CA1089534A - Non-aqueous cell having a cathode of lead monoxide- coated lead dioxide particles - Google Patents
Non-aqueous cell having a cathode of lead monoxide- coated lead dioxide particlesInfo
- Publication number
- CA1089534A CA1089534A CA293,196A CA293196A CA1089534A CA 1089534 A CA1089534 A CA 1089534A CA 293196 A CA293196 A CA 293196A CA 1089534 A CA1089534 A CA 1089534A
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- Prior art keywords
- lead
- cell
- oxide cell
- lead oxide
- monoxide
- Prior art date
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
NON-AQUEOUS CELL HAVING A CATHODE
OF LEAD MONOXIDE-COATED LEAD DIOXIDE PARTICLES
ABSTRACT OF THE DISCLOSURE
A non-aqueous lead oxide cell having a negative electrode, such as lithium, a non-aqueous electrolyte and a positive lead oxide electrode, said lead oxide electrode comprising lead dioxide particles each having an outer layer of lead monoxide.
S P E C I F I C A T I O N
_ _ _ _ _ _ _ _ _ _ _ _ _
OF LEAD MONOXIDE-COATED LEAD DIOXIDE PARTICLES
ABSTRACT OF THE DISCLOSURE
A non-aqueous lead oxide cell having a negative electrode, such as lithium, a non-aqueous electrolyte and a positive lead oxide electrode, said lead oxide electrode comprising lead dioxide particles each having an outer layer of lead monoxide.
S P E C I F I C A T I O N
_ _ _ _ _ _ _ _ _ _ _ _ _
Description
10~'3S34 Field of the Invention The invention relates to non-aqueous lead oxide cells, and specifically to such cells wherein the positive electrode comprises lead dioxide particles having an outer layer of lead monoxide.
Back~round of the Invention The development of high energy cell systems requires the compatibility of an electrolyte possessing desirable electrochemical properties with highly active anode materials, such as lithium, calcium, sodium and the like, and the efficient use of high energy density cathode materials, such as FeS2, Co304, PbO2 and the like. The use of aqueous electrolytes is precluded in these systems since the anode materials are suffi- -ciently active to react with water chemically. There-fore, in order to realize the high energy density obtainable through use of these highly reactive anodes and high energy density cathodes, it is necessary to use a non-aqueous electrolyte system.
One of the major disadvantages of employing lead dioxide as the active cathode material in a non-aqueous electrolyte system is that it will discharge at two different potentials. The first step in the discharge curve is attributed to the reduction of the lead dioxide to lead monoxide, while the second step is attributed to the reduction of the reaction product, ~ ~
lead monoxide. Contrary to lead dioxide, lead monoxide ",.... - .. . . . - .
. . .................................. .. .. . . .... .
.~ . , .: . . . . . .
will discharge in a non-aqueous cell system at a uni-potential level. One advantage in employing lead dioxide as the cathode material over lead monoxide is that it has almost double the capacity of lead monoxide, Thus in a non-aqueous electrolyte system, lead monoxide will have the advantagP of discharging at a unipotential plateau with the disadvantage of having a relatively low capacity while lead dioxide will have the advantage of having a relatively high capacity with the disad-vantage of discharging at two distinct voltage plateaus.
Many cell or battery applications, particularly in transistorized devices such as hearing aids, watches and the like, require a substantial unipotential dis-charge source for proper operation and, therefore, cannot use the dual voltage level discharge which is characteristic of non-aqueous lead dioxide cells.
This du~l voltage level discharge characteristic is similar to the dual voltage discharge characteristic of aqueous alkaline divalent silver oxide cells.
Although many approaches have been proposed for obtain-ing a unipotential discharge from an aqueous alkaline divalent silver oxide cell, the approaches are not needed when lead dioxide is employed in an aqueous electrolyte cell system. Specifically, in an aqueous electrolyte cell system, lead dioxide will discharge almost entirely at its higher voltage level so that, in effect, the cell will produce a substantially - ,'' '' -unipotential discharge over the useful life of the cell. Contrary to this, when lead dioxide is used as the cathode material in a non-aqueous electrolyte system, the cell will discharge at a first potential for a significant time period and then decrease to a distinct lower potential for the remainder of the discharge, A problem usually encountered in various cell systems is that although an electrode-couple can function in an aqueous electrolyte, it is practically impossible to predict in advance how well, if at all, it will function in a non-aqueous electrolyte. Thus a cell must be considered as a unit having three parts - a cathode, an anode and an electrolyte - and it i9 to be understood that the parts of one cell may not be predictably interchangeable with parts of another cell to produce an efficient and workable cell.
A French Patent 2,288,401 published on June 18, 1976 (counterpart to German application
Back~round of the Invention The development of high energy cell systems requires the compatibility of an electrolyte possessing desirable electrochemical properties with highly active anode materials, such as lithium, calcium, sodium and the like, and the efficient use of high energy density cathode materials, such as FeS2, Co304, PbO2 and the like. The use of aqueous electrolytes is precluded in these systems since the anode materials are suffi- -ciently active to react with water chemically. There-fore, in order to realize the high energy density obtainable through use of these highly reactive anodes and high energy density cathodes, it is necessary to use a non-aqueous electrolyte system.
One of the major disadvantages of employing lead dioxide as the active cathode material in a non-aqueous electrolyte system is that it will discharge at two different potentials. The first step in the discharge curve is attributed to the reduction of the lead dioxide to lead monoxide, while the second step is attributed to the reduction of the reaction product, ~ ~
lead monoxide. Contrary to lead dioxide, lead monoxide ",.... - .. . . . - .
. . .................................. .. .. . . .... .
.~ . , .: . . . . . .
will discharge in a non-aqueous cell system at a uni-potential level. One advantage in employing lead dioxide as the cathode material over lead monoxide is that it has almost double the capacity of lead monoxide, Thus in a non-aqueous electrolyte system, lead monoxide will have the advantagP of discharging at a unipotential plateau with the disadvantage of having a relatively low capacity while lead dioxide will have the advantage of having a relatively high capacity with the disad-vantage of discharging at two distinct voltage plateaus.
Many cell or battery applications, particularly in transistorized devices such as hearing aids, watches and the like, require a substantial unipotential dis-charge source for proper operation and, therefore, cannot use the dual voltage level discharge which is characteristic of non-aqueous lead dioxide cells.
This du~l voltage level discharge characteristic is similar to the dual voltage discharge characteristic of aqueous alkaline divalent silver oxide cells.
Although many approaches have been proposed for obtain-ing a unipotential discharge from an aqueous alkaline divalent silver oxide cell, the approaches are not needed when lead dioxide is employed in an aqueous electrolyte cell system. Specifically, in an aqueous electrolyte cell system, lead dioxide will discharge almost entirely at its higher voltage level so that, in effect, the cell will produce a substantially - ,'' '' -unipotential discharge over the useful life of the cell. Contrary to this, when lead dioxide is used as the cathode material in a non-aqueous electrolyte system, the cell will discharge at a first potential for a significant time period and then decrease to a distinct lower potential for the remainder of the discharge, A problem usually encountered in various cell systems is that although an electrode-couple can function in an aqueous electrolyte, it is practically impossible to predict in advance how well, if at all, it will function in a non-aqueous electrolyte. Thus a cell must be considered as a unit having three parts - a cathode, an anode and an electrolyte - and it i9 to be understood that the parts of one cell may not be predictably interchangeable with parts of another cell to produce an efficient and workable cell.
A French Patent 2,288,401 published on June 18, 1976 (counterpart to German application
2,545,498 published on April 27, 1976~ discloses a non-aqueous cell which employs a negative electrode, such as lithium, a non-aqueous-solvent electrolyte and a positive active electrode consisting of a positive active ~aterial of the oxides and oxidizing salts, the dis-charged reduction of which leads to metals of the group including lead, tin, gold, bismuth, zinc, cadmium and their alloys and an electronic conductor consisting ~
at least on ~he surface of a material selected -4.
lU~ 34 11279 from the group including lead, tin, gold, bismuth, zinc, cadmium and their alloys. Several examples are disclosed in this reference in which lead monoxide is employed as the positive active material and lead, tin or graphite is employed as the electronic conductor. Although this reference teaches one means for obtaining a unipotential discharge for certain non-aqueous cell systems, as, for example, a cell employing lead monoxide as the positive active material, the subject invention is directed to the use of lead dioxide particles having a lead monoxide outer layer as the positive active material of a non-aqueous cell. The positive active material of this in-vention could also be expressed as lead monoxide particles having a lead dioxide core.
Accordingly, it is the primary object of this invention to provide a non-aqueous lead oxide cell which employs a positive electrode comprising lead dioxide particles each having a lead monoxide outer layer, and which has a substantially unipotential discharge voltage.
Another object of this invention is to provide a non-aqueous lead oxide cell which employs a lithium anode and a positive cathode composed of lead dioxide particles each having a lead monoxide outer layer, and which has a substantially unipotential discharge voltage.
at least on ~he surface of a material selected -4.
lU~ 34 11279 from the group including lead, tin, gold, bismuth, zinc, cadmium and their alloys. Several examples are disclosed in this reference in which lead monoxide is employed as the positive active material and lead, tin or graphite is employed as the electronic conductor. Although this reference teaches one means for obtaining a unipotential discharge for certain non-aqueous cell systems, as, for example, a cell employing lead monoxide as the positive active material, the subject invention is directed to the use of lead dioxide particles having a lead monoxide outer layer as the positive active material of a non-aqueous cell. The positive active material of this in-vention could also be expressed as lead monoxide particles having a lead dioxide core.
Accordingly, it is the primary object of this invention to provide a non-aqueous lead oxide cell which employs a positive electrode comprising lead dioxide particles each having a lead monoxide outer layer, and which has a substantially unipotential discharge voltage.
Another object of this invention is to provide a non-aqueous lead oxide cell which employs a lithium anode and a positive cathode composed of lead dioxide particles each having a lead monoxide outer layer, and which has a substantially unipotential discharge voltage.
3 ~
Another object of this invention is to provide a non-aqueous lead oxide cell which employs a positive electrode composed of lead dioxide particles each having a lead monoxide outer layer, and wherein said lead monoxide varies between about 1 per cent and 60 per cent by weight of the lead oxides.
Summarv o~ the Invention The invention relates to a non-aqueous lead oxide cell comprising a highly active metal negative electrode, a positive electrode and a non-aqueous elec-trolyte; said positive electrode comprising lead dioxide particles each having a substantially complete outer layer of lead monoxide, and said cell having a sub-stantially unipotential discharge voltage. ~ ~
A unipotential discharge voltage shall mean ~ -a relatively constant voltage level extending over at least 85 per cent of a cell's discharge capacity when discharged across a fixed load, and wherein the voltage varies no more than + 10 per cent of the average ~oltage of said voltage level. For example, a unipotential dis-charge level can be represented by a voltage-time curve substantially free from voltage excursions or steps during at least 85 per cent of the time of discharge across a constant load, such steps or excursions being defined as voltage readings outside of + 10 per cent of the average voltage over the said 85 per cent portion ~ -of the time of discharge. As shown in Figure 1, it is 3 ~
the object of this invention to effectively eliminate or effectively suppress the portion of the curve to the leEt of point A to yield a unipoten~ial discharge level as generally shown by the curve between points A and B.
It is also within the scope of this invention to add a binder, an electronically conductive material, an electrolyte-absorbent material or mixtures thereof to the positive electrode of this invention.
The size of the lead monoxide~coated lead dioxide particles comprising the cathode of this invention should preferably be between about 0.04 mm and about 0.47 mm and more preferably between about 0.07 mm and about 0.23 mm. Particles sized smaller than about 0.04 mm will provide a large true surface area but, however, when fabricated into a cathode, the electronic conductivity of the cathode will generally be insufficient for commercial cell application due to the large number of particle-to-particle contacts providing the conductive path through the cathode to the cathode collector of the cell. A cathode fabricated with lead monoxide-coated lead dioxide particles sized larger than about 0.47 mm will have a small true surface area which will generally not support a current density generally required for cu~ercial cell application.
The per cent by weight of lead monoxide in the lead dioxide-containing positive electrode of this ', ' 9 5 3~
invention should be between about 1 per cent and about 60 per cent based on the weight of the lead oxldes and preferably between about 10 per cent and about 40 per cent based on the weight of the lead oxides, A
lead monoxide amount less than about 1 per cent by weight of the lead dioxides would be insufficient to reliably and substantially eliminate the two voltage plateau discharge characteristic of lead dioxide in a non-aqueous electrolyte cell system. An amount of lead monoxide greater than about 60 per cent by weight of the lead;~
oxides would be inefficient since too ~uch of the high capacity lead dioxide material would be replaced by the lower capacity lead monoxide material.
Useful highly active negative anode materials are generally consumable metals and include aluminum, the alkali metals, alkaline earth metals and alloys of alkali metals or alkaline earth metals with each other and other metals. The term "alloy" as used herein and in the appended claims is intended to include mixtures, solid solutions, such as lithium-magnesium, and inter-;~
metallic compounds, such as llthium monoaluminide.
The preferred anode ma~erials are lithium, sodium, potassium, calcium, and alloys thereof. ~;
Useful organic solvents employed alone or mixed with one or more other solvents for use in this ;
invention include the following classes of compounds:
, 80 ,: -, . ., . : , :
Alkylene nit riles: e.g., cro t onitrile (li~uid range -51.1C. to 120C.) Trialkyl borates: e.g., trimethyl borate, (CH30)3B
(liquid range -29 3 to 67C.) Tetraalkyl silicates: e.g , tetramethyl silicate, (CH30)4Si (boiling po~nt 121C.) Nitroalkanes- e g., nitromethane, CH3N02 (li~uid range -17 to 100.8C.) Alkylnitriles: e.g., acetonitrile, CH3CN
(li~uid range -45 to 81.6C.) D~alkylamides: e.g , dimethylformamide, HCON(CH3)2 (liquid range -60;48 to 149C.) Lactams: e.g " N-methylpyrro~idone, H2-CH2-CH2-CO-N-CH3 (l~quid range -16 to 202C,) Tetraalkylureas: e g., tetramethylurea, (CH3)2N-CO-NtCH3)2 (ll~uid range -1.2 to 166C.) Monocarboxylic acid esters: e.g., ethyl acetate (liquid range -83.6 to 77.06C.) -Orthoesters: e,g" trimethylorthoformate, HC(OCH3)3 ~bo~ling point 103C.) -Lactones: e.g., ~r~amma)butyrolactone, CH2 CH2-CH2-0-CO
(li~uid ran~e -42 to 206C.) D~alkyl carbonates: e.g., dimethyl carbonate, OC(OCH3)2 (liquid range 2 to 90C.) Alkylene carbonates: e,g., propylene carbonate, CH(CH3)CH2-0-CO-0 (liquid range -48 to 242C,) ~
Monoethers: e.g., diethyl ether (liquid range -116 ~ -to 34.5C.) 9S 3 ~
Polyethers: e.g., 1,1- and 1~2-~dimethoxyethane (liquid ranges -113.2 to 64,5C. and -58 to 83C., respectively) Cyclic ethers: e g., tetra~ydrofuran (liquid range -65 to 67C.); l,3-dioxolane (llquid range -95 to 78C.) Nitroaromatics: e.g., nitrobenzene (liquid range 5.7 to 210.8C.) Aromatic carboxylic acid halides: e.g., benzoyl chloride (liquid range 0 to 197C.); benzoyl bromide (liquid range _~6 to 218C.) Aromatic sulfonic acid halides- e.g., benzene sulfonyl chloride (liquid range 14.5 to 251C ) Aromatic phosphonic acid dihalides: e.g., benzene phosphonyl dichloride (boiling point 258~C ) Aromatic th~ophosphonic acid dihalides: e,g., benzene thiophosphonyl dlchloride (boiling point 124C. at S mm.) ;
Cyclic sulfones: e.g., sulfo~ane, CH2'C~2-CH2-CH2-S2 (melting point 22C );
3-methylsulfolane (melting point -1C.) ~
Alkyl sulfonic acid halides: e,g., methanesulfonyl ~ -chloride (boiling point 161C.) -Al~yl carboxylic acid halides: e.g,, acetyl chloride ~ (liquid range -112 to 50.9C.); acetyl br~mide (liquid range -96 to 76.C.~; propionyl chloride (liquid range ~94 to 8Q~
10 ~
10~9~3~
Saturated heterocyclics: e.g., tetrahydrothiophene (liquid range -96 to 121C.); 3-methyl-2-oxa-zolidone (~elting po~nt 15,9C.) Dialkyl sulfamic scid halides: e.g., d~methyl sulfamyl chloride (boiling point 80C, at 16 mm.) Alkyl halosulfonates: e.g., ethyl chlorosulfonate (boiling point 151C.) Unsaturated heterocyclic carboxylic acid halides:
e.g., 2-furoyl chloride (liquid range -2 to 173C.) Five-membered unsaturated heteroc~clics: e.g., 3,5-dimethylisoxazole (boillng po~nt 140C.);
l-methylpyrrole (boiling point 114C.);
2,4-dimethylthia201e (boiling point 144C.);
furan (liquid range -85.65 to 31,36C.) -Este~s andlor halides of dibàsic carboxylic acids:
e.g., ethyl oxalyl chloride (boiling point 135C.) Mixed alkyl sulfonic acid halides and carboxylic acid halides: e.g., chlorosulfonyl acetyl chloride (boiling point 98C. at 10 mm.) 0 Dialkyl sulfoxides: e.g., dimethyl sulfoxide (liquid range 18.4 to 189C.) Dialkyl sulfates: e.g., dimethylsulfate (liquid range -31.75 to 188.5C.) Dialkyl sulfites: e.g., dimethylsulfite (boiling -point 126C.) Alkylene sulfites: e.g., ethylene glycol sulfite - (liquid range -11 to 173C.) -- 10~9~34 Halogenated alkanes: e.g., methylene chloride (liquid range -95 to 40C:.); 1,3-dichloro-propane ~liquid range -99.5 to 120.4C.) Of the above, the preferred solvents are sulfolane; crotonitrile; nitrobenzene; tetrahydrofuran;
1,3-dioxolane; 3-methyl-2-oxazolidone; propylene car-bonate; ~ -butyrolactone; ethylene glycol sulfite;
dimethylsulfite; dimethyl sulfoxide; and 1,1- and 1,2-dimethoxyethane. Of the preferred solvents, the best are sulfolane; 3-methyl-2-oxazolidone; propylene car- -bonate, 1,3-dioxolane and dimethoxyethane because they ap-pear more chemically inert to battery components and have wide liquid ranges, and especially because they ;~
permit highly efficient utilization of the cathode -~
materials. `
The ionizing solute for use in the invention may be a simple or double salt, or mixtures thereof, - which will produce an ionically conductive solution when dissolved in one or more solvents. Preferred solutes are complexes of inorganic or organic Lewis acids and inorganic ionizable salts. The only require~
ments for utility are that the salts, whether simple ;
or complex, be compatible with the solvent or solvents being employed and that they yield a solution which is sufficiently ionically conductive. According to the ~
Lewis or electronic concept of acids and bases, many -substances which contain no active hydrogen can act as ~ ~
12. -- . , - :. . , : - . .: ;.. . ~ - :--9~ 4 acids or acceptors of electron doublets. The basicconcept is set forth in the chemical literature (Journal of the Franklin Institute, Vol. 226 - July/
December 1938, pages 293-313 by Lewis).
A suggested reaction mechanism for the manner in which these complexes function in a solvent is described in detail in U. S. Patent No. 3,542,602 wherein it is suggested that the complex or double salt formed between the Lewis acid and the ionizable salt yields an entity which is more stable than either of the components alone.
