CA2077796A1 - Low-lead zinc alloy powders for zero-mercury alkaline batteries - Google Patents
Low-lead zinc alloy powders for zero-mercury alkaline batteriesInfo
- Publication number
- CA2077796A1 CA2077796A1 CA002077796A CA2077796A CA2077796A1 CA 2077796 A1 CA2077796 A1 CA 2077796A1 CA 002077796 A CA002077796 A CA 002077796A CA 2077796 A CA2077796 A CA 2077796A CA 2077796 A1 CA2077796 A1 CA 2077796A1
- Authority
- CA
- Canada
- Prior art keywords
- ppm
- zinc alloy
- iron
- zinc
- mercury
- 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.)
- Abandoned
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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Powder Metallurgy (AREA)
Abstract
Abstract of the Disclosure A mercury-free zinc alloy powder having a low gassing rate in the presence of iron up to 30 ppm, and consisting of 0.001 to 0.1 wt % lead, 0.01 to 0.1 wt %
bismuth, 0.01 to 0.1 wt % indium and 0.01 wt % to 0.1 wt % Al, the balance being Zn and unavoidable impurities.
bismuth, 0.01 to 0.1 wt % indium and 0.01 wt % to 0.1 wt % Al, the balance being Zn and unavoidable impurities.
Description
2B~7~
LOW-L~AD ZINC ALLOY POWD~RS FOR ZERO-M~RCURY
ALKALIN~ BATTERIXS
This invention relates to low-lead zinc alloy powders for zero-mercury alkaline batteries displaying low and iron resistant after discharge gassing, hereinafter simply called gassing.
sackground of the Invention The role of mercury in suppressing gassing (due to hydrogen evolution) of zinc powders in alkaline battery electrolytes is well known. However, mercury is toxic and it has become highly desirable to provide mercury-free alkaline batteries.
Addition of alloying elements to zinc, namely bismuth, indium, gallium, aluminum, and other elements is known to reduce corrosion of mercury-free alkaline batteries, such as disclosed in U.S. patent No. 5,082,622.
However, as disclosed in U.S. patent No. 5,108,494, gassing of mercury-free alkaline batteries made of zinc alloy powders is strongly dependent upon the iron content ~ ~ 7 P~
of the zinc power. According to the above patent, the iron content of the zinc powder used for making mercury-free alkaline batteries must be kept below 1 ppm.
It is the object of the invention to provide zinc alloy powders for mercury-free alkaline batteries which display low gassing even in the presence of higher amounts of iron.
Summary of the Invention The present invention provides mercury-free (also called non-amalgamated) zinc alloy powders which are characterized by a low gassing rate in the presence of iron up to 30 ppm. The zinc alloy powder in accordance with the present invention consists of 0.001 to 0.1 wt %
lead, 0.01 to 0.1 wt % bismuth, 0.01 to 0.1 wt % indium and 0.01 to 0.1 wt % Al, the balance being zinc and unavoidable impurities.
The bismuth or indium content of the zinc alloy powder is preferably from 0.05 to 0.1 wt % so as to produce a zinc alloy powder exhibiting negligible sensitivity to iron concentration up to 30 ppm.
Short Description of the Drawing The invention will now be disclosed, by way of example, with reference to specific examples and to the accompanying drawing which illustrates the iron effect on gassing for various zinc alloy powders.
3 ~ 7 ~ ~
Detailed Description of the Invention Preliminary tests have shown that the addition of bismuth, or indium to a zinc alloy containing 500 ppm of lead and less than 5 ppm iron increases gassing, while the combination of bismuth and indium is not efficient in reducing gassing. Only aluminum was found to reduce gassing. The above is shown in the following table.
TAB~ I
I~ . =
Nominal composition (ppm) Gassing Bi In Al microl/g-day 0~- __ 0 44~-0 0 300 ~5 I
. 11 .. _ 11 ___ .. _ It also has been found that a reduction in impurity content such as antimony, is not sufficient to 20~7~
suppress gassing of regular lead-zinc alloys (lead at 500 ppm), unless iron is also reduced to the lowest level (1 ppm). Indeed, a linear relationship was found between gassing of regular lead-zinc alloys and the corresponding iron content. The sensitivity was found to be 20 microl/g-day per ppm.
Applicant has surprisingly found, in accordance with the present invention, that the problem of sensitivity of zinc powder towards iron contamination can be solved by adding to a low-lead zinc powder specific combinations of Bi, In and Al.
The following describes the embodiments of the present invention. The requisite alloys were prepared by addition of the respective alloying elements in their metallic form to molten zinc. The molten alloys were converted to powder using low-pressure, dry-air atomizing.
The obtained product was not sieved.
Examples 1 to 4 Zinc containing 250 ppm lead was alloyed with bismuth, indium and aluminium. The starting material was zinc ingot having an iron content around 2 ppm. Iron was successively added by dissolving steel in molten zinc.
As shown in Table 2, Bi-In-Al zinc alloys containing 250 ppm lead and more than 200 ppm of indium or/and bismuth display a strong resistance to iron contamination. In comparison, a lead (250 ppm) - zinc - ~777~
powder containing less than 5 ppm iron exhibits a gassing rate of 130 microl/g-day.
TABL~ 2 _ _ .. __ Added elements Gassing . _ Lead Bismuth Indium Aluminium Iron .___ (ppm) (ppm) (ppm) (ppm) (ppm)microl/g-day I
250 200 500 300 2 34 l __. 11 2~'77~
Exam~les 5 to ~
Zinc containing less than 25 ppm of lead was alloyed with bismuth, indium and aluminium. The starting material was zinc ingot having an iron content lower than 2 ppm. Iron was successively added by dissolving steel in molten zinc.
As shown in Table 3, Bi-In-Al zinc alloys containing less than 25 ppm lead and more than 200 ppm of Indium or/and Bismuth display a strong resistance to iron contamination. In comparison, the gassing of zinc powder containing no alloying element and less than 5 ppm of iron is around 400 microl/g-day.
~1~777~
TABLE: 3 _ _ Added elemen~s Gassing L0ad Bismuth Indium Aluminium Iron (ppm) (ppm) (ppm) (ppm) (ppm)microl/g-day 5 ~ 25 200 200 300 5 42 .
I
~777~
A graph showing the effect of iron composition in zinc alloys powder on the gassing rate is shown in the accompanying drawing. All the alloys described in example 1 to 8 above are plotted. The dependence of regular lead zinc powder on iron contamination is also shown by a dashed line.
LOW-L~AD ZINC ALLOY POWD~RS FOR ZERO-M~RCURY
ALKALIN~ BATTERIXS
This invention relates to low-lead zinc alloy powders for zero-mercury alkaline batteries displaying low and iron resistant after discharge gassing, hereinafter simply called gassing.
sackground of the Invention The role of mercury in suppressing gassing (due to hydrogen evolution) of zinc powders in alkaline battery electrolytes is well known. However, mercury is toxic and it has become highly desirable to provide mercury-free alkaline batteries.
Addition of alloying elements to zinc, namely bismuth, indium, gallium, aluminum, and other elements is known to reduce corrosion of mercury-free alkaline batteries, such as disclosed in U.S. patent No. 5,082,622.
However, as disclosed in U.S. patent No. 5,108,494, gassing of mercury-free alkaline batteries made of zinc alloy powders is strongly dependent upon the iron content ~ ~ 7 P~
of the zinc power. According to the above patent, the iron content of the zinc powder used for making mercury-free alkaline batteries must be kept below 1 ppm.
It is the object of the invention to provide zinc alloy powders for mercury-free alkaline batteries which display low gassing even in the presence of higher amounts of iron.
Summary of the Invention The present invention provides mercury-free (also called non-amalgamated) zinc alloy powders which are characterized by a low gassing rate in the presence of iron up to 30 ppm. The zinc alloy powder in accordance with the present invention consists of 0.001 to 0.1 wt %
lead, 0.01 to 0.1 wt % bismuth, 0.01 to 0.1 wt % indium and 0.01 to 0.1 wt % Al, the balance being zinc and unavoidable impurities.
The bismuth or indium content of the zinc alloy powder is preferably from 0.05 to 0.1 wt % so as to produce a zinc alloy powder exhibiting negligible sensitivity to iron concentration up to 30 ppm.
Short Description of the Drawing The invention will now be disclosed, by way of example, with reference to specific examples and to the accompanying drawing which illustrates the iron effect on gassing for various zinc alloy powders.
3 ~ 7 ~ ~
Detailed Description of the Invention Preliminary tests have shown that the addition of bismuth, or indium to a zinc alloy containing 500 ppm of lead and less than 5 ppm iron increases gassing, while the combination of bismuth and indium is not efficient in reducing gassing. Only aluminum was found to reduce gassing. The above is shown in the following table.
TAB~ I
I~ . =
Nominal composition (ppm) Gassing Bi In Al microl/g-day 0~- __ 0 44~-0 0 300 ~5 I
. 11 .. _ 11 ___ .. _ It also has been found that a reduction in impurity content such as antimony, is not sufficient to 20~7~
suppress gassing of regular lead-zinc alloys (lead at 500 ppm), unless iron is also reduced to the lowest level (1 ppm). Indeed, a linear relationship was found between gassing of regular lead-zinc alloys and the corresponding iron content. The sensitivity was found to be 20 microl/g-day per ppm.
Applicant has surprisingly found, in accordance with the present invention, that the problem of sensitivity of zinc powder towards iron contamination can be solved by adding to a low-lead zinc powder specific combinations of Bi, In and Al.
The following describes the embodiments of the present invention. The requisite alloys were prepared by addition of the respective alloying elements in their metallic form to molten zinc. The molten alloys were converted to powder using low-pressure, dry-air atomizing.
The obtained product was not sieved.
Examples 1 to 4 Zinc containing 250 ppm lead was alloyed with bismuth, indium and aluminium. The starting material was zinc ingot having an iron content around 2 ppm. Iron was successively added by dissolving steel in molten zinc.
As shown in Table 2, Bi-In-Al zinc alloys containing 250 ppm lead and more than 200 ppm of indium or/and bismuth display a strong resistance to iron contamination. In comparison, a lead (250 ppm) - zinc - ~777~
powder containing less than 5 ppm iron exhibits a gassing rate of 130 microl/g-day.
TABL~ 2 _ _ .. __ Added elements Gassing . _ Lead Bismuth Indium Aluminium Iron .___ (ppm) (ppm) (ppm) (ppm) (ppm)microl/g-day I
250 200 500 300 2 34 l __. 11 2~'77~
Exam~les 5 to ~
Zinc containing less than 25 ppm of lead was alloyed with bismuth, indium and aluminium. The starting material was zinc ingot having an iron content lower than 2 ppm. Iron was successively added by dissolving steel in molten zinc.
As shown in Table 3, Bi-In-Al zinc alloys containing less than 25 ppm lead and more than 200 ppm of Indium or/and Bismuth display a strong resistance to iron contamination. In comparison, the gassing of zinc powder containing no alloying element and less than 5 ppm of iron is around 400 microl/g-day.
~1~777~
TABLE: 3 _ _ Added elemen~s Gassing L0ad Bismuth Indium Aluminium Iron (ppm) (ppm) (ppm) (ppm) (ppm)microl/g-day 5 ~ 25 200 200 300 5 42 .
I
~777~
A graph showing the effect of iron composition in zinc alloys powder on the gassing rate is shown in the accompanying drawing. All the alloys described in example 1 to 8 above are plotted. The dependence of regular lead zinc powder on iron contamination is also shown by a dashed line.
Claims (3)
1. A mercury-free zinc alloy powder having a low gassing rate in the presence of iron up to 30 ppm, consisting of 0.001 to 0.1 wt % lead, 0.01 to 0.1 wt %
bismuth, 0.01 to 0.1 wt % indium and 0.01 wt % to 0.1 wt % Al, the balance being Zn and unavoidable impurities.
bismuth, 0.01 to 0.1 wt % indium and 0.01 wt % to 0.1 wt % Al, the balance being Zn and unavoidable impurities.
2. A mercury-free zinc alloy powder as defined in claim 1, containing 0.05 to 0.1 wt % bismuth, exibiting a negligible sensitivity to iron concentration up to 30 ppm.
3. A mercury-free zinc alloy powder as defined in claim 1, containing 0.05 to 0.1 wt % indium, exibiting a negligible sensitivity to iron concentration up to 30 ppm.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002077796A CA2077796A1 (en) | 1992-09-09 | 1992-09-09 | Low-lead zinc alloy powders for zero-mercury alkaline batteries |
| DE4329431A DE4329431A1 (en) | 1992-09-09 | 1993-09-01 | Zinc@ alloy powder for alkali batteries - is free from mercury and contains lead, bismuth, indium and aluminium |
| BE9300935A BE1006664A5 (en) | 1992-09-09 | 1993-09-08 | Powder zinc alloys low lead battery alkaline containing no mercury. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002077796A CA2077796A1 (en) | 1992-09-09 | 1992-09-09 | Low-lead zinc alloy powders for zero-mercury alkaline batteries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2077796A1 true CA2077796A1 (en) | 1994-03-10 |
Family
ID=4150388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002077796A Abandoned CA2077796A1 (en) | 1992-09-09 | 1992-09-09 | Low-lead zinc alloy powders for zero-mercury alkaline batteries |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE1006664A5 (en) |
| CA (1) | CA2077796A1 (en) |
| DE (1) | DE4329431A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284410B1 (en) | 1997-08-01 | 2001-09-04 | Duracell Inc. | Zinc electrode particle form |
| US6472103B1 (en) | 1997-08-01 | 2002-10-29 | The Gillette Company | Zinc-based electrode particle form |
| US6521378B2 (en) | 1997-08-01 | 2003-02-18 | Duracell Inc. | Electrode having multi-modal distribution of zinc-based particles |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE359890T1 (en) * | 2002-08-05 | 2007-05-15 | Noranda Inc | USE OF A ZINC POWDER IN ELECTROCHEMICAL CELLS |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1003415A6 (en) * | 1989-11-10 | 1992-03-17 | Acec Union Miniere | Zinc powder for alkaline batteries. |
| JPH03263761A (en) * | 1990-03-12 | 1991-11-25 | Sanyo Electric Co Ltd | Zinc-alkaline battery |
| US5168018A (en) * | 1990-05-17 | 1992-12-01 | Matsushita Electric Industrial Co., Ltd. | Method of manufacturing zinc-alkaline batteries |
| US5108494A (en) * | 1991-02-19 | 1992-04-28 | Mitsui Mining & Smelting Co., Ltd. | Zinc alloy powder for alkaline cell and method for production of the same |
-
1992
- 1992-09-09 CA CA002077796A patent/CA2077796A1/en not_active Abandoned
-
1993
- 1993-09-01 DE DE4329431A patent/DE4329431A1/en not_active Withdrawn
- 1993-09-08 BE BE9300935A patent/BE1006664A5/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284410B1 (en) | 1997-08-01 | 2001-09-04 | Duracell Inc. | Zinc electrode particle form |
| US6472103B1 (en) | 1997-08-01 | 2002-10-29 | The Gillette Company | Zinc-based electrode particle form |
| US6521378B2 (en) | 1997-08-01 | 2003-02-18 | Duracell Inc. | Electrode having multi-modal distribution of zinc-based particles |
Also Published As
| Publication number | Publication date |
|---|---|
| BE1006664A5 (en) | 1994-11-08 |
| DE4329431A1 (en) | 1994-03-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |