CN111900414A - Preparation method of waterproof breathable film and air electrode positive plate of zinc-air battery - Google Patents
Preparation method of waterproof breathable film and air electrode positive plate of zinc-air battery Download PDFInfo
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- CN111900414A CN111900414A CN202010688053.2A CN202010688053A CN111900414A CN 111900414 A CN111900414 A CN 111900414A CN 202010688053 A CN202010688053 A CN 202010688053A CN 111900414 A CN111900414 A CN 111900414A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8896—Pressing, rolling, calendering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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Abstract
The invention discloses a waterproof breathable film for a zinc-air battery and a preparation method of an air electrode positive plate. The waterproof breathable film of the zinc-air battery is a PTFE film. The thickness of the PTFE film is 0.10-0.25 mm. The PTFE membrane is adopted as the waterproof breathable membrane of the zinc-air battery, so that the problem that electrolyte directly penetrates through the PTFE membrane to leak can be avoided while the good discharge performance is ensured. The preparation method of the air electrode positive plate of the zinc-air battery is a dry-method sheet preparation method, and water or other solvents are not required to be added in the whole positive plate preparation process, so that the process of drying powder is not required, and the preparation method is energy-saving and environment-friendly.
Description
Technical Field
The invention relates to the technical field of zinc-air batteries, in particular to a waterproof breathable film of a zinc-air battery positive electrode material and a preparation method of an air electrode positive plate.
Background
Zinc-air batteries typically comprise a metallic zinc-based negative electrode and an air positive electrode, separated from each other by an ion-conducting electrolyte. Zinc-air batteries have an extremely high energy density because the oxygen required for the air cathode reaction can be supplied by the ambient atmosphere. Accordingly, sufficient oxygen must be able to enter the cell from the environment during discharge. The metal shell of the conventional button zinc-air battery has an air inlet hole. Generally, the air inlet holes with proper size are obtained by laser drilling or direct mechanical punching, and the number of the air inlet holes is 1-5.
Since the carbon dioxide in the air poisons the positive electrode material when it contacts the positive electrode material for a long time, the discharge time of the zinc-air battery is shortened or the discharge failure occurs, the rate of the air entering the battery is generally controlled. When the inlet gas velocity is too low, sufficient oxygen is not introduced for the reaction, and the cell discharge time may become short. The general metal-air battery can adjust the air inlet speed through the number and the size of the air inlet holes. In addition, it is desirable to regulate the rate of air ingress through the air permeability of the waterproof breathable membrane.
The more common zinc-air cell is the zinc-air cell with button height below 5.4mm, the most important safety problem of this type of button cell is the leakage of electrolyte, which if leaked out could corrode and damage the expensive hearing aid. One of the more common leakage paths is that the alkali solution directly passes through the waterproof breathable film and leaks out from the air hole. Therefore, the quality of the waterproof breathable film directly affects the quality of the zinc-air battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a waterproof breathable film and an air electrode positive plate of a zinc-air battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a waterproof breathable film for a zinc-air battery is a PTFE film.
Preferably, in the above waterproof breathable film for zinc-air batteries, the PTFE film has a thickness of 0.10 to 0.25 mm.
Preferably, in the above waterproof breathable film for zinc-air batteries, the PTFE film has a thickness of 0.15 to 0.22 mm. When the thickness of the waterproof breathable film is too high, the occupied space is too large, and the capacity of the battery can be reduced. As the waterproof breathable film needs to completely prevent alkali liquor from overflowing so as to ensure safety, the waterproof breathable film is difficult to ensure complete waterproofing and does not leak from the waterproof breathable film when the thickness is too low.
Preferably, in the waterproof breathable film for the zinc-air battery, the air permeability of the PTFE film is 1000-4000s/in 2-100 cc-1.22 kPa.
Preferably, in the waterproof breathable film for the zinc-air battery, the air permeability of the PTFE film is 2000-3000s/in 2-100 cc-1.22 kPa.
Preferably, in the waterproof breathable film for zinc-air batteries, the density of the PTFE film is more than 1.2g/cm3And the electrolyte can not directly penetrate through the waterproof breathable layer to leak. When the density of the PTFE film is too low, electrolyte easily passes through the PTFE film to leak, and when the density of the PTFE film is too high, the PTFE film is easy to peel off and separate after being pressed with a positive electrode catalyst layer containing a current collector, and the processability is not strong.
A preparation method of a zinc-air battery air electrode positive plate comprises the following steps:
(1) mixing and stirring activated carbon, graphite, manganese dioxide and PTFE powder at a high speed to obtain anode catalytic powder, and mixing and stirring the anode catalytic powder at a high speed to increase the density of the anode catalytic powder to form small-block-shaped particulate anode powder;
(2) rolling the current collector and the anode powder to obtain an anode catalyst layer containing the current collector; when the current collector and the anode powder are rolled together, the current collector is completely sunk into the anode powder layer, the thickness of the anode powder before and after rolling is unchanged, and the thickness tolerance of the obtained anode catalyst layer containing the current collector is not more than +/-0.02 mm.
(3) And (3) combining the anode catalyst layer containing the current collector and the waterproof breathable film together under pressure to prepare a sheet to obtain the anode plate, wherein the obtained anode plate has relatively uniform color and air permeability.
Preferably, in the above preparation method, the current collector is a 25-40 mesh pure nickel mesh, nickel-plated stainless steel mesh, nickel-plated steel, nickel-plated iron, gold or platinum, and the hardness of the current collector is 110 microvickers or more.
Preferably, in the above production method, the thickness of the current collector-containing cathode catalyst layer is in the range of 0.2 to 0.3mm, and the thickness of the cathode sheet is between 0.4 and 0.5 mm.
Compared with the prior art, the invention has the following beneficial effects: the PTFE membrane is adopted as the waterproof breathable membrane of the zinc-air battery, so that the problem that electrolyte directly penetrates through the PTFE membrane to leak can be avoided while the good discharge performance is ensured. The preparation method of the air electrode positive plate of the zinc-air battery is a dry-method sheet preparation method, and water or other solvents are not required to be added in the whole positive plate preparation process, so that the process of drying powder is not required, and the preparation method is energy-saving and environment-friendly.
Drawings
Fig. 1 is a partially cut-away illustration of a zinc-air button cell of the present invention. The cathode comprises a cathode shell 1, a cathode zinc slurry 2, a sealing ring 3, an anode shell 4, a diaphragm 5, a current collector 6, a catalyst layer 7, a waterproof breathable film 8, diffusion paper 9 and air holes 10. Wherein the current collector 6, the catalytic layer 7 and the waterproof breathable film 8 form a positive plate of the metal-air battery.
FIG. 2 is a discharge diagram of example 2;
fig. 3 is a discharge diagram of comparative example 1.
Detailed Description
Example 1:
a waterproof breathable film of a zinc-air battery is prepared by selecting a PTFE film of Gore company of America with the thickness of 0.2 +/-0.015 mm and the density of 1.4g/cm3 to prepare a positive plate with the thickness of 0.40-0.45mm, wherein the air permeability of PTFE is respectively 100, 500, 1000, 2000, 3000, 4000, 5000 and 6000s/in 2.100 cc.1.22 kPa, and the PTFE film is respectively assembled into a PR41 zinc-air battery with the height of 3.5mm and the outer diameter of 7.8 mm. The battery is subjected to a discharge test according to the IEC60086(2015) high-rate discharge process step, and is also subjected to a leakage-resistant test at a high-temperature storage time of 60 ℃ for 20 days.
The results of the experiments are shown in Table 1, and when the air permeability of the PTFE film is lower than 1000s/in2 & 100cc & 1.22kPa or higher than 4000s/in2 & 100cc & 1.22kPa, the battery will have discharge failure with a certain probability, but there is no leakage problem. The preferred PTFE membrane permeability range is 1000-4000s/in 2-100 cc 1.22kPa, and the most preferred PTFE membrane permeability range is 2000-3000s/in 2-100 cc 1.22 kPa.
TABLE 1
Example 2:
a preparation method of a zinc-air battery air electrode positive plate comprises the following steps:
(1) mixing and stirring activated carbon, graphite, manganese dioxide and PTFE powder at a high speed to obtain anode catalytic powder, and mixing and stirring the anode catalytic powder at a high speed to increase the density of the anode catalytic powder to form small-block-shaped particulate anode powder;
(2) rolling the current collector and the anode powder to obtain an anode catalyst layer containing the current collector; when the current collector and the anode powder are rolled together, the current collector is completely sunk into the anode powder layer, the thickness of the anode powder before and after rolling is unchanged, and the thickness tolerance of the obtained anode catalyst layer containing the current collector is not more than +/-0.02 mm. The current collector is made of 25-40 mesh pure nickel mesh, nickel-plated stainless steel mesh, nickel-plated steel, nickel-plated iron, gold or platinum, and has hardness of more than 110 microvickers.
(3) The anode catalytic layer containing the current collector and a waterproof breathable film (a PTFE film with the thickness of 0.2 +/-0.015 mm and the density of 1.5g/cm3 is selected) are combined together under pressure to prepare an anode sheet with the thickness of 0.40-0.45mm, and the obtained anode sheet has relatively uniform color and air permeability. The thickness of the positive electrode catalyst layer containing the current collector is in the range of 0.2 to 0.3 mm. The PTFE air permeability is 2000s/in2 & 100cc & 1.22kPa, and the PR41 zinc air battery with the height of 3.5mm and the outer diameter of 7.8mm is assembled. The battery is subjected to discharge test according to the working procedure of IEC60086(2015) high-rate discharge, and is also subjected to leakage-resistant test at high temperature storage for 20 days at 60 ℃. The experimental result shows that 5 batteries have good discharge, and 30 batteries have no liquid leakage after being stored for 20 days at high temperature of 60 ℃. The detailed discharge diagram is shown in fig. 2.
Comparative example 1:
according to the manufacturing process of the positive plate in the embodiment 2, a PTFE film with the thickness of 0.2 +/-0.015 mm and the density of 1.0g/cm3 is selected to manufacture a positive plate with the thickness of 0.40-0.45mm, the PTFE air permeability is 2000s/in 2.100 cc.1.22 kPa, and a PR41 zinc air battery with the height of 3.5mm and the outer diameter of 7.8mm is assembled. The battery is subjected to a 2mA/10mA pulse discharge test and a 60-degree 20-day high-temperature storage test. The experimental results show that 5 batteries are all discharged poorly and leak during discharging, and 30 batteries are stored at high temperature of 60 ℃ for 20 days and all leak. The detailed discharge diagram is shown in fig. 3.
Claims (9)
1. A waterproof breathable film for a zinc-air battery is characterized in that the breathable film is a PTFE film.
2. The waterproof breathable film for zinc-air batteries according to claim 1, wherein the PTFE film has a thickness of 0.10 to 0.25 mm.
3. The waterproof breathable film for zinc-air batteries according to claim 1, wherein the PTFE film has a thickness of 0.15 to 0.22 mm.
4. The waterproof breathable film for zinc-air batteries according to claim 1, wherein the air permeability of the PTFE film is 1000-4000s/in 2-100 cc-1.22 kPa.
5. The waterproof breathable film for zinc-air batteries according to claim 4, wherein the air permeability of the PTFE film is 2000-3000s/in 2-100 cc-1.22 kPa.
6. The waterproof breathable film for zinc-air batteries according to claim 1, wherein the density of the PTFE film is greater than 1.2g/cm3And the electrolyte can not directly penetrate through the waterproof breathable layer to leak.
7. A preparation method of a zinc-air battery air electrode positive plate is characterized by comprising the following steps:
(1) mixing and stirring activated carbon, graphite, manganese dioxide and PTFE powder at a high speed to obtain anode catalytic powder, and mixing and stirring the anode catalytic powder at a high speed to increase the density of the anode catalytic powder to form small-block-shaped particulate anode powder;
(2) rolling the current collector and the anode powder to obtain an anode catalyst layer containing the current collector;
(3) and (3) combining the anode catalyst layer containing the current collector and the waterproof breathable film together under pressure to prepare a sheet to obtain the anode sheet.
8. The method according to claim 1, wherein the current collector is a 25-40 mesh pure nickel mesh, nickel-plated stainless steel mesh, nickel-plated steel, nickel-plated iron, gold, or platinum, and the hardness of the current collector is 110 microvex or more.
9. The production method according to claim 1, wherein the thickness of the positive electrode catalyst layer containing the current collector is in the range of 0.2 to 0.3mm, and the thickness of the positive electrode sheet is in the range of 0.4 to 0.5 mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010688053.2A CN111900414A (en) | 2020-07-16 | 2020-07-16 | Preparation method of waterproof breathable film and air electrode positive plate of zinc-air battery |
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| CN202010688053.2A CN111900414A (en) | 2020-07-16 | 2020-07-16 | Preparation method of waterproof breathable film and air electrode positive plate of zinc-air battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745608A (en) * | 2020-12-29 | 2021-05-04 | 施柏德（厦门）科技有限公司 | PTFE composite material with excellent uniformity and manufacturing process and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258256A (en) * | 2018-01-09 | 2018-07-06 | 广州鹏辉能源科技股份有限公司 | Zinc-air battery anode and its positive powder dry preparation process and zinc-air battery |
| CN110176658A (en) * | 2019-05-28 | 2019-08-27 | 中国科学技术大学 | Available composite zinc air secondary battery in a kind of oxygen-free environment |
| CN111092279A (en) * | 2020-01-13 | 2020-05-01 | 广州鹏辉能源科技股份有限公司 | Zinc-air battery and preparation method thereof |
| CN111180748A (en) * | 2020-01-16 | 2020-05-19 | 广州鹏辉能源科技股份有限公司 | Air electrode of air battery, preparation method of air electrode, air battery and electric device |
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- 2020-07-16 CN CN202010688053.2A patent/CN111900414A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258256A (en) * | 2018-01-09 | 2018-07-06 | 广州鹏辉能源科技股份有限公司 | Zinc-air battery anode and its positive powder dry preparation process and zinc-air battery |
| CN110176658A (en) * | 2019-05-28 | 2019-08-27 | 中国科学技术大学 | Available composite zinc air secondary battery in a kind of oxygen-free environment |
| CN111092279A (en) * | 2020-01-13 | 2020-05-01 | 广州鹏辉能源科技股份有限公司 | Zinc-air battery and preparation method thereof |
| CN111180748A (en) * | 2020-01-16 | 2020-05-19 | 广州鹏辉能源科技股份有限公司 | Air electrode of air battery, preparation method of air electrode, air battery and electric device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745608A (en) * | 2020-12-29 | 2021-05-04 | 施柏德（厦门）科技有限公司 | PTFE composite material with excellent uniformity and manufacturing process and application thereof |
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Application publication date: 20201106 |