Typical Lewis acids suitable for use in the present invention include aluminum fluoride, aluminum bromide, aluminum chloride, antimony pentachloride, zirconium tetrachloride, phosphorus pentachloride, boron fluoride, boron chloride and boron bromide.
Ionizable salts useful in combination with the Lewis acids include lithium fluoride, lithium chloride, lithium bromide, lithium sulfide, sodium fluoride, sodium chloride, sodium bromide, potassium -fluoride, potassium chloride and potassium bromide.
It will be obvious to those skilled in the art that the double salts formed by a Lewis acid and an inorganic ionizable salt may be used as such or the individual components may be added to the solvent separately to form the double salt or the resulting ions in situ. One such double salt, for example, is that 13.
9 S~l4 formed by the combination of alu~inum chloride and lithium chloride to yield lithium aluminum tetrachloride.
Brief Description o~ the Drawin~s Figure 1 is a curve showing the discharge characteristics of a non-aqueous lead oxide-lithium cell employing a lead dioxide positive electrode (cathode).
Figure 2 is a curve showing the discharge characteristics of a non-a~ueous lead oxide-lithium cell employing a lead monoxide positive electrode.
Figure 3 is a curve showing the discharge characteristics of a non-aqueous lead oxide-lithium ~`
cell employing a positive electrode composed of lead monoxide-coated lead dioxide particles in accordance with the present invention.
Figure 4 is a curve showing the discharge characteristics of a non-aqueous lead oxide-lithium -cell employing a positive electrode composed of lead dioxide particles and an electrolyte containing hydrazine for surface reduction of the lead dioxide particles in accordance with the present invention.
EXAMPLE I
A flat-type cell was constructed utilizing a nickel metal base having therein a l-inch diameter ~!
shallow depression into which the cell contents were placed and over which a nickel metal cap was placed to close the cell. The contents of the cell consisted of five sheets of lithium foil having a total thickness 1~;)89534 of 0.10 inch, about 4 ml of an electrolyte, two porous nonwoven polypropylene separator~ (0.005 ~nch thick each) which absorbed some of the electrolyte, and a lead dioxide cathode mix.
The electrolyte was a lM LiC104 in 77 volume per cent dioxolane, 23 volume per cent dimethoxyethane (DME) with a trace of about 0.1 volume per cent dimethyl isoxazole (DMI) as a polymerization inhibitor. The cathode was a pressed layer of 4.3 grams of lead dioxide.
The cell was discharged across a constant load at a 3-milliampere drain and the voltage observed as a function of time is shown plotted as the curve on the graph in Figure 1. Also observed and as recorded on Figure 1 is the open circuit voltage of the cell which wa~ 3.5 volts. As is apparent from the curve in Figure 1, it took approximately four days before the voltage decreased to a substantially unipotential level of approximately 1.2 volts. As stated above, many cell and battery operated devices which require an essentially uni-potential power source could not use this type of cell system because of its significant dual voltage level discharge characteristic.
EXAMPLE II
A flat-type cell was constructed using the -~
same components as described in Example I except that the cathode mix was a compressed layer of a mixture of 15. ~ :
lV8~53~
3 grams of lead monoxide and 0.5 gram of carbon black added for conductivity. As in Example I, the cathode mix was placed into the shallow depression in a nickel metal base along with other cell componentsO ~;
The cell was discharged on a 3-milliampere drain and the voltage observed as a function of time is shown plotted as the curve on the graph in Figure 2.
Also observed and as recorded on Figure 2 is the open circuit voltage of the cell which was about 3.2 volts.
This high open circuit voltage for the cell is believed to be due to the presence of oxygen and/or oxide~ on the surface of the carbon black in the cathode mix.
As is apparent from the curve in Figure 2, the substantially unipotential voltage level output of this cell makes it an admirable candidate as a power source for many cell and battery operated devices. As stated above, however, although this type of cell has the advantage of discharging at a substantially unipotential level, it has the disadvantage of having a rather low capacity as comparet to a cell employing lead dioxide as the cathode material.
EXAMPLE III
A flat-type cell was constructed using the same components as described in Example I except that the cathode was composed of lead monoxide-coated lead dioxide particles which were prepared in the following manner:
16.
- ~ ' 6 grams of reagent grade PbO2 were mixed with 900 milliliters of an aqueous 0.0015 M hydrazine (N2H4) solution and stirred for one-half hour. The mixture was then filtered and t~e treated PbO2 was dried over-night in a vacuum oven at approximately 82C. This reduced the PbO2 capacity by about 30% producing lead monoxide coated lead dioxide particles. Two grams of the partially reduced PbO2 particles were placed into the shallow depression in a nickel metal base along with the other cell components as described in Example I.
To vary the reduction of PbO2 capacity all that is necessary is to vary the amount and/or concentration of the hydrazine solution and, if desired, the time and/or temperature of the reaction.
The cell so produced in accordance with this invention was then discharged across a lK-ohm load - (about 1.2-milliampere drain) and the voltage observed as a function of time is shown plotted as the curve on the graph in Figure 3. Also observed and as recorded on Figure 3 is the open circuit voltage of the cell which was about 2.95 voltsO
As is apparent from the curve in Figure 3, the output voltage of the cell discharged at a substan-tially unipotential level almost immediately, even at this lower current train, and then continued at the lead monoxide-lithium voltage level for more than 11 days. Thus using the teachings of this invention, a 17.
~. , . - . . . ~ - ~
.
.
- ~089S;34 non-aqueous lead dioxide cell can be made which takes advantage of the high capacity characteristic of lead dioxide while simultaneously effectively eliminating the disadvantage of the dual voltage level output charac-teristic of lead dioxide in a non-aqueous cell system.
EXAMPLE IV
A flat-type cell wa~ constructed using the same components as described in Example I except that the cathode was composed of 1.5 grams of lead tioxide particles sized between 0.07 mm and 0.15 mm and the electrolyte was lM LiCF3S03 and 0.5M hydrazine in 40 volume per cent dioxolane, 30 volume per cent dimethoxy-ethane and 30 volume per cent 3-methyl-2-oxazolidone.
As in Example III, the surface of the lead dioxide particles contacted by the hydrazine was reduced thereby -forming a lead monoxide layer on said particles.
The cell so produced in accordance with this invention was then discharged across a 2.4K-ohm load -(about 0.6 milliampere drain) and the voltage observed as a function of time is shown plotted as the curve on the graph in Figure 4. Also observed and as recorded on Figure 4 is the open circuit voltage of the cell which was about 2.7 volts.
