CA1117591A - Galvanic electrodes of amalgamated zinc and tin for alkaline cells - Google Patents
Galvanic electrodes of amalgamated zinc and tin for alkaline cellsInfo
- Publication number
- CA1117591A CA1117591A CA000313313A CA313313A CA1117591A CA 1117591 A CA1117591 A CA 1117591A CA 000313313 A CA000313313 A CA 000313313A CA 313313 A CA313313 A CA 313313A CA 1117591 A CA1117591 A CA 1117591A
- Authority
- CA
- Canada
- Prior art keywords
- tin
- weight
- anode
- mass
- zinc
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The element has an amalgamated zinc anode with tin additive, thereby producing a down-step in voltage prior to capacity exhaustion.
The element has an amalgamated zinc anode with tin additive, thereby producing a down-step in voltage prior to capacity exhaustion.
Description
p~
The invention relates to a galvanic element with alkaline electrolyte and an amalgamated zinc anode which contains an additional electrochemically active material.
Known alkaline cells which use zinc as the active~mponent~ and mercury as the corrosion impeding add:itive in the negative electrode mass, customarily use metal oxides such as Mn02, ~IgO, Ag20 and AgO or their mixtures as positive electrode material. All such cells are characterized in that their discharge potential remains approximately constant during the entire discharge time. On the other hand, this desirable property is accompanied by the disadvantage that lo the point in time at which capacity exhaustion occurs cannot be determined from the potential variation, because the potential abruptly drops of-f at the end of discharge.
However, an advance indication of the end of current delivery would be desirable, particularly in those cases in which the cell, for ~easons of relia-bility, should be exchanged for a fresh cell while still at a stage of fully operating capability.
The impending capacity exhaustion may be signaled by having the terminal portions of the capacity, e.g. 10% of the total capacity, delivered at a potential which, on the one hand, lies easily measurably below the normal operating potent~l, but on the other hand, still suffices to maintain in operation the equipment which is powered by the cell.
Such a cell is described in German patent publication (Offenlegungssch-rift) 2,657,085 (Takeda~ published July 7, 1977. Its active anode mass consists of a zinc-indium-mercury alloy. A disadvantage of such a mass is that indium is dif-ficult to obtain in large quantities, and its use is costly.
Accordingly, it is an object of the present invention to replace the known indium by an additive which is less costly, and which is readily obtainable in large quantities.
.
' This and other objects wl~ich will appear are achieved in accordance Witil the invention by using tin as the additional electrochemically active material.
This invention relatcs to a galvanic elemcnt with alkaline electrolyte and an amalgamated zinc anode whic~l anode contains an additional electrochemically active material, the additional electrochemically active material being tin. Andan active anode mass consisting of 70 to 92% by weight zinc, 3 to 10% by weight mercury and 5 to 20% by weight tin.
This invention further relates to the method of making an anode for use in a galvanic element with alkaline electrolyte, comprising the steps of reacting tin chloride in aqueous solution with amalgamated zinc powder in pro-portions of 70 to 92% by weight zinc, 3 to 10% by weight mercury, and 5 to 20%
by weight tin, washing, drying and grinding the reaction product and forming the same into the mass of the anode.
Further details are provided below, and also by reference to the accompanying drawing wherein the single figure illustrates certain comparative operating characteristics of the invention.
Dealing now with the anode mass, more particularly, it consists in accordance with the invention, of between 70 and 92% by weight of zinc, 3 to 10%by weight of mercury, and 5 to 20% by weight tin, preferably 12 to 18% by weighttin.
Essential for the suitability of the tin for the above-mentioned object-ive is not only its potential in an alkaline electrolyte, but also sufficient in-hibition of hydrogen evolution for a degree of subdivision of the tin which is necessary for its utilization as active anode material.
Particularly usable anode masses according to the invention are pro-duced by reaction of dissolved tin chloride with amalgamated zinc powder, or of dissolved tin chloride and dissolved mercury chloride with non-amalgamated zinc powder.
