 5, stored the least amount of time. Cell 5 still required 295 seconds to recover, while cell 9 with Li2BloCllo although stored one day longer required only about 1 second to recover past three volts.
Thus, it is clear that after stor~ge at elevated temperatures electrolyte salts containing clovoborate anions , with SOC12 as the electrolyte solvent and soluble cathode produce substantially less start-up delay than comparable cells using a I,iAlC14 - SOC12 system, and this does not result from discharge prior to storage.
:
The electrolyte salts of the present invention are also useful in electrochemical cells utilizing a solvent selected from a fluid oxyhalide, or non-metallic oxide or non-metallic halide and mixtures thereof such as phosphorous oxychloride (POC13), selenium oxychloride (SeOC12), sulfur di-' oxide (S02), sulfur trioxide (S03), vanadium oxytrichloride VOC13, chromyl i chloride (CrO2C12), sulfuric oxychloride (S02C12), Nitryl chloride (N02Cl), nitrosyl chloride (NOCl), nitrogen dioxide (N02), sulfur monochloride (S2C12) ; and sulfur monobromide (S2Br2). Each of the above can be used together with thionyl chloride (SOC12) as electrolyte solvent/cathode depolarizer or separately. Cosolvents or solvents other than SOC12 may also be electro-chemically reduced on the cathode, but this reduction will not occur at the same potential as that for SOC12. Cosolvents will thus alter the energy ~ density of such cells, either lowering .~ :
~ `
1~766~S
lt or raising it dependlng upon the solvent or cosolyent chosen, Howeyer, co-solvents may be necessary or useful in improving high and low temperature characteristics of the cell or in modifying properties of the system.
Fluid oxyhalldes such as phosphorous oxychloride (pOC13)~ fluid non-metallic oxides or fluid non-metallic halides or mixtures thereof may entirely replace thionyl chloride, SOC12, for the purposes of the pxesent invention even though the disc~large voltage may be generally lower.
Halogenated clovoborate anion and, in particular, the anion having the formula BloCllo are generally prepared by the halogenation of the hydride form of the corresponding anion having the formula (BnHn) , The preparation o the clovoborate anion BloHlo has been discussed by Hawthorne and Muetterties and their co-workers in a series of articles appearing in J, ~m.
Chem. Soc. 81, 5519 (1959); 84, 1056 (1962); 84, 1057 (1962), The formation , . , =
o~ B12H12 was reported and discussed by Ellis, Gaines and Schaeffer (J, Am. Chem. Soc. 85, 3885 (1963), by Miller, Miller, and Muetterties (idem.) and by ~dams, Siedle, and Grant (Inorg. Chem, 3~ 461 (1964), BloHlo and ~12H12 ls disclosed by Muetterties and co-wor~ers in Inorg.
Chem. 3, 159 (1964), Examples o the halogenated anions include (Bl2Xl2) , (BloXlo) , and (B6Br6) (observation by W.R, Hertler in article by Klanberg, Muetterties, Inorg. Chem. 5, 1955 (1966 )) where X is a halogen i.e. fluorine?
chlorine, bromine oX iodlne, The anions having n=6, 10? 12 are more resistant to de~radati~n as a result of more st~ble bonding and thus ~re pre~erred ~or purpoaes of the present invention.
, , ~ ~
1076~45 Figure 6 shows the ca~yed structure of the stable Blo clovoborate anion with the boron atoms depicted and numbered.
The caged structure remains substantially the same with other constituents including halogens replacing some or all of the original hydrogens.
The cells utilizing the novel electrolyte according to this invention are constructed with cathode current collectors of acetylene black with a Teflon binder applied to a nickel screen.
Teflon is a trademark registered by E.I. du Pont De Nemours Company, Wilmington, Delaware, U.S.A. After treating the screen to insure proper adherence of the acetylene black, the cells are assembled. Typical cells can be constructed in the "C" and "D" configurations using flat lithium metal anodes and separators of borosilicate glass fibers. The cathode current collectors for cell of the "C" configuration should preferably measure about 8 l/2" x 1 1/2" and each contain from 1 to 1.6 grams of acetylene black applied to the nickel screen. The anode, separator, and cathode current collector strip assembly are then convolutely wound for insertion into a container for the cell.
Because of the various properties discovered in cells using the novel electrolyte of this invention several test cells are used to determine more precisely those properties Thus, test cells of standard D size are utilized in testing the low temperature capabilities of the cells after extending high temperature storage while cells of the standard C size are used in ambient temperature start-up characteristics determinations.
Both sizes are constructed as above with the C size cells having Teflon cases and rubber seals and the D cells having metal cases and glass seals. Cell size, does not ho~ever affect cell per-formance except for total capacity.
'I'he invention will be more fully described by the followir,g examples, wherein EXAMPI,E 1 describes the preparation of 1,i2BloCllo as an example of the halogenated salts of this invention, EXAMPI,E 2 describes the preparation and handling of an electrolyte containing -the Li2BloCllo dissolved in thionyl chloride for utilization in electrochemical energy generating cells. EXAMPI,E 2 additionally shows the stable nature of the salt when dissolved in the thionyl chloride. It is postulated that the salt is substantially soluble and ionically dissociates in the thionyl chloride through formation of a com-plex between the anion and the SOC12. The anion is the active principle of this invention, and is also believed to be the agent which helps prevent the passivation of the lithium anode.