The curve in Figure 4 shows that the cell dis-charged at a substantially unipotential level after about two tays at this very low drain and then continued at the lead monoxide-lithium voltage level until the : :
, .
10~9~34 cathode was exhausted after the seventh day. Although the test results of the cell using this method of reducing PbO2 were not as good as the test results of the cell using the method disclosed in Example III, the disclosed method does demonstrate that lt can be employed to make a non-aqueous lead dioxide cell which takes advantage of the high capacity characteristic of lead dioxide while simultaneously effectively elim-inating the disadvantage of the dual voltage level output characteristic of lead dioxide in a non-aqueous cell system.
It is to be understood that other modifications and changes to the preferred embodiments of the invention J
herein shown and described can also be made without ~: departing from the spirit and scope of the invention.
' . '' ~' ~
:, 19. ,~.
~' - ' -: .
.
Another object of this invention is to provide a non-aqueous lead oxide cell which employs a positive electrode composed of lead dioxide particles each having a lead monoxide outer layer, and wherein said lead monoxide varies between about 1 per cent and 60 per cent by weight of the lead oxides.
Summarv o~ the Invention The invention relates to a non-aqueous lead oxide cell comprising a highly active metal negative electrode, a positive electrode and a non-aqueous elec-trolyte; said positive electrode comprising lead dioxide particles each having a substantially complete outer layer of lead monoxide, and said cell having a sub-stantially unipotential discharge voltage. ~ ~
A unipotential discharge voltage shall mean ~ -a relatively constant voltage level extending over at least 85 per cent of a cell's discharge capacity when discharged across a fixed load, and wherein the voltage varies no more than + 10 per cent of the average ~oltage of said voltage level. For example, a unipotential dis-charge level can be represented by a voltage-time curve substantially free from voltage excursions or steps during at least 85 per cent of the time of discharge across a constant load, such steps or excursions being defined as voltage readings outside of + 10 per cent of the average voltage over the said 85 per cent portion ~ -of the time of discharge. As shown in Figure 1, it is 3 ~
the object of this invention to effectively eliminate or effectively suppress the portion of the curve to the leEt of point A to yield a unipoten~ial discharge level as generally shown by the curve between points A and B.
It is also within the scope of this invention to add a binder, an electronically conductive material, an electrolyte-absorbent material or mixtures thereof to the positive electrode of this invention.
The size of the lead monoxide~coated lead dioxide particles comprising the cathode of this invention should preferably be between about 0.04 mm and about 0.47 mm and more preferably between about 0.07 mm and about 0.23 mm. Particles sized smaller than about 0.04 mm will provide a large true surface area but, however, when fabricated into a cathode, the electronic conductivity of the cathode will generally be insufficient for commercial cell application due to the large number of particle-to-particle contacts providing the conductive path through the cathode to the cathode collector of the cell. A cathode fabricated with lead monoxide-coated lead dioxide particles sized larger than about 0.47 mm will have a small true surface area which will generally not support a current density generally required for cu~ercial cell application.
The per cent by weight of lead monoxide in the lead dioxide-containing positive electrode of this ', ' 9 5 3~
invention should be between about 1 per cent and about 60 per cent based on the weight of the lead oxldes and preferably between about 10 per cent and about 40 per cent based on the weight of the lead oxides, A
lead monoxide amount less than about 1 per cent by weight of the lead dioxides would be insufficient to reliably and substantially eliminate the two voltage plateau discharge characteristic of lead dioxide in a non-aqueous electrolyte cell system. An amount of lead monoxide greater than about 60 per cent by weight of the lead;~
oxides would be inefficient since too ~uch of the high capacity lead dioxide material would be replaced by the lower capacity lead monoxide material.
Useful highly active negative anode materials are generally consumable metals and include aluminum, the alkali metals, alkaline earth metals and alloys of alkali metals or alkaline earth metals with each other and other metals. The term "alloy" as used herein and in the appended claims is intended to include mixtures, solid solutions, such as lithium-magnesium, and inter-;~
metallic compounds, such as llthium monoaluminide.
The preferred anode ma~erials are lithium, sodium, potassium, calcium, and alloys thereof. ~;
Useful organic solvents employed alone or mixed with one or more other solvents for use in this ;
invention include the following classes of compounds:
, 80 ,: -, . ., . : , :
Alkylene nit riles: e.g., cro t onitrile (li~uid range -51.1C. to 120C.) Trialkyl borates: e.g., trimethyl borate, (CH30)3B
(liquid range -29 3 to 67C.) Tetraalkyl silicates: e.g , tetramethyl silicate, (CH30)4Si (boiling po~nt 121C.) Nitroalkanes- e g., nitromethane, CH3N02 (li~uid range -17 to 100.8C.) Alkylnitriles: e.g., acetonitrile, CH3CN
(li~uid range -45 to 81.6C.) D~alkylamides: e.g , dimethylformamide, HCON(CH3)2 (liquid range -60;48 to 149C.) Lactams: e.g " N-methylpyrro~idone, H2-CH2-CH2-CO-N-CH3 (l~quid range -16 to 202C,) Tetraalkylureas: e g., tetramethylurea, (CH3)2N-CO-NtCH3)2 (ll~uid range -1.2 to 166C.) Monocarboxylic acid esters: e.g., ethyl acetate (liquid range -83.6 to 77.06C.) -Orthoesters: e,g" trimethylorthoformate, HC(OCH3)3 ~bo~ling point 103C.) -Lactones: e.g., ~r~amma)butyrolactone, CH2 CH2-CH2-0-CO
(li~uid ran~e -42 to 206C.) D~alkyl carbonates: e.g., dimethyl carbonate, OC(OCH3)2 (liquid range 2 to 90C.) Alkylene carbonates: e,g., propylene carbonate, CH(CH3)CH2-0-CO-0 (liquid range -48 to 242C,) ~
Monoethers: e.g., diethyl ether (liquid range -116 ~ -to 34.5C.) 9S 3 ~
Polyethers: e.g., 1,1- and 1~2-~dimethoxyethane (liquid ranges -113.2 to 64,5C. and -58 to 83C., respectively) Cyclic ethers: e g., tetra~ydrofuran (liquid range -65 to 67C.); l,3-dioxolane (llquid range -95 to 78C.) Nitroaromatics: e.g., nitrobenzene (liquid range 5.7 to 210.8C.) Aromatic carboxylic acid halides: e.g., benzoyl chloride (liquid range 0 to 197C.); benzoyl bromide (liquid range _~6 to 218C.) Aromatic sulfonic acid halides- e.g., benzene sulfonyl chloride (liquid range 14.5 to 251C ) Aromatic phosphonic acid dihalides: e.g., benzene phosphonyl dichloride (boiling point 258~C ) Aromatic th~ophosphonic acid dihalides: e,g., benzene thiophosphonyl dlchloride (boiling point 124C. at S mm.) ;
Cyclic sulfones: e.g., sulfo~ane, CH2'C~2-CH2-CH2-S2 (melting point 22C );
3-methylsulfolane (melting point -1C.) ~
Alkyl sulfonic acid halides: e,g., methanesulfonyl ~ -chloride (boiling point 161C.) -Al~yl carboxylic acid halides: e.g,, acetyl chloride ~ (liquid range -112 to 50.9C.); acetyl br~mide (liquid range -96 to 76.C.~; propionyl chloride (liquid range ~94 to 8Q~
10 ~
10~9~3~
Saturated heterocyclics: e.g., tetrahydrothiophene (liquid range -96 to 121C.); 3-methyl-2-oxa-zolidone (~elting po~nt 15,9C.) Dialkyl sulfamic scid halides: e.g., d~methyl sulfamyl chloride (boiling point 80C, at 16 mm.) Alkyl halosulfonates: e.g., ethyl chlorosulfonate (boiling point 151C.) Unsaturated heterocyclic carboxylic acid halides:
e.g., 2-furoyl chloride (liquid range -2 to 173C.) Five-membered unsaturated heteroc~clics: e.g., 3,5-dimethylisoxazole (boillng po~nt 140C.);
l-methylpyrrole (boiling point 114C.);
2,4-dimethylthia201e (boiling point 144C.);
furan (liquid range -85.65 to 31,36C.) -Este~s andlor halides of dibàsic carboxylic acids:
e.g., ethyl oxalyl chloride (boiling point 135C.) Mixed alkyl sulfonic acid halides and carboxylic acid halides: e.g., chlorosulfonyl acetyl chloride (boiling point 98C. at 10 mm.) 0 Dialkyl sulfoxides: e.g., dimethyl sulfoxide (liquid range 18.4 to 189C.) Dialkyl sulfates: e.g., dimethylsulfate (liquid range -31.75 to 188.5C.) Dialkyl sulfites: e.g., dimethylsulfite (boiling -point 126C.) Alkylene sulfites: e.g., ethylene glycol sulfite - (liquid range -11 to 173C.) -- 10~9~34 Halogenated alkanes: e.g., methylene chloride (liquid range -95 to 40C:.); 1,3-dichloro-propane ~liquid range -99.5 to 120.4C.) Of the above, the preferred solvents are sulfolane; crotonitrile; nitrobenzene; tetrahydrofuran;
1,3-dioxolane; 3-methyl-2-oxazolidone; propylene car-bonate; ~ -butyrolactone; ethylene glycol sulfite;
dimethylsulfite; dimethyl sulfoxide; and 1,1- and 1,2-dimethoxyethane. Of the preferred solvents, the best are sulfolane; 3-methyl-2-oxazolidone; propylene car- -bonate, 1,3-dioxolane and dimethoxyethane because they ap-pear more chemically inert to battery components and have wide liquid ranges, and especially because they ;~
permit highly efficient utilization of the cathode -~
materials. `
The ionizing solute for use in the invention may be a simple or double salt, or mixtures thereof, - which will produce an ionically conductive solution when dissolved in one or more solvents. Preferred solutes are complexes of inorganic or organic Lewis acids and inorganic ionizable salts. The only require~
ments for utility are that the salts, whether simple ;
or complex, be compatible with the solvent or solvents being employed and that they yield a solution which is sufficiently ionically conductive. According to the ~
Lewis or electronic concept of acids and bases, many -substances which contain no active hydrogen can act as ~ ~
12. -- . , - :. . , : - . .: ;.. . ~ - :--9~ 4 acids or acceptors of electron doublets. The basicconcept is set forth in the chemical literature (Journal of the Franklin Institute, Vol. 226 - July/
December 1938, pages 293-313 by Lewis).
A suggested reaction mechanism for the manner in which these complexes function in a solvent is described in detail in U. S. Patent No. 3,542,602 wherein it is suggested that the complex or double salt formed between the Lewis acid and the ionizable salt yields an entity which is more stable than either of the components alone.
Typical Lewis acids suitable for use in the present invention include aluminum fluoride, aluminum bromide, aluminum chloride, antimony pentachloride, zirconium tetrachloride, phosphorus pentachloride, boron fluoride, boron chloride and boron bromide.
Ionizable salts useful in combination with the Lewis acids include lithium fluoride, lithium chloride, lithium bromide, lithium sulfide, sodium fluoride, sodium chloride, sodium bromide, potassium -fluoride, potassium chloride and potassium bromide.
It will be obvious to those skilled in the art that the double salts formed by a Lewis acid and an inorganic ionizable salt may be used as such or the individual components may be added to the solvent separately to form the double salt or the resulting ions in situ. One such double salt, for example, is that 13.
9 S~l4 formed by the combination of alu~inum chloride and lithium chloride to yield lithium aluminum tetrachloride.
Brief Description o~ the Drawin~s Figure 1 is a curve showing the discharge characteristics of a non-aqueous lead oxide-lithium cell employing a lead dioxide positive electrode (cathode).
Figure 2 is a curve showing the discharge characteristics of a non-a~ueous lead oxide-lithium cell employing a lead monoxide positive electrode.
Figure 3 is a curve showing the discharge characteristics of a non-aqueous lead oxide-lithium ~`
cell employing a positive electrode composed of lead monoxide-coated lead dioxide particles in accordance with the present invention.
Figure 4 is a curve showing the discharge characteristics of a non-aqueous lead oxide-lithium -cell employing a positive electrode composed of lead dioxide particles and an electrolyte containing hydrazine for surface reduction of the lead dioxide particles in accordance with the present invention.
EXAMPLE I
A flat-type cell was constructed utilizing a nickel metal base having therein a l-inch diameter ~!
shallow depression into which the cell contents were placed and over which a nickel metal cap was placed to close the cell. The contents of the cell consisted of five sheets of lithium foil having a total thickness 1~;)89534 of 0.10 inch, about 4 ml of an electrolyte, two porous nonwoven polypropylene separator~ (0.005 ~nch thick each) which absorbed some of the electrolyte, and a lead dioxide cathode mix.
The electrolyte was a lM LiC104 in 77 volume per cent dioxolane, 23 volume per cent dimethoxyethane (DME) with a trace of about 0.1 volume per cent dimethyl isoxazole (DMI) as a polymerization inhibitor. The cathode was a pressed layer of 4.3 grams of lead dioxide.
