CN102569760A - Mercury-free zinc paste for button alkaline zinc-manganese dioxide battery and preparation method thereof - Google Patents
Mercury-free zinc paste for button alkaline zinc-manganese dioxide battery and preparation method thereof Download PDFInfo
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- CN102569760A CN102569760A CN2012100222671A CN201210022267A CN102569760A CN 102569760 A CN102569760 A CN 102569760A CN 2012100222671 A CN2012100222671 A CN 2012100222671A CN 201210022267 A CN201210022267 A CN 201210022267A CN 102569760 A CN102569760 A CN 102569760A
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- 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
Abstract
The invention provides a mercury-free zinc paste for a button alkaline zinc-manganese dioxide battery and a manufacturing method thereof. The preparation method comprises the following steps: the raw materials are 98-99.05 of mercury-free zinc powder, 0.4-1.9 of adhesive, 0.01-0.6 of indium hydroxide and 0.05-1.5 of zinc oxide according to the mass fraction ratio, the adhesive is sodium carboxymethylcellulose and sodium polyacrylate, and the mass ratio of the sodium carboxymethylcellulose to the sodium polyacrylate is 0.1-10; putting the raw materials into three-dimensional non-metal ball milling and mixing equipment for grinding for 5-100 minutes, then adding electrolyte accounting for 38-43% of the mass of the mixture into the ball milling and mixing equipment, vacuumizing to below 0.01 MPa, and mixing for 10-100 minutes to obtain the zinc paste. The invention mixes the used substances into paste and processes the paste in a vacuum state, thus removing the gas generated in the preparation process of the zinc paste, and adding indium hydroxide to replace mercury to prevent the generation of the gas, thus having no pollution to the environment. And the sodium carboxymethyl cellulose is added to prevent the zinc electrode from settling and agglomerating the dispersed zinc powder due to the reduction of viscosity, and the zinc electrode and the indium hydroxide act together to ensure that the battery shows good discharge performance. Therefore, the battery can not expand and deform, the storage of the battery is facilitated, and the indium hydroxide is added into the zinc paste to replace mercury to prevent the generation of gas, so that the environment is not polluted. The zinc paste prepared by the preparation method can be applied to a mercury-free button cell.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of batteries, and particularly relates to mercury-free zinc paste for a button alkaline zinc-manganese battery and preparation thereof.
[ background ] A method for producing a semiconductor device
In alkaline zinc manganese cells, it is generally necessary to add a certain amount of mercury as a zinc corrosion inhibitor. The mercury battery has large capacity and good storage performance. The traditional production method of the current button cell is that the anode active material and the binder are mixed and then added on the anode cup, and then the electrolyte is added, so that the gas generated by the contact of the electrolyte and the active material is sealed in the cell, which is not beneficial to the storage of the cell; and mercury is added to the anode active material to prevent the generation of gas, thus causing environmental pollution. The zinc paste manufacture is a key ring of the mercury-free button cell. The zinc paste consists of main materials and additives, wherein the main materials usually adopt zinc powder and electrolyte, the zinc is easy to separate out hydrogen in the electrolyte aqueous solution to cause self-discharge, and when mercury is added, the mercury forms a protective layer-zinc amalgam-on the zinc surface to inhibit the hydrogen separation. However, mercury causes environmental pollution to some extent, and therefore, alternatives to mercury are being sought. The invention CN 1913199A uses indium hydroxide and indium oxide to make mercury-free button cell zinc paste, but needs to use indium hydroxide and indium oxide at the same time, and the total amount of both is not less than 1% of zinc powder, so the cost is high.
[ summary of the invention ]
The invention aims to provide mercury-free zinc paste for a button alkaline zinc-manganese dioxide battery and a preparation method thereof.
The purpose of the invention is realized as follows: the anode active material is mixed into paste and processed in vacuum state, which discharges the gas generated in the preparation process of the calamine cream and is beneficial to the storage of the battery.
The preparation method of the mercury-free zinc paste for the button alkaline zinc-manganese dioxide battery comprises the following steps:
the raw materials are proportioned according to mass fraction:
the thickening agent is sodium carboxymethylcellulose and sodium polyacrylate, and the mass ratio of the sodium carboxymethylcellulose to the sodium polyacrylate is 0.1-10; the high-viscosity sodium carboxymethyl cellulose has a good effect.
The method comprises the steps of putting raw materials into three-dimensional non-metal ball-milling mixing equipment for milling for 5-100 minutes, adding electrolyte accounting for 38-43% of the mixture by mass into the ball-milling mixing equipment, vacuumizing to be below 0.01 MPa, and mixing for 10-100 minutes to obtain the zinc paste.
The invention adds sodium polyacrylate and sodium carboxymethyl cellulose, so that the anode active substance is mixed into paste and generates cohesiveness. Because the sodium carboxymethyl cellulose has higher viscosity than sodium polyacrylate and better conductivity than polyacrylate, the dispersed zinc powder is prevented from settling and agglomerating due to the reduction of viscosity of the zinc electrode, and the battery shows good discharge performance. In addition, because the invention is processed in a vacuum state, gas generated in the process of preparing the zinc paste is discharged.
