CA1089533A - Non-aqueous cell having as cathode a mixture of lead dioxide and lead monoxide and/or lead particles - Google Patents
Non-aqueous cell having as cathode a mixture of lead dioxide and lead monoxide and/or lead particlesInfo
- Publication number
- CA1089533A CA1089533A CA292,277A CA292277A CA1089533A CA 1089533 A CA1089533 A CA 1089533A CA 292277 A CA292277 A CA 292277A CA 1089533 A CA1089533 A CA 1089533A
- Authority
- CA
- Canada
- Prior art keywords
- lead
- oxide cell
- lead oxide
- cell
- particles
- 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
-
- 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
-
- 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
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 a substantially uniform mixture of lead dioxide particles and lead monoxide and/or lead particles.
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 a substantially uniform mixture of lead dioxide particles and lead monoxide and/or lead particles.
Description
Field of the Inventior The invention relates to non-aqueous lead oxide cells, and specifically to such cells wherein the positive electrode comprises a substantially uniform mixture of lead and/or lead monoxide particles and lead dioxide particles.
Background 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 ma~erials, such as FeS2, Co304, PbO2 and the like.
The use of aqueous electrolytes is precluded in these systems since the anode materials are sufficiently active to react with water chemically. The~efore, in order tre~
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 (PbO2) 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, 1089~33 lead monoxide. Contrary to lead dioxide, lead monoxide ~r will discharge in a non-aqueous cell system at a uni-potential level. One advantage in employing lead di-oxide 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 advantage 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 disadvantage ~ ;
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 charac-teristic of non-aqueOus lead dioxide cells. This dual 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 obtaining 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 3.
` 108~S33 almost entirely at its higher voltage level so that, in effect, the cell will produce a substantially uni-potential 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, che cell will discharge at a firg~ 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 is 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 material of the ~ides and oxidizing salts, the discharged 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 the surface of a material selected .... .
~O 8 9'j3 3 9954 from the group ~ncluding 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 i9 employed as the electronic conductor. Although this reference teaches one means for obtaining a unipotential discharge for certain non-aqueous cell systems, a~, for example, a cell employing lead monoxide as the positive active material, the subject invention is directed to the use of lead dioxide mixed with lead monoxide and/or lead particles as the positive active material of a non-aqueous cell.
Accord~ngly, it is the primary object of this invention to provide a non-aqueous lead oxide cell which employs a positive electrode comprising a ~ubstantially uniform mixture of lead dioxide particles and lead monoxide particles 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 a substantially uniform mixture of lead monoxide particles and lead dioxide p æ ticles 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 positive 1()89~313 electrode composed of a substantially uniform mixture of lead dioxide particleR and lead monoxide particle~ and wherein said lead monoxide particles vary between about 5 per cent and 60 per cent by weight of the lead oxides.
It is another ob;ect of this invention to provide a non-aqueous lead oxide cell which employs a positive electrode comprising a substantially unifonm mixture of lead particles and lead dioxide particles and which has a substantially unipotential discharge voltage.
L0 Another ob;ect of this invention is to provide a non-aqueous lead oxide cell which employs a lithium anode and a positive cathode composed of a substantially unifonm mixture of lead particles and lead dioxide particles 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 positive electrode composed of a substantially uniform mixture of lead dioxide particles and lead particles and wherein said lead particles vary between about 5 per cent and about 40 percent by weight of the lead and lead dioxide.
Another object of this invention is to provide a non-aqueous lead dioxide cell which employs a positive electrode comprising a substantially uniform mixture of lead particles, lead monoxide particles and lead dioxide particles and which has a substantially unipotential discharge voltage.
6.
ummary of the Invention The invention relates to a non-aqueous lead oxide cell comprlsing a highly active metal negative electrode, a positive electrode and a non-aqueous electrolyte; said positive electrode comprising a sub-stantially uniform mixture of lead dioxide particles and lead monoxide and/or lead particles, and said cell having a substantially unipotential discharge voltage~
A unipotential discharge voltage shall mean a relatively constant voltage level extending over at least 85 per cent of a cell'~ discharge capacity when discharged acrogs a fixed load, and wherein the voltage varies no more than + 10 per cent of the average voltage of said vol~age level. For example, a uni-potential discharge 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, ~uch 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. Accordingly, it is the ob~ect of this invention to effectively ~
eliminate or effectively suppress the portion of the curve to the left of point A to yield a unipotential discharge level as generally shown by the curve between points A and Bo ~U~9533~ 9954 The lead monoxide particles for use in thi~
invention could compri~e sub~tantially pure lead monoxide particles or lead particles ha~ing an outer layer of lead monoxide. This latter form of lead monoxide particles having an inner core of lead could be fabricated by oxidiz-ing lead particles in any conventional manner.
The size of the lead oxide particles and, when applicable, the lead 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, how-ever, 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 oxide particles and, w~en applicable, lead 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 commercial cell application. ~ -The per cent by weight of the lead monoxide in a lead dioxide-containing positive electrode of this invention should be between about 5 per cent and about 60 per cent based on the weight of the lead oxides and 1 ~ ~ 9 5 331 9954 preferably between about 10 per cent and about 40 per cent based on the weight of the lead oxide~. A lead monoxide amount less than about 5 per cent by weight of the lead oxides would be insufficient to reliably and substantially eliminate the two voltage plateau discharge characteri tic of lead dioxide in a non-aqueous electrolyte cell syYtem.
An amount of lead monoxide greater than about 60 per cent by weight of the lead oxides would be inefficient since too much of the high capacity lead dioxide material would be replaced by the lower capacity lead monoxide material.
The per cent by weight of the lead particles in the lead dioxide-containing positive electrode should be between about 5 per cent and about 40 per cent based on the weight of the lead and lead dioxide and preferably between about 10 per cent and about 30 per cent based on the weight of the lead and lead dioxide. A lead amount less than about 5 per cent by weight of the lead and lead dioxide would be insufficient to reliably and sub-stantially eliminate the two voltage plateau discharge characteristic of lead dioxide in a non-a~ueous electro-lyte cell system. An amount of lead greater than about 40 per cent by weight of the lead and lead dioxide would be inefficient ~ince too much of the high capacity lead dioxide material would be chemically reduced and physically replaced by the lead material.
1 O ~ 9tj3;3 9954 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 th~is invention.
Useful highly active negative metal 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 intermetallic compounds, such as lithium mono- ~ -aluminide. The preferred anode materials are lithium, sodium, potassium, calcium and alloys thereof. Of the preferred anode materials, lithium would be the best because, in addition to being a ductile, safe metal that can ea~ily be assembled in a cell, it possesses the highest energy-to-weight ratio of the group of suitable anode metals.
` ;
10. ~ ~
1089~33 9954 Useful organic solvents employed alone or mixed with one or more other solvents for use in this invention include the following classes of compounds:
Alkylene nitriles: e.g., crotonitrile (liquid 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 poine 121C.) 10Nitroalkanes: e.g., nitromethane, CH3N02 (liquid range -17 to 100.8C.) Alkylnitriles: e.g., acetonitrile, CH3CN
(liquid range -45 to 81.6C.) Dialkylamides: e.g., dimethylformamide, HCON(CH3)2 (liquid range -60.48 to 149C.) Lactams: e.g., N-methylpyrrolidone, CH2-CH2-CH2-CO-N-CH3 (liquid range -16 to 202C.) TetraalkylureaQ: e.g., tetramethylurea, (CH3)2N-C0-N~CH3)2 (liquid range -1.2 to 166C.
20Monocarboxylic acid esters: e.g., ethyl acetate (liquid range -83.6 to 77.06C.) 11. `
~089~33 Orthoesters: e g" trimethylorthoformate, HC(OCH3)3 (boiling point 103C.) Lactones: e.g , ~f~gamma)butyrolactone, CH2~CH2-CH2-0-CO
(liquid range -42 to 206C.) Dlalkyl carbonates: e.g., dimeth~l carbonate, OC(OCH3)2 (liquid range 2 to 90C.) Alkylene carbonates: e.g., propylene carbonate~
CH(CH3)CH2-O-CO-O (liquld range -48 to 242C.) Monoether8: e.g., diethyl ether (liquid range -116 to 34.5C.) Polyethers: e.g., 19 1- and 1,2-dimethoxyethane (liquid ranges -113.2 to 64.5C. and -58 to 83C., re~pectively) Cyclio ethers: e.g., tetrahydrofuran (liquid range -65 to 67C.); 1,3-dioxolane (liquid range -95 to 78C.) Nitroaromatic8: e.g., nitrobenzene (liquid range 5.7 to 210.8C.) Aromatic carboxylic acid halides: e.g., benzoyl chloride (liquid range O to 197C.); benzoyl bromide tliquid range -26 to 218C.) Aromatic sulfonic acid halidès: e.g., benzene sulfonyl chloride (liquid range 14.5 to 251C.) Aromatic phosphonic acid dihalides: e g., benzene phosphonyl dichloride (boiling point 258C.) 10~'3S33 Aromatic thiophosphonic acid dihalides: e.g., benzene thiophosphonyl dichloride (boiling point 124C. at 5 mm.) Cyclic sulfones: e.g., sulfolane, i CH2-CH2-CH2-CH2-S0~ (melting point 22 C-);
3-methylsulfolane (melting point -1C.) Alkyl sulfonic acid halide8: e.g., methanesulfonyl chloride (boiling point 161C.) Alkyl carboxylic acid halides: e.g., acetyl chloride - 10 (liquid range -112 to 50.9C.); acetyl bromide (liquid range -96 to 76,C.~; propionyl chloride (liquid range ~94 to 80C.) Saturated heterocyclics: e.g., tetrahydrothiophene (liquid range -96 to 121C,); 3-methyl-2-oxa-zolidone (melting point 15.9C.) Dialkyl sulfamic acid halides: e.g., dimethyl 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 heterocyclics: e.g~, 3,5-dimethylisoxazole (boiling point 140C.);
l-methyi~L,ole (boiling point 114C.);
Background 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 ma~erials, such as FeS2, Co304, PbO2 and the like.
The use of aqueous electrolytes is precluded in these systems since the anode materials are sufficiently active to react with water chemically. The~efore, in order tre~
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 (PbO2) 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, 1089~33 lead monoxide. Contrary to lead dioxide, lead monoxide ~r will discharge in a non-aqueous cell system at a uni-potential level. One advantage in employing lead di-oxide 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 advantage 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 disadvantage ~ ;
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 charac-teristic of non-aqueOus lead dioxide cells. This dual 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 obtaining 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 3.
` 108~S33 almost entirely at its higher voltage level so that, in effect, the cell will produce a substantially uni-potential 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, che cell will discharge at a firg~ 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 is 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 material of the ~ides and oxidizing salts, the discharged 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 the surface of a material selected .... .
~O 8 9'j3 3 9954 from the group ~ncluding 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 i9 employed as the electronic conductor. Although this reference teaches one means for obtaining a unipotential discharge for certain non-aqueous cell systems, a~, for example, a cell employing lead monoxide as the positive active material, the subject invention is directed to the use of lead dioxide mixed with lead monoxide and/or lead particles as the positive active material of a non-aqueous cell.
