CN101702430A - Alkaline zinc battery composite additive and preparation method and application thereof - Google Patents
Alkaline zinc battery composite additive and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an alkaline zinc battery composite additive and a preparation method and application thereof. The invention obtains a composite additive by mixing polyethylene glycol and imidazole, and applies the composite additive to the preparation of negative pole liquid and negative pole zinc paste of an alkaline zinc battery, the negative pole cover or current collector of the obtained alkaline zinc battery does not need to be electroplated or replace rare noble metals such as indium and the like, heavy metals such as mercury, indium, lead, cadmium and the like or harmful metals are not needed to be added into zinc powder, rare noble metal compounds such as indium oxide, indium hydroxide, lead compounds, mercury and compounds thereof and substances polluting the environment are not needed to be added into zinc paste, and an organic additive with high price is not needed to be added into the negative pole liquid. Therefore, the alkaline zinc battery obtained by using the alkaline zinc battery composite additive is environment-friendly, the production cost is reduced, and the market potential is large.
Description
Technical Field
The invention relates to a manufacturing technology of an alkaline zinc battery, in particular to a composite additive of the alkaline zinc battery, a preparation method and application thereof.
Background
China is a large country of production and consumption of alkaline zinc batteries including alkaline zinc-manganese batteries, zinc-silver batteries, zinc-nickel batteries and zinc-air batteries. However, due to the high activity of zinc, zinc is easily corroded in alkaline solution, and the corrosion of Zn is the result of the conjugate reaction of Zn anode dissolution and hydrogen cathode precipitation. The conjugation reaction is as follows:
anodic oxidation reaction:
Zn+2OH - ～2e - →ZnO+H 2 O
ZnO+OH - →HZnO 2 - or ZnO 2 2- +H 2 O
Cathode reduction reaction:
2H 2 O+2e - →2OH - +H 2 ↑
the total reaction is as follows:
Zn+H 2 O→H 2 ↑+ZnO
the self-discharge of negative zinc powder is the main reason of the self-discharge of alkaline zinc battery. The self-discharge of the battery easily causes the problems of battery capacity reduction, service life shortening, battery leakage and even battery failure.
In order to solve the problem of self-discharge of the battery and simultaneously not affect the activation and dissolution of zinc during the discharge of the battery, people have made extensive research for a long time on inhibiting the self-discharge of negative zinc powder: for example, chinese patent (or patent application) with patent number ZL200410026985.1 and patent application number 200610037178.9 adopts the technical means that a certain amount of metal and compound thereof with higher hydrogen overpotential, such as indium, indium hydroxide, indium oxide, bismuth, tin and the like, are added into zinc paste; the technical means adopted by Chinese invention patents with patent numbers of ZL200410026835.0, ZL200620057487.8, ZL200420045131.3, ZL200410026834.6 and the like is to plate metal or alloy with higher hydrogen overpotential, such as indium, tin cobalt, copper tin zinc alloy and the like, on the negative electrode cover; also, the technology is a combination of the two, such as chinese inventions (or patent applications) with patent numbers ZL01234722.1, ZL200620063306.2, patent application numbers 200610035286.2, 200610037177.4, etc.; the patent number is 200410019885.6, and calcium zincate, transition metal and rare earth metal oxide are added into the secondary alkaline zinc cathode.
Indium or zinc-indium alloy is plated on the current collector of the negative electrode, and mercury, lead, cadmium, indium and other rare metals which pollute the environment or are precious are added into zinc paste, so that the production process of the battery is relatively complex, the cost is relatively high, and the battery obviously does not accord with the environmental protection, production and consumption concepts of the modern society. Although mercury substitute additives or mercury-free technologies are developed, the cost is high, the corrosion inhibition effect is greatly influenced by the working environment of the battery, or the process is complex, which is extremely unfavorable for the sustainable development of the alkaline zinc battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the alkaline zinc battery composite additive without adding harmful heavy metals such as mercury, lead, cadmium and the like or rare noble metals such as indium and the like into zinc paste.
The invention also aims to provide a preparation method of the alkaline zinc battery composite additive.
The invention also aims to provide application of the alkaline zinc battery composite additive.
The purpose of the invention is realized by the following technical scheme: an alkaline zinc battery composite additive comprises imidazole and polyethylene glycol;
the imidazole and the polyethylene glycol are preferably mixed according to the mass ratio of 1: 3-3: 1;
the polyethylene glycol is preferably at least one of polyethylene glycol 600, polyethylene glycol 400 or polyethylene glycol 900;
the polyethylene glycol is more preferably polyethylene glycol 600.
The preparation method of the alkaline zinc battery composite additive comprises the following steps: mixing imidazole and polyethylene glycol.
The imidazole and the polyethylene glycol are preferably mixed according to the mass ratio of 1: 3-3: 1.
The alkaline zinc battery composite additive is applied to the preparation of an alkaline zinc battery;
the alkaline zinc battery composite additive is used for preparing an alkaline zinc battery, and is used for preparing one or two of negative electrode solution or negative electrode zinc paste of the alkaline zinc battery;
the negative electrode solution consists of a potassium hydroxide solution added with zinc oxide and a composite additive, wherein the composite additive is equivalent to 500-1500 ppm of the potassium hydroxide solution added with zinc oxide in mass;
the potassium hydroxide solution added with zinc oxide comprises the following components in percentage by mass:
41.5 to 42.5 percent of potassium hydroxide
52 to 52.5 percent of pure water
5.5 to 6 percent of zinc oxide;
the negative electrode zinc paste consists of a substance A and a composite additive, wherein the mass of the composite additive is 500-1500 ppm of that of the substance A;
the substance A comprises the following components in percentage by mass:
95 to 97 percent of mercury-free zinc powder
2 to 4 percent of carboxymethyl cellulose (CMC)
0.5 to 1 percent of expanding agent
0.2 to 0.8 percent of zinc oxide;
the expanding agent is sodium polyacrylate (QP-3);
the alkaline zinc battery is a button alkaline zinc-manganese battery;
the button alkaline zinc-manganese dioxide battery comprises a positive electrode cover, a negative electrode cover, a positive electrode solution, a negative electrode solution, a positive electrode manganese cake and a negative electrode zinc paste, wherein the negative electrode solution consists of a potassium hydroxide solution added with zinc oxide and a composite additive, and the composite additive is equivalent to 500-1500 ppm of the mass of the potassium hydroxide solution added with zinc oxide;
the zinc oxide-added potassium hydroxide solution comprises the following components in percentage by mass:
41.5 to 42.5 percent of potassium hydroxide
52 to 52.5 percent of water
5.5 to 6 percent of zinc oxide;
the negative electrode zinc paste consists of a substance A and a composite additive, wherein the mass of the composite additive is 500-1500 ppm of that of the substance A;
the substance A comprises the following components in percentage by mass:
95 to 97 percent of mercury-free zinc powder
2 to 4 percent of carboxymethyl cellulose
0.5 to 1 percent of expanding agent
0.2 to 0.8 percent of zinc oxide;
the expanding agent is sodium polyacrylate (QP-3);
the treatment mode of the negative electrode cover is replacement tinning;
the plating solution used for the replacement tinning consists of the following components in percentage by mass:
4 to 6 percent of stannous chloride
2 to 4 percent of sodium hypophosphite
4 to 6 percent of hydrofluoric acid
9 to 11 percent of hydrochloric acid
1 to 3 percent of thiourea
72 to 78 percent of water;
the pH is less than 1.
The condition of the replacement tin plating is preferably 5 minutes at room temperature.
The principle of the invention is as follows: polyethylene glycol is a chain surfactant, imidazole is a cyclic surfactant, when the two are used independently, a complete and uniform compact protective layer is difficult to form on the surface of zinc, and when the two are used in combination, the two are adsorbed on the surface of zinc powder at intervals, so that the compact protective layer is formed on the surface of zinc, hydroxide ions are effectively prevented from contacting with the zinc, the self-corrosion of the zinc is avoided, and when the battery discharges, the two are desorbed from the surface of the zinc powder without influencing the normal discharge of the battery.
Compared with the prior art, the invention has the following advantages and effects:
(1) The alkaline zinc battery composite additive disclosed by the invention is composed of imidazole and polyethylene glycol with low price, does not contain traditional mercury, lead, cadmium, bismuth and other heavy metals and indium precious metals, is beneficial to environmental protection, reduces the production cost, and has large market potential.
(2) By using the alkaline zinc battery composite additive, the negative electrode cover or the current collector of the battery does not need to be electroplated or replaced with rare noble metals such as indium and the like, heavy metals or harmful metals such as mercury, indium, lead, cadmium and the like are not needed to be added into zinc powder, indium oxide, indium hydroxide, lead compounds, mercury, compounds thereof and other rare noble metal compounds and substances polluting the environment are not needed to be added into zinc paste, and an organic additive with high price is not needed to be added into negative electrode liquid.
Drawings
Fig. 1 shows the results of the ballooning test of AG13 button alkaline zn-mn cells prepared in examples 1 to 3, respectively, at 57 ℃.
Fig. 2 is a discharge curve of AG13 button alkaline zinc-manganese dioxide cell prepared in example 1 and its regular AG13 button alkaline zinc-manganese dioxide cell of the same specification under 3mA continuous discharge condition.
Fig. 3 is a discharge curve of AG13 button alkaline zinc-manganese dioxide cell prepared in example 2 and its regular AG13 button alkaline zinc-manganese dioxide cell of the same specification under 3mA continuous discharge condition.
Fig. 4 is a discharge curve of AG13 button alkaline zinc-manganese dioxide cell prepared in example 3 and its regular AG13 button alkaline zinc-manganese dioxide cell of the same specification under 3mA continuous discharge condition.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
AG13 button alkaline zinc-manganese cell was prepared, the specific procedures and materials used are shown in table 1. Wherein the alkaline zinc battery composite additive used in the negative solution is prepared by mixing imidazole and polyethylene glycol 600 according to the mass ratio of 1: 3; the alkaline zinc battery composite additive used by the cathode zinc paste is prepared by mixing imidazole and polyethylene glycol 600 according to the mass ratio of 1: 1.
Example 2
AG13 button alkaline zinc-manganese cell was prepared, the specific procedures and materials used are shown in table 1. Wherein the alkaline zinc battery composite additive used in the negative electrode solution is prepared by mixing imidazole and polyethylene glycol 600 according to the mass ratio of 1: 1; the alkaline zinc battery composite additive used by the cathode zinc paste is prepared by mixing imidazole and polyethylene glycol 600 according to the mass ratio of 1: 1.
Example 3
AG13 button alkaline zinc-manganese dioxide cells were prepared, and the specific procedures and materials used are shown in table 1. Wherein the alkaline zinc battery composite additive used in the negative electrode solution is prepared by mixing imidazole and polyethylene glycol 600 according to the mass ratio of 3: 1; the alkaline zinc battery composite additive used by the cathode zinc paste is prepared by mixing imidazole and polyethylene glycol 600 according to the mass ratio of 1: 1.
TABLE 1
Effect of button alkaline zinc manganese cell prepared in example:
the composite additive consisting of imidazole and polyethylene glycol 600 was examined for its effect on the inhibition of self-discharge and discharge of the battery: the AG13 button type alkaline zinc-manganese dioxide batteries assembled in examples 1 to 3 were placed in a constant temperature oven at a constant temperature of 57 ℃ for 10 days, and the ballooning heights of the batteries were respectively measured, and the discharge capacities thereof were compared with those of the ordinary batteries of the same specification under the same discharge system, with the results shown in fig. 1 to 4. As can be seen from FIG. 1, the degree of ballooning of the AG13 button type alkaline Zn-Mn battery assembled in the embodiments 1-3 is lower than the upper limit of national standard height of the battery by 0.25mm, and the degree of ballooning meets the requirement. As seen from fig. 2 to 4, the AG13 button type alkaline zn-mn batteries assembled in examples 1 to 3 all had higher discharge capacity than the ordinary AG13 batteries of the same specification when discharging continuously to 0.9V at 3mA, indicating that the batteries assembled by the technique of the present invention have better performance than the ordinary batteries of the same specification.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The composite additive for alkaline zinc battery is characterized in that: the alkaline zinc battery composite additive consists of imidazole and polyethylene glycol.
2. The alkaline zinc battery additive package according to claim 1, wherein: the imidazole and the polyethylene glycol are mixed according to the mass ratio of 1: 3-3: 1.
3. The alkaline zinc battery additive package according to claim 1, wherein: the polyethylene glycol is at least one of polyethylene glycol 600, polyethylene glycol 400 or polyethylene glycol 900.
4. A method for preparing the alkaline zinc battery composite additive as claimed in any one of claims 1 to 3, wherein: mixing imidazole and polyethylene glycol to obtain the alkaline zinc battery composite additive.
5. Use of the composite additive for alkaline zinc batteries according to any one of claims 1 to 3, characterized in that: the alkaline zinc battery composite additive is applied to preparation of one or two of negative electrode solution or negative electrode zinc paste of an alkaline zinc battery.
6. Use according to claim 5, characterized in that: the negative electrode solution also contains a zinc oxide-added potassium hydroxide solution which is composed of the following components in percentage by mass:
41.5 to 42.5 percent of potassium hydroxide
52 to 52.5 percent of pure water
5.5 to 6 percent of zinc oxide;
wherein the mass of the alkaline zinc battery composite additive in the negative electrode solution is 500-1500 ppm of the mass of the potassium hydroxide solution added with zinc oxide.
7. Use according to claim 5, characterized in that: the negative electrode zinc paste also contains a substance A consisting of the following substances in percentage by mass:
95 to 97 percent of mercury-free zinc powder
2 to 4 percent of carboxymethyl cellulose
0.5 to 1 percent of expanding agent
0.2 to 0.8 percent of zinc oxide;
wherein the mass of the alkaline zinc battery composite additive in the negative electrode zinc paste is 500-1500 ppm of the mass of the substance A.
8. Use according to claim 7, characterized in that: the expanding agent is sodium polyacrylate.
9. Use according to any one of claims 5 to 8, characterized in that: the negative electrode cover of the alkaline zinc-manganese battery is obtained by replacement tinning;
the plating solution used for replacement tin plating consists of the following components in percentage by mass:
4 to 6 percent of stannous chloride
2 to 4 percent of sodium hypophosphite
4 to 6 percent of hydrofluoric acid
9 to 11 percent of hydrochloric acid
1 to 3 percent of thiourea
72 to 78 percent of water;
the pH value of the plating solution is less than 1.
10. Use according to claim 9, characterized in that: the alkaline zinc battery is a button alkaline zinc-manganese battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910193636.1A CN101702430A (en) | 2009-11-03 | 2009-11-03 | Alkaline zinc battery composite additive and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910193636.1A CN101702430A (en) | 2009-11-03 | 2009-11-03 | Alkaline zinc battery composite additive and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017183110A (en) * | 2016-03-30 | 2017-10-05 | 株式会社Ｇｓユアサ | Zinc electrode, and storage battery including the same |
| CN109786774A (en) * | 2018-12-28 | 2019-05-21 | 福建南平南孚电池有限公司 | Alkaline zinc-manganese battery |
| CN111342155A (en) * | 2020-04-28 | 2020-06-26 | 连州市凌力电池配件有限公司 | Anode surfactant for alkaline battery and preparation method thereof |
-
2009
- 2009-11-03 CN CN200910193636.1A patent/CN101702430A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017183110A (en) * | 2016-03-30 | 2017-10-05 | 株式会社Ｇｓユアサ | Zinc electrode, and storage battery including the same |
| CN109786774A (en) * | 2018-12-28 | 2019-05-21 | 福建南平南孚电池有限公司 | Alkaline zinc-manganese battery |
| CN109786774B (en) * | 2018-12-28 | 2020-12-25 | 福建南平南孚电池有限公司 | Alkaline zinc-manganese battery |
| CN111342155A (en) * | 2020-04-28 | 2020-06-26 | 连州市凌力电池配件有限公司 | Anode surfactant for alkaline battery and preparation method thereof |
| CN111342155B (en) * | 2020-04-28 | 2022-02-08 | 连州市凌力电池配件有限公司 | Anode surfactant for alkaline battery and preparation method thereof |
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Application publication date: 20100505 |