Therefore, the battery can not expand and deform, the storage of the battery is facilitated, and the indium hydroxide is added into the zinc paste to replace mercury to prevent the generation of gas, so that the environment is not polluted.
The electrolyte is prepared by the following method:
the raw materials are proportioned according to mass fraction: potassium hydroxide 45
5 to 10 portions of zinc oxide
45-50 parts of pure water
The electrolyte is 30-45% potassium hydroxide aqueous solution containing zinc oxide.
The configuration method comprises the following steps:
adding pure water into a preparation tank, adding potassium hydroxide into the preparation tank under a stirring state, dissolving the potassium hydroxide, adding zinc oxide into the preparation tank under a stirring state, dissolving the zinc oxide, cooling, filtering by using a filter element (the aperture is 1 mu m), and finally adjusting the filtered electrolyte to a potassium hydroxide solution with the concentration of 30-45% by using the pure water to obtain the electrolyte.
Compared with the prior art, the invention has the following advantages and effects:
the invention adds sodium polyacrylate and sodium carboxymethyl cellulose, so that the anode active substance is mixed into paste and generates cohesiveness. Because the sodium carboxymethyl cellulose has higher viscosity than sodium polyacrylate and better conductivity than polyacrylate, the dispersed zinc powder is prevented from settling and agglomerating due to the reduction of viscosity of the zinc electrode, and the battery shows good discharge performance. In addition, the invention discharges gas generated in the process of preparing the zinc paste because the zinc paste is processed in a vacuum state. Therefore, the battery can not expand and deform, the battery storage is facilitated, only indium hydroxide is added to replace mercury to prevent gas generation, the environment is not polluted, the cost is reduced, and the formula is simple.
[ detailed description (in examples, parts are by mass) ]
Example 1
(1) Taking 90kg of potassium hydroxide, 15kg of zinc oxide and 95kg of pure water, firstly pouring 95kg of pure water into a preparation tank, adding 90kg of potassium hydroxide into the preparation tank under the stirring state to dissolve the potassium hydroxide, then adding 15kg of zinc oxide into the preparation tank while the zinc oxide is hot under the stirring state to dissolve the zinc oxide, filtering the solution by using a filter element with the aperture of 1 micron after cooling, and adjusting the concentration of the potassium hydroxide in the filtered electrolyte to be 42.5% to obtain the electrolyte;
(2) Weighing 9,810g of mercury-free zinc powder, 60g of sodium carboxymethylcellulose, 30g of sodium polyacrylate, 10g of indium hydroxide and 90g of zinc oxide, pouring the materials into an agate cup of three-dimensional ball-milling mixing equipment for grinding, starting mixing for 30 minutes, slowly adding 4kg of the electrolyte into the mixing cup, vacuumizing to below one thousand pascals after the materials are added, grinding for 45 minutes, stopping stirring, starting an air valve, taking out the zinc paste, and putting the zinc paste for production.
The mercury-free button cell made of the zinc paste is used for a calculator for 1 year, and expansion deformation does not occur.
The mercury-free button cell made of the zinc paste has the zinc powder utilization rate of 82% after 2mA constant current discharge to the voltage of 0.9V.
Example 2
(1) Taking 90kg of potassium hydroxide, 15kg of zinc oxide and 93kg of pure water, firstly pouring 93kg of pure water into a preparation tank, adding 90kg of potassium hydroxide into the preparation tank under the stirring state to dissolve the potassium hydroxide, then adding 15kg of zinc oxide into the preparation tank under the stirring state while the zinc oxide is hot to dissolve the zinc oxide, filtering by using a filter element with the aperture of 1 micrometer after cooling, and then adding the filtered electrolyte into the pure water to adjust the concentration of the potassium hydroxide to be 32.5%, thus obtaining the electrolyte;
(2) Weighing 9.800kg of mercury-free zinc powder, 65g of sodium carboxymethylcellulose (FH 9), 35g of sodium polyacrylate, 40g of indium hydroxide and 60g of zinc oxide, pouring the materials into an agate cup of three-dimensional ball-milling mixing equipment for grinding, starting mixing for 25 minutes, slowly adding 2kg of the electrolyte into the mixing cup, vacuumizing to below one thousand pascals after finishing adding, grinding for 60 minutes, stopping stirring, starting an air valve, taking out zinc paste, and putting the zinc paste for production and use.
The mercury-free zinc air button cell made of the zinc paste has no expansion deformation and liquid leakage when being used in hearing aids.
Example 3
(1) Taking 90kg of potassium hydroxide, 15kg of zinc oxide and 95kg of pure water, firstly pouring 95kg of pure water into a preparation tank, adding 90kg of potassium hydroxide into the preparation tank under the stirring state to dissolve the potassium hydroxide, then adding 15kg of zinc oxide into the preparation tank while the zinc oxide is hot under the stirring state to dissolve the zinc oxide, cooling, filtering by using a filter element with the aperture of 1 mu m, and adjusting the concentration of potassium hydroxide in the filtered electrolyte to be 42.5% to obtain the electrolyte;
(2) Weighing 9,820g of zinc powder containing 1.5% of mercury, 60g of polyacrylate, 30g of sodium polyacrylate and 90g of zinc oxide, pouring the materials into an agate cup of three-dimensional ball-milling mixing equipment for grinding, starting mixing for 30 minutes, slowly adding 4kg of the electrolyte into the mixing cup, vacuumizing to below one thousand Pa after adding, grinding for 45 minutes, stopping stirring, starting an air valve, taking out the zinc paste, and putting the zinc paste for production.
The button cell made of the zinc paste has the zinc powder utilization rate of 72.8 percent after 2mA constant current discharge to the voltage of 0.9V.
Compared with the example 1, the utilization rate of the zinc powder is greatly reduced, and the fact that the sodium carboxymethyl cellulose is added into the zinc electrode to prevent the zinc electrode from settling and agglomerating the dispersed zinc powder due to the reduction of viscosity is proved, and the sodium carboxymethyl cellulose and the indium hydroxide act together to enable the battery to show good discharge performance and improve the utilization rate of the zinc powder.
The invention mixes the used substances into paste and processes the paste in a vacuum state, thus removing the gas generated in the preparation process of the zinc paste, and adding indium hydroxide to replace mercury to prevent the generation of the gas, thus having no pollution to the environment. And the sodium carboxymethyl cellulose is added to prevent the zinc electrode from settling and agglomerating the dispersed zinc powder due to the reduction of viscosity, and the zinc electrode and the indium hydroxide act together to ensure that the battery shows good discharge performance. The zinc paste prepared by the preparation method can be applied to a mercury-free button cell.
Claims (3)
1. A preparation method of mercury-free zinc paste for a button alkaline zinc-manganese dioxide battery is characterized by comprising the following steps:
the raw materials are proportioned by mass fraction:
putting the raw materials into three-dimensional non-metal ball milling and mixing equipment for grinding for 5-100 minutes, then adding electrolyte with the mass being 20-43% of the mass of the mixture into the ball milling and mixing equipment, vacuumizing to below 0.01 MPa, and mixing for 10-100 minutes to obtain the zinc paste.
2. The method for preparing mercury-free zinc paste for the button alkaline zinc-manganese dioxide battery as claimed in claim 1, wherein the thickener is sodium carboxymethylcellulose and sodium polyacrylate, and the mass ratio of the sodium carboxymethylcellulose to the sodium polyacrylate is 0.1-10.
3. The method for preparing mercury-free zinc paste for button alkaline zinc-manganese dioxide batteries according to claim 1, wherein the electrolyte is prepared by the following method:
the raw materials are proportioned according to mass fraction: potassium hydroxide 45
5 to 10 portions of zinc oxide
45-47.5 parts of pure water
The electrolyte is 30-45% potassium hydroxide aqueous solution containing zinc oxide. The configuration method comprises the following steps:
adding pure water into a preparation tank, adding potassium hydroxide into the preparation tank under a stirring state, dissolving the potassium hydroxide, adding zinc oxide into the preparation tank under a stirring state, dissolving the zinc oxide, cooling, filtering by using a filter element (with the aperture of 1 mu m), and finally adjusting the filtered electrolyte to a potassium hydroxide solution with the concentration of 30-45% by using the pure water to obtain the electrolyte.
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| CN2012100222671A CN102569760A (en) | 2012-02-01 | 2012-02-01 | Mercury-free zinc paste for button alkaline zinc-manganese dioxide battery and preparation method thereof |
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| CN2012100222671A CN102569760A (en) | 2012-02-01 | 2012-02-01 | Mercury-free zinc paste for button alkaline zinc-manganese dioxide battery and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078119A (en) * | 2013-01-22 | 2013-05-01 | 中银（宁波）电池有限公司 | Mercury-free alkaline battery negative electrode material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1571191A (en) * | 2004-04-26 | 2005-01-26 | 四会永利五金电池有限公司 | An alkaline non-mercury button battery calamine cream and method for making same |
| CN1913199A (en) * | 2006-08-24 | 2007-02-14 | 广州市天球实业有限公司 | Non-mercury button cell negative zinc cream and its making method |
| CN101271973A (en) * | 2008-05-09 | 2008-09-24 | 华南师范大学 | Non-mercury alkaline zinc-manganese and zinc-silver button cell cathode and manufacturing method thereof |
-
2012
- 2012-02-01 CN CN2012100222671A patent/CN102569760A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1571191A (en) * | 2004-04-26 | 2005-01-26 | 四会永利五金电池有限公司 | An alkaline non-mercury button battery calamine cream and method for making same |
| CN1913199A (en) * | 2006-08-24 | 2007-02-14 | 广州市天球实业有限公司 | Non-mercury button cell negative zinc cream and its making method |
| CN101271973A (en) * | 2008-05-09 | 2008-09-24 | 华南师范大学 | Non-mercury alkaline zinc-manganese and zinc-silver button cell cathode and manufacturing method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078119A (en) * | 2013-01-22 | 2013-05-01 | 中银（宁波）电池有限公司 | Mercury-free alkaline battery negative electrode material and preparation method thereof |
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Application publication date: 20120711 |