The cell was discharged across a constant load at a 3-milliampere drain and the voltage observed as a function of time is shown plotted as the curve on the graph in Figure 1. Also observed and as recorded on Figure 1 is the open circuit voltage of the cell which wa~ 3.5 volts. As is apparent from the curve in Figure 1, it took approximately four days before the voltage decreased to a substantially unipotential level of approximately 1.2 volts. As stated above, many cell and battery operated devices which require an essentially uni-potential power source could not use this type of cell system because of its significant dual voltage level discharge characteristic.
EXAMPLE II
A flat-type cell was constructed using the -~
same components as described in Example I except that the cathode mix was a compressed layer of a mixture of 15. ~ :
lV8~53~
3 grams of lead monoxide and 0.5 gram of carbon black added for conductivity. As in Example I, the cathode mix was placed into the shallow depression in a nickel metal base along with other cell componentsO ~;
The cell was discharged on a 3-milliampere drain and the voltage observed as a function of time is shown plotted as the curve on the graph in Figure 2.
Also observed and as recorded on Figure 2 is the open circuit voltage of the cell which was about 3.2 volts.
This high open circuit voltage for the cell is believed to be due to the presence of oxygen and/or oxide~ on the surface of the carbon black in the cathode mix.
As is apparent from the curve in Figure 2, the substantially unipotential voltage level output of this cell makes it an admirable candidate as a power source for many cell and battery operated devices. As stated above, however, although this type of cell has the advantage of discharging at a substantially unipotential level, it has the disadvantage of having a rather low capacity as comparet to a cell employing lead dioxide as the cathode material.
EXAMPLE III
A flat-type cell was constructed using the same components as described in Example I except that the cathode was composed of lead monoxide-coated lead dioxide particles which were prepared in the following manner:
16.
- ~ ' 6 grams of reagent grade PbO2 were mixed with 900 milliliters of an aqueous 0.0015 M hydrazine (N2H4) solution and stirred for one-half hour. The mixture was then filtered and t~e treated PbO2 was dried over-night in a vacuum oven at approximately 82C. This reduced the PbO2 capacity by about 30% producing lead monoxide coated lead dioxide particles. Two grams of the partially reduced PbO2 particles were placed into the shallow depression in a nickel metal base along with the other cell components as described in Example I.
To vary the reduction of PbO2 capacity all that is necessary is to vary the amount and/or concentration of the hydrazine solution and, if desired, the time and/or temperature of the reaction.
The cell so produced in accordance with this invention was then discharged across a lK-ohm load - (about 1.2-milliampere drain) and the voltage observed as a function of time is shown plotted as the curve on the graph in Figure 3. Also observed and as recorded on Figure 3 is the open circuit voltage of the cell which was about 2.95 voltsO
As is apparent from the curve in Figure 3, the output voltage of the cell discharged at a substan-tially unipotential level almost immediately, even at this lower current train, and then continued at the lead monoxide-lithium voltage level for more than 11 days. Thus using the teachings of this invention, a 17.
~. , . - . . . ~ - ~
.
.
- ~089S;34 non-aqueous lead dioxide cell can be made which takes advantage of the high capacity characteristic of lead dioxide while simultaneously effectively eliminating the disadvantage of the dual voltage level output charac-teristic of lead dioxide in a non-aqueous cell system.
EXAMPLE IV
A flat-type cell wa~ constructed using the same components as described in Example I except that the cathode was composed of 1.5 grams of lead tioxide particles sized between 0.07 mm and 0.15 mm and the electrolyte was lM LiCF3S03 and 0.5M hydrazine in 40 volume per cent dioxolane, 30 volume per cent dimethoxy-ethane and 30 volume per cent 3-methyl-2-oxazolidone.
As in Example III, the surface of the lead dioxide particles contacted by the hydrazine was reduced thereby -forming a lead monoxide layer on said particles.
The cell so produced in accordance with this invention was then discharged across a 2.4K-ohm load -(about 0.6 milliampere drain) and the voltage observed as a function of time is shown plotted as the curve on the graph in Figure 4. Also observed and as recorded on Figure 4 is the open circuit voltage of the cell which was about 2.7 volts.
The curve in Figure 4 shows that the cell dis-charged at a substantially unipotential level after about two tays at this very low drain and then continued at the lead monoxide-lithium voltage level until the : :
, .
10~9~34 cathode was exhausted after the seventh day. Although the test results of the cell using this method of reducing PbO2 were not as good as the test results of the cell using the method disclosed in Example III, the disclosed method does demonstrate that lt can be employed to make a non-aqueous lead dioxide cell which takes advantage of the high capacity characteristic of lead dioxide while simultaneously effectively elim-inating the disadvantage of the dual voltage level output characteristic of lead dioxide in a non-aqueous cell system.
It is to be understood that other modifications and changes to the preferred embodiments of the invention J
herein shown and described can also be made without ~: departing from the spirit and scope of the invention.
' . '' ~' ~
:, 19. ,~.
~' - ' -: .
.
Claims (10)
1. A lead oxide cell comprising a highly active metal negative electrode, a positive electrode and a non-aqueous electrolyte comprising a salt dissolved in an organic solvent; said positive electrode comprising lead dioxide particles having a substantially complete outer layer of lead monoxide, and said cell having a substantially unipotential discharge voltage.
2. The lead oxide cell of claim 1 wherein the lead monoxide layer on the lead dioxide particles varies between about 1 per cent and about 60 per cent based on the weight of the lead oxides.
3. The lead oxide cell of claim 1 wherein said lead dioxide particles having a substantially complete outer layer of lead monoxide vary between about 0.4 mm and about 0.47 mm.
4. The lead oxide cell of claim 3 wherein the lead monoxide layer on the lead dioxide particles varies between about 1 per cent and about 60 per cent based on the weight of the lead oxides.
5. The lead oxide cell of claim 1 wherein the active metal negative electrode is selected from the group consisting of aluminum, the alkali metals, alkaline earth metals and alloys thereof.
20.
20.
6. The lead oxide cell of claim 5 wherein the active metal negative electrode is selected from the group consisting of lithium, sodium, potassium, calcium and alloys thereof.
7. The lead oxide cell of claim 6 wherein the active metal negative electrode is lithium.
8. The lead oxide cell of claim 1 wherein the solute of the electrolyte is a complex salt of a Lewis acid and an inorganic ionizable salt.
9. The lead oxide cell of claim 1 wherein the solvent of the electrolyte is at least one solvent selected from the group consisting of sulfolane, crotonitrile, nitrobenzene, tetrahydrofuran, 1,3-dioxolane, 3-methyl-2-oxazolidone, propylene carbonate, ?-butyrolactone, ethylene glycol sulfite, dimethyl-sulfite, dimethyl sulfoxide, 1,1- and 1,2-dimethoxy-ethane, and dimethyl isoxazole.
10. The lead oxide cell of claim 8 wherein said at least one solvent is selected from the group consisting of sulfolane, 3-methyl-2-oxazolidone, propylene carbonate, 1,3-dioxolane, and dimethoxyethane.
21.
21.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US754,531 | 1976-12-27 | ||
| US05/754,531 US4048402A (en) | 1976-12-27 | 1976-12-27 | Non-aqueous cell having a cathode of lead monoxide-coated lead dioxide particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1089534A true CA1089534A (en) | 1980-11-11 |
Family
ID=25035204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA293,196A Expired CA1089534A (en) | 1976-12-27 | 1977-12-16 | Non-aqueous cell having a cathode of lead monoxide- coated lead dioxide particles |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US4048402A (en) |
| JP (2) | JPS5383026A (en) |
| AT (1) | AT361059B (en) |
| AU (1) | AU510791B2 (en) |
| BE (1) | BE862352A (en) |
| BR (1) | BR7708624A (en) |
| CA (1) | CA1089534A (en) |
| CH (1) | CH621436A5 (en) |
| DE (1) | DE2757028C3 (en) |
| DK (1) | DK579477A (en) |
| ES (1) | ES465437A1 (en) |
| FR (1) | FR2375727A1 (en) |
| IE (1) | IE46021B1 (en) |
| IT (1) | IT1089991B (en) |
| NL (1) | NL7714360A (en) |
| SE (1) | SE426998B (en) |
| SU (1) | SU698561A3 (en) |
| ZA (1) | ZA777387B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187328A (en) * | 1976-12-30 | 1980-02-05 | Saft-Societe Des Accumulateurs Fixes Et De Traction | Method of preparing positive active material for electric primary cells |
| FR2404313A1 (en) * | 1977-09-23 | 1979-04-20 | Accumulateurs Fixes | SPECIFIC HIGH ENERGY ELECTROCHEMICAL GENERATOR CONTAINING AN IMPROVED POSITIVE ACTIVE MATERIAL |
| US4271244A (en) * | 1978-09-14 | 1981-06-02 | Saft-Societe Des Accumulateurs Fixes Et De Traction | High specific energy battery having an improved positive active material |
| US4271243A (en) * | 1979-02-14 | 1981-06-02 | Saft Leclanche | Positive active material for an electrical cell |
| US4298663A (en) * | 1979-10-01 | 1981-11-03 | Duracell International Inc. | Predischarged nonaqueous cell |
| FR2493606B1 (en) * | 1980-10-31 | 1985-11-22 | Duracell Int | CATHODE STABILIZER AND METHOD FOR MANUFACTURING ELECTROCHEMICAL CELLS |
| US6849360B2 (en) | 2002-06-05 | 2005-02-01 | Eveready Battery Company, Inc. | Nonaqueous electrochemical cell with improved energy density |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1216394B (en) * | 1958-02-03 | 1966-05-12 | Yardney International Corp | Galvanic element with anhydrous electrolyte |
| DE1671745C3 (en) * | 1967-01-13 | 1979-01-25 | Esb Inc., Philadelphia, Pa. (V.St.A.) | Galvanic element and process for its production |
| JPS5549387B2 (en) * | 1972-03-23 | 1980-12-11 | ||
| US3877983A (en) * | 1973-05-14 | 1975-04-15 | Du Pont | Thin film polymer-bonded cathode |
| US3907597A (en) * | 1974-09-27 | 1975-09-23 | Union Carbide Corp | Nonaqueous cell having an electrolyte containing sulfolane or an alkyl-substituted derivative thereof |
| FR2288401A1 (en) * | 1974-10-17 | 1976-05-14 | Accumulateurs Fixes | ELECTROCHEMICAL GENERATOR |
-
1976
- 1976-12-27 US US05/754,531 patent/US4048402A/en not_active Expired - Lifetime
-
1977
- 1977-12-12 ZA ZA00777387A patent/ZA777387B/en unknown
- 1977-12-16 CA CA293,196A patent/CA1089534A/en not_active Expired
- 1977-12-21 DE DE2757028A patent/DE2757028C3/en not_active Expired
- 1977-12-22 IE IE2621/77A patent/IE46021B1/en unknown
- 1977-12-23 AU AU31959/77A patent/AU510791B2/en not_active Expired
- 1977-12-23 NL NL7714360A patent/NL7714360A/en active Search and Examination
- 1977-12-23 AT AT928577A patent/AT361059B/en not_active IP Right Cessation
- 1977-12-23 FR FR7738965A patent/FR2375727A1/en active Granted
- 1977-12-23 DK DK579477A patent/DK579477A/en unknown
- 1977-12-23 CH CH1600477A patent/CH621436A5/fr not_active IP Right Cessation
- 1977-12-26 SU SU772560055A patent/SU698561A3/en active
- 1977-12-26 BR BR7708624A patent/BR7708624A/en unknown
- 1977-12-26 JP JP15717877A patent/JPS5383026A/en active Pending
- 1977-12-26 ES ES465437A patent/ES465437A1/en not_active Expired
- 1977-12-27 BE BE183871A patent/BE862352A/en not_active IP Right Cessation
- 1977-12-27 IT IT31313/77A patent/IT1089991B/en active
- 1977-12-27 SE SE7714779A patent/SE426998B/en unknown
-
1983
- 1983-08-09 JP JP1983123727U patent/JPS59112471U/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE2757028B2 (en) | 1980-10-23 |
| ES465437A1 (en) | 1978-09-16 |
| IE46021L (en) | 1978-06-27 |
| SU698561A3 (en) | 1979-11-15 |
| AU3195977A (en) | 1979-06-28 |
| BE862352A (en) | 1978-06-27 |
| FR2375727A1 (en) | 1978-07-21 |
| JPS5383026A (en) | 1978-07-22 |
| FR2375727B1 (en) | 1982-04-16 |
| DK579477A (en) | 1978-06-28 |
| AT361059B (en) | 1981-02-25 |
| SE7714779L (en) | 1978-06-27 |
| IE46021B1 (en) | 1983-01-26 |
| BR7708624A (en) | 1979-07-24 |
| US4048402A (en) | 1977-09-13 |
| ATA928577A (en) | 1980-07-15 |
| AU510791B2 (en) | 1980-07-10 |
| IT1089991B (en) | 1985-06-18 |
| SE426998B (en) | 1983-02-21 |
| DE2757028A1 (en) | 1978-06-29 |
| DE2757028C3 (en) | 1981-08-13 |
| JPS59112471U (en) | 1984-07-30 |
| ZA777387B (en) | 1978-10-25 |
| CH621436A5 (en) | 1981-01-30 |
| NL7714360A (en) | 1978-06-29 |
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