阅读说明：本技术 一种金属空气电池中空气电极热合硫化压制方法 (Heat seal vulcanization pressing method for air electrode in metal-air battery ) 是由 刘伟春 于 2019-11-13 设计创作，主要内容包括：本发明提供一种金属空气电池中空气电极热合硫化压制方法,具体涉及电化学技术和电池制造技术领域,S1、空气电极防水材料质量配比如下,180～220目的乙炔黑50％～60％；聚乙烯树脂(悬浮细粉)20％～30％；JF-4TM聚四氟乙烯树脂5～10％；溶剂10～15％；S2、催化材料质量配比如下,300目的活性炭65％～75％；钙态矿型催化剂10％～15％；氧化锶2％～5％；JF-4TM聚四氟乙烯树脂(悬浮细粉)8％～10％；TX-10分散剂5％；S3、制膜成膜厚度0.15～0.2mm；S4、将热合硫化式空气电极压制成型后,进行萃取处理,即完成热合式空气电极制造。本发明实现空气电极量化生产,热合硫化压制方法制造空气电极,透气孔分布均匀一致,孔隙率高,机械强度高,提高空气电极组装成电池在电动车领域应用稳定性和可靠性。(The invention provides a heat seal vulcanization pressing method for an air electrode in a metal-air battery, and particularly relates to the technical field of electrochemistry technology and battery manufacturing, wherein S1 and the air electrode waterproof material are mixed according to the following mass ratio, namely 50% -60% of acetylene black with 180-220 meshes; 20 to 30 percent of polyethylene resin (suspended fine powder); 5-10% of JF-4TM polytetrafluoroethylene resin; 10-15% of a solvent; s2, preparing 300-mesh active carbon 65-75% by mass of the catalytic material; 10 to 15 percent of calcium mineral catalyst; 2 to 5 percent of strontium oxide; 8 to 10 percent of JF-4TM polytetrafluoroethylene resin (suspended fine powder); 5% of TX-10 dispersant; s3, film forming thickness is 0.15-0.2 mm; and S4, pressing and forming the heat seal vulcanization type air electrode, and then carrying out extraction treatment to finish the manufacture of the heat seal type air electrode. The invention realizes the quantitative production of the air electrode, the air electrode is manufactured by a heat seal vulcanization pressing method, the air holes are uniformly distributed, the porosity is high, the mechanical strength is high, and the application stability and the reliability of the battery assembled by the air electrode in the field of electric vehicles are improved.)

1. A heat seal vulcanization pressing method for an air electrode in a metal-air battery is characterized by comprising the following specific steps:

s1, preparing a waterproof material:

the air electrode waterproof material comprises, by mass, 50% -60% of 180-220-mesh acetylene black; 20 to 30 percent of polyethylene resin (suspended fine powder); 5-10% of JF-4TM polytetrafluoroethylene resin; 10-15% of a solvent;

mixing and stirring the waterproof material in a reaction kettle at the temperature of 180-250 ℃ for 80-100 minutes, cooling to room temperature, drying in a drying box at the temperature of 75 ℃ for 4 hours, crushing into 80-150 meshes by a crusher, and sieving into three stages: less than 80 meshes, 80 to 100 meshes and more than 100 meshes, and mixing according to the granularity proportion to complete the preparation of the waterproof material;

s2, preparing a heat seal vulcanization type catalytic material:

the mass ratio of the catalytic material is as follows, 65-75% of 300-mesh active carbon; 10 to 15 percent of calcium mineral catalyst; 2 to 5 percent of strontium oxide; 8 to 10 percent of JF-4TM polytetrafluoroethylene resin (suspended fine powder); 5% of TX-10 dispersant; firstly, mixing and homogenizing the catalytic materials at 240-300 ℃ for 60 minutes;

then mixing and homogenizing the catalytic material for 50-80 minutes, immersing for 24 hours, then drying for 4-8 hours at 75 ℃ in an electric oven, crushing and sieving by a 200-mesh sieve to finish the preparation of the catalytic material;

s3, film making:

spreading a copper pull net or a nickel net or foamed nickel on the waterproof material dry powder, and carrying out heat seal on a vulcanizing machine at the temperature of 180-220 ℃; uniformly bonding the waterproof material with a copper pull net or a nickel net or foam nickel into a whole, and shaping on a cooling machine under equal pressure; spraying a catalytic material on the inner side surface of the waterproof electrode after the thermal synthesis molding, wherein the temperature of a vulcanizing machine is 200 ℃, the pressure is 30MP, the film combination time is 180-220 s, and the film forming thickness is 0.15-0.2 mm, so that the film preparation is finished;

s4, finishing the electrode manufacture

And (3) after the heat seal vulcanization type air electrode is pressed and formed, carrying out extraction treatment for 20-36 hours, and drying for 2-4 hours in an electric oven at 65 ℃ to finish the manufacture of the heat seal type air electrode.

2. The method for hot-sealing, vulcanizing and pressing the air electrode in the metal-air battery according to claim 1, characterized in that: the granularity of the waterproof material is uniformly mixed according to the proportion of 70 percent, 25 percent and 5 percent, and the preparation of the waterproof material is completed.

3. The method for hot-sealing, vulcanizing and pressing the air electrode in the metal-air battery according to claim 1, characterized in that: the polyethylene resin adopts dry powder, and the polytetrafluoroethylene also can adopt emulsion with solid content of 60 percent, and a coagulant and a dispersant are added. The air electrode molding is carried out on a special flat vulcanizing machine, the waterproof material is flatly laid on the foam nickel of the mold and is melted at high temperature, the waterproof material is crosslinked into a whole under the action of polyethylene resin and polytetrafluoroethylene fibers, the granularity of the waterproof material is different and permeates the middle and two sides of the foam nickel current collector respectively, and the current collector meshes are filled with the waterproof material and are crosslinked into a whole.

4. The method for hot-sealing, vulcanizing and pressing the air electrode in the metal-air battery according to claim 1, characterized in that: in the step S4, the straight porosity of the electrode is 12-17%, and the curved straight porosity is 83-88%.

Technical Field

The invention belongs to the technical field of electrochemistry and battery manufacturing, and particularly relates to a heat seal vulcanization pressing method for an air electrode in a metal-air battery.

Background

The metal-air battery has high specific energy, and has the advantages of stable working voltage, large capacity and safe and reliable work; the metal-air battery has the core problems of air electrode (oxygen electrode) which is required to have high porosity, uniform pore distribution, good air permeability, certain mechanical strength, good anti-permeation capability and good catalytic capability of oxygen. How to meet the requirements for manufacturing the air electrode, a large number of tests and explorations are carried out to research a manufacturing method of the heat seal vulcanization pressing air electrode, and the air electrode is manufactured by adopting a heat seal vulcanization method from the mixing preparation of waterproof materials and the proportioning preparation of catalytic materials.

In view of the above disadvantages, there is a need for a heat-sealing vulcanization pressing method for an air electrode in a metal-air battery, which realizes the quantitative production of the air electrode, and the heat-sealing vulcanization pressing method for manufacturing the air electrode has uniform and consistent distribution of air holes, high porosity and high mechanical strength, meets the application requirements of a power metal-air fuel battery, and improves the application stability and reliability of the battery assembled by the air electrode in the field of electric vehicles.

Disclosure of Invention

In view of the above disadvantages, there is a need for a heat-sealing vulcanization pressing method for an air electrode in a metal-air battery, which realizes the quantitative production of the air electrode, and the heat-sealing vulcanization pressing method for manufacturing the air electrode has uniform and consistent distribution of air holes, high porosity and high mechanical strength, meets the application requirements of a power metal-air fuel battery, and improves the application stability and reliability of the battery assembled by the air electrode in the field of electric vehicles.

The invention provides the following technical scheme:

a heat seal vulcanization pressing method for an air electrode in a metal-air battery comprises the following specific steps:

s1, preparing a waterproof material:

the air electrode waterproof material comprises, by mass, 50% -60% of 180-220-mesh acetylene black; 20 to 30 percent of polyethylene resin (suspended fine powder); 5-10% of JF-4TM polytetrafluoroethylene resin; 10-15% of a solvent;

mixing and stirring the waterproof material in a reaction kettle at the temperature of 180-250 ℃ for 80-100 minutes, cooling to room temperature, drying in a drying box at the temperature of 75 ℃ for 4 hours, crushing into 80-150 meshes by a crusher, and sieving into three stages: less than 80 meshes, 80 to 100 meshes and more than 100 meshes, and mixing according to the granularity proportion to complete the preparation of the waterproof material;

s2, preparing a heat seal vulcanization type catalytic material:

the mass ratio of the catalytic material is as follows, 65-75% of 300-mesh active carbon; 10 to 15 percent of calcium mineral catalyst; 2 to 5 percent of strontium oxide; 8 to 10 percent of JF-4TM polytetrafluoroethylene resin (suspended fine powder); 5% of TX-10 dispersant; firstly, mixing and homogenizing the catalytic materials at 240-300 ℃ for 60 minutes;

then mixing and homogenizing the catalytic material for 50-80 minutes, immersing for 24 hours, then drying for 4-8 hours at 75 ℃ in an electric oven, crushing and sieving by a 200-mesh sieve to finish the preparation of the catalytic material;

s3, film making:

spreading a copper pull net or a nickel net or foamed nickel on the waterproof material dry powder, and carrying out heat seal on a vulcanizing machine at the temperature of 180-220 ℃; uniformly bonding the waterproof material with a copper pull net or a nickel net or foam nickel into a whole, and shaping on a cooling machine under equal pressure; spraying a catalytic material on the inner side surface of the waterproof electrode after the thermal synthesis molding, wherein the temperature of a vulcanizing machine is 200 ℃, the pressure is 30MP, the film combination time is 180-220 s, and the film forming thickness is 0.15-0.2 mm, so that the film preparation is finished; the process can ensure that the catalytic material can be uniformly sprayed on the inner surface of the waterproof layer of the air electrode, the thickness of the catalytic layer of the air electrode is uniform and the density is consistent after the catalytic layer is formed, and a good three-phase interface can be formed during the operation of the battery.

S4, finishing the electrode manufacture

After the heat seal vulcanization type air electrode is pressed and formed, carrying out extraction treatment, wherein the extraction time is 20-36 hours, and drying the heat seal vulcanization type air electrode in an electric oven at 65 ℃ for 2-4 hours to finish the manufacture of the heat seal type air electrode; the heat seal vulcanization type air electrode has high mechanical strength, high porosity and uniform pore distribution; and the polyethylene material has high melting crosslinking hydrophobicity, the mechanical strength of the air electrode is increased, and the service life of the air electrode is prolonged

Preferably, the granularity of the waterproof material is uniformly mixed according to the proportion of 70%, 25% and 5%, so that the preparation of the waterproof material is completed; the preparation of the special waterproof material for the heat seal vulcanization type air electrode is carried out in a reaction kettle to prepare discrete fine particles of the waterproof material.

Preferably, the polyethylene resin is dry powder, and the polytetrafluoroethylene can also be emulsion with the solid content of 60 percent, and a coagulant and a dispersant are added. The air electrode is molded on a special flat vulcanizing machine, the waterproof material is flatly laid on the foam nickel of the mold and is crosslinked into a whole under the action of polyethylene resin and polytetrafluoroethylene fibers through high-temperature melting, the granularity of the waterproof material is different and penetrates the middle and two sides of a foam nickel current collector respectively, and the meshes of the current collector are filled with the waterproof material and are crosslinked into a whole; reducing air electrode polarization resistance

Preferably, the straight porosity of the electrode in the step S4 is 12-17%, and the curved straight porosity is 83-88%; and the polyethylene material can be melted and crosslinked in the warp direction and the weft direction, the mechanical strength of the electrode is improved, and the service life of the air electrode is prolonged.

The invention has the beneficial effects that:

the air electrode in the metal-air battery is produced by adopting a heat-seal vulcanization pressing method, and has the advantages of high porosity, good air permeability, high mechanical strength and high power density. The unit discharge density is more than or equal to 200mA/cm2 (more than 1.0V for a zinc electrode). The material selection, the material formula and the material thermalization synthesis have short process path, less production links and high quality control; the air electrode produced by the heat seal vulcanization pressing method realizes the mass production of the air electrode by extraction and drying, and can ensure the consistency of products. The selected raw materials are rich and easily available. The production process has no pollution and no emission, and meets the requirement of environmental protection.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the attached drawings

FIG. 1, schematic view of an air electrode

FIG. 2 is a schematic view of a metal-air battery

1a, a waterproof layer; 2a, a current collector; 3a, a catalyst layer; 1. a plastic housing; 2. an air electrode; 3. a diaphragm; 4. a zinc electrode; 5. an electrolyte; 6. upper cover

Detailed Description