EXAMPLE 3 describes the preparation of the C size cells according to this invention (the D size cells are prepared in basically the same manner) and the initial discharge character-,~ istics of the C cells, EXAMPLE 3 demons~rates that the electro-lyte of the present invention when added to the aforementioned cell functions both as a useful electr~lyte and as a soluble cathode or depolarizer.
EXAMPLE 4 demonstrates the low temperature characteristics of the D cell using the novel electrolyte of this invention as compared to the performance of prior art cells, EXAMPLE 5 demonstrates, in tabular form, the discharge characteristics of the cells according to this invention and : those of the prior art after prolonged periods of storage at 72 C, EXAMPLE S demonstrates that the start-up delay for cells according to the present invention is bhorter and less severe than cells using LiAlC14 as the dissolved conductive species for the : _9_ 107~64s electrolyte.
It is understood that the attached examples are merely exemplary and that all art recognized equivalents of the materials may be utilized and that such interchangeable utiliza-tion of equivalents is intended to be within the scope of this invention.
It may be further noted, that the invention may be practiced with other metal anodes. In such circumstances, the specific active metal salts of such active metals with the halogenated clovoborate anions preferably may be substituted, but the lithium salts may also be used.
~rhe preparation of novel electrolytically conductive lithium halogenated clovoborate salts is exemplified by the pre-paration of Li2BloCllo:
The anion BloCllo is prepared starting with decaborane, B1oH14. About 5 grams of BloH14 (41 millimoles) are dissolved in about~ 30 ml. of anhydrous benzene in a 200 ml round bottom flask. In a separate vessel about 14.5 ml of 20 distilled triethylamine (104 mm) and about 35 ml of anhydrous benzene are mixed. The mixture is then added slowly to the flask containing the solution of decaborane and the total mixture is refluxed for about 16 to about 24 hours. After this time, a white solid separated whose composition is (NEt3H)2BloHlo, i.e. the bistriethylammonium salt of the anion BloHlo . The procedure to this point is described by M.F. Hawthorne and A.R. Pitochelli (J. Am. Chem. Soc. 81, 5519, (1959)).
The BloHlo anion is then chlorinated in aqueous solution and the~ BloHlo is transformed to BloCllo by the following pro-cedure which differs from the one described by Muetteries et al , . .
- : , - - ,. :
107~45 (Inorganic Chem. 3, 159, (1964)) in that higher concentrations in the order of 2.5 x 10 M and the sodium salt are used in place of the ammonium salt and lower concentrations in the reference in the order of 4.3 x 10 4 M.
About 6.45 grams (40 mm) of (NEt3H)2BloHlo are dissolved in a solution of about 3.52 grams of NaOH (88 mm, a 10~ excess) in about 60 ml of water. The released triethyl amine is removed first by using a separatory funnel, then by using the funnel and washing the solution with several 30 ml portions of benzene. The remaining solution is then ad~usted to about pH
5 using acetic acid, and diluted to about 160 ml with water. Chlorine gas is then slowly introduced into the agitated solution. After about 12 to 15 hours, excess chlorine is removed by boiling from the resultant deep green solution. An aqueous solution of about 12.3 ml of triethylamine (88 mm) in a slight excess of 6 m hydrochloric acid is then added to the reaction vessel. The slightly soluble salt (NEt3H)2BloCllo is precipitated and is then filtered and washéd to remove sodium chloride, sodium acetate, hydro-chloric acid and water.
The lithium salt is then prepared and purified by the following method:
About 2.11 grams of lithium hydroxide (88 mm) are dissolved in 50 ml of water. About 26.7 grams (40 mm) of(NEt3H)2BlOCl10 are then introduced and dissolved. The released triethylamine is extracted with about three 50 ml portions of benzene. The aqueous solution i8 then acidified with con-centrated hydrochloric acid while agitating. The remaining amine precipitates and is filtered to substantially remove it from the solution. The solution is ; then made basic again with a slight excess of solid LiOH. About 4.2 grams (100 mm) of lithium chloride are :, , ., then dissolved ln the basic solution and the solution is mixed with about 50 ml of tetrahydrofuran in a separatory funnel. The lighter phase then con-tains essentially all of the desired product, along with some water and lithium chloride. This phase is mixed with one gram of solid lithium chloride. The salt removes most of the water from the ethereal solution, forming a heavier aqueous phase which is removed. The process is repeated until solid lithium chloride remains after mixing and standing. The lighter phase after separa-tion from all solids and droplets of aqueous phase is then transferred to a 100 ml flask which includes a small fractionating column leaving an azeo-tropic mixture of THF and water with the dissolved desired product. Frac-tional distillation of the mixture results in the removal of the wet azeo-trope of the THF and water at a temperature of 64C, rendering the solution gradually drier. Crystals of the product form as the liquid distilled from the flask is replaced with dry tetrahydrofuran. These are filtered and washed with dry tetrahydrofuran, then dried at about 1~0C (available oven temperature) for about 48 hours. The resulting Li2BlQCllo crystals are checked for purity by infrared spectroscopy.
