CA1133578A - Aluminum additive for cells using divalent silver oxide electrodes - Google Patents
Aluminum additive for cells using divalent silver oxide electrodesInfo
- Publication number
- CA1133578A CA1133578A CA387,243A CA387243A CA1133578A CA 1133578 A CA1133578 A CA 1133578A CA 387243 A CA387243 A CA 387243A CA 1133578 A CA1133578 A CA 1133578A
- Authority
- CA
- Canada
- Prior art keywords
- silver oxide
- positive electrode
- cell
- electrolyte
- divalent silver
- 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
-
- 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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- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
ALUMINUM ADDITIVE FOR
CELLS USING DIVALENT SILVER
OXIDE ELECTRODES
ABSTRACT OF THE INVENTION
An alkaline silver oxide cell having a nega-tive electrode, an alkaline electrolyte and a positive electrode comprising a major amount of divalent silver oxide and wherein a minor amount of an aluminum addi-tive is incorporated into the electrolyte and/or positive electrode to improve the chemical stability of the divalent silver oxide in contact with the alkaline electrolyte.
S P E C I F I C A T I O N
1.
CELLS USING DIVALENT SILVER
OXIDE ELECTRODES
ABSTRACT OF THE INVENTION
An alkaline silver oxide cell having a nega-tive electrode, an alkaline electrolyte and a positive electrode comprising a major amount of divalent silver oxide and wherein a minor amount of an aluminum addi-tive is incorporated into the electrolyte and/or positive electrode to improve the chemical stability of the divalent silver oxide in contact with the alkaline electrolyte.
S P E C I F I C A T I O N
1.
Description
3~ ~ 121~5 FIELD OF THE INVENTION
-The invention relates to a silver oxide alkaline cell employing a divalent silver oxide-con-~aining positive electrode and wherein a minor amount of an aluminum additive is inco~orated into the posi-tive electrode and/or the electrolyte so as to improve ~he chemical stab~lity of the divalent silver ox~de in contact with alkaline electrolyte.
BACXGROUND OF THE INYE~T~ON
The battery has become a primary power source for many portable electronic devices such as radios, hearing aids, watches, calculators and the like. In order to maintain the overall electronic device as compact as possible the electronic devices are usually designed with cavities to accommodate miniature cells as their source of power. The cavieies are usually made so that a cell can be snugly positioned therein thus making electronic contact with appropriate terminals within the de~ice. A maior potential probl~m in the use of a high energy density cell such as a divalent silver oxide/zinc/alkaline cell, is that if the cell bulges, it usually becomes wedged within the cavity of the device whi.ch sometimes can result in damage to the device. In addi~ion, when the cell bulges it may
-The invention relates to a silver oxide alkaline cell employing a divalent silver oxide-con-~aining positive electrode and wherein a minor amount of an aluminum additive is inco~orated into the posi-tive electrode and/or the electrolyte so as to improve ~he chemical stab~lity of the divalent silver ox~de in contact with alkaline electrolyte.
BACXGROUND OF THE INYE~T~ON
The battery has become a primary power source for many portable electronic devices such as radios, hearing aids, watches, calculators and the like. In order to maintain the overall electronic device as compact as possible the electronic devices are usually designed with cavities to accommodate miniature cells as their source of power. The cavieies are usually made so that a cell can be snugly positioned therein thus making electronic contact with appropriate terminals within the de~ice. A maior potential probl~m in the use of a high energy density cell such as a divalent silver oxide/zinc/alkaline cell, is that if the cell bulges, it usually becomes wedged within the cavity of the device whi.ch sometimes can result in damage to the device. In addi~ion, when the cell bulges it may
2.
33~
disturl) ;:he seal whereupon the electrolyte might escape to cause damage to the device and'or oxygen from the at~mosphere may enter which could ceuse wasteful corrosion of the anode. On the other hand, if the seal of the cell ~s maintained, high internal gas pressure may develop which could cause not only bulging of the cell but even possible disassembly of the cell.
Although divalent silver oxide is a good high capacity positive active material when used in alkal~ne cells, it is rather unstable when in contact with an aqueous alkaline electrolyte. Specifically, divalent silver oxide is a highly oxidizing material and as such it is capable of decomposing the water in an aqueous alkaline electrolyte. Divalent silver oxide can also attack cellulosic materials ~n ehe cell, such as the separator, to form carbona~e ~on at the expense - of even more electrolyte. These are undesirable proces-ses because they lead to bulging of the cell, de~eriora-tion of its parts, and loss of service.
U.S. Patent 3,853,623 discloses one approach to stabilizing divalent silver oxide in a silver oxide/-zinc/alkaline cell through the use of gold ions incor-porated into the alkaline electrolyte on the positive side of the cell's separator or gold oxide added to the positive active material of the cell.
Canadian application Serial Number ~ 335 ~ 12145 322,622 by applicant relates to a divalent silver oxide cell in which a minor amount of a ca~mium compound is incorpora~ed in the cell's alkaline electro-lyte and/or positive elPctrode to improve the chemical stability of the divalent silver oxide in contact with the alkaline electrolyt~. Also clisclosed is the ad-dition of an aluminum additive to the cell in con-unction with the cadmium c~mpoulld for chemical stabilization of divalent silver oxide in alkaline mediums.
It is an object of the present invention to provide a divalent silver oxide cell that will mini-mize internal gas pressure buildup so as to effectively eliminate distortion of the cell's housing.
I~ is another object of the present invention to provide a divalent silver oxide cell wherein an alum-inum additive is incorporated into the cell's electrolyte and/or the positive electrode so as to effectively control gas pressure buildup within the cell and thereby effectively eliminate distortion of the cell's housing.
It is another object of the present invention to incorporate an aluminum additive in a divalent silver oxide cell to chemically stabilize the divalent silver oxide when in contact with the cell's aqueous alkaline electrolyte.
33~
The foregoing and additional objects will become more fully apparent fr~m the follow~ng descip-tion. -- SUMMARY OF THE INVENTION
The invention relates to a silver oxide cell having a negative electrode, an aqueous alkaline elec-trolyte, a positive electrode co¢prising a m~jor portion of divalent silver oxide and a separaeor between said negative and positive electrodes, the improvement ~mprising the incorporation of a minor amount of an aluminum additive into the positive electrode and/or into the electrolyte of the cell to improve the stabil-ity of the divalent silver oxide-containing electrode in contact with the aqueous alkaline electrolyte.
As used herein, a positive electrode or a silver oxide electrode shall mean an electrode wherein the active cathode material is divalent silver oxide (AgO) or an electrode wherein ~he major active material is divalent silver oxide in conjunct~on with an smount below 50% by we~ght of monovalent silver oxide (Ag~O) and/or some oth~er electrochemically active positive material.
The aluminum additive may be added in the solid posi~ive electrode and/or dissolved in the electrolyte.
The aluminum adlditive, such as aluminum oxide, incDr-porated in the positive electrode may be either admixed ~ ~3~ ~ 12145 with the divalent silver oxide or incorporated withîn the divalent silver oxide crystallites th~mselves through coprecipitation or absorption during synthesis.
Admixture of the aluminum additive and divalent silver oxide material has the advantage oi- greater flexibiltty in the choice of the divalent silver ox de material with regard to particle size, purity and the like.
The minor amount of the aluminum additive, such as aluminum oxide, for use in the positive electrode lb of this invention to improve the stability of the diva~ent silver oxide when in contac~ with the cell's aqueous alkaline electrolyte should be between about 0 OOl and about 5 per ce~t based on the dry weight of the divalent silver oxide in the positive electrode and preferably between about 0.005 and about 0.05 weight per cent based on ~he dry weight of the divalent silver oxide in the positive electrode. An amount of the aluminum additive less than, for example, about O.OOlweight per cent, would not provide sufficient material to effectively improve the stability of the divalent silver oxide material when in contact with the aqueous alkaline electrolyte. An amount of the aluminum additive more tha~, ~or example, about 5 weight per cent added to the positive elec-trode would not further improve the stability of the divalent silver oxide when in contact with the aqueous alkaline electrolyte and would replace too mNch of the high capaclty silver oxide material.
6.
33~
The aluminum additive, such as aluminate ion~, in accordancs with this invention ~hould be added in an amount between about 0. Ol and about lO per cent based on the weight of the aqueous alkaline electrolyte, preferably between about 0. 5 and about 2. 0 per cent based on the weight of the electrolyte, An amount of the aluminum additive less then, for example, about 0. 01 pe~ cent would not provide - sufficie~t material to effectively improve the ~tability of the divalent ~ilver oxide material when in contact with the aqueous al~aline electrolyte. An amount of the aluminum additive more than, for example 10 per cent would not be soluble in the aqueous alkaline slectrolyte.
Electrolytes containing the aluminum additive can be prepared either by saturation of the electrolyte with Al203, or by dissolution of sodium or potassium aluminate.
It i9 also within the scope of this invention to additionally add a minor amount of a stabilizer, a flow agent and/or a lubricating agent to the active positive mix to further alter the physical character-istics of the active positive mix for molding purposes to produce various Qize and type electrodes. Examples of some of these additives are ethylene bis-stearamide, zinc stearate, lead stearate, calcium stearate and the like.
The silver oxide electrodes of this invention may be - employed in an aqueous cell system using an anode such as zinc, cadmiumt indiu~n or the like. The electrode .. : .~, . : -~ ~3~ 12145 couple so selected can be employed with a compatible electrolyte and preferably an alkaline electrolyte.
Examples of suitable electrolytes include aqueous sol-utions of alkaline earth metal hydroxides, such as stron~ium hydroxide and alkali metal hydroxides, exempli-fied by sodium hydroxide, potassium hydroxide, lithi~m hydroxide, rubidium hydroxide and cesium hydroxide.
Compatible mixtures of the preceding may be utilized. Preferably, the electrode of this invention should be porous so that the walls of the pores and interstices of the electrode can become wetted by the electrolyte EXAMPLE I
Several lots of test cells were produced each using a divalent silver oxide-containing positive pellet having a density o~ 90 grams per cubic inch, a negative electrode of zinc, and a 33% KOH electrolyte. The positive electrode was positioned in a cathode collector cup with a zinc screen disposed between the lnner surface of ~he cup and the positive pellet as disclosed in U.S. Patent
33~
disturl) ;:he seal whereupon the electrolyte might escape to cause damage to the device and'or oxygen from the at~mosphere may enter which could ceuse wasteful corrosion of the anode. On the other hand, if the seal of the cell ~s maintained, high internal gas pressure may develop which could cause not only bulging of the cell but even possible disassembly of the cell.
Although divalent silver oxide is a good high capacity positive active material when used in alkal~ne cells, it is rather unstable when in contact with an aqueous alkaline electrolyte. Specifically, divalent silver oxide is a highly oxidizing material and as such it is capable of decomposing the water in an aqueous alkaline electrolyte. Divalent silver oxide can also attack cellulosic materials ~n ehe cell, such as the separator, to form carbona~e ~on at the expense - of even more electrolyte. These are undesirable proces-ses because they lead to bulging of the cell, de~eriora-tion of its parts, and loss of service.
U.S. Patent 3,853,623 discloses one approach to stabilizing divalent silver oxide in a silver oxide/-zinc/alkaline cell through the use of gold ions incor-porated into the alkaline electrolyte on the positive side of the cell's separator or gold oxide added to the positive active material of the cell.
Canadian application Serial Number ~ 335 ~ 12145 322,622 by applicant relates to a divalent silver oxide cell in which a minor amount of a ca~mium compound is incorpora~ed in the cell's alkaline electro-lyte and/or positive elPctrode to improve the chemical stability of the divalent silver oxide in contact with the alkaline electrolyt~. Also clisclosed is the ad-dition of an aluminum additive to the cell in con-unction with the cadmium c~mpoulld for chemical stabilization of divalent silver oxide in alkaline mediums.
It is an object of the present invention to provide a divalent silver oxide cell that will mini-mize internal gas pressure buildup so as to effectively eliminate distortion of the cell's housing.
I~ is another object of the present invention to provide a divalent silver oxide cell wherein an alum-inum additive is incorporated into the cell's electrolyte and/or the positive electrode so as to effectively control gas pressure buildup within the cell and thereby effectively eliminate distortion of the cell's housing.
It is another object of the present invention to incorporate an aluminum additive in a divalent silver oxide cell to chemically stabilize the divalent silver oxide when in contact with the cell's aqueous alkaline electrolyte.
33~
The foregoing and additional objects will become more fully apparent fr~m the follow~ng descip-tion. -- SUMMARY OF THE INVENTION
The invention relates to a silver oxide cell having a negative electrode, an aqueous alkaline elec-trolyte, a positive electrode co¢prising a m~jor portion of divalent silver oxide and a separaeor between said negative and positive electrodes, the improvement ~mprising the incorporation of a minor amount of an aluminum additive into the positive electrode and/or into the electrolyte of the cell to improve the stabil-ity of the divalent silver oxide-containing electrode in contact with the aqueous alkaline electrolyte.
As used herein, a positive electrode or a silver oxide electrode shall mean an electrode wherein the active cathode material is divalent silver oxide (AgO) or an electrode wherein ~he major active material is divalent silver oxide in conjunct~on with an smount below 50% by we~ght of monovalent silver oxide (Ag~O) and/or some oth~er electrochemically active positive material.
The aluminum additive may be added in the solid posi~ive electrode and/or dissolved in the electrolyte.
The aluminum adlditive, such as aluminum oxide, incDr-porated in the positive electrode may be either admixed ~ ~3~ ~ 12145 with the divalent silver oxide or incorporated withîn the divalent silver oxide crystallites th~mselves through coprecipitation or absorption during synthesis.
Admixture of the aluminum additive and divalent silver oxide material has the advantage oi- greater flexibiltty in the choice of the divalent silver ox de material with regard to particle size, purity and the like.
The minor amount of the aluminum additive, such as aluminum oxide, for use in the positive electrode lb of this invention to improve the stability of the diva~ent silver oxide when in contac~ with the cell's aqueous alkaline electrolyte should be between about 0 OOl and about 5 per ce~t based on the dry weight of the divalent silver oxide in the positive electrode and preferably between about 0.005 and about 0.05 weight per cent based on ~he dry weight of the divalent silver oxide in the positive electrode. An amount of the aluminum additive less than, for example, about O.OOlweight per cent, would not provide sufficient material to effectively improve the stability of the divalent silver oxide material when in contact with the aqueous alkaline electrolyte. An amount of the aluminum additive more tha~, ~or example, about 5 weight per cent added to the positive elec-trode would not further improve the stability of the divalent silver oxide when in contact with the aqueous alkaline electrolyte and would replace too mNch of the high capaclty silver oxide material.
6.
33~
The aluminum additive, such as aluminate ion~, in accordancs with this invention ~hould be added in an amount between about 0. Ol and about lO per cent based on the weight of the aqueous alkaline electrolyte, preferably between about 0. 5 and about 2. 0 per cent based on the weight of the electrolyte, An amount of the aluminum additive less then, for example, about 0. 01 pe~ cent would not provide - sufficie~t material to effectively improve the ~tability of the divalent ~ilver oxide material when in contact with the aqueous al~aline electrolyte. An amount of the aluminum additive more than, for example 10 per cent would not be soluble in the aqueous alkaline slectrolyte.
Electrolytes containing the aluminum additive can be prepared either by saturation of the electrolyte with Al203, or by dissolution of sodium or potassium aluminate.
It i9 also within the scope of this invention to additionally add a minor amount of a stabilizer, a flow agent and/or a lubricating agent to the active positive mix to further alter the physical character-istics of the active positive mix for molding purposes to produce various Qize and type electrodes. Examples of some of these additives are ethylene bis-stearamide, zinc stearate, lead stearate, calcium stearate and the like.
The silver oxide electrodes of this invention may be - employed in an aqueous cell system using an anode such as zinc, cadmiumt indiu~n or the like. The electrode .. : .~, . : -~ ~3~ 12145 couple so selected can be employed with a compatible electrolyte and preferably an alkaline electrolyte.
Examples of suitable electrolytes include aqueous sol-utions of alkaline earth metal hydroxides, such as stron~ium hydroxide and alkali metal hydroxides, exempli-fied by sodium hydroxide, potassium hydroxide, lithi~m hydroxide, rubidium hydroxide and cesium hydroxide.
Compatible mixtures of the preceding may be utilized. Preferably, the electrode of this invention should be porous so that the walls of the pores and interstices of the electrode can become wetted by the electrolyte EXAMPLE I
Several lots of test cells were produced each using a divalent silver oxide-containing positive pellet having a density o~ 90 grams per cubic inch, a negative electrode of zinc, and a 33% KOH electrolyte. The positive electrode was positioned in a cathode collector cup with a zinc screen disposed between the lnner surface of ~he cup and the positive pellet as disclosed in U.S. Patent
3,920,478.
Next a dual separator consisting of a cellulosic barrier film and an absorbent layer was disposed on top of the positive pellet containing divalent silver oxide, An anode cup containing the zinc electrode was then placed over the cathode cup and seal thereto in a conventlonal manner. ~
~ 3~'7~ 12145 The exact constituents of the positive electrode and any additives to the electrolyte are shown in Table 1.
The cells were stored :Eor three months under various temperature conditions. Thereafter the cells were meaured for any bùlging and the results obtained for - each test lot were averaged and are shown in Table 2 along with the maximum cell bulge observed in each lot. In addition, the service life to a 1.3 volt cu~off was observed for most cells and is also shown in Table 2.
~L~IL3~5'7~
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:
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cr~ ~ ~ cr~ x u~ ~ ~
s: ~ ~ ~ ~ ~ ~ O o O ~6 ,D ~
X u~ ~n u~ u~ u o O O O O o o o O u~ 6 c ~! ~ ~ o ~ O x ~! ~ ~ o ~ ~ O _ I O O O O 0: 0 1 o O I O ~
. ~5 1';
Z E ., 11. ~
:
~3~
The results of the data shown in Table 2 illustrate~ ~hat using the teaching of this invention an aluminum additive cian be added to a divalent silver oxide cell to improve the chemical stability of the di-~alent silver oxide when it contacts the cell's alkaline electrolyte.
Numerous variations and modificat~ons of the invention herein described can be made without departing from the ~pirit iqnd scope thereof, and, accordingly, ~he sime is not limited to lts specific embodiments disclosed herein except as in the appended claims.
12.
Next a dual separator consisting of a cellulosic barrier film and an absorbent layer was disposed on top of the positive pellet containing divalent silver oxide, An anode cup containing the zinc electrode was then placed over the cathode cup and seal thereto in a conventlonal manner. ~
~ 3~'7~ 12145 The exact constituents of the positive electrode and any additives to the electrolyte are shown in Table 1.
The cells were stored :Eor three months under various temperature conditions. Thereafter the cells were meaured for any bùlging and the results obtained for - each test lot were averaged and are shown in Table 2 along with the maximum cell bulge observed in each lot. In addition, the service life to a 1.3 volt cu~off was observed for most cells and is also shown in Table 2.
~L~IL3~5'7~
_~
~ ~ o o ~ O O o ,~
., ? ~ o~ o~ ' ~ 3 ~ ~ 6 0 5 c U'~
~2 o C ~
~: E E
6 o O . 00 E~l- a~! I I -' I I : - ~ -? o0 o~ o 3 , ¢ . ¢ - . 6 - ~
o ~ o Cl~ ~ o ~ ~ cr~ 0 a~ 0 ~
:
o CS~- ~ o 5 . -' ~ E E
Z ,~ ~
~ ~J . ~ E L~
E~ ~ ~ ~ 0 Cl~
o o ~, U C
,~, h g~
~ t~
~ E o y r ~ 3 ~ ~ o ~~D ~ ,~ o 1~ ~ ~ ~ ~o .
8~ = ~ ~ ~ O ~ ~ ~
_ ~ ~ ~ ~_, ~ ~ ~ ~ ~ ~ ~ o ~
O O ~ r X O ~ O U~ O O O U~ O O
O ~ ~ ~ ~ ~
~0 X ~ O ~O ~ C~ O ~O ~O~D *
c~
X U~ Irl O~ U~ O U~ O OU~
~4 ~ u~ "E o C o . C s-~ :
~S _ ~ ~D ~O O ~ ~ U~ ~ CO
W¢ u~ ~ ~ o D
E~ c~ O ~ :
x o u~ o ~ O ~ O u~ ~ Oo c~
~ ~ ~ ~ o 0'~ e= ;
cr~ ~ ~ cr~ x u~ ~ ~
s: ~ ~ ~ ~ ~ ~ O o O ~6 ,D ~
X u~ ~n u~ u~ u o O O O O o o o O u~ 6 c ~! ~ ~ o ~ O x ~! ~ ~ o ~ ~ O _ I O O O O 0: 0 1 o O I O ~
. ~5 1';
Z E ., 11. ~
:
~3~
The results of the data shown in Table 2 illustrate~ ~hat using the teaching of this invention an aluminum additive cian be added to a divalent silver oxide cell to improve the chemical stability of the di-~alent silver oxide when it contacts the cell's alkaline electrolyte.
Numerous variations and modificat~ons of the invention herein described can be made without departing from the ~pirit iqnd scope thereof, and, accordingly, ~he sime is not limited to lts specific embodiments disclosed herein except as in the appended claims.
12.
Claims (9)
1. A silver oxide cell having a negative electrode, an aqueous alkaline electrolyte, a positive electrode com-prising a major portion of divalent silver oxide and a separator between said negative electrode and the positive electrode, the improvement comprising the incorporation of an aluminum additive into the electrolyte in an amount between about 0.01 and about 10% based on the weight of the electrolyte to improve the stability of the divalent silver oxide-containing electrode in contact with the aqueous alkaline electrolyte.
2. The silver oxide cell of claim 1 wherein the positive electrode contains less than 50 per cent by weight of the divalent silver oxide in the positive electrode.
3. The silver oxide cell of claim 1 wherein the aqueous alkaline electrolyte contains zinc oxide.
4. The silver oxide cell of claim 1 wherein the positive electrode contains zinc oxide.
5. The silver oxide cell of claim 1 wherein the negative electrode is selected from the group consisting of zinc, cadmium and indium.
6. The silver oxide cell of claim 1 wherein the aluminum additive is present in the electrolyte between about 0.5 and about 2 per cent based on the weight of the electrolyte.
7. The silver oxide cell of claim 1 wherein the positive electrode contains an aluminum additive.
8. The silver oxide cell of claim 7 wherein the aluminum additive is present in the positive electrode in an amount between about 0.001 and about 5 weight per cent based on the dry weight of the divalent silver oxide in the positive electrode.
13.
13.
9. The silver oxide cell of claim 8 wherein the positive electrode contains a minor amount of a material selected from the group consisting of ethylene bis-stearamide, zinc stearate, lead stearate and calcium stearate.
14.
14.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA387,243A CA1133578A (en) | 1979-03-15 | 1981-10-02 | Aluminum additive for cells using divalent silver oxide electrodes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA323,519A CA1127707A (en) | 1978-03-30 | 1979-03-15 | Aluminum additive for cells using divalent silver oxide electrodes |
CA387,243A CA1133578A (en) | 1979-03-15 | 1981-10-02 | Aluminum additive for cells using divalent silver oxide electrodes |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1133578A true CA1133578A (en) | 1982-10-12 |
Family
ID=25668892
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA387,243A Expired CA1133578A (en) | 1979-03-15 | 1981-10-02 | Aluminum additive for cells using divalent silver oxide electrodes |
Country Status (1)
Country | Link |
---|---|
CA (1) | CA1133578A (en) |
-
1981
- 1981-10-02 CA CA387,243A patent/CA1133578A/en not_active Expired
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