CN102832372B - Preparation method of battery zinc paste - Google Patents
Preparation method of battery zinc paste Download PDFInfo
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- CN102832372B CN102832372B CN201210315871.3A CN201210315871A CN102832372B CN 102832372 B CN102832372 B CN 102832372B CN 201210315871 A CN201210315871 A CN 201210315871A CN 102832372 B CN102832372 B CN 102832372B
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Abstract
The invention discloses a preparation method of a zinc paste of an alkaline zinc-manganese dioxide battery. The zinc powder mixture used in the method comprises: the lead-free and mercury-free zinc alloy particle comprises a lead-free and mercury-free zinc alloy particle, polyacrylic acid, polyacrylate, sodium polyacrylate powder and indium oxide powder, wherein the lead-free and mercury-free zinc alloy particle comprises the following elements: aluminum, bismuth, lanthanum, yttrium, cerium rare earth elements and zinc. The alkaline zinc-manganese dioxide cell zinc paste prepared by the method is tried by cell manufacturers, compared with other zinc paste materials in the market, the discharge capacity is greatly improved, the service life is effectively prolonged, and the alkaline zinc-manganese dioxide cell zinc paste is more environment-friendly due to no lead or mercury.
Description
Technical Field
The invention relates to a preparation method of a battery material, in particular to a preparation method of battery zinc paste.
Background
Alkaline zinc-manganese batteries are the most widely used commercial battery products to date. With the popularization of digital technology, the functions of small-sized electric appliances are increasing day by day, and the requirement for high-power discharge of alkaline batteries is higher and higher. The zinc paste is used as an important component material for preparing the alkaline zinc-manganese battery, and the performance of the zinc paste plays a key role in the discharge capacity and the service life of the alkaline battery. In addition, most of the zinc pastes of the current alkaline zinc-manganese dioxide batteries contain mercury and lead, so that the environment is adversely affected after the batteries are discarded. Therefore, there is a strong need to provide a zinc paste for alkaline batteries which has a high discharge capacity, a long service life, and is lead-free and mercury-free.
Disclosure of Invention
The invention aims to provide a method for preparing zinc paste for an alkaline zinc-manganese battery, and the alkaline zinc-manganese battery prepared by using the zinc paste has the advantages of strong discharge capacity, long service life, no lead, no mercury and the like.
In order to achieve the purpose, the invention provides a manufacturing method of zinc paste of an alkaline zinc-manganese dioxide battery, which comprises the following steps:
step 1, preparing a zinc powder mixture with the particle size of 50-100 microns according to the following mass ratio:
80-90 parts of lead-free and mercury-free zinc alloy particles
Polyacrylic acid or methacrylic acid 0.5-1
Polyacrylate or methacrylate 1-2
Polyacrylate or methacrylate 0.2-0.5
Indium oxide powder 1-1.5
Wherein, the lead-free and mercury-free zinc alloy particles comprise the following elements in percentage by mass:
20-30ppm of aluminum
20-70ppm of bismuth
200-300ppm of rare earth elements of lanthanum, yttrium and cerium
The balance of zinc;
step 2, preparing electrolyte according to the following parts by mass:
40-50 parts of potassium hydroxide
10-15 parts of zinc oxide
50-60% of pure water
And 3, putting the prepared zinc powder mixture and the electrolyte into a mixing reaction container according to the volume ratio of 1:1, heating to 50-70 ℃, and stirring and mixing for 30-60 minutes at the stirring speed of 1000-2000 rpm to uniformly mix the substances to form the zinc paste.
When preparing zinc alloy particles, the mass ratio of lanthanum to yttrium to cerium in the rare earth elements is preferably 2: 1, and the rare earth elements, aluminum and bismuth are preferably pressed into zinc liquid in a molten state to directly produce zinc alloy, and then the zinc alloy particles are crushed into particles.
Wherein, the polyacrylate in the step 1 is sodium polyacrylate.
Wherein the methyl polyacrylate in the step 1 is sodium methyl polyacrylate.
The alkaline zinc-manganese dioxide cell zinc paste prepared by the preparation method is tried by cell manufacturers, compared with other zinc paste materials in the market, the discharge capacity is greatly improved, the service life is effectively prolonged, and the alkaline zinc-manganese dioxide cell zinc paste is lead-free and mercury-free and is more environment-friendly.
Detailed Description
Example one
Preparation of Zinc alloy particles
Preparing raw materials of the zinc alloy according to the following mass fractions:
aluminum 20ppm
Bismuth 20ppm
Lanthanum, yttrium and cerium rare earth elements 200ppm
The balance of zinc.
Wherein, the mass ratio of lanthanum, yttrium and cerium is 2: 1.
Putting the small chippy rare earth metals of lanthanum, yttrium and cerium, aluminum and bismuth in parts by mass into a pressure melting device, heating to be molten, pressing into the zinc liquid in parts by mass to directly generate zinc alloy, and crushing to form zinc alloy particles.
Preparing a zinc powder mixture:
mixing the prepared zinc alloy particles with polyacrylic acid, polyacrylate and sodium polyacrylate powder indium oxide powder according to the following mass ratio:
zinc alloy particles 80
Polyacrylic acid 0.5
Polyacrylate 1
Sodium polyacrylate powder 0.2
Indium oxide powder 1
After mixing, grinding to a powder with a particle size of 50 microns.
Preparing an electrolyte
Preparing an electrolyte according to the following parts by mass:
potassium hydroxide 40
Zinc oxide 10
Pure water 50
Preparation of calamine cream
The prepared zinc powder mixture and electrolyte are put into a mixing reaction container according to the volume ratio of 1:1, then heated to 50 ℃, and stirred and mixed for 30 minutes at the stirring speed of 1000 r/min, so that the substances are uniformly mixed to form the zinc paste.
Example two
Preparation of Zinc alloy particles
Preparing raw materials of the zinc alloy according to the following mass fractions:
aluminum 30ppm
Bismuth 70ppm
Lanthanum, yttrium and cerium rare earth element 300ppm
The balance of zinc.
Wherein, the mass ratio of lanthanum, yttrium and cerium is 2: 1.
Putting the small chippy rare earth metals of lanthanum, yttrium and cerium, aluminum and bismuth in parts by mass into a pressure melting device, heating to be molten, pressing into the zinc liquid in parts by mass to directly generate zinc alloy, and crushing to form zinc alloy particles.
Preparing a mixture of zinc powders
Mixing the prepared zinc alloy particles with polyacrylic acid, polyacrylate and sodium polyacrylate powder indium oxide powder according to the following mass ratio:
zinc alloy particles 90
Polyacrylic acid 1
Polyacrylate 2
Sodium polyacrylate powder 0.5
Indium oxide powder 1.5
After mixing, grinding to a powder with a particle size of 100 microns.
Preparing an electrolyte
Preparing an electrolyte according to the following parts by mass:
50 parts of potassium hydroxide
Zinc oxide 15
Pure water 60
Preparation of calamine cream
The prepared zinc powder mixture and the electrolyte are put into a mixing reaction container according to the volume ratio of 1:1, then heated to 70 ℃, and stirred and mixed for 60 minutes at the stirring speed of 2000 rpm, so that the substances are uniformly mixed to form the zinc paste.
Comparative example
Zinc powder particles to which 100ppm of the rare earth metals lanthanum, yttrium and cerium were added were prepared in a similar conventional manner to examples 1 and 2, the zinc powder mixture having the following composition:
91-94.2 parts of lead-free and mercury-free zinc powder
Polyacrylic acid 0.9-1.5
Polyacrylate 0.9-1.5
3.5 to 6.5 portions of indium hydroxide.
The electrolyte comprises the following components:
50-55 parts of potassium hydroxide
Zinc oxide 7-8
38-43 parts of pure water
The other steps were the same as in examples 1 and 2.
The performance of the pastes prepared in examples 1 and 2 and the conventional paste prepared in the comparative example for an alkaline zinc-manganese battery was measured as follows:
the zinc-manganese battery is discharged under the condition of 25 +/-2 ℃ by a discharge system of 2 watts for 3 seconds, 500 milliwatts for 20 seconds, 10 times per hour and 24 hours per day until the voltage is 1 volt. The discharge results are shown in Table 1. It can be seen from the table that the discharge capacity and the service life of the pastes obtained by the methods and compositions of examples 1 and 2 are greatly improved.
Table 1: summary of discharge results and service life of the example and comparative batteries
| Comparative example | Example 1 | Example 2 | |
| Discharge result (times) | 50 | 75 | 80 |
| Discharge capacity enhancement (%) | 100 | 150 | 160 |
| Life ratio (%) | 100 | 120 | 125 |
Although the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (4)
1. A method for preparing zinc paste of an alkaline zinc-manganese dioxide battery is characterized by comprising the following steps:
step 1, preparing a zinc powder mixture with the particle size of 50-100 microns according to the following mass portion:
80-90 parts of lead-free and mercury-free zinc alloy particles
Polyacrylic acid or polymethacrylic acid 0.5-1
Polyacrylate or polymethacrylate 1-2
Polyacrylate or polymethacrylate 0.2-0.5
Indium oxide powder 1-1.5
Wherein, the lead-free and mercury-free zinc alloy particles comprise the following elements in percentage by mass:
20-30ppm of aluminum
20-70ppm of bismuth
200-300ppm of rare earth elements of lanthanum, yttrium and cerium
The balance of zinc;
step 2, preparing electrolyte according to the following parts by mass:
40-50 parts of potassium hydroxide
10-15 parts of zinc oxide
50-60% of pure water
Step 3, putting the prepared zinc powder mixture and the electrolyte into a mixing reaction container according to the volume ratio of 1:1, heating to 50-70 ℃, and stirring and mixing for 30-60 minutes at the stirring speed of 1000-2000 rpm to uniformly mix the substances to form zinc paste;
when preparing the lead-free and mercury-free zinc alloy particles, the mass ratio of lanthanum, yttrium and cerium in the rare earth elements is 2: 1.
2. The method of claim 1, wherein the polyacrylate salt in step 1 is sodium polyacrylate.
3. The method of claim 1, wherein the polymethacrylate in step 1 is sodium polymethacrylate.
4. The method according to claim 1 or 3, wherein in preparing the lead-free and mercury-free zinc alloy particles, the rare earth element and aluminum and bismuth are pressed into a zinc liquid in a molten state to directly produce a zinc alloy, and then the zinc alloy is crushed into particles.
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| CN201210315871.3A CN102832372B (en) | 2012-08-30 | 2012-08-30 | Preparation method of battery zinc paste |
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| CN201210315871.3A CN102832372B (en) | 2012-08-30 | 2012-08-30 | Preparation method of battery zinc paste |
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| CN102832372B true CN102832372B (en) | 2016-12-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103060846B (en) * | 2013-02-15 | 2015-05-20 | 桂林理工大学 | Method for preparing Zn-Pb-Bi-La alloy electrode material through pulse electrodeposition |
| CN103695714A (en) * | 2013-12-11 | 2014-04-02 | 高建军 | Preparation method of zinc paste of alkaline zinc-manganese battery |
| CN109309218A (en) * | 2018-08-21 | 2019-02-05 | 浙江长虹飞狮电器工业有限公司 | Alkaline dry battery |
| CN109390581A (en) * | 2018-10-10 | 2019-02-26 | 嘉兴华荣电池有限公司 | Alkaline battery negative paste |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101667639A (en) * | 2009-10-20 | 2010-03-10 | 深圳市中金岭南科技有限公司 | Method for manufacturing rare earth alloy battery zinc powder |
| CN101901894A (en) * | 2010-08-13 | 2010-12-01 | 东莞市天荣电子科技有限公司 | Lead-free and mercury-free alkali button battery zinc cream and preparation method thereof |
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| US7008723B2 (en) * | 2001-08-21 | 2006-03-07 | Ecosol Solar Technologies Inc. | Method of manufacture of an anode composition for use in a rechargeable electrochemical cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101667639A (en) * | 2009-10-20 | 2010-03-10 | 深圳市中金岭南科技有限公司 | Method for manufacturing rare earth alloy battery zinc powder |
| CN101901894A (en) * | 2010-08-13 | 2010-12-01 | 东莞市天荣电子科技有限公司 | Lead-free and mercury-free alkali button battery zinc cream and preparation method thereof |
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