The preparation of electrolyte including thionyl chloride soluble cathode material:
A solution is prepared by dissolving about 3 grams of Li2BloCllo in about 12 ml distilled thionyl chloride, refluxing in a glass vessel with strips of freshly cut lithium for about 2 hours, then adding distilled thionyl chloride to a total volume of about 25 ml. The resulting mixture is deep violet in color and contains no precipitate. The bistriethylammonium salts of substituted clovoborate anions are only :
'~
1~766~S
slightly soluble in water and may be easily recovered by precipitation. A sample of this amine salt is prepared in water from the original L,i2BloCllo and another from a hydrolized aliquot of the solution Li2BloCllo in thionyl chloride. The two samples produced substantially identical infrared spectra, demonstrating that no harmful substitution or alternation of the anion occurs during reflux in SOC12 with lithium metal present. After hydrolysis, the solution of Li2BloClo in water was colorless, suggesting that the color is produced by a complex formation between the anion and SOC12.
Figure 1 is a cross sectional view of the electro-chemical test cell assembly used for testing the electrochemical generator of this invention. The test cells having C and D
cell size configuration are substantially alike with the C cells being described as follows and the D cells differing by having metal cases and glass seals instead of the Teflon casing and rubber seals used in the C size test cell:
The assembly as shown in Figure 1 consists of an aluminum cell holder 2 holding the cell elements consisting of Teflon cell body 3 and Teflon cover 4 enclosing and sealing via "0" ring 6 of neoprene and helically wound electrode stack 5. The electrode stack S consists of cathode collector sheet 8 of nickel expanded metal mesh and lithium ribbon 9 separated from each other by separator mats 7. The electrode stack is con-volutely wound. The dimensions are selected so that the wound stack assembly 5 has the approximate dimensions of a commercial C cell, i.e. 0.90 inches in diameter and 1.75 inches in height.
As the electrolyte and the anode are air-sensitive the cell and its elements are sealed from the external environment by the "O" ring 6 and electrode septums 15 for cathode terminal 12 and anode terminal 13 respectively which reach the exterior of the cell through the insulating screws 14. The terminals are connected via cathode lead 10 and anode lead 11 respectively to the cathode and anode elements 8 and 9.
The electrolyte is lntroduced into the cell via electrolyte fill port 16 through the self-sealing neoprene septum 18 and about 25 ml of the electrolyte are used to fill the cell.
The test cell i8 provided with a lithium reference electrode 17, similar to the feed throughs 14, to monitor electrode polarization. The anode 9 in the test cell contains about 6 ampere hours of lithium.
The open circuit potential of the Li/SOC12 cells of both the prior art and this invention is about 3.62 - 0.05 volts.
When the electrolyte according to EXAMPLE 2 is introduced into the above described cell having glass fiber separators between the anode 9 and the cathode collector 8 such cells show the polarization potentials under loads as in Figure 2. When polypropylene separators are substituted for the glass fiber separators such cells exhibit the polarization potentials at the different loads as shown in Figure 3.
Low temperature characteristics of cells using the novel electro-lyte of this invention as compared to prior art cells:
All of the cells used were of standard D size and stored for either 1 month or 4 weeks at 72C. The cells were cooled to -30C for two hours prior to discharge.
~¦ Prior art cells using LiAlC14 as the electrolyte ' . :~- . , . : - .
~076645 performed as depicted in Figure 4 at various constant current loads. The e]ectrolyte consists of about 1 Molar LiAlC14 in SOC12 as the only solvent.
The discharge curve ofcell A is taken under a load of about 0.25 amperes.
The discharge curve of cell B is taken under a load of about 1.00 amperes.
As shown in figure 4, cell B required about 0.8 amp-hours, or about 0.8 hours, or 48 minutes before its terminal potential recovered above zero volts. Cell A delayed to about 2.4 volts for several seconds and this delay is not shown in Fig. 4.
In comparison substantially identical cells using the novel electrolyte with 0.4333 N Li2BloCllo in SOC12 only, are discharged after storage of about 72 C for 1 month.
Cell D which discharges at a rate of 1 ampere delayed to about 2.6 volts, but recovered to about 3.3 volts in less than 1 second. Cell C which discharges at a rate of about 0.25 amp did not drop below 3 volts on startup. Figure 5 shows the , 20 above-mentioned cells with the novel clovoborate electrolyte during the rest of their discharge. The discharge curve of cell C shows that this cell which runs at about 0.25 amp realizes about 4.8 amp hours before the output drops to 2 volts. This cell has a running potential above 2.75 volts. In contrast the prior art cell A discharged at this rate realizes only 3.5 amp "
hours to about 2 volts and has a less desirable sloping dis-` charge curve (Figure 4). The cell containing Li2BloCllo functions well at 1 amp in marked contrast to the functioning of cell B
which uses LiAlC14 (Fig. 4).
~07664S
Room temperature discharge characteristics after about 72C storage as compared to prior art cells:
'I'est cells are constructed in the slze C configuration for both the prior art material containing about 1.5 M LiAlC14 in SOC12 only, as the electrolyte and electrolyte solvent re- .
spectively, and the cells utilizing the novel electrolyte of this invention in the concentration of about 0.50 N Li2BloCllo in SOC12 only. All the cells are discharged at about 0.50 amp constant current at room temperature following storage.
The following -tables illustrate advantage of cells utilizing the novel electrolyte of this invention particularly when compared to cells utilizing the electrolyte, LiAlC14, of the prior art. Table 1 shows the recovery time when discharged at ambient temperature for prior art cells when stored at about 72 C for varying lengths of time without any discharge before storage.
Table II shows the prior art cells' recovery time after being discharged at about 0.5 amp constant current for an hour prior to storage at about 72 C.
Table III shows the recovery time for cells using the novel electrolyte containing the clovoborate anion of this invention after discharge for a short period of time shown in Figures 2 & 3 prior to storage which discharge was performed to obtain the polarization curve of Figures 2 & 3.
, ~ -16-. .
~O ~0 ~ n ~ _ ~
0 r r r ::~
o~
tD
o ~ ~ ~3 D~ C') C~` 4 ~ ~ ~ ~
~3 ~ Y ~ g ~:~ ~ ~ g g ~ ~ .
0 e: ~ ~3 ~ ~~ ~3 ~ ~ ~ ~ ~3 ~ ~ cn cncl~ ~ ~ .
~ r~ .
H
u~ c~ cn ~ ~ ~ ~ r o. P~ o ~ .
r~ _, ~I ~ , ~) ~o ~ ~ ~ ~O o O ~ ~_ O o O o ~ tD * ~ (D ~ ~
" ~ ., æ ~ ~ ~ c ~ ,t :' rr ~ ~r ~ ~t- rl ~ SCI O ~3 , ~D W P~ ~1 r w o w ~ 1- :~
. ~ ~o w ~,_ e~ ~ ~
. ~D ~ ~ ~ C ~: ~ ~ W
C ~ O ~ ,_ r~ ~ ~ D. rr n o o ~ On ~n o ~ ~ g ~ ;~
O æ ,~ CO 3~ ~ w O
o r o u~ o ~,o r r~ o w w w w o ~ E~ ~ & Z 3 ~ ' 8 z z g~ 03 ~1-- a ~ w~ r3 ~
8 rr ~. o rr 8 o ~ a ~ ~ 0 O~ r~ 3 . ~ ~ ~
r~ ::
~1 ~ O ~ ~o O W~ r~
I~ O ~ ~n ~3g cn ~n ~ cn ~ C
.. ~ W ~ ~ ~ ~
: Z 3 wo ~ ' o c~
cn r~ c ~r3 r .
.
. .
~.07~6~5 F`rom a comparison between 'I'ables I and II it is evident that discharge prior to storage will improve the time needed for recovery of those cells to 2 volts. ~owever, a comparison between 'I'ables II and III shows that though both are discharged prior to storage the recovery capabilities of`
the cells using the novel electrolyte of this invention are far greater than those of the prior art. In fact, the only cell with LiAlC14 which recovered past 3 volts was cell 5, stored the least amount of time. Cell 5 still required 295 seconds to recover, while cell 9 with Li2BloCllo although stored one day longer required only about 1 second to recover past three volts.
Thus, it is clear that after stor~ge at elevated temperatures electrolyte salts containing clovoborate anions , with SOC12 as the electrolyte solvent and soluble cathode produce substantially less start-up delay than comparable cells using a I,iAlC14 - SOC12 system, and this does not result from discharge prior to storage.
:
Claims (7)
IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An electrochemical cell including a metal anode, a cathode, and as electrolyte salt a salt including a metal cation and a clovoborate anion.
2. The electrochemical cell of claim 1 wherein said metal anode is comprised of metals selected from the group Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba or combinations thereof.
3. The electrochemical cell of claim 1, wherein said cathode comprises a material selected from a fluid oxyhalide or a fluid non-metallic oxide or a fluid non-metallic halide and mixtures thereof.
4. The electrochemical cell of claim 3, wherein said material is selected from the group of SO2, SO3, VOCl3, CrO2Cl2 , SO2Cl2, NO2Cl, NOCl, NO2, SeOCl2, POCl3, SOCl2, S2Cl2, S2Br2.
5. The electrochemical cell of claim 1, wherein the clovoborate anion has a formula (BmXn)-k wherein m, n and k are integers with m ranging from 6-20, n ranging from 6-18 and k ranging from 1-4, B is boron, and X
is selected from the group consisting of H, F, Cl, Br, I, OH and combinations thereof.
is selected from the group consisting of H, F, Cl, Br, I, OH and combinations thereof.
6. The electrochemical cell of claim 1 wherein said metal anode and said metal cation are lithium, and said cathode is SOCl2.
7. The electrochemical cell of claim 3 wherein said electrolyte salt is Li2B10Cl10 and said oxyhalide is SOl2.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/610,518 US4020240A (en) | 1975-09-03 | 1975-09-03 | Electrochemical cell with clovoborate salt in electrolyte and method of operation and composition of matter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1076645A true CA1076645A (en) | 1980-04-29 |
Family
ID=24445341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA258,520A Expired CA1076645A (en) | 1975-09-03 | 1976-08-05 | Electrochemical cell with clovoborate salt in electrolyte |
Country Status (22)
| Country | Link |
|---|---|
| US (2) | US4020240A (en) |
| JP (1) | JPS5232539A (en) |
| AR (1) | AR217630A1 (en) |
| BE (1) | BE845801A (en) |
| BR (1) | BR7605816A (en) |
| CA (1) | CA1076645A (en) |
| CH (1) | CH628184A5 (en) |
| CS (1) | CS207366B2 (en) |
| DD (1) | DD131316A5 (en) |
| DE (1) | DE2639121C3 (en) |
| DK (1) | DK396776A (en) |
| ES (1) | ES451238A1 (en) |
| FR (1) | FR2323238A1 (en) |
| GB (1) | GB1535989A (en) |
| IL (1) | IL50161A (en) |
| IT (1) | IT1065252B (en) |
| MX (1) | MX143471A (en) |
| NL (1) | NL7609828A (en) |
| PL (1) | PL110476B1 (en) |
| SE (1) | SE7609600L (en) |
| SU (2) | SU799682A3 (en) |
| ZA (1) | ZA765208B (en) |
Families Citing this family (64)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4020240A (en) * | 1975-09-03 | 1977-04-26 | P. R. Mallory & Co., Inc. | Electrochemical cell with clovoborate salt in electrolyte and method of operation and composition of matter |
| US4071664A (en) * | 1977-04-01 | 1978-01-31 | P. R. Mallory & Co. Inc. | Electrolyte salt additive |
| US4296185A (en) * | 1977-10-11 | 1981-10-20 | Catanzarite Vincent Owen | Coating for lithium anode, thionyl chloride active cathode electrochemical cell |
| US4170693A (en) * | 1977-10-11 | 1979-10-09 | Catanzarite Vincent Owen | Coating for lithium anode, thionyl chloride active cathode electrochemical cell |
| US4366616A (en) * | 1978-10-10 | 1983-01-04 | Catanzarite Vincent Owen | Coating for lithium anode, thionyl chloride active cathode electrochemical cell |
| US4201839A (en) * | 1978-11-01 | 1980-05-06 | Exxon Research And Engineering Co. | Cell containing an alkali metal anode, a solid cathode, and a closoborane and/or closocarborane electrolyte |
| US4219443A (en) * | 1978-12-20 | 1980-08-26 | Gte Laboratories Incorporated | Method of preparing a cathode current collector for use in an electrochemical cell |
| FR2446014A1 (en) * | 1979-01-08 | 1980-08-01 | Accumulateurs Fixes | Lithium thionyl chloride cell - using calcium or barium oxide-aluminium chloride complex as electrolyte |
| US4218523A (en) * | 1979-02-28 | 1980-08-19 | Union Carbide Corporation | Nonaqueous electrochemical cell |
| US4238552A (en) * | 1979-07-03 | 1980-12-09 | P. R. Mallory & Co. Inc. | Electrolyte salt for non-aqueous electrochemical cells |
| US4238554A (en) * | 1979-09-04 | 1980-12-09 | Duracell International Inc. | Abuse resistant active metal anode/fluid cathode depolarized cells |
| FR2485271A1 (en) * | 1980-05-07 | 1981-12-24 | Saft Leclanche | ELECTROLYTE FOR ELECTROCHEMICAL GENERATOR LITHIUM-THIONYL CHLORIDE, PROCESS FOR PREPARING THE SAME, AND GENERATOR COMPRISING SAID ELECTROLYTE |
| US4403021A (en) * | 1980-05-08 | 1983-09-06 | Gte Laboratories Incorporated | Electrochemical cell and electrolytic solution therefor |
| US4331743A (en) * | 1980-09-02 | 1982-05-25 | Duracell International Inc. | Method for increasing recycling life of non-aqueous cells |
| IL63515A (en) * | 1980-09-12 | 1984-05-31 | Duracell Int | Rechargeable,non-aqueous electrochemical cell |
| IL63336A (en) * | 1981-07-16 | 1984-03-30 | Univ Ramot | Electrochemical cell |
| IL67250A (en) * | 1981-12-14 | 1986-01-31 | Duracell Int | Inorganic rechargeable non-aqueous electrochemical cell |
| US4410608A (en) * | 1981-12-21 | 1983-10-18 | Gte Products Corporation | Electrochemical cell |
| WO1983003322A1 (en) * | 1982-03-18 | 1983-09-29 | Armand, Michel | Electrolytes formed of solid solutions of closoboranes in a plastic macromolecular material and electrochemical generators containing such electrolytes |
| US4619874A (en) * | 1982-05-06 | 1986-10-28 | Medtronic, Inc. | Electrochemical cells with end-of-life indicator |
| US4487822A (en) * | 1982-06-21 | 1984-12-11 | Samuel Ruben | Galvanic cell with tin fluoborate electrolyte |
| US4440836A (en) * | 1982-12-14 | 1984-04-03 | Union Carbide Corporation | Nonaqueous cell employing an anode having a boron-containing surface film |
| US4516317A (en) * | 1982-12-14 | 1985-05-14 | Union Carbide Corporation | Nonaqueous cell employing an anode having a boron-containing surface film |
| US4482616A (en) * | 1983-06-27 | 1984-11-13 | Standard Oil Company (Indiana) | Controlling solubility of lithium salts in liquid sulfur dioxide |
| JPS60131768A (en) * | 1983-12-19 | 1985-07-13 | Mitsui Mining & Smelting Co Ltd | Organic electrolyte battery |
| US4581305A (en) * | 1984-06-25 | 1986-04-08 | Cordis Corporation | Electrochemical cell |
| FR2574223B1 (en) * | 1984-12-03 | 1987-05-07 | Accumulateurs Fixes | ELECTROCHEMICAL GENERATOR OF WHICH THE NEGATIVE ACTIVE MATERIAL IS BASED ON AN ALKALINE OR ALKALINOTERROUS METAL |
| US4654280A (en) * | 1984-12-27 | 1987-03-31 | Eveready Battery Company | Nonaqueous cell employing a cathode-electrolyte solution containing a boron-containing additive |
| EP0186200A3 (en) * | 1984-12-27 | 1988-03-23 | Eveready Battery Company, Inc. | Nonaqueous cell employing a cathode-electrolyte solution containing a boron-containing additive |
| EP0191569A3 (en) * | 1985-02-11 | 1987-01-14 | Saft America Inc. | Battery cell with woven glass fiber separator |
| DK155560C (en) * | 1985-06-17 | 1989-09-18 | Hellesens As | ELECTRICAL BATTERY |
| US4835074A (en) * | 1987-09-25 | 1989-05-30 | The Electrosynthesis Company, Inc. | Modified carbons and electrochemical cells containing the same |
| US4869977A (en) * | 1988-04-25 | 1989-09-26 | Amoco Corporation | Electrolyte additive for lithium-sulfur dioxide electrochemical cell |
| US5147739A (en) * | 1990-08-01 | 1992-09-15 | Honeywell Inc. | High energy electrochemical cell having composite solid-state anode |
| US5284721A (en) * | 1990-08-01 | 1994-02-08 | Alliant Techsystems Inc. | High energy electrochemical cell employing solid-state anode |
| US5332631A (en) * | 1990-10-24 | 1994-07-26 | E.I.C. Corp. | Solid polymer electrolytes to alleviate voltage delay of lithiium cells |
| US5953204A (en) * | 1994-12-27 | 1999-09-14 | Asahi Glass Company Ltd. | Electric double layer capacitor |
| US5632784A (en) * | 1996-08-07 | 1997-05-27 | Daewoo Electronics, Co., Ltd. | Method of manufacturing a lithium battery |
| EP0824278A1 (en) | 1996-08-15 | 1998-02-18 | Daewoo Electronics Co., Ltd | Method of manufacturing a lithium battery |
| US5729116A (en) * | 1996-12-20 | 1998-03-17 | Total Battery Management, Inc. | Shunt recognition in lithium batteries |
| US5900718A (en) * | 1996-08-16 | 1999-05-04 | Total Battery Management, | Battery charger and method of charging batteries |
| US6040685A (en) * | 1996-08-16 | 2000-03-21 | Total Battery Management, Inc. | Energy transfer and equalization in rechargeable lithium batteries |
| US6017656A (en) * | 1996-11-27 | 2000-01-25 | Medtronic, Inc. | Electrolyte for electrochemical cells having cathodes containing silver vanadium oxide |
| US5766797A (en) * | 1996-11-27 | 1998-06-16 | Medtronic, Inc. | Electrolyte for LI/SVO batteries |
| US6043631A (en) * | 1998-01-02 | 2000-03-28 | Total Battery Management, Inc. | Battery charger and method of charging rechargeable batteries |
| US6180284B1 (en) * | 1998-06-05 | 2001-01-30 | Mine Safety Appliances Company | Electrochemical power cells and method of improving electrochemical power cell performance |
| US6274265B1 (en) * | 1999-07-21 | 2001-08-14 | Medtronic, Inc. | Method and system for evaluating an electrochemical cell for use with an implantable medical device |
| US6511773B1 (en) | 2000-06-30 | 2003-01-28 | Lithium Energy Associates, Inc. | Lithium rechargeable inorganic electrolyte cell |
| US6911280B1 (en) * | 2001-12-21 | 2005-06-28 | Polyplus Battery Company | Chemical protection of a lithium surface |
| US7482096B2 (en) * | 2003-06-04 | 2009-01-27 | Polyplus Battery Company | Alleviation of voltage delay in lithium-liquid depolarizer/electrolyte solvent battery cells |
| US20040253510A1 (en) * | 2003-06-04 | 2004-12-16 | Polyplus Battery Company | Aliovalent protective layers for active metal anodes |
| CA2479589C (en) * | 2003-09-04 | 2011-05-24 | Air Products And Chemicals, Inc. | Polyfluorinated boron cluster anions for lithium electrolytes |
| US7311993B2 (en) * | 2003-09-04 | 2007-12-25 | Air Products And Chemicals, Inc. | Polyfluorinated boron cluster anions for lithium electrolytes |
| US7785740B2 (en) * | 2004-04-09 | 2010-08-31 | Air Products And Chemicals, Inc. | Overcharge protection for electrochemical cells |
| US7981388B2 (en) * | 2004-08-23 | 2011-07-19 | Air Products And Chemicals, Inc. | Process for the purification of lithium salts |
| US7465517B2 (en) * | 2004-08-23 | 2008-12-16 | Air Products And Chemicals, Inc. | High purity lithium polyhalogenated boron cluster salts useful in lithium batteries |
| US20060216612A1 (en) * | 2005-01-11 | 2006-09-28 | Krishnakumar Jambunathan | Electrolytes, cells and methods of forming passivation layers |
| US20080026297A1 (en) * | 2005-01-11 | 2008-01-31 | Air Products And Chemicals, Inc. | Electrolytes, cells and methods of forming passivaton layers |
| US20060204843A1 (en) * | 2005-03-10 | 2006-09-14 | Ivanov Sergei V | Polyfluorinated boron cluster anions for lithium electrolytes |
| US20070048605A1 (en) * | 2005-08-23 | 2007-03-01 | Pez Guido P | Stable electrolyte counteranions for electrochemical devices |
| US20070072085A1 (en) * | 2005-09-26 | 2007-03-29 | Zonghai Chen | Overcharge protection for electrochemical cells |
| CN101805000B (en) * | 2009-02-12 | 2012-05-30 | 比亚迪股份有限公司 | Production method of lithium terachloroaluminate |
| US20140038037A1 (en) * | 2012-08-02 | 2014-02-06 | Toyota Motor Engineering & Manufacturing North America, Inc. | Magnesium borohydride and its derivatives as magnesium ion transfer media |
| FI126390B (en) * | 2015-09-30 | 2016-11-15 | Broadbit Batteries Oy | Electrochemical accumulators for high energy or high power battery use |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3073884A (en) * | 1959-08-03 | 1963-01-15 | Ethyl Corp | High energy batteries |
| FR1496704A (en) * | 1961-10-10 | 1967-10-06 | E I Du Pont De Neumours And Co | Ionic boron compounds and their manufacture |
| US3372006A (en) * | 1962-05-31 | 1968-03-05 | Du Pont | Halogen derivatives of polyhedral boron compounds |
| US3551120A (en) * | 1962-12-21 | 1970-12-29 | Du Pont | Substituted dodecaborates |
| US3493433A (en) * | 1964-10-13 | 1970-02-03 | American Cyanamid Co | Electrodeposition of alkali metals from nonaqueous solvents |
| US3578500A (en) * | 1968-07-08 | 1971-05-11 | American Cyanamid Co | Nonaqueous electro-chemical current producing cell having soluble cathode depolarizer |
| US3923543A (en) * | 1972-11-13 | 1975-12-02 | Gte Laboratories Inc | Electrochemical cell |
| US3897264A (en) * | 1972-11-13 | 1975-07-29 | Gte Laboratories Inc | Electrochemical cells with inorganic oxyhalide or thiohalide solvent |
| US3891457A (en) * | 1973-11-29 | 1975-06-24 | Gte Laboratories Inc | Electrochemical cell |
| US3998657A (en) * | 1975-07-25 | 1976-12-21 | Gte Laboratories Incorporated | Electrochemical cells |
| US4020240A (en) * | 1975-09-03 | 1977-04-26 | P. R. Mallory & Co., Inc. | Electrochemical cell with clovoborate salt in electrolyte and method of operation and composition of matter |
-
1975
- 1975-09-03 US US05/610,518 patent/US4020240A/en not_active Expired - Lifetime
-
1976
- 1976-07-28 IL IL50161A patent/IL50161A/en unknown
- 1976-08-05 CA CA258,520A patent/CA1076645A/en not_active Expired
- 1976-08-25 MX MX166024A patent/MX143471A/en unknown
- 1976-08-31 SE SE7609600A patent/SE7609600L/en not_active Application Discontinuation
- 1976-08-31 ZA ZA765208A patent/ZA765208B/en unknown
- 1976-08-31 DE DE2639121A patent/DE2639121C3/en not_active Expired
- 1976-09-01 CH CH1106776A patent/CH628184A5/en not_active IP Right Cessation
- 1976-09-02 BR BR7605816A patent/BR7605816A/en unknown
- 1976-09-02 AR AR264559A patent/AR217630A1/en active
- 1976-09-02 DK DK396776A patent/DK396776A/en not_active Application Discontinuation
- 1976-09-02 PL PL1976192159A patent/PL110476B1/en not_active IP Right Cessation
- 1976-09-03 NL NL7609828A patent/NL7609828A/en not_active Application Discontinuation
- 1976-09-03 JP JP51105706A patent/JPS5232539A/en active Pending
- 1976-09-03 ES ES451238A patent/ES451238A1/en not_active Expired
- 1976-09-03 GB GB36656/76A patent/GB1535989A/en not_active Expired
- 1976-09-03 IT IT26868/76A patent/IT1065252B/en active
- 1976-09-03 CS CS765745A patent/CS207366B2/en unknown
- 1976-09-03 BE BE2055280A patent/BE845801A/en not_active IP Right Cessation
- 1976-09-03 FR FR7626677A patent/FR2323238A1/en active Granted
- 1976-09-03 DD DD7600194626A patent/DD131316A5/en unknown
- 1976-09-03 SU SU762393511A patent/SU799682A3/en active
-
1977
- 1977-03-09 US US05/775,829 patent/US4139680A/en not_active Expired - Lifetime
- 1977-03-31 SU SU772465656A patent/SU753371A3/en active
Also Published As
| Publication number | Publication date |
|---|---|
| SE7609600L (en) | 1977-03-04 |
| BR7605816A (en) | 1977-08-16 |
| ES451238A1 (en) | 1977-12-01 |
| FR2323238A1 (en) | 1977-04-01 |
| DE2639121C3 (en) | 1980-06-19 |
| IT1065252B (en) | 1985-02-25 |
| AU1709776A (en) | 1978-03-02 |
| PL192159A1 (en) | 1978-03-28 |
| ZA765208B (en) | 1977-08-31 |
| GB1535989A (en) | 1978-12-13 |
| US4020240A (en) | 1977-04-26 |
| NL7609828A (en) | 1977-03-07 |
| AR217630A1 (en) | 1980-04-15 |
| JPS5232539A (en) | 1977-03-11 |
| DE2639121B2 (en) | 1979-07-26 |
| SU753371A3 (en) | 1980-07-30 |
| PL110476B1 (en) | 1980-07-31 |
| DK396776A (en) | 1977-03-04 |
| CH628184A5 (en) | 1982-02-15 |
| DD131316A5 (en) | 1978-06-14 |
| IL50161A (en) | 1979-12-30 |
| FR2323238B1 (en) | 1980-05-16 |
| SU799682A3 (en) | 1981-01-23 |
| IL50161A0 (en) | 1976-09-30 |
| CS207366B2 (en) | 1981-07-31 |
| MX143471A (en) | 1981-05-18 |
| BE845801A (en) | 1976-12-31 |
| US4139680A (en) | 1979-02-13 |
| DE2639121A1 (en) | 1977-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1076645A (en) | Electrochemical cell with clovoborate salt in electrolyte | |
| Peled et al. | Lithium‐sulfur battery: evaluation of dioxolane‐based electrolytes | |
| Besenhard et al. | High energy density lithium cells: Part I. Electrolytes and anodes | |
| CA1066763A (en) | Metal-halogen electrochemical cell | |
| CN102742062B (en) | Rechargeable electrochemical cell | |
| Rauh et al. | A lithium/dissolved sulfur battery with an organic electrolyte | |
| EP1527488B2 (en) | Electrolyte additive for non-aqueous electrochemical cells | |
| CA1079800A (en) | Electrolyte salt additive | |
| US4869977A (en) | Electrolyte additive for lithium-sulfur dioxide electrochemical cell | |
| Watanabe et al. | Solvents effects on electrochemical characteristics of graphite fluoride—lithium batteries | |
| US20130196224A1 (en) | Intermediate Temperature Sodium Metal-Halide Energy Storage Devices | |
| JPS5949673B2 (en) | A battery with a cathode made of a light metal, a nonaqueous electrolyte, and an anode | |
| JP2711545B2 (en) | Non-aqueous battery | |
| Dunning et al. | A secondary, nonaqueous solvent battery | |
| US4499161A (en) | Electrochemical cell using dimethoxymethane and/or trimethoxymethane as solvent for electrolyte | |
| KR101875785B1 (en) | Cathode material for rechargeable magnesium battery and its preparation method | |
| Mamantov et al. | The use of tetravalent sulfur in molten chloroaluminate secondary batteries | |
| AU593980B2 (en) | Electrolyte for lithium-sulfur dioxide electrochemical cell | |
| Morita et al. | Effects of crown ether addition to organic electrolytes on the cycling behavior of the TiS2 electrode | |
| US4766045A (en) | Metal halogen electrochemical cell | |
| KR900007729B1 (en) | Electrolyte additive for lithiumsulfur dioxide electrochemical cells | |
| CA3092785A1 (en) | Solid ionic conductor for rechargeable electrochemical battery cells | |
| US6168889B1 (en) | Battery electrolytes and batteries | |
| US4925753A (en) | Lithium/sulfur dioxide cell | |
| Morehouse et al. | A Technique for Evaluating Various Cathode Materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19970429 |