CN112952109A - Air electrode with double-layer diffusion layer and preparation method and application thereof - Google Patents
Air electrode with double-layer diffusion layer and preparation method and application thereof Download PDFInfo
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- CN112952109A CN112952109A CN202110273977.0A CN202110273977A CN112952109A CN 112952109 A CN112952109 A CN 112952109A CN 202110273977 A CN202110273977 A CN 202110273977A CN 112952109 A CN112952109 A CN 112952109A
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- polytetrafluoroethylene
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
Abstract
The invention discloses an air electrode with a double-layer diffusion layer and a preparation method and application thereof. The air electrode with the double-layer diffusion layer structurally comprises a polytetrafluoroethylene film layer, a polytetrafluoroethylene/conductive agent film layer and a metal mesh of a charging current collector from bottom to top in sequence. Dispersing a conductive agent in an alcohol solvent, adding a polytetrafluoroethylene suspension, uniformly mixing to prepare a film, and drying to obtain a polytetrafluoroethylene/conductive agent film; and finally, superposing the pure polytetrafluoroethylene film, the polytetrafluoroethylene/conductive agent film and the metal mesh in sequence from bottom to top, pressing into a whole, and spraying a solution containing a catalyst on the metal mesh to obtain the air electrode with the double-layer diffusion layer. The preparation method of the invention has low cost, and the prepared double-layer diffusion layer has high hydrophobicity, alkali liquor resistance and low interface resistance, so that the corresponding air electrode has stable structure, long service life, high cycle efficiency and good application prospect.
Description
Technical Field
The invention relates to an air electrode with a double-layer diffusion layer and a preparation method and application thereof, belonging to the technical field of new energy storage.
Background
Along with the rapid development of economy, the demand of people for various power sources is also increasing. Therefore, the development of energy storage batteries with high specific energy and clean and safe performance is an important requirement for social development. The zinc-air battery has high specific energy density (the theoretical energy density is 1350 Wh/kg)-1) And the safety performance is good, and the material price is low, so the device has wide attention in the directions of large-scale energy storage, efficient electric energy conversion and the like. The rechargeable zinc-air battery has great application potential as a low-cost green sustainable energy source. The rechargeable zinc-air battery mainly comprises an air anode, a zinc cathode and electrolyte. The air electrode mainly comprises a diffusion layer, a catalyst layer and a current collector, and oxygen in the air is used as a positive electrode reaction active substance to respectively generate oxygen reduction and oxygen precipitation reactions in the charging and discharging processes. The air electrode layer needs to realize gas phase (oxygen) and liquid phase (electrolyte) conduction, and meets the three-phase (gas-liquid-solid) electrochemical reaction process. Therefore, the preparation of the air electrode is particularly important for the development of the chargeable and dischargeable zinc-air battery, wherein the air diffusion layer provides a diffusion channel for oxygen and plays a role of preventing liquid leakage, and the electrocatalyst is also loaded on the surfaces of the diffusion layer and the current collectorTherefore, the diffusion layer structure has a large influence on the redox reaction.
At present, the most widely used zinc-air battery diffusion layer is a membrane material prepared from polytetrafluoroethylene, and the membrane material is alkali-resistant and has better water resistance. However, polytetrafluoroethylene is not electrically conductive, and when an electrocatalyst is loaded on the surface thereof, polarization resistance is large, thereby affecting the cell performance. If the conductive material is added, the structure of the polytetrafluoroethylene membrane is damaged, and the water resistance of the diffusion layer is affected. Therefore, it is necessary to develop a diffusion layer with high hydrophobicity, alkali-resistant liquid, low interfacial resistance and corresponding air electrode to meet the growing use requirements of rechargeable zinc-air batteries.
Disclosure of Invention
The technical problem solved by the invention is as follows: the diffusion layer of the existing air electrode can not simultaneously give consideration to high hydrophobicity and alkali-resistant liquid, and can ensure sufficient gas diffusion and passing and low interface resistance.
In order to solve the technical problem, the invention provides an air electrode with a double-layer diffusion layer, which sequentially comprises a polytetrafluoroethylene film layer, a polytetrafluoroethylene/conductive agent film layer and a metal mesh serving as a current collector from bottom to top.
Preferably, the conductive agent in the polytetrafluoroethylene/conductive agent thin film layer comprises at least one of acetylene black, carbon fibers, carbon nanotubes, graphite and graphene, and the metal mesh is a nickel mesh.
Preferably, the metal mesh is provided with a catalyst.
Preferably, the thicknesses of the polytetrafluoroethylene film layer, the polytetrafluoroethylene/conductive agent film layer and the metal net are all 0.1-0.4 mm.
The invention also provides a preparation method of the air electrode with the double-layer diffusion layer, which comprises the following steps:
step 1): dispersing a conductive agent in an alcohol solvent, adding a polytetrafluoroethylene suspension, and uniformly mixing to obtain a mixture;
step 2): preparing the mixture obtained in the step 1) into a film, and drying to obtain a polytetrafluoroethylene/conductive agent film;
step 3): and laminating the polytetrafluoroethylene film, the polytetrafluoroethylene/conductive agent film and the metal net in sequence from bottom to top, pressing into a whole, and spraying a solution containing a catalyst on the metal net to obtain the air electrode with the double-layer diffusion layer.
Preferably, the alcohol solvent in the step 1) is ethanol, and the solid content in the polytetrafluoroethylene suspension is 50-70 wt%; the mass ratio of the polytetrafluoroethylene suspension to the conductive agent is 1: 1-6: 1, and the concentration of the conductive agent dispersed in the alcohol solvent is 0.5-8 mg/mu L.
Preferably, the drying conditions in step 2) are as follows: the temperature is 120-180 ℃, and the time is 2-10 h.
Preferably, the film manufactured in step 2) and the pressing in step 3) are rolled in a roll press.
The invention also provides application of the air electrode with the double-layer diffusion layer.
Preferably, the application includes an application in a zinc-air secondary battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method has low cost and good controllability;
2. the air electrode with the double-layer diffusion layer has high hydrophobicity and good mechanical strength, can ensure sufficient oxygen to diffuse and pass, and has the advantages of good conductivity, small resistance and the like of the diffusion layer, so the air electrode has good application prospect in the related fields of electro-catalysis and secondary zinc-air batteries.
Drawings
FIG. 1 is a schematic structural diagram of an air electrode with a double-layered diffusion layer according to the present invention;
FIG. 2 is a SEM image of a double-layered diffusion layer of the air electrode prepared in example 1, wherein A is a SEM image of a PTFE/conductive agent thin film layer, and B is a SEM image of a PTFE thin film layer;
fig. 3 is a graph showing the cycle charge and discharge performance of the air electrode prepared in example 1 in a zinc-air secondary battery.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
A preparation method of an air electrode with a double-layer diffusion layer comprises the following steps:
1) ultrasonically cleaning a pure polytetrafluoroethylene film in ethanol, and drying in the shade at room temperature;
2) weighing 5mg of carbon nano tube, adding the carbon nano tube into 10 mu L of ethanol, stirring, adding 25mg of polytetrafluoroethylene suspension (with solid content of 60 percent), and continuously stirring and uniformly mixing;
3) rolling the mixture obtained in the step 2) on a roller press to form a layer of thin film with the thickness of 0.2mm, and drying the thin film in an oven at 150 ℃ for 5 hours;
4) the pure polytetrafluoroethylene film, the mixture film and the nickel screen are sequentially overlapped from bottom to top, the mixture film and the nickel screen are placed in a roller press for rolling, the final thickness is 0.6mm, a solution containing a catalyst is sprayed on the nickel screen, and the air electrode with the double-layer diffusion layer is obtained.
FIG. 2 is a scanning electron microscope topography of a double-layer diffusion layer, which is characterized by a microstructure of the double-layer diffusion layer using a field emission electron microscope. Under a high power electron microscope, the polytetrafluoroethylene/conductive agent thin film layer close to the catalyst side has a high porosity as shown in fig. 2A, so that the conductive agent therein can be ensured to exert a good conductive effect, and the polytetrafluoroethylene thin film layer close to the air side has a low porosity as shown in fig. 2B, so that good water resistance can be ensured.
Comparative example 1
Preparation of an air electrode with a single diffusion layer (teflon film layer):
1) ultrasonically cleaning a pure polytetrafluoroethylene film in ethanol, and drying in the shade at room temperature;
2) and superposing the polytetrafluoroethylene film and the nickel mesh current collector in the sequence from bottom to top, putting the mixture into a roll squeezer for rolling, wherein the final thickness is 0.4mm, and spraying a solution containing a catalyst on the nickel mesh to obtain the air electrode with the single-layer polytetrafluoroethylene film layer.
And (3) performance testing:
the air electrodes prepared in example 1 and comparative example 1 were applied to a zinc-air secondary battery, and electrochemical performance tests were performed respectively at a constant current with a charging current density of 5mA cm-2Charging for 5min, then performing a discharge test at the same current density for 5min, and performing a cyclic charge-discharge test under the condition to obtain a cyclic charge-discharge performance curve; wherein, the cyclic charge and discharge performance curve of the air electrode with the double-layer diffusion layer prepared in example 1 is shown in fig. 3; in the embodiment 1, the charging voltage of the first circle of the corresponding battery is about 2.27V, the discharging voltage is about 1.23V, the energy efficiency of the first circle is 54.2%, the stable charging and discharging is kept for 5000 circles, and the energy efficiency of the last circle can still reach 44.5%. Compared with the air electrode of example 1, the air electrode with the single-layer diffusion layer of comparative example 1 corresponds to a battery with a first-turn charging voltage of about 2.01V, a discharging voltage of about 1.09V and a first-turn energy efficiency of 54.2%, but the charging and discharging cycle only reaches 717 turns, and the last-turn energy efficiency is reduced to 38.2%. Thus, the air electrode prepared in example 1 exhibited better stability and electrochemical properties. The double-layer diffusion layer of the air electrode has high hydrophobicity, high mechanical strength and good stability, and can ensure sufficient oxygen to diffuse and pass, so that the double-layer diffusion layer is applied to a zinc-air secondary battery, and the performance and the cycle operation life of the zinc-air battery can be effectively improved.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. The air electrode with the double-layer diffusion layer is characterized by sequentially comprising a polytetrafluoroethylene film layer, a polytetrafluoroethylene/conductive agent film layer and a metal mesh serving as a current collector from bottom to top.
2. The air electrode having a double-layered diffusion layer according to claim 1, wherein the conductive agent in the teflon/conductive agent thin film layer comprises at least one of acetylene black, carbon fiber, carbon nanotube, graphite, and graphene, and the metal mesh is a nickel mesh.
3. The air electrode having a double-layered diffusion layer according to claim 1, wherein the metal mesh is provided with a catalyst.
4. The air electrode with the double-layer diffusion layer according to claim 1, wherein the polytetrafluoroethylene film layer, the polytetrafluoroethylene/conductive agent film layer and the metal mesh are all 0.1-0.4 mm thick.
5. The method for preparing an air electrode with a double-layer diffusion layer as claimed in any one of claims 1 to 4, comprising the steps of:
step 1): dispersing a conductive agent in an alcohol solvent, adding a polytetrafluoroethylene suspension, and uniformly mixing to obtain a mixture;
step 2): preparing the mixture obtained in the step 1) into a film, and drying to obtain a polytetrafluoroethylene/conductive agent film;
step 3): and laminating the polytetrafluoroethylene film, the polytetrafluoroethylene/conductive agent film and the metal mesh in sequence from bottom to top, pressing into a whole, and spraying a solution containing a catalyst on the metal mesh to obtain the air electrode with the double-layer diffusion layer.
6. The method for preparing the air electrode with the double-layer diffusion layer according to claim 5, wherein the alcohol solvent in the step 1) is ethanol, and the solid content in the polytetrafluoroethylene suspension is 50-70 wt%; the mass ratio of the polytetrafluoroethylene suspension to the conductive agent is 1: 1-6: 1, and the concentration of the conductive agent dispersed in the alcohol solvent is 0.5-8 mg/mu L.
7. The method for preparing an air electrode having a double diffusion layer according to claim 5, wherein the drying conditions in the step 2) are as follows: the temperature is 120-180 ℃, and the time is 2-10 h.
8. The method for preparing an air electrode having a double-layer diffusion layer according to claim 5, wherein the film prepared in step 2) and the film prepared in step 3) are rolled in a roll press.
9. Use of the air electrode with a double diffusion layer according to any one of claims 1 to 4.
10. The use of claim 9, including use in a zinc air secondary battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114703496A (en) * | 2022-04-12 | 2022-07-05 | 中国科学院生态环境研究中心 | Air electrode and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114703496A (en) * | 2022-04-12 | 2022-07-05 | 中国科学院生态环境研究中心 | Air electrode and preparation method thereof |
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Effective date of registration: 20221017 Address after: 201600 room 506, 5th floor, building 11, 300 Dingyuan Road, Songjiang District, Shanghai Applicant after: Shanghai cluster Rui Low Carbon Energy Technology Co.,Ltd. Applicant after: Shanghai lanze Energy Technology Co.,Ltd. Address before: 201600 room 506, 5th floor, building 11, 300 Dingyuan Road, Songjiang District, Shanghai Applicant before: Shanghai cluster Rui Low Carbon Energy Technology Co.,Ltd. Applicant before: SHANGHAI ADVANCED Research Institute CHINESE ACADEMY OF SCIENCES |
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