CN1318877A - Cylindrical alkaline primary zinc-air battery and manufacturing method thereof - Google Patents
Cylindrical alkaline primary zinc-air battery and manufacturing method thereof Download PDFInfo
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Abstract
A cylindrical alkaline primary zinc-air battery is composed of central current collecting needle, zinc paste, air electrode, isolating film for separating zinc paste from air electrode, battery shell, top cover with two small peaks, positive electrode contact, lower end cover and negative electrode contact.
Description
The invention relates to the technical field of directly converting chemical energy into electric energy, in particular to a cylindrical alkaline primary zinc-air battery and a manufacturing method thereof.
Zinc air cells have been known for over a hundred years since their advent. The metal zinc is used as a negative active substance, oxygen in the air is used as a positive active substance, and the two active substances are subjected to chemical reaction under the catalytic action of a catalyst to generate electric energy. As long as the zinc electrode is not consumed, the oxygen can continuously reach the electrochemical reaction interface through the air diffusion electrode to react with the zinc to generate electric energy. Since air does not occupy the volume and weight of the battery, the battery system makes the battery have high specific energy in principle. The alkaline zinc-air battery has greater advantages because the electromotive force of the battery is higher in the alkaline electrolyte. The main ones that have been widely used in the market today are square, button zinc air cells. However, the demand for cylindrical batteries is greatest in the battery market, and square and button batteries account for a smaller market share; in addition, the current square and button zinc-air batteries have smaller working current, thereby further limiting the application range of the square and button zinc-air batteries.
Chinese patent zl97241293.x discloses an external oxygen type structure of a cylindrical zinc-air battery and a manufacturing process thereof. The structure of the device is shown in figure 1, and the device mainly comprises a current collecting needle 1 positioned in the center, zinc paste 2 around the current collecting needle, an air electrode 3, a diaphragm 4 for separating the current collecting needle 2 from the air electrode 3, a battery shell 5, an upper end cover 6, a positive electrode contact 7 on the upper end cover, a lower end cover 8, a negative electrode contact 9 and an air inlet 10. The manufacturing method of the battery comprises the following steps: -making air electrodes
The ingredients of the waterproof breathable layer and the catalyst layer are repeatedly rolled to form a sheet-shaped film, the film is cut into a proper size, and a current collecting net is attached to the outer side of the waterproof breathable layer and then pressed to form the sheet-shaped air electrode plate. The air electrode comprises a current collecting net, a waterproof breathable layer and a catalytic layer from outside to inside in sequence. Preparation of Zinc electrode, separator and Battery case
The zinc electrode adopts pasty zinc paste, the diaphragm material is polypropylene non-woven fabric, and the battery shell is the same as the shell of a common zinc-manganese battery, namely a stainless steel shell. The positive end of the anode needs to be additionally provided with a hole as an air inlet hole. Assembly of sample cells
And (2) forming the sheet air electrode, the upper end cover and the lower end cover into a cylindrical air electrode by adopting a special injection mold, then placing the air electrode with one end sealed into a battery shell, lining the cylindrical diaphragm cylinder, sleeving the negative electrode contact after injecting zinc paste, and finally sealing the battery shell to obtain the sample battery shown in the attached drawing 1.
The main disadvantages of the above battery and the manufacturing method thereof are as follows:
1. because the lower end cover 8 is embedded into the lower end of the battery, and the negative contact is arranged below the lower end cover, a seam is formed between the lower end cover and the negative contact, the sealing is difficult, and the leakage and alkali climbing are easily caused;
2. the adhesive material used for preparing the air electrode is polytetrafluoroethylene emulsion which has good waterproofness, but has low surface energy and strong surface inertia, and is difficult to be tightly bonded with a plastic sealing end, so that the battery can not be completely sealed, and the phenomena of liquid leakage and alkali climbing can occur;
3. the upper end cap 6 is trapezoidal in shape, and forms a large gap with the battery case 5 so that air can enter the air electrode 3, and the air inlet hole 10 is formed at the edge of the upper end of the battery. Therefore, the edge of the battery shell at the upper end is less, and the battery is not easy to be firmly wrapped;
4. the preparation process is complex, and a complex special mold is required for injection molding.
The invention aims to provide a cylindrical alkaline primary zinc-air battery with good sealing performance.
The invention also aims to provide a manufacturing method of the cylindrical alkaline primary zinc-air battery, which simplifies the existing preparation process.
The structure of the cylindrical alkaline primary zinc-air battery is shown in figure 2 and mainly comprises a current collecting needle 1 positioned in the center, zinc paste 2 around the current collecting needle, an air electrode 3, a diaphragm 4 for separating the zinc paste 2 from the air electrode 3, a battery shell 5, an upper end cover 6 with two small vertexes at the top, a positive electrode contact 7, a lower end cover and a negative electrode contact 8 on the upper end cover. The lower end cover and the negative contact are integrated, no seam exists, and the sealing performance is good; the upper end cover is in a disc shape, a due gap is reserved between the upper end cover and the upper wall of the battery shell by utilizing two small vertexes of the top upper end cover 6, and the air inlet hole can be opened at the position close to the center of the end face of the positive electrode, so that the battery is convenient to package.
The manufacturing method of the cylindrical alkaline primary zinc-air battery comprises the following steps: the method comprises the following steps of firstly, repeatedly rolling and uniformly mixing materials of the waterproof breathable layer and the catalytic layer on a large-roll mixing device, fiberizing the materials, then adding the fiberized materials on a small-roll forming device to be formed in a roll covering mode, so that a cylindrical film is manufactured, and rolling two layers of the cylindrical film and a current collecting net on the small-roll forming device to form the cylindrical air electrode in a roll covering mode. The air electrode comprises a current collecting net layer, a waterproof breathable layer and a catalytic layer from outside to inside in sequence. Preparing a zinc electrode, a diaphragm and a battery shell, wherein the zinc electrode adopts pasty zinc paste, the diaphragm is made of polypropylene non-woven fabric, and the battery shell is the same as that of a common zinc-manganese battery, namely the stainless steel shell. The positive pole end of the air-permeable cover needs to be additionally provided with a hole as an air inlet hole. Assembling the sample battery, namely sleeving the upper top cover after the cylindrical air electrode is formed, performing thermal fusion on the upper top cover and the cylindrical air electrode through an external heating source, then placing the upper top cover and the cylindrical air electrode into a battery shell, lining the cylindrical diaphragm cylinder, sleeving the lower top cover after injecting zinc paste into the cylinder, performing thermal fusion on the lower top cover and the air electrode, and finally sealing the battery shell to obtain the sample battery shown in the attached drawing 2.
In order to achieve the purpose, the invention mainly adopts the following technical measures: the cylindrical waterproof breathable air electrode is bonded by adding polyhexafluoropropylene into polytetrafluoroethylene and using a modified adhesive, so that the air electrode has excellent surface bonding performance and is well bonded with a sealing buckle; the air electrode and the plastic sealing ends of the positive electrode and the negative electrode are sealed by adopting a thermal fusion method, the negative electrode cover and the lower sealing button are integrated, and the sealing performance is good.
The key point for fundamentally solving the problem of leakage and alkali climbing sealing of the zinc-air battery is to select the novel adhesive material. Polytetrafluoroethylene emulsion is mostly adopted as the former binder material. Although the waterproof performance is good, the surface energy is low, the surface inertia is strong, and the battery is difficult to be tightly bonded with a plastic sealing end, so that the battery cannot be completely sealed, and the problems of leakage and alkali climbing often occur. The novel adhesive material adopted by the invention is a blending and using system of polytetrafluoroethylene and polyhexafluoropropylene, has good waterproof performance and surface bonding performance, and can bond the air electrode and the plastic sealing end by adopting a thermal fusion method to integrate the air electrode and the plastic sealing end, thereby fundamentally solving the problem of leakage, alkali climbing and sealing of the zinc-air battery.
Compared with the prior art, the cylindrical alkaline primary zinc-air battery has the following advantages: the novel adhesive obtained by adopting a blending modification method obviously improves the bonding performance of the air electrode and the plastic sealing button. The blending and adhesive agent thoroughly solves the problems of leakage, alkali climbing and sealing of the battery; the thermal fusion method also simplifies the production process of the battery.
Fig. 1 is a schematic diagram of a zl97241293.X cylindrical zinc-air cell structure;
fig. 2 is a schematic structural view of a cylindrical alkaline primary zinc-air battery of the present invention.
The process and steps for manufacturing a sample cell using the adhesive material and the bonding method according to the preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.
In the embodiment, the air electrode is made of a three-layer composite membrane, and the air electrode comprises a current collecting net, a waterproof breathable layer and a catalytic layer from outside to inside in sequence. The three layers of films are pressed to form the pole piece. The pole pieces are pressed into cylindrical air electrodes by a special double-roller forming machine roller. The preparation method of the waterproof breathable film comprises the following steps: the acetylene black and sodium sulfate in certain proportion are first mixed with alcohol, the new adhesive is then added slowly, and the mixture is coagulated, dried and rolled to form film. The weight ratio of the materials is as follows: acetylene black, sodium sulfate, polytetrafluoroethylene and polyhexafluoropropene = 2: 1: 6: 1-4; the process method of the catalytic membrane is the same as above, and the formula of the catalytic membrane mainly comprises a catalytic material, active carbon, sodium sulfate and the novel adhesive. The weight ratio of the materials is as follows: catalytic material, active carbon, sodium sulfate, polytetrafluoroethylene, polyhexafluoropropene = 2: 1-3: 1. The solid content of the polytetrafluoroethylene and polyhexafluoropropylene emulsion is about 60%, and the operation temperature is room temperature. Preparation of zinc electrode, diaphragm and battery case, the zinc electrode is paste zinc paste. The main components of the electrolyte are metal zinc powder, zinc oxide, corrosion inhibitor, viscous agent, potassium hydroxide electrolyte and the like. The diaphragm material is polypropylene non-woven fabric. The battery shell is the same as that of a common zinc-manganese battery and is a stainless steel shell. The positive end of the air-permeable cover plate needs to be additionally provided with a hole as an air inlet hole. Assembling the sample battery, namely sleeving the cylindrical air electrode into the upper top cover after molding, and performing thermal fusion by an external heating source. And then the air electrode with one sealed end is placed in a battery case, a cylindrical diaphragm cylinder is lined, the lower top cover is sleeved after zinc paste is injected, the lower top cover and the air electrode are also thermally fused, and finally the battery case is sealed to obtain the sample battery shown in the attached figure 2.
The external dimension of the assembled battery is as follows: diameter 14.0mm and height 49.5mm. The open circuit voltage of the battery is about 1.4V, the discharge capacity is about 4200mAh, and the average working voltage is about 1.2V.
Claims (3)
1. A cylindrical alkaline primary zinc-air battery is characterized by mainly comprising a current collecting needle (1) positioned in the center, zinc paste (2) around the current collecting needle, an air electrode (3), a diaphragm (4) for separating the zinc paste (2) from the air electrode (3), a battery shell (5), an upper end cover (6) with two small vertexes on the top, and a positive contact (7), a lower end cover and a negative contact (8) on the upper end cover; the lower end cover and the negative contact are integrated; the upper end cover is in a disc shape, a gap is reserved between the upper end cover 6 and the upper wall of the battery shell by utilizing two small vertexes of the upper end cover on the top, and the air inlet hole can be opened at the position close to the center of the end face of the positive electrode.
2. A manufacturing method of a cylindrical alkaline primary zinc-air battery is characterized by comprising the following steps: the method comprises the following steps of firstly, repeatedly rolling and uniformly mixing materials of a waterproof breathable layer and a catalytic layer on a large-roll mixing device, fiberizing the materials, adding the fiberized materials on a small-roll forming device to be roll-coated and formed to prepare a cylindrical film, rolling two layers of the cylindrical film and a current collecting net on the small-roll forming device to form a cylindrical air electrode, wherein the air electrode sequentially comprises a current collecting net layer, a waterproof breathable layer and a catalytic layer from outside to inside; preparing a zinc electrode, a diaphragm and a battery shell, wherein the zinc electrode adopts pasty zinc paste, the diaphragm is made of polypropylene non-woven fabric, the battery shell is the same as the shell of a common zinc-manganese battery, and the positive electrode end of the battery needs to be additionally provided with a hole as an air inlet; assembling a sample battery, namely sleeving an upper top cover after a cylindrical air electrode is formed, performing thermal fusion on the upper top cover and the cylindrical air electrode through an external heating source, then putting the upper top cover and the cylindrical air electrode into a battery shell, lining a cylindrical diaphragm cylinder, sleeving a lower top cover after zinc paste is injected into the cylinder, performing thermal fusion on the lower top cover and the air electrode, and finally sealing the battery shell; the adhesive used for bonding the cylindrical waterproof breathable air electrode is polytetrafluoroethylene added with polyhexafluoropropylene.
3. The method of claim 2 for manufacturing a cylindrical alkaline primary zinc-air battery, comprising: the air electrode is made of a three-layer composite membrane, namely a current collecting net, a waterproof breathable layer and a catalytic layer from outside to inside; the three layers of films are pressed into pole pieces, and the pole pieces are pressed into cylindrical air electrodes by a special double-roll forming mechanical roller; the preparation method of the waterproof breathable film comprises the following steps: mixing acetylene black and sodium sulfate in certain proportion with alcohol, adding the new adhesive slowly, coagulating, drying and rolling to form film; the weight ratio of the materials is as follows: acetylene black, sodium sulfate, polytetrafluoroethylene and polyhexafluoropropene = 2: 1: 6: 1-4; the process method of the catalytic membrane is the same as above, and the formula of the catalytic membrane mainly comprises a catalytic material, active carbon, sodium sulfate and the novel adhesive; the weight ratio of the materials is as follows: catalytic material, active carbon, sodium sulfate, polytetrafluoroethylene, polyhexafluoropropylene = 2: 1-3: 1; the solid content of the polytetrafluoroethylene and polyhexafluoropropylene emulsion used is about 60 percent; preparing a zinc electrode, a diaphragm and a battery shell, wherein the zinc electrode is pasty zinc paste; the main components of the zinc-zinc composite material are metal zinc powder, zinc oxide, a corrosion inhibitor, a thickening agent, potassium hydroxide electrolyte and the like; the diaphragm material is polypropylene non-woven fabric; the battery shell is the same as the shell of a common zinc-manganese battery and is a stainless steel shell; the positive electrode end needs to be additionally provided with a hole as an air inlet hole; assembling a sample battery, namely sleeving the cylindrical air electrode into an upper top cover after molding, and performing thermal fusion by an external heating source; and then the air electrode with one sealed end is placed in a battery case, a cylindrical diaphragm cylinder is lined, the lower top cover is sleeved after zinc paste is injected, the lower top cover and the air electrode are thermally fused, and finally the battery case is sealed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011074183A CN1152450C (en) | 2001-01-07 | 2001-01-07 | Cylindrical alkaline primary zinc-air battery and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011074183A CN1152450C (en) | 2001-01-07 | 2001-01-07 | Cylindrical alkaline primary zinc-air battery and manufacturing method thereof |
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| CN1318877A true CN1318877A (en) | 2001-10-24 |
| CN1152450C CN1152450C (en) | 2004-06-02 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102429312A (en) * | 2011-10-31 | 2012-05-02 | 华南理工大学 | Quick deoxidizer for in-situ generation of primary battery and preparation method thereof |
| CN107579312A (en) * | 2017-08-03 | 2018-01-12 | 中国科学技术大学 | A kind of zinc and air cell with takeup type structure |
| CN107910618A (en) * | 2017-10-27 | 2018-04-13 | 清华大学 | Portable machinery fills formula zinc air secondary battery again |
| CN109103550A (en) * | 2018-08-24 | 2018-12-28 | Cnus技术公司 | A kind of power metal-air battery |
| CN112397821A (en) * | 2020-11-12 | 2021-02-23 | 横店集团东磁股份有限公司 | Alkaline manganese battery and sealing method thereof |
| 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 |
-
2001
- 2001-01-07 CN CNB011074183A patent/CN1152450C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102429312A (en) * | 2011-10-31 | 2012-05-02 | 华南理工大学 | Quick deoxidizer for in-situ generation of primary battery and preparation method thereof |
| CN107579312A (en) * | 2017-08-03 | 2018-01-12 | 中国科学技术大学 | A kind of zinc and air cell with takeup type structure |
| CN107910618A (en) * | 2017-10-27 | 2018-04-13 | 清华大学 | Portable machinery fills formula zinc air secondary battery again |
| CN109103550A (en) * | 2018-08-24 | 2018-12-28 | Cnus技术公司 | A kind of power metal-air battery |
| CN109103550B (en) * | 2018-08-24 | 2022-02-18 | Cnus技术公司 | Power metal-air battery |
| CN112397821A (en) * | 2020-11-12 | 2021-02-23 | 横店集团东磁股份有限公司 | Alkaline manganese battery and sealing method thereof |
| 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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| Publication number | Publication date |
|---|---|
| CN1152450C (en) | 2004-06-02 |
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