Accord~ngly, it is the primary object of this invention to provide a non-aqueous lead oxide cell which employs a positive electrode comprising a ~ubstantially uniform mixture of lead dioxide particles and lead monoxide particles 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 a substantially uniform mixture of lead monoxide particles and lead dioxide p æ ticles 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 positive 1()89~313 electrode composed of a substantially uniform mixture of lead dioxide particleR and lead monoxide particle~ and wherein said lead monoxide particles vary between about 5 per cent and 60 per cent by weight of the lead oxides.
It is another ob;ect of this invention to provide a non-aqueous lead oxide cell which employs a positive electrode comprising a substantially unifonm mixture of lead particles and lead dioxide particles and which has a substantially unipotential discharge voltage.
L0 Another ob;ect of this invention is to provide a non-aqueous lead oxide cell which employs a lithium anode and a positive cathode composed of a substantially unifonm mixture of lead particles and lead dioxide particles 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 positive electrode composed of a substantially uniform mixture of lead dioxide particles and lead particles and wherein said lead particles vary between about 5 per cent and about 40 percent by weight of the lead and lead dioxide.
Another object of this invention is to provide a non-aqueous lead dioxide cell which employs a positive electrode comprising a substantially uniform mixture of lead particles, lead monoxide particles and lead dioxide particles and which has a substantially unipotential discharge voltage.
6.
ummary of the Invention The invention relates to a non-aqueous lead oxide cell comprlsing a highly active metal negative electrode, a positive electrode and a non-aqueous electrolyte; said positive electrode comprising a sub-stantially uniform mixture of lead dioxide particles and lead monoxide and/or lead particles, and said cell having a substantially unipotential discharge voltage~
A unipotential discharge voltage shall mean a relatively constant voltage level extending over at least 85 per cent of a cell'~ discharge capacity when discharged acrogs a fixed load, and wherein the voltage varies no more than + 10 per cent of the average voltage of said vol~age level. For example, a uni-potential discharge 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, ~uch 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. Accordingly, it is the ob~ect of this invention to effectively ~
eliminate or effectively suppress the portion of the curve to the left of point A to yield a unipotential discharge level as generally shown by the curve between points A and Bo ~U~9533~ 9954 The lead monoxide particles for use in thi~
invention could compri~e sub~tantially pure lead monoxide particles or lead particles ha~ing an outer layer of lead monoxide. This latter form of lead monoxide particles having an inner core of lead could be fabricated by oxidiz-ing lead particles in any conventional manner.
The size of the lead oxide particles and, when applicable, the lead 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, how-ever, 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 oxide particles and, w~en applicable, lead 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 commercial cell application. ~ -The per cent by weight of the lead monoxide in a lead dioxide-containing positive electrode of this invention should be between about 5 per cent and about 60 per cent based on the weight of the lead oxides and 1 ~ ~ 9 5 331 9954 preferably between about 10 per cent and about 40 per cent based on the weight of the lead oxide~. A lead monoxide amount less than about 5 per cent by weight of the lead oxides would be insufficient to reliably and substantially eliminate the two voltage plateau discharge characteri tic of lead dioxide in a non-aqueous electrolyte cell syYtem.
An amount of lead monoxide greater than about 60 per cent by weight of the lead oxides would be inefficient since too much of the high capacity lead dioxide material would be replaced by the lower capacity lead monoxide material.
The per cent by weight of the lead particles in the lead dioxide-containing positive electrode should be between about 5 per cent and about 40 per cent based on the weight of the lead and lead dioxide and preferably between about 10 per cent and about 30 per cent based on the weight of the lead and lead dioxide. A lead amount less than about 5 per cent by weight of the lead and lead dioxide would be insufficient to reliably and sub-stantially eliminate the two voltage plateau discharge characteristic of lead dioxide in a non-a~ueous electro-lyte cell system. An amount of lead greater than about 40 per cent by weight of the lead and lead dioxide would be inefficient ~ince too much of the high capacity lead dioxide material would be chemically reduced and physically replaced by the lead material.
1 O ~ 9tj3;3 9954 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 th~is invention.
Useful highly active negative metal 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 intermetallic compounds, such as lithium mono- ~ -aluminide. The preferred anode materials are lithium, sodium, potassium, calcium and alloys thereof. Of the preferred anode materials, lithium would be the best because, in addition to being a ductile, safe metal that can ea~ily be assembled in a cell, it possesses the highest energy-to-weight ratio of the group of suitable anode metals.
` ;
10. ~ ~
1089~33 9954 Useful organic solvents employed alone or mixed with one or more other solvents for use in this invention include the following classes of compounds:
Alkylene nitriles: e.g., crotonitrile (liquid 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 poine 121C.) 10Nitroalkanes: e.g., nitromethane, CH3N02 (liquid range -17 to 100.8C.) Alkylnitriles: e.g., acetonitrile, CH3CN
(liquid range -45 to 81.6C.) Dialkylamides: e.g., dimethylformamide, HCON(CH3)2 (liquid range -60.48 to 149C.) Lactams: e.g., N-methylpyrrolidone, CH2-CH2-CH2-CO-N-CH3 (liquid range -16 to 202C.) TetraalkylureaQ: e.g., tetramethylurea, (CH3)2N-C0-N~CH3)2 (liquid range -1.2 to 166C.
20Monocarboxylic acid esters: e.g., ethyl acetate (liquid range -83.6 to 77.06C.) 11. `
~089~33 Orthoesters: e g" trimethylorthoformate, HC(OCH3)3 (boiling point 103C.) Lactones: e.g , ~f~gamma)butyrolactone, CH2~CH2-CH2-0-CO
(liquid range -42 to 206C.) Dlalkyl carbonates: e.g., dimeth~l carbonate, OC(OCH3)2 (liquid range 2 to 90C.) Alkylene carbonates: e.g., propylene carbonate~
CH(CH3)CH2-O-CO-O (liquld range -48 to 242C.) Monoether8: e.g., diethyl ether (liquid range -116 to 34.5C.) Polyethers: e.g., 19 1- and 1,2-dimethoxyethane (liquid ranges -113.2 to 64.5C. and -58 to 83C., re~pectively) Cyclio ethers: e.g., tetrahydrofuran (liquid range -65 to 67C.); 1,3-dioxolane (liquid range -95 to 78C.) Nitroaromatic8: e.g., nitrobenzene (liquid range 5.7 to 210.8C.) Aromatic carboxylic acid halides: e.g., benzoyl chloride (liquid range O to 197C.); benzoyl bromide tliquid range -26 to 218C.) Aromatic sulfonic acid halidès: e.g., benzene sulfonyl chloride (liquid range 14.5 to 251C.) Aromatic phosphonic acid dihalides: e g., benzene phosphonyl dichloride (boiling point 258C.) 10~'3S33 Aromatic thiophosphonic acid dihalides: e.g., benzene thiophosphonyl dichloride (boiling point 124C. at 5 mm.) Cyclic sulfones: e.g., sulfolane, i CH2-CH2-CH2-CH2-S0~ (melting point 22 C-);
3-methylsulfolane (melting point -1C.) Alkyl sulfonic acid halide8: e.g., methanesulfonyl chloride (boiling point 161C.) Alkyl carboxylic acid halides: e.g., acetyl chloride - 10 (liquid range -112 to 50.9C.); acetyl bromide (liquid range -96 to 76,C.~; propionyl chloride (liquid range ~94 to 80C.) Saturated heterocyclics: e.g., tetrahydrothiophene (liquid range -96 to 121C,); 3-methyl-2-oxa-zolidone (melting point 15.9C.) Dialkyl sulfamic acid halides: e.g., dimethyl 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 heterocyclics: e.g~, 3,5-dimethylisoxazole (boiling point 140C.);
l-methyi~L,ole (boiling point 114C.);
2,4-dimethylthiazole (boiling point 144C.);
furan ~liquid range -85.65 to 31.36C.) 13.
ll)~9S3,3 Esters and/or halides of dibasic carboxylic acids:
e.gO, 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.) ~ialkyl sulfoxides: e.g., dimethyl sulfoxide (liquid range 18.4 to 189C.) Dialkyl sulfates: e.g., dimethylsulfate (liquid range -31.75 to 188.5C.) 0 Dialkyl sulfites: e.g., dimethylsulfite (boiling point 126C.) -Alkylene sulfites: e.g., ethylene glycol sulfite (liquid range -11 to 173C.) 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 carbonate;
~ -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 carbonate and 1,3-tioxolane because they appear more chemically inert to battery components and have wide liquid ranges, and especially because they permit highly efficient utilization of the cathode materials.
14.
~0~9~313 The ionizing solute for use in the invention may be a simple or double salt,or mixtures thereof, which will produce an ionic~lly 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 acids or acceptors of electron doublets. The basic concept 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 describet in detail in U. S. Patent No. 3,542,602 wherein it is suggested that the complex or double saltJ
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 chIoride, antimony pentachloride, zirconium tetrachloride, phosphorus pentachloride, 15.
10~9S3~
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 individualcomponents 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 formed by the combination of aluminum chloride and lithium chloride to yield lithium aluminum tetrachloride.
Brief Description of the Drawings Figure 1 is a curve showing the discharge characteristics of a non-aqueous lead ~xide-lithium cell employing a lead dioxide positive electrode (cathode).
Figure 2 is a curve showing the discharge characteristics of a non-aqueous lead oxide-lithium cell ~mploying a lead monoxide positive electrode.
Figure 3 is a curve showing the discharge characteristics of a non-aqueous lead ~xide-lithium cell employing a cathode composed of a mixture of lead dioxide particles and lead particles in accordance with the present invention.
Figure 4 is a curve showing the discharge 16.
' 1~9~33 9954 characteristics of a non-aqueous lead oxide-lithium cell employing a cathode composed of a mixture of lead dioxide particles and lead monoxide 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 con-sisted of five sheets of lithium foil having a total thickness of 0.10 inch, about 4 ml of an electrolyte, two porous nonwoven polypropylene separators (0.005 inch 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 pressed layer of 4.3 grams of lead dioxide.
108953~ 9954 The cell was discharged across a con~tant load on ~ ~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 was 3.5 volts. As is apparent from the curve in Figure 1, it took approximately four days before the voltage de-creased to a substantially unipotential level of approximately 1.2 volts. As stated above, many cell and battery operated devices which require an essentially unipotential power source could not use this type of cell ~ystem 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 3 grams of lead monoxide and 0.5 grams of carbon black added for conductivity, A~ in Example I, the cathode mix was placed into the shallow depression in a nickel metal base along with the other cell components.
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. m is high open circuit voltage for the cell is believed to be due to t,he presence of oxygen and/or oxides on the surface 18.
. ~ . .
lO ~ 9 5 3 3 9954 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 ~pera~ed devices. ~lowever, slthough this type of cell has the advantage of discharg-ing at a substantially unipotential level, it has the disadvantage of having a rather low capacity as compared 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 mix was a compres~ed layer of a mixture of 2 grams of lead dioxide and 2 grams of lead powder sized 0.07 mm.
The cell made in accordance with this invention was discharged across a lK-ohm load (about 1.2 milliampere drain) and the voltage observed as a function of time i5 shown plotted as the curve on the graph in Figure 3. Also observed and as recorded on ~igure 3 is the open circuit voltage of the ceLl which was about 3.1 volts.
As is apparent from the curve in Figure 3, the output voltage of this cell decreased,even at this lower current drain, to the lead monoxide-lithium level within one day and then continued at this substantially uni-potential level for more than twenty days. Thus using the teachings of this invention, a non-aqueous lead dioxide cell can be made which take~ ~dvantage of the 19 .
1089S~3 9954 high capacity characteristic of lead dioxide while qimultaneou~Ly substantially eliminating the diqadvantage of the dual voltage-level output characteristic of lead dioxide in a non-aqueous cell sy~tem.
EXAMPLE IV
A flat-type cell wa~ constructed using the same components as described in Example I except that the cathode was composed of a substantially uniform mixture of lead dioxide and lead monoxide particles. The cathode ~ ?
material was prepared in the following manner:
22.4 grams of lead monoxide and 20 cubic centi-meters of formic acid (88 weight per cent aqueou~ solution) were reacted to produce a lead formate precipitate which was then rinsed with water, filtered and dried overnight at 85C. A 1:1 molar ratio of lead dioxide (10 grams) and the lead formate (12 grams) were mixed in dioxolane whereupon the solvent was evaporated. The product ao formed was heated overnight at approximately 190C. in a vacuum oven to decompose the lead formate thereby producing lead monoxide finely dispersed throughout the lead dioxide.
Two grams of the cathode material so formed was then placed into the shallow depression in a nickel metal base :as described in Example I.
The cell SQ produced in accordance with this invention was then discharged across a lK-ohm load (about 1.5 milliampere drain) and the voltage observed as a 20 .
. . .
.... . .
1~89S3,3 9954 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 2.2 volts.
As is apparent from the curve in Figure 4, the cell discharged at a substantially unipotential level almost immediately even at this lower current drain and then continued to discharge at the lead monoxide-lithium voltage level for more than 11 days. ThuR using the teach-ings of this invention, a non-aqueous lead dioxide cell can be made which takes advantage of the high capacity characteristic of lead dioxide while simultaneously effect-ively eliminating the disadvantage of the duaL voltage level output characteristic of lead dioxide in a non-aqueous cell system.
It i8 to be understood that other modific~tions and changes to the preferred embodiments of the invention herein shown and described can also be made without depart-ing from the spirit and scope of the invention.
21.
furan ~liquid range -85.65 to 31.36C.) 13.
ll)~9S3,3 Esters and/or halides of dibasic carboxylic acids:
e.gO, 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.) ~ialkyl sulfoxides: e.g., dimethyl sulfoxide (liquid range 18.4 to 189C.) Dialkyl sulfates: e.g., dimethylsulfate (liquid range -31.75 to 188.5C.) 0 Dialkyl sulfites: e.g., dimethylsulfite (boiling point 126C.) -Alkylene sulfites: e.g., ethylene glycol sulfite (liquid range -11 to 173C.) 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 carbonate;
~ -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 carbonate and 1,3-tioxolane because they appear more chemically inert to battery components and have wide liquid ranges, and especially because they permit highly efficient utilization of the cathode materials.
14.
~0~9~313 The ionizing solute for use in the invention may be a simple or double salt,or mixtures thereof, which will produce an ionic~lly 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 acids or acceptors of electron doublets. The basic concept 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 describet in detail in U. S. Patent No. 3,542,602 wherein it is suggested that the complex or double saltJ
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 chIoride, antimony pentachloride, zirconium tetrachloride, phosphorus pentachloride, 15.
10~9S3~
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 individualcomponents 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 formed by the combination of aluminum chloride and lithium chloride to yield lithium aluminum tetrachloride.
Brief Description of the Drawings Figure 1 is a curve showing the discharge characteristics of a non-aqueous lead ~xide-lithium cell employing a lead dioxide positive electrode (cathode).
Figure 2 is a curve showing the discharge characteristics of a non-aqueous lead oxide-lithium cell ~mploying a lead monoxide positive electrode.
Figure 3 is a curve showing the discharge characteristics of a non-aqueous lead ~xide-lithium cell employing a cathode composed of a mixture of lead dioxide particles and lead particles in accordance with the present invention.
Figure 4 is a curve showing the discharge 16.
' 1~9~33 9954 characteristics of a non-aqueous lead oxide-lithium cell employing a cathode composed of a mixture of lead dioxide particles and lead monoxide 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 con-sisted of five sheets of lithium foil having a total thickness of 0.10 inch, about 4 ml of an electrolyte, two porous nonwoven polypropylene separators (0.005 inch 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 pressed layer of 4.3 grams of lead dioxide.
108953~ 9954 The cell was discharged across a con~tant load on ~ ~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 was 3.5 volts. As is apparent from the curve in Figure 1, it took approximately four days before the voltage de-creased to a substantially unipotential level of approximately 1.2 volts. As stated above, many cell and battery operated devices which require an essentially unipotential power source could not use this type of cell ~ystem 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 3 grams of lead monoxide and 0.5 grams of carbon black added for conductivity, A~ in Example I, the cathode mix was placed into the shallow depression in a nickel metal base along with the other cell components.
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. m is high open circuit voltage for the cell is believed to be due to t,he presence of oxygen and/or oxides on the surface 18.
. ~ . .
lO ~ 9 5 3 3 9954 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 ~pera~ed devices. ~lowever, slthough this type of cell has the advantage of discharg-ing at a substantially unipotential level, it has the disadvantage of having a rather low capacity as compared 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 mix was a compres~ed layer of a mixture of 2 grams of lead dioxide and 2 grams of lead powder sized 0.07 mm.
The cell made in accordance with this invention was discharged across a lK-ohm load (about 1.2 milliampere drain) and the voltage observed as a function of time i5 shown plotted as the curve on the graph in Figure 3. Also observed and as recorded on ~igure 3 is the open circuit voltage of the ceLl which was about 3.1 volts.
As is apparent from the curve in Figure 3, the output voltage of this cell decreased,even at this lower current drain, to the lead monoxide-lithium level within one day and then continued at this substantially uni-potential level for more than twenty days. Thus using the teachings of this invention, a non-aqueous lead dioxide cell can be made which take~ ~dvantage of the 19 .
1089S~3 9954 high capacity characteristic of lead dioxide while qimultaneou~Ly substantially eliminating the diqadvantage of the dual voltage-level output characteristic of lead dioxide in a non-aqueous cell sy~tem.
EXAMPLE IV
A flat-type cell wa~ constructed using the same components as described in Example I except that the cathode was composed of a substantially uniform mixture of lead dioxide and lead monoxide particles. The cathode ~ ?
material was prepared in the following manner:
22.4 grams of lead monoxide and 20 cubic centi-meters of formic acid (88 weight per cent aqueou~ solution) were reacted to produce a lead formate precipitate which was then rinsed with water, filtered and dried overnight at 85C. A 1:1 molar ratio of lead dioxide (10 grams) and the lead formate (12 grams) were mixed in dioxolane whereupon the solvent was evaporated. The product ao formed was heated overnight at approximately 190C. in a vacuum oven to decompose the lead formate thereby producing lead monoxide finely dispersed throughout the lead dioxide.
Two grams of the cathode material so formed was then placed into the shallow depression in a nickel metal base :as described in Example I.
The cell SQ produced in accordance with this invention was then discharged across a lK-ohm load (about 1.5 milliampere drain) and the voltage observed as a 20 .
. . .
.... . .
1~89S3,3 9954 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 2.2 volts.
As is apparent from the curve in Figure 4, the cell discharged at a substantially unipotential level almost immediately even at this lower current drain and then continued to discharge at the lead monoxide-lithium voltage level for more than 11 days. ThuR using the teach-ings of this invention, a non-aqueous lead dioxide cell can be made which takes advantage of the high capacity characteristic of lead dioxide while simultaneously effect-ively eliminating the disadvantage of the duaL voltage level output characteristic of lead dioxide in a non-aqueous cell system.
It i8 to be understood that other modific~tions and changes to the preferred embodiments of the invention herein shown and described can also be made without depart-ing from the spirit and scope of the invention.
21.
Claims (30)
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 com-prising a substantially uniform mixture of lead dioxide and lead monoxide and said cell having a substantially unipotential discharge voltage.
2. The leadoxide cell of claim 1 wherein said lead monoxide varies between about 5 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 oxide and lead monoxide are in the form of particles sized between about 0.04 mm and about 0.47 mm.
4. The lead oxide cell of claim 3 wherein the lead monoxide particles have an inner core of lead.
5. The lead oxide cell of claim 3 wherein said lead monoxide varies between about 5 per cent and about 60 per cent based on the weight of the lead oxides.
6. The lead oxide cell of claim 1 wherein the active metal negative electrode is selected from the group consisting of aluminum, the alkali metals, the alkaline earth metals and alloys thereof.
7. The lead oxide cell of claim 6 wherein the active metal negative electrode is selected from the group consisting of lithium, sodium, potassium, calcium, and alloys thereof.
8. The lead oxide cell of claim 7 wherein the active metal negative electrode is lithium.
9. 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.
10. 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; cro-tonitrile; nitrobenzene; tetrahydrofuran; 1,3-dioxolane;
3-methyl-2-oxazolidone; propylene carbonate; ?-butyrola-tone; ethylene glycol sulfite; dimethylsulfite; dimethyl sulfoxide; 1,1- and 1,2- dimethoxyethane; and dimethyl isoxazole.
3-methyl-2-oxazolidone; propylene carbonate; ?-butyrola-tone; ethylene glycol sulfite; dimethylsulfite; dimethyl sulfoxide; 1,1- and 1,2- dimethoxyethane; and dimethyl isoxazole.
11. The lead oxide cell of claim 10 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.
12. 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 23.
a substantially uniform mixture of lead dioxide and lead particles and said cell having a substantially unipotential discharge voltage.
a substantially uniform mixture of lead dioxide and lead particles and said cell having a substantially unipotential discharge voltage.
130 The lead oxide cell of claim 12 wherein said lead dioxide and lead particles are sized between about 0.04 mm and about 0.47 mm.
14. The lead oxide cell of claim 12 wherein the lead varies between about 5 per cent and about 40 per cent based on the weight of the lead and lead dioxide.
15. The lead oxide cell of claim 14 wherein said lead dioxide and lead particles are sized between about 0.04 mm and about 0.47 mm.
16, The lead oxide cell of claim 12 wherein the active metal negative electrode is selected from the group consisting of aluminum, the alkali metals, the alkaline earth metals and alloys thereof.
17. The lead oxide cell of claim 16 wherein the active metal negative electrode is selected from the group consisting of lithium, sodium, potassium, calcium, and alloys thereof.
18. The lead oxide cell of claim 17 wherein the active metal negative electrode is lithium.
24.
24.
19. The lead oxide cell of claim 12 wherein the solute of the electrolyte is a complex salt of a Lewis acid and an inorganic ionizable salt.
20. The lead oxide cell of claim 12 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; dimethylsulfite;
dimethyl sulfoxide; 1,1- and 1,2-dimethoxyethane; and dimethyl isoxazole.
crotonitrile; nitrobenzene; tetrahydrofuran; 1,3-dioxolane; 3-methyl-2-oxazolidone; propylene carbonate;
?-butyrolactone; ethylene glycol sulfite; dimethylsulfite;
dimethyl sulfoxide; 1,1- and 1,2-dimethoxyethane; and dimethyl isoxazole.
21, The lead oxide cell of claim 20 wherein said at least one solvent is selected from the group con-sisting of sulfolane; 3-methyl-2-oxazolidone; propylene carbonate; 1,3-dioxolane; and dimethoxyethane.
22. 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 a substantially uniform mixture of lead dioxide, lead monoxide and lead particles; and said cell having a substantially unipotential discharge voltage.
23. The lead oxide cell of claim 22 wherein said lead dioxide, lead monoxide and lead are in the form of particles sized between about 0.04 mm and about 0.47 mm.
25.
25.
24. The lead oxide cell of claim 23 wherein the lead monoxide particles have an inner core of lead.
25. The lead oxide cell of claim 22 wherein the active metal negative electrode is selected from the group consisting of aluminum, the alkali metals, the alkaline earth metals and alloys thereof.
26. The lead oxide cell of claim 25 wherein the active metal negative electrode is selected from the group consisting of lithium, sodium, potassium, calcium, and alloys thereof.
27. The lead oxide cell of claim 26 wherein the active metal negative electrode is lithium.
28. The lead oxide cell of claim 22 wherein the solute of the electrolyte is a complex salt of a Lewis acid and an inorganic ionizable salt.
29, The lead oxide cell of claim 22 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; dimethylsulfite; dimethyl sulfoxide;
1,1- and 1,2-dimethoxyethane; and dimethyl isoxazole.
nitrobenzene; tetrahydrofuran; 1,3-dioxolane; 3-methyl-2-oxazolidone; propylene carbonate; ?-butyrolactone; ethylene glycol sulfite; dimethylsulfite; dimethyl sulfoxide;
1,1- and 1,2-dimethoxyethane; and dimethyl isoxazole.
30. The lead oxide cell of claim 29 wherein said at least one solvent is selected from the group con-sisting of sulfolane; 3-methyl-2-oxazolidone; propylene carbonate; 1,3-dioxolane; and dimethoxyethane.
26.
26.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/754,362 US4049892A (en) | 1976-12-27 | 1976-12-27 | Non-aqueous cell having as cathode a mixture of lead dioxide and lead monoxide and/or lead particles |
| US754,362 | 1976-12-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1089533A true CA1089533A (en) | 1980-11-11 |
Family
ID=25034464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,277A Expired CA1089533A (en) | 1976-12-27 | 1977-12-02 | Non-aqueous cell having as cathode a mixture of lead dioxide and lead monoxide and/or lead particles |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US4049892A (en) |
| JP (1) | JPS53115026A (en) |
| AR (1) | AR215282A1 (en) |
| AT (1) | AT361058B (en) |
| AU (1) | AU510117B2 (en) |
| BE (1) | BE862350A (en) |
| BR (1) | BR7708623A (en) |
| CA (1) | CA1089533A (en) |
| CH (1) | CH620051A5 (en) |
| DE (1) | DE2756926C3 (en) |
| DK (1) | DK579377A (en) |
| ES (1) | ES465435A1 (en) |
| FR (1) | FR2375726A1 (en) |
| GB (1) | GB1592269A (en) |
| IE (1) | IE46357B1 (en) |
| IT (1) | IT1089724B (en) |
| NL (1) | NL179857C (en) |
| SE (1) | SE427705B (en) |
| SU (1) | SU665827A3 (en) |
| ZA (1) | ZA777250B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2404313A1 (en) * | 1977-09-23 | 1979-04-20 | Accumulateurs Fixes | SPECIFIC HIGH ENERGY ELECTROCHEMICAL GENERATOR CONTAINING AN IMPROVED POSITIVE ACTIVE MATERIAL |
| US4142028A (en) * | 1977-12-23 | 1979-02-27 | Union Carbide Corporation | Nonaqueous cells utilizing aluminum, magnesium, and calcium anodes in amide-based electrolytes |
| FR2414253A1 (en) * | 1978-01-10 | 1979-08-03 | Accumulateurs Fixes | NON-AQUEOUS ELECTROLYTE ELECTROCHEMICAL GENERATOR WITH IMPROVED CONSERVATION |
| US4221851A (en) * | 1978-07-03 | 1980-09-09 | Honeywell Inc. | Stable electrolyte for lithium batteries |
| 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 |
| US4176214A (en) * | 1978-12-26 | 1979-11-27 | Gte Laboratories Incorporated | Lithium-lead sulfate primary electrochemical cell |
| JPH07125783A (en) * | 1993-10-29 | 1995-05-16 | Fujitsu P & S Kk | Package case and structure for storage medium |
| DE19904496A1 (en) | 1999-02-04 | 2000-08-10 | Wacker Chemie Gmbh | Aqueous creams of organosilicon compounds |
| US6849360B2 (en) | 2002-06-05 | 2005-02-01 | Eveready Battery Company, Inc. | Nonaqueous electrochemical cell with improved energy density |
| WO2022046438A2 (en) * | 2020-08-14 | 2022-03-03 | Trustees Of Dartmouth College | Acyclic/cyclic ether based electrolytes outstretching the low temperature limit of sodium metal anode |
Family Cites Families (7)
| 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 |
| JPS4912929A (en) * | 1972-05-18 | 1974-02-04 | ||
| US3877983A (en) * | 1973-05-14 | 1975-04-15 | Du Pont | Thin film polymer-bonded cathode |
| JPS50139940A (en) * | 1974-04-30 | 1975-11-10 | ||
| 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 US05/754,362 patent/US4049892A/en not_active Expired - Lifetime
-
1977
- 1977-12-02 CA CA292,277A patent/CA1089533A/en not_active Expired
- 1977-12-05 ZA ZA00777250A patent/ZA777250B/en unknown
- 1977-12-21 DE DE2756926A patent/DE2756926C3/en not_active Expired
- 1977-12-22 IE IE2620/77A patent/IE46357B1/en unknown
- 1977-12-23 DK DK579377A patent/DK579377A/en unknown
- 1977-12-23 NL NLAANVRAGE7714366,A patent/NL179857C/en not_active IP Right Cessation
- 1977-12-23 AU AU31957/77A patent/AU510117B2/en not_active Expired
- 1977-12-23 CH CH1600377A patent/CH620051A5/fr not_active IP Right Cessation
- 1977-12-23 GB GB53658/77A patent/GB1592269A/en not_active Expired
- 1977-12-23 AT AT928477A patent/AT361058B/en not_active IP Right Cessation
- 1977-12-23 FR FR7738963A patent/FR2375726A1/en active Granted
- 1977-12-23 IT IT31250/77A patent/IT1089724B/en active
- 1977-12-26 SU SU772559008A patent/SU665827A3/en active
- 1977-12-26 AR AR270500A patent/AR215282A1/en active
- 1977-12-26 JP JP15717677A patent/JPS53115026A/en active Granted
- 1977-12-26 BR BR7708623A patent/BR7708623A/en unknown
- 1977-12-26 ES ES465435A patent/ES465435A1/en not_active Expired
- 1977-12-27 SE SE7714778A patent/SE427705B/en unknown
- 1977-12-27 BE BE183869A patent/BE862350A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2756926A1 (en) | 1978-06-29 |
| ATA928477A (en) | 1980-07-15 |
| DE2756926C3 (en) | 1981-08-13 |
| BR7708623A (en) | 1979-07-24 |
| SE7714778L (en) | 1978-06-28 |
| FR2375726A1 (en) | 1978-07-21 |
| JPS53115026A (en) | 1978-10-07 |
| DE2756926B2 (en) | 1980-10-23 |
| AU510117B2 (en) | 1980-06-05 |
| ZA777250B (en) | 1978-09-27 |
| JPS6151382B2 (en) | 1986-11-08 |
| AU3195777A (en) | 1979-06-28 |
| AR215282A1 (en) | 1979-09-28 |
| GB1592269A (en) | 1981-07-01 |
| US4049892A (en) | 1977-09-20 |
| NL7714366A (en) | 1978-06-29 |
| NL179857B (en) | 1986-06-16 |
| IE46357L (en) | 1978-06-27 |
| DK579377A (en) | 1978-06-28 |
| SU665827A3 (en) | 1979-05-30 |
| AT361058B (en) | 1981-02-25 |
| IE46357B1 (en) | 1983-05-18 |
| CH620051A5 (en) | 1980-10-31 |
| FR2375726B1 (en) | 1982-04-16 |
| IT1089724B (en) | 1985-06-18 |
| NL179857C (en) | 1986-11-17 |
| BE862350A (en) | 1978-06-27 |
| ES465435A1 (en) | 1979-01-01 |
| SE427705B (en) | 1983-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4163829A (en) | Metallic reducing additives for solid cathodes for use in nonaqueous cells | |
| US4218523A (en) | Nonaqueous electrochemical cell | |
| JP3318675B2 (en) | Electrolyte for non-aqueous electrochemical cells | |
| US4379815A (en) | Cell having mixed solid cathode materials for controlling cell expansion on discharge | |
| US4913988A (en) | Li2 CO3 -Ca(OH)2 additive for cathodes in nonaqueous cells | |
| US4444855A (en) | Non-aqueous electrochemical cell | |
| CA1089533A (en) | Non-aqueous cell having as cathode a mixture of lead dioxide and lead monoxide and/or lead particles | |
| GB2046506A (en) | Non-aqueous battery | |
| US4302520A (en) | Cathode comprising the reaction product of bismuth, sulfur and lead or iron | |
| US4091191A (en) | Battery having an electrode comprising mixtures of Al and TiS2 | |
| US4167609A (en) | Zinc oxide additive for divalent silver oxide electrodes | |
| US4390604A (en) | Complex metal sulfide cathodes for nonaqueous cells | |
| US4113929A (en) | Non-aqueous primary battery having a pure silver chromate cathode | |
| US4399204A (en) | Solid cathode comprising a lead fluoride/tin fluoride compound | |
| AU593980B2 (en) | Electrolyte for lithium-sulfur dioxide electrochemical cell | |
| CA1089534A (en) | Non-aqueous cell having a cathode of lead monoxide- coated lead dioxide particles | |
| US4048403A (en) | Non-aqueous lead dioxide cell having a unipotential discharge voltage | |
| US4301220A (en) | Nonaqueous cell with cathode comprising the reaction product of bismuth trioxide and molybdenum trioxide | |
| US4385103A (en) | Nonaqueous cell having an antimony trisulfide cathode | |
| GB2146835A (en) | Cell solvent | |
| GB2046507A (en) | Non-aqueous battery | |
| US4419422A (en) | Sulfide-containing cathode for nonaqueous cells | |
| US4298665A (en) | Cathode comprising the reaction product of Bi2 O3 and WO3 | |
| US4327159A (en) | Non-aqueous electrochemical cell | |
| GB1592289A (en) | Lead oxide electric cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |