CN101908661B - Sealing method of cylindrical zinc-air battery - Google Patents
Sealing method of cylindrical zinc-air battery Download PDFInfo
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- CN101908661B CN101908661B CN200910085971XA CN200910085971A CN101908661B CN 101908661 B CN101908661 B CN 101908661B CN 200910085971X A CN200910085971X A CN 200910085971XA CN 200910085971 A CN200910085971 A CN 200910085971A CN 101908661 B CN101908661 B CN 101908661B
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Abstract
A 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 modified material and a conductive agent according to a 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 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 that in alkaline electrolyte, a cathode reaction of reducing oxygen to hydroxyl ions occurs on an air electrode, the electrode potential is positive, an anode reaction of oxidizing zinc to generate zinc oxide occurs on a zinc electrode, the electrode potential is negative, and when the zinc electrode and the zinc electrode form the 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 much higher 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 density, 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 sealing method of a cylindrical zinc-air battery, which adopts a heating mould pressing 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 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; according to the weight ratio of 10-35%: 40-60%: 20-30% of the weight ratio is added with adhesive, conductive agent and modified material, and waterproof powder is prepared for standby after 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 for zinc-air batteries are to seal the air electrode by gluing after filling the air electrode and the diaphragm sleeve with the zinc paste, and at this time, the qualification rate of gluing cannot reach the level of industrial production due to the existence of alkaline electrolyte. The cylindrical zinc-air battery produced by adopting the 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) which restrict the development of the cylindrical zinc-air battery, and has the advantages of simple and easy operation and easy realization of 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 method of the present invention includes a metal battery case (formed by butting a positive electrode case 5 and a negative electrode case 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 disposed in the case 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 mould 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 the steel shell, when the battery is assembled, the air electrode is pressed into the battery shell under certain pressure, and the sealing is realized by the tight contact of the outer edge of the air electrode and the inner wall of the battery shell.
The invention relates to a sealing method of a cylindrical zinc-air battery, which comprises the following 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: according to the weight ratio of 10-35%: 40-60%: 20-30% of the weight ratio is added with adhesive, conductive agent and modified material, and waterproof powder is prepared for standby after 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 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 (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 components together into a prefabricated perforated stainless steel battery shell.
The inner layer of the air electrode prepared by the method is a catalyst layer, and the outer layer is a waterproof diffusion layer.
The waterproof powder material has the following components in parts by weight in the following range, and has better sealing and waterproof effects: 15-30% of adhesive, conductive agent: 40-55%, modified material: 20 to 30 percent. Furthermore, 20 to 30 percent of adhesive, 50 to 55 percent of conductive agent and 20 to 25 percent 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. According to the proportion of 10%:60%: adding 30% of adhesive, conductive agent and modified material, and preparing waterproof powder for later use through heat seal 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 a thickness of 0.05mm, and using as a pre-buried catalytic membrane for standby.
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 the same as example 1, but the differences are as follows:
Example 3
The specific method is different from the embodiment 1 in that:
in step 2, according to 20:60:20 weight percent of polytetrafluoroethylene,OP-10 and carbon black. 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:
Example 5
The specific method is different from the embodiment 1 in that:
Example 6
The specific method is different from the embodiment 1 in that:
in step 2, according to 25:55:20 weight percent of polytetrafluoroethylene, OP-10 and carbon black. 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 the same as example 1, but the differences are as follows:
in step 2, according to 20:50:30 weight percent of polytetrafluoroethylene, OP-10 and acetylene black. 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%: 40-60%: 20 to 30 percent
In step 2, according to 30:45:25 weight percent of polytetrafluoroethylene, OP-10 and carbon black. 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％；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 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; according to the weight ratio of 10-35%: 40-60%: 20-30% of the weight ratio is added with adhesive, conductive agent and modified material, and waterproof powder is prepared for standby after 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 acetylene black or 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 sealing method of a cylindrical zinc-air battery according to claim 1, characterized in that: 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 sealing method of a cylindrical zinc-air battery according to claim 1, characterized in that: 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 sealing method of a cylindrical zinc-air battery according to claim 1 or 2, characterized in that: 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 sealing method of a cylindrical zinc-air battery according to claim 1, characterized in that: the air electrode is produced by using low-pressure polyethylene or polytetrafluoroethylene as a binder and acetylene black or carbon black to form powder through hot-press forming.
6. The sealing method of a cylindrical zinc-air battery according to claim 1, characterized in that: the thickness of the pre-embedded catalytic membrane of the air electrode is 0.05-0.2 mm.
7. The sealing method of a cylindrical zinc-air battery according to claim 1, characterized in that: 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 sealing method of a cylindrical zinc-air battery according to claim 1, characterized in that: 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161734A (en) * | 2015-08-05 | 2015-12-16 | 中国科学院宁波材料技术与工程研究所 | Catalyst slurry and preparation method for air cathode |
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| JP6229994B2 (en) * | 2012-04-18 | 2017-11-15 | 日産自動車株式会社 | Positive electrode for air battery and method for producing the same |
| 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 |
| 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 |
| 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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| CN2932636Y (en) * | 2006-04-11 | 2007-08-08 | 北京长力联合能源技术有限公司 | A zinc-air metal fuel battery oxygen electrode made by way of thermal bonding technique |
| CN101212075A (en) * | 2006-12-29 | 2008-07-02 | 比亚迪股份有限公司 | Method for producing zinc-air battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2932636Y (en) * | 2006-04-11 | 2007-08-08 | 北京长力联合能源技术有限公司 | A zinc-air metal fuel battery oxygen electrode made by way of thermal bonding technique |
| CN101212075A (en) * | 2006-12-29 | 2008-07-02 | 比亚迪股份有限公司 | Method for producing zinc-air battery |
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| CN105161734A (en) * | 2015-08-05 | 2015-12-16 | 中国科学院宁波材料技术与工程研究所 | Catalyst slurry and preparation method for air cathode |
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