CA1127707A - Aluminum additive for cells using divalent silver oxide electrodes - Google Patents
Aluminum additive for cells using divalent silver oxide electrodesInfo
- Publication number
- CA1127707A CA1127707A CA323,519A CA323519A CA1127707A CA 1127707 A CA1127707 A CA 1127707A CA 323519 A CA323519 A CA 323519A CA 1127707 A CA1127707 A CA 1127707A
- Authority
- CA
- Canada
- Prior art keywords
- silver oxide
- cell
- positive electrode
- divalent
- electrode
- 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
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 49
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000654 additive Substances 0.000 title claims abstract description 18
- 230000000996 additive effect Effects 0.000 title claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical compound [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 235000010210 aluminium Nutrition 0.000 description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229940065285 cadmium compound Drugs 0.000 description 2
- 150000001662 cadmium compounds Chemical class 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- -1 aluminate ions Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
-
- 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
- H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
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)
- Primary Cells (AREA)
Abstract
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.
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.
Description
~lZ~7~7 12145 FIELD OF THE INVENTION
The invention relates to a silver oxide alkaline cell employing a divalent silver oxide-con-taining positive electrode and wherein a minor amount of an aluminum atditive is incorporated into the posi-tive electrode and/or the electrolyte so as to improve the chemical stability of the divalent silver oxide in contact with alkaline electrolyte.
BACKGROUND OF THE I~E~T W N
The battery has become a pr~mary 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 cavities are usually m2de ~o that a cell can be snugly positioned therein thus making electronic contact with appropriate terminals within the device. A ma~or potential problem in the use of a high energy density cell Quch as a divalent silver oxide/zinc/alkaline cell, is that if the cell bulges, it usually becomes wedged within the ca~ity of the device which sometimes can result in damage to the device. In addition, when the cell bulges it may ~ Z~r7n 7 12145 - disturl~ ~he seal whereupon the electrolyte might escape to cause damage to the devics and~or ~xygen from the at~m~sphere may enter whlch could c~use wasteful corrosion of the anode. On the other hand, if the seal of the cell is maintainet, high internal gas pressure may develop which could cause not only bulging of the cell ~ut even posslble disassembly of the cell.
Although divalent silver oxide is a good high capacity positive active matcrial when used in alkaline cells, St is rather unstable when in contact w~th an aqueous alkaline electrolyte. Specifically, divalent ~ilver oxide is a highly oxidizing material and as ~uch it is capable of decomposing the water in an aqueous alkaline electrolyte. Dlvalent silver oxide can ~lso attack cellulosic materials in the cell, such as tbe eparator, to form carbonate ion at the expense of even more electrolyte. These are undesirable proces-~es because they leat to bulging of the cell, deteriora-tion of its parts, and 1088 of service.
U.S. Patent 3,853,623 discloses one approach to ~tabilizlng tivalent silver oxide ln a silver ox~de/-zinc/alkaline cell through the use of golt ions incor-porated into the alkaline electrolyte on the positive side of the cell's separator or golt oxide added to the positive active material of the céll.
Canadian application Serial Number llZ77~7 12145 322, 622 by applicant relates to a divalent silver oxide cell in which a mlnor amount of a cadmium compound is incorporated in the ceLl's alkaline electro-lyte and/or positive electrode to improve the chemical ~tability of the tivalent silver oxide in co~tact with the alkaline electrolyte. Also disclosed is the ad-dition of an aluminum additive to the cell in con-~unction with the cadmium compound for chemical ~tsbilizatlon of tlvalent silver oxide in alkaline medium~. ~
It is an ob~ect of the present invention to provite a divalent silver oxlde cell that will mini-mize internal gas pressure buildup 60 as to effe`ctively el~minate distortion of the cell's housing.
It i~ anotber ob~ect of the present invention to provide a divalent silver oxide cell wherein an alum- -inum adtitive is incorporated into the cell's electrolyte nd/or the po~itive electrode so as to effectively control gas pressure buildup within the cell and thereby effectively eliminate tistortion of the cell's hou~ng, It i9 another ob~ect 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 céll's aqueous alkaline electrolyte.
1~ .
llZ7707 12145 The foregoLng and addîtional objects will become more fully apparent from the following descip-tion.
SU~1ARY OF THE INVENTION
The invention relates to a silver oxide cell having a negative electrode, an aqueous alkaline elec-trolyte, a positive electrode comprising a major portion - of divalent silver oxide and a separator between said negative and positive electrodes, the improvement comprising the incorporation of a minor amount of an aluminum additive into the iositive 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 oxite electrode shall mean an electrode wherein the active cathode material is divalent silver oxide (AgO) or an electrode wherein the ma~or active material is divalent silver oxide in con~unction with an amount below 50% by weight of monovalent silver oxide (Ag,0) and/or ~ome other electrochemically active positive material.
The aluminum additive may be added in the solid po~itive electrode and/or dissolved in the electrolyte.
The aluminum additive, such as aluminum oxide, incor-porated in the po~itive electrote mRy be either admixed - 112~07 12145 with the divalent silver oxide or incorporated within the divalent silver oxide crystalli~es themselves through coprecipitation or absorption during synthesLs.
Admixture of the aluminum additive and divalent silver oxide material has the advantage of greater flexibiltty in the choice of the divalent silver oxide material with regard to particle s~ze, purity ant the like.
The minor amount of the aluminum additive, such as aluminum oxide, for use in the positive eLectrode of this invention to improve the stability of the divalent silver oxide when in contact with the cell s aqueous alkaline electrolyte should be between about 0.001 and about 5 per cent based on the dry weight of the divalent silver oxide in the positive electrode and preferably between about 0.005 ant about 0.05 weight per cent based on the dry weight of the divalent silver oxide in the positive electrode. An amount of~the aluminum additive less than, for example, about 0~oolweight per cent, would not provide suffic~ent~material to effectively improve the ~tdbility of the divalent silver oxide material when ~n contact with the aqueous alkaline electrolyte. An amount of the aluminum atditive more than, for 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 much of the high capacity silver oxide material.
6.
1127!70'7 12145 The aluminum additivo, such as aluminate ions, in accordance with this invention should be added in an amount between about 0. 01 and about 10 per cent based on the weight of the aqueous a~kaline electrolyte, preferablY between about 0. 5 and about 2. 0 per cont basod on the weight of the electrolyte. An amount of the aluminum additive less then, for example, about 0. 01 per cent would not provide sufficiont material to effectively improve the stability of the divalent ailver oxide material when in contact with the aqueous aLkaline olectrolyte. An amount of the aluminum additive more than, for ~nple 10 per cent would not be soluble in the aqueous alkaline electrolyte.
Electrolyte~ containing the aluminum additive can be prop~rod eithcr by saturation of the eloctrolyte with Alz03, or by diaaolution of aodium or potasaium aluminate.
It ia alao within the ~cope of thi~ in~rention to additionally add a minor amount of a stabilizer, a flow agent and/or a lubricating agoQt to the activo poaitive mix to further alter the physical character-iatica of the active poaitive mix for molding purposes to produce various aize and typo oloctrodea. Examples of some of the~e additives are ethylene b1a-atearamlto, z~nc ~tearate, lead atearate, calcium stearate and th Iilco.
Tho ailvor oxide electrodoa of this invention may be omployod In an aqùeoua cell system uaing an anode such as zinc, cadmlum, intium or the like. The electrode 7.
.
. :
~ 7cr7 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 strontium 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 8hould 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 of 90 grams per cubic inch, a negative electrode of zinc, and a 33Z KDH electrolyte. The positive electrode was positioned in a cathode collector cup with a zinc ~creen disposed between the inner surface of the 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 conventional msnner.
11 2~7cr7 12145 The exact constituents of the positi~e electrode and any additives to the electrolyte are shown in Table 1.
The cells were stored for three months under various temperature conditions. Thereafter the cells were meaured for any bulging 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 cutoff was observed for most cells and is al~o shown in Table 2.
. ' ' I .. .. o o ~ o o o ~ ~ _ _ ? c~ o~ o~
The invention relates to a silver oxide alkaline cell employing a divalent silver oxide-con-taining positive electrode and wherein a minor amount of an aluminum atditive is incorporated into the posi-tive electrode and/or the electrolyte so as to improve the chemical stability of the divalent silver oxide in contact with alkaline electrolyte.
BACKGROUND OF THE I~E~T W N
The battery has become a pr~mary 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 cavities are usually m2de ~o that a cell can be snugly positioned therein thus making electronic contact with appropriate terminals within the device. A ma~or potential problem in the use of a high energy density cell Quch as a divalent silver oxide/zinc/alkaline cell, is that if the cell bulges, it usually becomes wedged within the ca~ity of the device which sometimes can result in damage to the device. In addition, when the cell bulges it may ~ Z~r7n 7 12145 - disturl~ ~he seal whereupon the electrolyte might escape to cause damage to the devics and~or ~xygen from the at~m~sphere may enter whlch could c~use wasteful corrosion of the anode. On the other hand, if the seal of the cell is maintainet, high internal gas pressure may develop which could cause not only bulging of the cell ~ut even posslble disassembly of the cell.
Although divalent silver oxide is a good high capacity positive active matcrial when used in alkaline cells, St is rather unstable when in contact w~th an aqueous alkaline electrolyte. Specifically, divalent ~ilver oxide is a highly oxidizing material and as ~uch it is capable of decomposing the water in an aqueous alkaline electrolyte. Dlvalent silver oxide can ~lso attack cellulosic materials in the cell, such as tbe eparator, to form carbonate ion at the expense of even more electrolyte. These are undesirable proces-~es because they leat to bulging of the cell, deteriora-tion of its parts, and 1088 of service.
U.S. Patent 3,853,623 discloses one approach to ~tabilizlng tivalent silver oxide ln a silver ox~de/-zinc/alkaline cell through the use of golt ions incor-porated into the alkaline electrolyte on the positive side of the cell's separator or golt oxide added to the positive active material of the céll.
Canadian application Serial Number llZ77~7 12145 322, 622 by applicant relates to a divalent silver oxide cell in which a mlnor amount of a cadmium compound is incorporated in the ceLl's alkaline electro-lyte and/or positive electrode to improve the chemical ~tability of the tivalent silver oxide in co~tact with the alkaline electrolyte. Also disclosed is the ad-dition of an aluminum additive to the cell in con-~unction with the cadmium compound for chemical ~tsbilizatlon of tlvalent silver oxide in alkaline medium~. ~
It is an ob~ect of the present invention to provite a divalent silver oxlde cell that will mini-mize internal gas pressure buildup 60 as to effe`ctively el~minate distortion of the cell's housing.
It i~ anotber ob~ect of the present invention to provide a divalent silver oxide cell wherein an alum- -inum adtitive is incorporated into the cell's electrolyte nd/or the po~itive electrode so as to effectively control gas pressure buildup within the cell and thereby effectively eliminate tistortion of the cell's hou~ng, It i9 another ob~ect 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 céll's aqueous alkaline electrolyte.
1~ .
llZ7707 12145 The foregoLng and addîtional objects will become more fully apparent from the following descip-tion.
SU~1ARY OF THE INVENTION
The invention relates to a silver oxide cell having a negative electrode, an aqueous alkaline elec-trolyte, a positive electrode comprising a major portion - of divalent silver oxide and a separator between said negative and positive electrodes, the improvement comprising the incorporation of a minor amount of an aluminum additive into the iositive 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 oxite electrode shall mean an electrode wherein the active cathode material is divalent silver oxide (AgO) or an electrode wherein the ma~or active material is divalent silver oxide in con~unction with an amount below 50% by weight of monovalent silver oxide (Ag,0) and/or ~ome other electrochemically active positive material.
The aluminum additive may be added in the solid po~itive electrode and/or dissolved in the electrolyte.
The aluminum additive, such as aluminum oxide, incor-porated in the po~itive electrote mRy be either admixed - 112~07 12145 with the divalent silver oxide or incorporated within the divalent silver oxide crystalli~es themselves through coprecipitation or absorption during synthesLs.
Admixture of the aluminum additive and divalent silver oxide material has the advantage of greater flexibiltty in the choice of the divalent silver oxide material with regard to particle s~ze, purity ant the like.
The minor amount of the aluminum additive, such as aluminum oxide, for use in the positive eLectrode of this invention to improve the stability of the divalent silver oxide when in contact with the cell s aqueous alkaline electrolyte should be between about 0.001 and about 5 per cent based on the dry weight of the divalent silver oxide in the positive electrode and preferably between about 0.005 ant about 0.05 weight per cent based on the dry weight of the divalent silver oxide in the positive electrode. An amount of~the aluminum additive less than, for example, about 0~oolweight per cent, would not provide suffic~ent~material to effectively improve the ~tdbility of the divalent silver oxide material when ~n contact with the aqueous alkaline electrolyte. An amount of the aluminum atditive more than, for 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 much of the high capacity silver oxide material.
6.
1127!70'7 12145 The aluminum additivo, such as aluminate ions, in accordance with this invention should be added in an amount between about 0. 01 and about 10 per cent based on the weight of the aqueous a~kaline electrolyte, preferablY between about 0. 5 and about 2. 0 per cont basod on the weight of the electrolyte. An amount of the aluminum additive less then, for example, about 0. 01 per cent would not provide sufficiont material to effectively improve the stability of the divalent ailver oxide material when in contact with the aqueous aLkaline olectrolyte. An amount of the aluminum additive more than, for ~nple 10 per cent would not be soluble in the aqueous alkaline electrolyte.
Electrolyte~ containing the aluminum additive can be prop~rod eithcr by saturation of the eloctrolyte with Alz03, or by diaaolution of aodium or potasaium aluminate.
It ia alao within the ~cope of thi~ in~rention to additionally add a minor amount of a stabilizer, a flow agent and/or a lubricating agoQt to the activo poaitive mix to further alter the physical character-iatica of the active poaitive mix for molding purposes to produce various aize and typo oloctrodea. Examples of some of the~e additives are ethylene b1a-atearamlto, z~nc ~tearate, lead atearate, calcium stearate and th Iilco.
Tho ailvor oxide electrodoa of this invention may be omployod In an aqùeoua cell system uaing an anode such as zinc, cadmlum, intium or the like. The electrode 7.
.
. :
~ 7cr7 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 strontium 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 8hould 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 of 90 grams per cubic inch, a negative electrode of zinc, and a 33Z KDH electrolyte. The positive electrode was positioned in a cathode collector cup with a zinc ~creen disposed between the inner surface of the 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 conventional msnner.
11 2~7cr7 12145 The exact constituents of the positi~e electrode and any additives to the electrolyte are shown in Table 1.
The cells were stored for three months under various temperature conditions. Thereafter the cells were meaured for any bulging 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 cutoff was observed for most cells and is al~o shown in Table 2.
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<5~ ~ O _1 0 0 0 0 0 0 1 0 0 ~ O Gl D
~,Z' g~
~12~707 12145 The results of the data shown in Table 2 illustrate; that using the teaching of this invention an aluminum additive can 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 modifications of the invention herein described can be made without departing - from the spirit and scope thereof, and, accordingly, the }O 8a~e ~s not limited to its specific embodiments disclosed herein except as in the appended claims.
' 12,
~1 ~ o ~t X o U~ o U~ o U) o4~ ~o o ~
O O ~ l ~JJ
o ~ ~ X ~ oo ~
¢ ~ o o o o o o ~ ~.
X U~ ~ o o o oo o o o o U~ ~ ~
~ ~ ~ , o ~ o ~ C
~ o o~ o ~ X ~ o ~ ~ ~o o C
<5~ ~ O _1 0 0 0 0 0 0 1 0 0 ~ O Gl D
~,Z' g~
~12~707 12145 The results of the data shown in Table 2 illustrate; that using the teaching of this invention an aluminum additive can 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 modifications of the invention herein described can be made without departing - from the spirit and scope thereof, and, accordingly, the }O 8a~e ~s not limited to its specific embodiments disclosed herein except as in the appended claims.
' 12,
Claims (7)
1. A silver oxide cell having a negative electrode, an aqueous alkaline electrolyte, a positive electrode comprising a major portion of divalent silver oxide and a separator between said negative electrode and positive electrode, the improvement comprising the incorporation of an aluminum additive 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 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 aluminum additive is present in an amount between about 0.005 and about 0.05 weight per cent based on the dry weight of the divalent silver oxide in the positive electrode.
3. The silver oxide cell of claim 1 wherein the positive electrode contains less than 50 per cent by weight.
of monovalent silver oxide based on the dry weight of the divalent silver oxide in the positive electrode.
of monovalent silver oxide based on the dry weight of the divalent silver oxide in the positive electrode.
4. The silver oxide cell of claim 1 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.
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 negative electrode is zinc.
7. The silver oxide cell of claim 1 wherein the negative electrode is zinc and the electrolyte comprises aqueous potassium hydroxide or sodium hydroxide.
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 |
|---|---|---|---|
| US89182878A | 1978-03-30 | 1978-03-30 | |
| US891,828 | 1978-03-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127707A true CA1127707A (en) | 1982-07-13 |
Family
ID=25398888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA323,519A Expired CA1127707A (en) | 1978-03-30 | 1979-03-15 | Aluminum additive for cells using divalent silver oxide electrodes |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS54132734A (en) |
| AU (1) | AU525207B2 (en) |
| BE (1) | BE875190A (en) |
| CA (1) | CA1127707A (en) |
| CH (1) | CH633910A5 (en) |
| DE (1) | DE2912177C2 (en) |
| DK (1) | DK129679A (en) |
| FR (1) | FR2421476A1 (en) |
| GB (1) | GB2019079B (en) |
| HK (1) | HK7783A (en) |
| NL (1) | NL7902463A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2079522B (en) * | 1980-06-23 | 1983-08-03 | Sumitomo Metal Mining Co | Silver oxide cell |
| JPS61107663A (en) * | 1984-06-29 | 1986-05-26 | ユニオン、カ−バイド、コ−ポレ−シヨン | Vermiform expanded graphite conductor for silver oxide batteries |
| JPS6250833A (en) * | 1985-08-30 | 1987-03-05 | Konishiroku Photo Ind Co Ltd | Supplying device for processing liquid of photosensitive material |
| US8936775B2 (en) | 2008-10-29 | 2015-01-20 | Zpower, Llc | Cathode active material (higher oxides of silver) |
| US20120164526A1 (en) * | 2009-03-27 | 2012-06-28 | Zpower, Llc | Cathode |
| US9184444B2 (en) | 2009-11-03 | 2015-11-10 | Zpower, Llc | Electrodes and rechargeable batteries |
| CA2812180C (en) | 2010-09-24 | 2019-03-05 | Zpower, Llc | Doped silver cathode |
| CA2816422A1 (en) | 2010-11-03 | 2012-05-10 | Zpower, Llc | Novel electrodes and rechargeable batteries |
| CA2886154A1 (en) | 2012-09-27 | 2014-04-03 | Zpower, Llc | Cathode |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH156553A (en) * | 1929-10-29 | 1932-08-15 | Limited Drumm Battery Company | Electric accumulator. |
| US2714624A (en) * | 1954-03-10 | 1955-08-02 | Costa Arquimedes Sayas | Storage batteries |
| US2829189A (en) * | 1956-08-24 | 1958-04-01 | Burgess Battery Co | Alkaline dry cell |
| DE1205597B (en) * | 1959-10-22 | 1965-11-25 | Witte & Sutor Kondensatoren U | Process for the production of a gas-tight sealed accumulator with silver electrode |
| JPS5234323A (en) * | 1975-09-10 | 1977-03-16 | Yuasa Battery Co Ltd | Method of producing silver peroxide battery |
-
1979
- 1979-03-15 CA CA323,519A patent/CA1127707A/en not_active Expired
- 1979-03-28 DE DE19792912177 patent/DE2912177C2/en not_active Expired
- 1979-03-29 NL NL7902463A patent/NL7902463A/en not_active Application Discontinuation
- 1979-03-29 CH CH294179A patent/CH633910A5/en not_active IP Right Cessation
- 1979-03-29 BE BE0/194297A patent/BE875190A/en not_active IP Right Cessation
- 1979-03-29 DK DK129679A patent/DK129679A/en not_active Application Discontinuation
- 1979-03-29 AU AU45582/79A patent/AU525207B2/en not_active Ceased
- 1979-03-29 JP JP3766179A patent/JPS54132734A/en active Pending
- 1979-03-29 FR FR7907906A patent/FR2421476A1/en active Granted
- 1979-03-29 GB GB7910982A patent/GB2019079B/en not_active Expired
-
1983
- 1983-03-03 HK HK7783A patent/HK7783A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2912177C2 (en) | 1981-12-03 |
| NL7902463A (en) | 1979-10-02 |
| DE2912177A1 (en) | 1979-10-04 |
| AU4558279A (en) | 1979-10-04 |
| BE875190A (en) | 1979-10-01 |
| CH633910A5 (en) | 1982-12-31 |
| AU525207B2 (en) | 1982-10-28 |
| HK7783A (en) | 1983-03-03 |
| FR2421476B1 (en) | 1984-05-18 |
| GB2019079A (en) | 1979-10-24 |
| GB2019079B (en) | 1982-08-18 |
| DK129679A (en) | 1979-10-01 |
| FR2421476A1 (en) | 1979-10-26 |
| JPS54132734A (en) | 1979-10-16 |
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