In this connection, the following examples are given:
Example l:
50 grams battery zinc powder with 6% mercury, grain size 150 to 400 microns, are suspended in 30 ml water. To this suspension there is added while stirring a solution of 17.3 grams SnC12 . 2ll20 in 60 ml water with 1 ml con-centrated hydrochloric acid. The initially soft metal mass is first coarsely fragmented. After 10 minutes of standing, the liquid is decanted, the metal mass is washed first with water and then with acetone, dried, and ground to the initial grain size of the zinc powder.
From 3 grams of the product there envolves 0.02 to 0.03 ml/day of ~ -2a-:
.
-S9~
hydr~gen at 2ncExample ?
32 grams of non amalgamated battery zinc powder, grain size 150 to 400 microns, are suspended ~n 50 ml of water. W~ile stirring, there is flowed into this an ~IgC12 solution, produced b~ dissolving 2.2 grams HgO in 25 ml of 1:5 diluted hydrochloric acid and immediately ~hereaf~er a solution of 10.8 grams SnC12 2 H2O in 40 ml of water. This produces a loose metal mass and a black precipitate. The latter disappears upon heating of the reaction mixture. Finally, the metal mass is washed, dried and ground as decribed in Example 1.
I`he gas evolution from 3 grams of this product is less than 0.01 ml/day at 20C.
Example 3:
Additive materials and quantities as in Example 2. However, the zinc powder is initially heated with the water, and then the zinc chloride solution is flowed in. There results a soft metal mass as in Example 1, which is coarsely fragmented. Upon addition of the HgC12 solution the mass becomes mainly loose, similar to the reaction product in Example 2. The mass is washed, dried and ground as in Example 1.
The gas evolution for 3 grams of this product is less than O.Ql ml/day at 20C.
If, in contrast, there is produced a Zn/Sn/Hg-mass by first heating tin ~e~g. 2 grams) with mercury ~3.9 grams~ to 100C, and grinding the semi-solid metal mass which is obtained af~er cooling together with battery zinc powder (38 grams), then the tin in this mass is indeed electrochemically sufficientl~ active, but causes greater hydrogen evolution in the alkaline electrolyte: for 3 grams of mass of the composition described immediately above there forms l ml/day of gas at 20C.
~1~75C3~
The constructlon of a cell embodylng the invention corresponds to that of known button cells: the housing consists of the cathode container of nick~l plated steel sheet and of the high grade stainless steel sheet anode container with interposed plastic ring seal, th~ latter having a copper-plated interior. In these two containers, the corresponding electrode masses are held and separated from each other by a porous plastic or cellulose membrane.
An absorbent mat of cellulose is provided on the side of this membrane facing the anode mass, mainly for storage of the electrolyte-ZnO containing KOH-solution. The absorbent mat may be omitted and in its place a swelling med-ium, e.g. caboxy methyl cellulose, may be added to the anode mass. The cathode mass consists optionally of MnO2, HgO, Ag2O, AgO and other metal oxides or their mixtures.
In the drawing, there is illustrated the variation with time of the operating potential during discharge of a cell embodying the invention, in ~hich the cathode material is Ag2O. When the cell, whose dimensions are ll.S mm diameter and 4 mm height, is discharged via a resistance of 400 ohms, the anode mass produces a voltage drop in two steps. The extended upper volt-age~step, which extends between l.S and 1.4 volts, corresponds to the anodic oxidation of the zinc. The lower step of about 1.2 volts corresponds to the anodic oxidation of the tin. In the absence of the tin, only the upper volt-age step exists, which then suddenly drops off at the end of the discharge ~as shown by the broken lines in the drawing).
Depending upon the load, the voltage levels become somewhat displac-ed. Particularly for higher resistance both steps exhibita nearly horizontal configuration. In principle, this does not change the two-step voltage characteristic. However, the relative lengths o~ the two steps, which are determined by the quantity relationship of zinc to tin, can be varied. The recipe provided above for the anode mass gives only recommended values, uhose modification within liMits may be left to a worker skilled in the art.
Howeverl values for the battery ~inc powder and the tin chloride (SnC12 2 H20) different from the quantiti.es stated may be utilized to advantage only to the extent that the zinc content o~ the inished anode mass remains in the range of 70 to ~2% and the tin content in the range of 5 to 20%. The mercury content may vary between 3 and 10%. Preferred is a tin content of 12 to 18%.
:.
The invention relates to a galvanic element with alkaline electrolyte and an amalgamated zinc anode which contains an additional electrochemically active material.
Known alkaline cells which use zinc as the active~mponent~ and mercury as the corrosion impeding add:itive in the negative electrode mass, customarily use metal oxides such as Mn02, ~IgO, Ag20 and AgO or their mixtures as positive electrode material. All such cells are characterized in that their discharge potential remains approximately constant during the entire discharge time. On the other hand, this desirable property is accompanied by the disadvantage that lo the point in time at which capacity exhaustion occurs cannot be determined from the potential variation, because the potential abruptly drops of-f at the end of discharge.
However, an advance indication of the end of current delivery would be desirable, particularly in those cases in which the cell, for ~easons of relia-bility, should be exchanged for a fresh cell while still at a stage of fully operating capability.
The impending capacity exhaustion may be signaled by having the terminal portions of the capacity, e.g. 10% of the total capacity, delivered at a potential which, on the one hand, lies easily measurably below the normal operating potent~l, but on the other hand, still suffices to maintain in operation the equipment which is powered by the cell.
Such a cell is described in German patent publication (Offenlegungssch-rift) 2,657,085 (Takeda~ published July 7, 1977. Its active anode mass consists of a zinc-indium-mercury alloy. A disadvantage of such a mass is that indium is dif-ficult to obtain in large quantities, and its use is costly.
Accordingly, it is an object of the present invention to replace the known indium by an additive which is less costly, and which is readily obtainable in large quantities.
.
' This and other objects wl~ich will appear are achieved in accordance Witil the invention by using tin as the additional electrochemically active material.
This invention relatcs to a galvanic elemcnt with alkaline electrolyte and an amalgamated zinc anode whic~l anode contains an additional electrochemically active material, the additional electrochemically active material being tin. Andan active anode mass consisting of 70 to 92% by weight zinc, 3 to 10% by weight mercury and 5 to 20% by weight tin.
This invention further relates to the method of making an anode for use in a galvanic element with alkaline electrolyte, comprising the steps of reacting tin chloride in aqueous solution with amalgamated zinc powder in pro-portions of 70 to 92% by weight zinc, 3 to 10% by weight mercury, and 5 to 20%
by weight tin, washing, drying and grinding the reaction product and forming the same into the mass of the anode.
Further details are provided below, and also by reference to the accompanying drawing wherein the single figure illustrates certain comparative operating characteristics of the invention.
Dealing now with the anode mass, more particularly, it consists in accordance with the invention, of between 70 and 92% by weight of zinc, 3 to 10%by weight of mercury, and 5 to 20% by weight tin, preferably 12 to 18% by weighttin.
Essential for the suitability of the tin for the above-mentioned object-ive is not only its potential in an alkaline electrolyte, but also sufficient in-hibition of hydrogen evolution for a degree of subdivision of the tin which is necessary for its utilization as active anode material.
Particularly usable anode masses according to the invention are pro-duced by reaction of dissolved tin chloride with amalgamated zinc powder, or of dissolved tin chloride and dissolved mercury chloride with non-amalgamated zinc powder.
In this connection, the following examples are given:
Example l:
50 grams battery zinc powder with 6% mercury, grain size 150 to 400 microns, are suspended in 30 ml water. To this suspension there is added while stirring a solution of 17.3 grams SnC12 . 2ll20 in 60 ml water with 1 ml con-centrated hydrochloric acid. The initially soft metal mass is first coarsely fragmented. After 10 minutes of standing, the liquid is decanted, the metal mass is washed first with water and then with acetone, dried, and ground to the initial grain size of the zinc powder.
From 3 grams of the product there envolves 0.02 to 0.03 ml/day of ~ -2a-:
.
-S9~
hydr~gen at 2ncExample ?
32 grams of non amalgamated battery zinc powder, grain size 150 to 400 microns, are suspended ~n 50 ml of water. W~ile stirring, there is flowed into this an ~IgC12 solution, produced b~ dissolving 2.2 grams HgO in 25 ml of 1:5 diluted hydrochloric acid and immediately ~hereaf~er a solution of 10.8 grams SnC12 2 H2O in 40 ml of water. This produces a loose metal mass and a black precipitate. The latter disappears upon heating of the reaction mixture. Finally, the metal mass is washed, dried and ground as decribed in Example 1.
I`he gas evolution from 3 grams of this product is less than 0.01 ml/day at 20C.
Example 3:
Additive materials and quantities as in Example 2. However, the zinc powder is initially heated with the water, and then the zinc chloride solution is flowed in. There results a soft metal mass as in Example 1, which is coarsely fragmented. Upon addition of the HgC12 solution the mass becomes mainly loose, similar to the reaction product in Example 2. The mass is washed, dried and ground as in Example 1.
The gas evolution for 3 grams of this product is less than O.Ql ml/day at 20C.
If, in contrast, there is produced a Zn/Sn/Hg-mass by first heating tin ~e~g. 2 grams) with mercury ~3.9 grams~ to 100C, and grinding the semi-solid metal mass which is obtained af~er cooling together with battery zinc powder (38 grams), then the tin in this mass is indeed electrochemically sufficientl~ active, but causes greater hydrogen evolution in the alkaline electrolyte: for 3 grams of mass of the composition described immediately above there forms l ml/day of gas at 20C.
~1~75C3~
The constructlon of a cell embodylng the invention corresponds to that of known button cells: the housing consists of the cathode container of nick~l plated steel sheet and of the high grade stainless steel sheet anode container with interposed plastic ring seal, th~ latter having a copper-plated interior. In these two containers, the corresponding electrode masses are held and separated from each other by a porous plastic or cellulose membrane.
An absorbent mat of cellulose is provided on the side of this membrane facing the anode mass, mainly for storage of the electrolyte-ZnO containing KOH-solution. The absorbent mat may be omitted and in its place a swelling med-ium, e.g. caboxy methyl cellulose, may be added to the anode mass. The cathode mass consists optionally of MnO2, HgO, Ag2O, AgO and other metal oxides or their mixtures.
In the drawing, there is illustrated the variation with time of the operating potential during discharge of a cell embodying the invention, in ~hich the cathode material is Ag2O. When the cell, whose dimensions are ll.S mm diameter and 4 mm height, is discharged via a resistance of 400 ohms, the anode mass produces a voltage drop in two steps. The extended upper volt-age~step, which extends between l.S and 1.4 volts, corresponds to the anodic oxidation of the zinc. The lower step of about 1.2 volts corresponds to the anodic oxidation of the tin. In the absence of the tin, only the upper volt-age step exists, which then suddenly drops off at the end of the discharge ~as shown by the broken lines in the drawing).
Depending upon the load, the voltage levels become somewhat displac-ed. Particularly for higher resistance both steps exhibita nearly horizontal configuration. In principle, this does not change the two-step voltage characteristic. However, the relative lengths o~ the two steps, which are determined by the quantity relationship of zinc to tin, can be varied. The recipe provided above for the anode mass gives only recommended values, uhose modification within liMits may be left to a worker skilled in the art.
Howeverl values for the battery ~inc powder and the tin chloride (SnC12 2 H20) different from the quantiti.es stated may be utilized to advantage only to the extent that the zinc content o~ the inished anode mass remains in the range of 70 to ~2% and the tin content in the range of 5 to 20%. The mercury content may vary between 3 and 10%. Preferred is a tin content of 12 to 18%.
:.
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A galvanic element with alkaline electrolyte and an amalgamated zinc anode which anode contains an additional electrochemically active material, the additional electrochemically active material being tin, and an active anode mass consisting of 70 to 92% by weight zinc, 3 to 10% by weight mercury and 5 to 20% by weight tin.
2. The galvanic element of claim 1, wherein the active anode mass consists of 12 to 18% by weight tin.
3. The method of making an anode for use in a galvanic element with alka-line electrolyte, comprising the steps of reacting tin chloride in aqueous solution with amalgamated zinc powder in proportions of 70 to 92% by weight zinc, 3 to 10% by weight mercury, and 5 to 20% by weight tin, washing, drying and grinding the reaction product and forming the same into the mass of the anode.
4. The method of making an anode for use in a galvanic element with alkaline electrolyte, comprising the steps of reacting dissolved tin chloride and dissolved mercury chloride with non-amalgamated zinc powder in proportions of 70 to 92% weight zinc, 3 to 10% by weight mercury, and 5 to 20% by weight tin, washing, drying and grinding the reaction product and forming the same into the mass of the electrode.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2748992.5 | 1977-11-02 | ||
| DE19772748992 DE2748992A1 (en) | 1977-11-02 | 1977-11-02 | GALVANIC ELEMENT WITH ALKALINE ELECTROLYTE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117591A true CA1117591A (en) | 1982-02-02 |
Family
ID=6022831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000313313A Expired CA1117591A (en) | 1977-11-02 | 1978-10-13 | Galvanic electrodes of amalgamated zinc and tin for alkaline cells |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5472435A (en) |
| BE (1) | BE870957A (en) |
| BR (1) | BR7807166A (en) |
| CA (1) | CA1117591A (en) |
| DE (1) | DE2748992A1 (en) |
| DK (1) | DK482978A (en) |
| FR (1) | FR2408224A1 (en) |
| GB (1) | GB2007421B (en) |
| IT (1) | IT1099939B (en) |
| NL (1) | NL7808915A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6251539B1 (en) * | 1999-06-14 | 2001-06-26 | The Gillette Company | Alkaline cell with improved anode |
-
1977
- 1977-11-02 DE DE19772748992 patent/DE2748992A1/en not_active Withdrawn
-
1978
- 1978-08-30 NL NL7808915A patent/NL7808915A/en not_active Application Discontinuation
- 1978-10-02 FR FR7828138A patent/FR2408224A1/en active Granted
- 1978-10-02 BE BE78190871A patent/BE870957A/en unknown
- 1978-10-13 CA CA000313313A patent/CA1117591A/en not_active Expired
- 1978-10-18 IT IT7828878A patent/IT1099939B/en active
- 1978-10-27 JP JP13175178A patent/JPS5472435A/en active Pending
- 1978-10-30 DK DK482978A patent/DK482978A/en unknown
- 1978-10-31 BR BR7807166A patent/BR7807166A/en unknown
- 1978-10-31 GB GB7842577A patent/GB2007421B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5472435A (en) | 1979-06-09 |
| FR2408224A1 (en) | 1979-06-01 |
| FR2408224B3 (en) | 1981-07-31 |
| GB2007421A (en) | 1979-05-16 |
| DE2748992A1 (en) | 1979-05-03 |
| DK482978A (en) | 1979-05-03 |
| BR7807166A (en) | 1979-07-10 |
| IT1099939B (en) | 1985-09-28 |
| BE870957A (en) | 1979-02-01 |
| NL7808915A (en) | 1979-05-04 |
| GB2007421B (en) | 1982-07-07 |
| IT7828878A0 (en) | 1978-10-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |