CN101908661A - Novel sealing method of cylindrical zinc-air battery - Google Patents
Novel sealing method of cylindrical zinc-air battery Download PDFInfo
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- CN101908661A CN101908661A CN200910085971XA CN200910085971A CN101908661A CN 101908661 A CN101908661 A CN 101908661A CN 200910085971X A CN200910085971X A CN 200910085971XA CN 200910085971 A CN200910085971 A CN 200910085971A CN 101908661 A CN101908661 A CN 101908661A
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Abstract
A novel sealing method of a cylindrical zinc-air battery comprises the steps of prefabricating a stainless steel battery shell with air holes, adding an adhesive, a modification material and a conductive agent according to the weight ratio, and preparing modified low-pressure polyethylene or polytetrafluoroethylene waterproof powder through heat sealing and crushing; preparing a mixed material of the catalyst according to the weight proportion; adding water solution into the mixed material, mixing and agglomerating to form slurry, and then drying; adding an organic solvent into the dried mixture, repeatedly rolling and fiberizing, and finally pressing into a specified thickness; preparing a catalytic film, and preparing the catalytic film into an air electrode by embedding the catalytic film into an air electrode forming film; and dip-coating an alkali-resistant adhesive layer on the edge of the air electrode, drying to form a thin sealing film, and filling the thin sealing film into a prefabricated stainless steel battery shell. The invention adopts a heating mould pressing mode, directly shapes and produces the air electrode of the cylindrical battery, and completely solves the sealing problem of the cylindrical zinc battery without using an adhesive mode.
Description
Technical Field
The invention relates to a battery manufacturing technology, in particular to a novel sealing method of a cylindrical zinc-air battery.
Background
The zinc-air battery has the advantages of large capacity, high specific energy, stable working voltage, safe use, low price, environmental protection and the like, and is always concerned by research units and enterprises at home and abroad. With the development of modern manufacturing technology, its potential is gradually expressed, and its application is gradually expanded, and not only it is continuously and widely applied in the traditional fields of portable communication machine, medical device, river navigation mark lamp, electronic watch and calculator, but also the power sources suitable for various advanced portable electronic products such as mobile phone and notebook computer, etc. and used for developing the power source of electric vehicle are being developed.
The electrochemical principle of the zinc-air battery is as follows: in the alkaline electrolyte, the air electrode generates a cathode reaction that oxygen is reduced into hydroxyl ions, and the electrode potential is positive; the zinc electrode has an anode reaction of zinc oxidation to zinc oxide, and the potential of the electrode is relatively negative, so that when the zinc electrode and the electrode form a battery, electric energy can be provided for the outside. Since half of the electrochemical equivalent of the reactant in the zinc-air battery is oxygen in the air, and does not need to be stored in the battery, the battery can provide a much larger specific energy than a common disposable battery, and saves a large amount of resources. The data prove that the discharge capacity of the AA type and AAA type cylindrical zinc-air batteries is respectively 3.5 times and more than 1.5 times higher than that of the common zinc-manganese battery and the alkaline zinc-manganese battery under the conditions of medium and small current densities, and the AA type and AAA type cylindrical zinc-air batteries are real high-capacity products.
In the development process of the zinc-air battery, only products with button type and square type structures enter the market for a long time, while the cylindrical structure mode is reported in the early stage, but because of special requirements on the structure and difficulty on the manufacturing process, a reliable product is not formed all the time, and the application field of the product is limited.
At present, the most widely used batteries by consumers are cylindrical batteries, such as alkaline manganese batteries, cadmium-nickel batteries, nickel-hydrogen batteries and lithium ion batteries, and if the sealing problem of the cylindrical batteries can be solved, the zinc-air batteries are bound to be widely popularized. The cylindrical air electrode is different from other button batteries and power batteries, the latter are flat plates, namely, the air electrode is produced continuously or discontinuously through plane or rolling, and is cut and assembled according to the area required by the battery after the production is finished, and the electrode of the cylindrical battery is in a cylindrical shape and is a special-shaped battery, so that a plurality of technologies are formed by winding and bonding the plane electrode, the efficiency is low, and the reliability is poor.
Most of the zinc-air batteries developed so far use adhesives to seal the openings by gluing, and the materials of the air electrodes are made of high molecular polymer polytetrafluoroethylene and low pressure polyethylene, and the materials have poor adhesion due to their own properties, so that the zinc-air batteries produced by the air electrodes by the adhesion method have the potential hazards of alkali leakage and leakage to different degrees.
Disclosure of Invention
The invention aims to provide a novel sealing method of a cylindrical zinc-air battery, which adopts a heating and molding mode to directly shape and produce an air electrode of the cylindrical battery, does not use an adhesive mode at all, and can completely solve the sealing problem of the cylindrical zinc battery.
In order to achieve the purpose, the invention adopts the following design scheme:
a novel sealing method of a cylindrical zinc-air battery comprises the following steps:
a novel sealing method of a cylindrical zinc-air battery comprises the following steps:
1) Firstly, prefabricating a stainless steel battery case with air holes, and producing an air electrode; adding adhesive, conductive agent and modified material according to the weight ratio of 10-35 percent to 40-60 percent to 20-30 percent, and preparing waterproof powder for later use through heat seal and crushing;
2) The inner layer of the air electrode is a catalytic membrane and is prepared according to the following mixture ratio; preparing a mixed material of the catalyst according to the weight ratio: wherein the weight ratio of polytetrafluoroethylene: 10 to 25 percent; acetylene black or carbon black: 45-75%, catalyst: 10 to 35 percent;
adding 2 times of water solution into the mixed material, fully mixing, stirring and agglomerating to form slurry, and drying to remove water in the slurry so that the soluble catalyst is dispersed and separated out on the surface of the carbon black; adding 3 times of organic solvent (such as alcohol) into the dried mixture, repeatedly rolling and fiberizing, and finally pressing into a specified thickness to obtain a pre-buried catalytic membrane for later use;
3) Forming preparation of air electrode
(1) Bonding the prepared catalytic membrane into a cylinder shape, embedding the catalytic membrane in an inner layer of a hot-pressing mould of an air electrode in advance, and filling modified waterproof powder;
(2) placing an air electrode hot-pressing mould designed according to the size of a cylindrical battery on heating equipment, and heating to a specified temperature of 220-400 ℃;
(3) closing the heated die, and maintaining the pressure for 5-10 minutes;
(4) cooling the pressure-maintained mold to 20-70 ℃ for shaping, opening the mold and taking out the air electrode for later use;
4) Dip-coating an alkali-resistant adhesive layer on the edge of the air electrode prepared by the method, and drying to form a thin sealing film;
5) Preparing a gas diffusion layer by using foamed nickel or a copper mesh on the periphery of the air electrode, wherein the diffusion layer is also used as a positive current collector; and putting the components together into a prefabricated perforated stainless steel battery shell.
Most of the existing sealing methods of zinc-air batteries are that after zinc paste is filled in an air electrode and a diaphragm sleeve, the air electrode is sealed by gluing, and at the moment, due to the existence of alkaline electrolyte, the gluing qualification rate cannot reach the level of industrial production. The cylindrical zinc-air battery produced by adopting the novel sealing method of the cylindrical zinc-air battery can realize complete sealing, solves the fatal defects of the key problems (namely difficult sealing, easy alkali leakage and liquid leakage) restricting the development of the cylindrical zinc-air battery, and is simple and easy to implement and extremely easy to realize industrialization.
The invention has the advantages that:
1. the manufacturing of high-quality cylindrical zinc-air batteries can be realized, the alkali-climbing and liquid-leaking phenomena are avoided, and the use requirements of the public are met.
2. The cylindrical zinc-air battery manufactured by the method has excellent sealing performance, the strength is superior to that of other batteries, and the cylindrical zinc-air battery manufactured by the method has the advantages of large capacity, high specific energy, stable working voltage, safe use, low price and environmental friendliness.
Drawings
FIG. 1 is a schematic view of a cylindrical zinc-air battery according to the present invention
FIG. 2 is a schematic view of an air electrode according to the present invention
The invention is described in further detail below with reference to the following figures and specific embodiments:
Detailed Description
Referring to fig. 1, the cylindrical zinc-air battery manufactured by the novel method of the invention comprises a metal battery outer shell (formed by butting a positive electrode shell 5 and a negative electrode shell 8) with air holes, and a metal mesh gas diffusion layer 3 (also used as a positive electrode current collector), an air electrode 2, a diaphragm sleeve 1 and a negative electrode zinc paste 4 are sequentially arranged in the shell from outside to inside. The bottom negative pole needle 6 (copper nail can be used) penetrates through the diaphragm tube to be inserted into the negative pole (used as the negative pole), and is sealed with the positive pole after being isolated by the sealing ring 7. The invention adopts a heating and pressing mode, firstly directly produces a cylindrical air electrode, as shown in figure 2, the bottom of the air electrode is dipped with a small amount of alkali-resistant glue to form a film, then the size of the outermost end of the conical part at the bottom of the air electrode is matched with the size of the inner diameter of a steel shell, when the battery is assembled, the air electrode is pressed into a battery shell under certain pressure, and the sealing is realized by utilizing the tight contact of the outer edge of the air electrode and the inner wall of the battery shell.
The invention discloses a novel sealing method of a cylindrical zinc-air battery, which comprises the following specific steps:
1. firstly, the stainless steel battery case with the air holes can be prefabricated by punching the side surface of a cylindrical primary battery steel case with a relevant international standard, such as IEC standard size.
2. The method of heating and pressing is adopted to produce the special-shaped air electrode: adding adhesive, conductive agent and modified material according to the weight ratio of 10-35 percent to 40-60 percent to 20-30 percent, and preparing waterproof powder for later use through heat seal and crushing; the adhesive can be low-pressure polyethylene or polytetrafluoroethylene; the modified material is a surfactant such as OP-10; the conductive agent may be acetylene black or carbon black.
3. Preparation of inner catalytic membrane of air electrode
The catalyst layer is prepared according to the following mixture ratio; preparing a mixed material of the catalyst according to the weight ratio: wherein the weight ratio of polytetrafluoroethylene: 10 to 25 percent; acetylene black or carbon black: 45-75%, catalyst: 10 to 35 percent.
The catalyst may be: mnO 2 ，KMnO 4 ，MnSO 4 ，SnO 2 ，Fe 2 O 3 ，Co 3 O 4 Co, coO, fe, pt, pd, etc.
Adding the mixed material into an aqueous solution with the weight 2 times that of the mixed material, fully mixing, stirring and agglomerating the mixed material into slurry, and drying the slurry to remove water in the slurry so as to ensure that the soluble catalyst is dispersed and separated out on the surface of the carbon black; adding 3 times of organic solvent (such as alcohol) into the dried mixture, repeatedly rolling and fiberizing, and finally pressing into a specified thickness (0.05-0.2 mm) to obtain a pre-buried catalytic membrane for later use.
4. Forming preparation of air electrode
(1) The catalytic membrane is adhered into a cylindrical shape (without requiring complete sealing), is pre-embedded in a hot-pressing mould of a special air electrode, and is positioned at the innermost layer of the air electrode, and then the waterproof powder prepared by the process is filled.
(2) The maximum outer diameter of the bottom of the air electrode is designed to be 0.1-0.25 mm (preferably 0.2 mm) larger than the inner diameter of the battery shell, a special air electrode hot-pressing mold designed according to the size of the cylindrical battery is placed on heating equipment, and the temperature is raised to 220-400 ℃ at a specified temperature.
(3) Closing the heated die; and keeping the pressure for 5 to 10 minutes.
(4) And cooling the pressure-maintained mold to 20-70 ℃ for shaping, opening the mold and taking out the air electrode for later use.
5. And (3) soaking the air electrode prepared by the method in alkali-resistant glue and drying for later use to obtain an air electrode finished product.
6. Covering the periphery of the air electrode with a gas diffusion layer prepared by foam nickel or a copper mesh, wherein the diffusion layer is also used as a positive current collector; and putting the stainless steel and the aluminum alloy into a prefabricated perforated stainless steel battery shell.
The air electrode prepared by the method has the inner layer as the catalyst layer and the outer layer as the waterproof diffusion layer.
The waterproof powder material has the following components in parts by weight, and has good sealing and water-resistant effects in the following range: 15-30% of adhesive, conductive agent: 40-55%, modified material: 20 to 30 percent. Furthermore, 20-30% of adhesive, 50-55% of conductive agent and 20-25% of modified material are better.
The following are several specific embodiments of the invention:
example 1
1. First, a stainless steel battery case with a gas hole was prepared.
2. Adding adhesive, conductive agent and modified material according to the weight ratio of 10% to 60% to 30%, and preparing waterproof powder for later use through heat sealing and crushing; the adhesive is low-pressure polyethylene; the modified material is OP-10; the conductive agent is acetylene black.
3. According to 10 percent of polytetrafluoroethylene; acetylene black 75%, mnO 2 Preparing a mixed material of the catalyst according to a weight ratio of 15%; adding 2 times of water solution into the mixture, fully mixing, stirring and agglomerating into slurry, and drying to remove water in the slurry so that the soluble catalyst is dispersed and separated out on the surface of the carbon black; adding 3 times of alcohol into the dried mixture, repeatedly rolling and fiberizing, pressing into 0.05mm thick, and pre-buryingThe catalytic membrane of (2) is ready for use.
4. Bonding the catalytic membrane into a cylindrical shape, embedding the catalytic membrane into a hot-pressing mould of the air electrode in an innermost layer of the air electrode, and then filling the waterproof powder prepared by the process to prepare a molded air electrode; and placing the air electrode hot-pressing mould on heating equipment, and heating to the specified temperature of 300 ℃.
(3) Closing the heated die; the pressure was maintained for 10 minutes.
(4) And cooling the pressure-maintained mold to 40 ℃ for shaping, opening the mold and taking out the air electrode for later use.
5. And (3) soaking the air electrode prepared by the method in alkali-resistant glue and drying for later use to obtain an air electrode finished product.
6. Sleeving the periphery of the air electrode with a gas diffusion layer prepared from foamed nickel; and putting the components together into a prefabricated perforated stainless steel battery shell.
Example 2
The specific method is different from the embodiment 1 in that:
adding the adhesive, the conductive agent and the modified material according to the weight ratio of 35: 40: 25 in the step 2, and preparing waterproof powder for later use through heat seal and crushing; the adhesive is polytetrafluoroethylene; the modified material is OP-10; the conductive agent is acetylene black.
Example 3
The specific method is the same as example 1, but the differences are as follows:
in the step 2, polytetrafluoroethylene, OP-10 and carbon black are added according to the weight ratio of 20: 60: 20. The inner catalyst layer of the air electrode is prepared according to the following mixture ratio: wherein the weight ratio of polytetrafluoroethylene: 10 percent; carbon black: 75 percent; KMnO 4 ：15％。
Example 4
The specific method is different from the embodiment 1 in that:
in step 2, polytetrafluoroethylene, OP-10 and carbon black are added according to the weight ratio of 25: 55: 20. The inner catalyst layer of the air electrode is prepared according to the following mixture ratio: wherein the weight ratio of polytetrafluoroethylene: 25 percent; carbon black: 40 percent; pd:35 percent.
Example 5
The specific method is the same as example 1, but the differences are as follows:
in the step 2, polytetrafluoroethylene, OP-10 and acetylene black are added according to the weight ratio of 25: 50: 25. The inner catalyst layer of the air electrode is prepared according to the following mixture ratio: wherein the weight ratio of polytetrafluoroethylene: 15 percent; acetylene black: 60 percent; fe 2 O 3 ：25％。
Example 6
The specific method is different from the embodiment 1 in that:
in step 2, polytetrafluoroethylene, OP-10 and carbon black are added according to the weight ratio of 25: 55: 20. The inner catalyst layer of the air electrode is prepared according to the following mixture ratio: wherein the weight ratio of polytetrafluoroethylene: 10 percent; carbon black: 70 percent; and (3) CoO:20 percent.
Example 7
The specific method is different from the embodiment 1 in that:
in the step 2, polytetrafluoroethylene, OP-10 and acetylene black are added according to the weight ratio of 20: 50: 30. The inner catalyst layer of the air electrode is prepared according to the following mixture ratio: wherein the weight ratio of polytetrafluoroethylene: 20 percent; acetylene black: 60 percent; snO 2 ：20％。
Example 8
The specific method is different from the embodiment 1 in that: 10-35 percent, 40-60 percent and 20-30 percent
In the step 2, polytetrafluoroethylene, OP-10 and carbon black are added according to the weight ratio of 30: 45: 25. The inner catalyst layer of the air electrode is prepared according to the following mixture ratio: wherein the weight ratio of polytetrafluoroethylene: 12 percent; carbon black: 70 percent; co 3 O 4 ：18％。
Since many changes may be made in the above-described embodiments without departing from the scope of the invention, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
Claims (8)
1. A novel sealing method of a cylindrical zinc-air battery is characterized by comprising the following steps:
1) Firstly, prefabricating a stainless steel battery case with air holes, and producing an air electrode; adding adhesive, conductive agent and modified material according to the weight ratio of 10-35 percent to 40-60 percent to 20-30 percent, and preparing waterproof powder for later use through heat seal and crushing;
2) The inner layer of the air electrode is a catalytic membrane and is prepared according to the following mixture ratio; preparing a mixed material of the catalyst according to the weight ratio: wherein the weight ratio of polytetrafluoroethylene: 10 to 25 percent; acetylene black or carbon black: 45-75%, catalyst: 10 to 35 percent;
adding 2 times of water solution into the mixed material, fully mixing, stirring and agglomerating to form slurry, and drying to remove water in the slurry so that the soluble catalyst is dispersed and separated out on the surface of the carbon black; adding 3 times of organic solvent into the dried mixture, repeatedly rolling and fiberizing, and finally pressing into a specified thickness to obtain a pre-buried catalytic membrane for later use;
3) Forming preparation of air electrode
(1) Bonding the prepared catalytic membrane into a cylinder shape, embedding the catalytic membrane in an inner layer of a hot-pressing mould of an air electrode in advance, and filling modified waterproof powder;
(2) placing an air electrode hot-pressing mould designed according to the size of a cylindrical battery on heating equipment, and heating to a specified temperature of 220-400 ℃;
(3) closing the heated die, and maintaining the pressure for 5-10 minutes;
(4) cooling the pressure-maintained mold to 20-70 ℃ for shaping, opening the mold and taking out the air electrode for later use;
4) Dip-coating an alkali-resistant adhesive layer on the edge of the air electrode prepared by the method, and drying to form a thin sealing film;
5) Preparing a gas diffusion layer by using foamed nickel or a copper mesh on the periphery of the air electrode, wherein the diffusion layer is also used as a positive current collector; and putting the components together into a prefabricated perforated stainless steel battery shell.
2. The novel sealing method for the cylindrical zinc-air battery according to claim 1, wherein: the waterproof powder comprises the following components in parts by weight: 15-30% of adhesive, conductive agent: 40-55%, modified material: 20 to 30 percent.
3. The novel sealing method for the cylindrical zinc-air battery according to claim 1, wherein: the waterproof powder comprises the following components in parts by weight: 20-30% of adhesive, 50-55% of conductive agent and 20-25% of modified material.
4. The novel sealing method for a cylindrical zinc-air battery according to claim 1 or 2, wherein: the adhesive can be low-pressure polyethylene or polytetrafluoroethylene; the modified material is OP-10; the conductive agent can be acetylene black or carbon black; the catalyst is MnO 2 ，KMnO 4 ，MnSO 4 ，SnO 2 ，Fe 2 O 3 ，Co 3 O 4 Co, coO, fe, pt or Pd.
5. The novel sealing method for the cylindrical zinc-air battery according to claim 1, wherein: the air electrode is produced by using low-pressure polyethylene or polytetrafluoroethylene as a binder, acetylene black and powder formed by carbon black through hot-pressing and shaping.
6. The novel sealing method for the cylindrical zinc-air battery according to claim 1, wherein: the thickness of the catalytic membrane pre-embedded in the air electrode is 0.05-0.2 mm.
7. The novel sealing method for the cylindrical zinc-air battery according to claim 1, wherein: the outer diameter of the air electrode is 0.1-0.25 mm larger than the inner diameter of the steel battery shell.
8. The novel sealing method for the cylindrical zinc-air battery according to claim 1, wherein: the outer diameter of the air electrode is 0.2mm larger than the inner diameter of the steel battery shell.
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| CN200910085971XA CN101908661B (en) | 2009-06-03 | 2009-06-03 | Sealing method of cylindrical zinc-air battery |
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| CN200910085971XA CN101908661B (en) | 2009-06-03 | 2009-06-03 | Sealing method of cylindrical zinc-air battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104221213A (en) * | 2012-04-18 | 2014-12-17 | 日产自动车株式会社 | Positive electrode for air battery and process for producing same |
| CN105024110A (en) * | 2015-07-14 | 2015-11-04 | 北京航空航天大学 | High-power oxygen-metal battery with array ultrathin electrodes |
| CN105304906A (en) * | 2015-09-24 | 2016-02-03 | 山东润昇电源科技有限公司 | Flexible lithium ion battery cathode and manufacturing method thereof |
| CN107994205A (en) * | 2017-11-29 | 2018-05-04 | 北京工业大学 | A kind of preparation method of the porous zinc-air battery anode based on braiding structure |
| CN108615895A (en) * | 2016-12-10 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of metal-air batteries air electrode and preparation and application |
| CN114628716A (en) * | 2020-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | Zinc-air battery |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104221213A (en) * | 2012-04-18 | 2014-12-17 | 日产自动车株式会社 | Positive electrode for air battery and process for producing same |
| CN104221213B (en) * | 2012-04-18 | 2017-12-05 | 日产自动车株式会社 | Air cell positive pole and its manufacture method |
| CN105024110A (en) * | 2015-07-14 | 2015-11-04 | 北京航空航天大学 | High-power oxygen-metal battery with array ultrathin electrodes |
| CN105024110B (en) * | 2015-07-14 | 2018-06-29 | 北京航空航天大学 | A kind of high-power array ultrathin electrodes oxygen-metal battery |
| CN105304906A (en) * | 2015-09-24 | 2016-02-03 | 山东润昇电源科技有限公司 | Flexible lithium ion battery cathode and manufacturing method thereof |
| CN108615895A (en) * | 2016-12-10 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of metal-air batteries air electrode and preparation and application |
| CN108615895B (en) * | 2016-12-10 | 2021-01-26 | 中国科学院大连化学物理研究所 | Air electrode for metal/air battery and preparation and application thereof |
| CN107994205A (en) * | 2017-11-29 | 2018-05-04 | 北京工业大学 | A kind of preparation method of the porous zinc-air battery anode based on braiding structure |
| CN114628716A (en) * | 2020-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | Zinc-air battery |
| CN114628716B (en) * | 2020-12-12 | 2023-07-14 | 中国科学院大连化学物理研究所 | Zinc-air battery |
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