WO2022141866A1 - 一种镁金属空气电池正极催化剂及其连续涂覆制备方法 - Google Patents

一种镁金属空气电池正极催化剂及其连续涂覆制备方法 Download PDF

Info

Publication number
WO2022141866A1
WO2022141866A1 PCT/CN2021/083990 CN2021083990W WO2022141866A1 WO 2022141866 A1 WO2022141866 A1 WO 2022141866A1 CN 2021083990 W CN2021083990 W CN 2021083990W WO 2022141866 A1 WO2022141866 A1 WO 2022141866A1
Authority
WO
WIPO (PCT)
Prior art keywords
slurry
catalyst
current collector
magnesium metal
catalytic slurry
Prior art date
Application number
PCT/CN2021/083990
Other languages
English (en)
French (fr)
Inventor
刘慧�
余琨
余鹏
宋觉敏
Original Assignee
长沙迅洋新材料科技有限公司
湖南汇动新材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 长沙迅洋新材料科技有限公司, 湖南汇动新材料有限公司 filed Critical 长沙迅洋新材料科技有限公司
Publication of WO2022141866A1 publication Critical patent/WO2022141866A1/zh

Links

Images

Classifications

    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to the technical field of development and application of new energy battery materials, in particular to a positive electrode catalyst material for a magnesium metal-air battery and a continuous coating preparation method thereof.
  • the cathode catalyst of magnesium metal-air battery is the key material to ensure its electrochemical reaction.
  • the catalyst also needs the combined action of oxygen and water participating in the electrochemical reaction to ensure the continuous discharge process of the battery. This requires the catalyst material itself to ensure the electrochemical reaction. Under the active performance, it has good air permeability and hydrophobicity.
  • the catalyst needs to be uniformly distributed on the current collector material and have an appropriate thickness, and the function and structural characteristics of the catalyst must be consistent in order to have a good catalytic effect. .
  • the catalyst for the positive electrode of the metal-air battery is mainly prepared by the single-piece rolling method, that is, after the catalyst-related materials of the positive electrode are mixed, colloid is added, kneaded to form a group, and then rolled by a counter-roller for many times, and the catalyst and the colloid are rolled together.
  • the thickness is generally thick, at least the thickness is more than 1mm, the patent CN201310745120.X mixes conductive carbon black powder, anhydrous ethanol and polytetrafluoroethylene emulsion, heats and stirs, and obtains solidified agglomerates.
  • Patent CN201811210775.6 mixes the catalyst and the polymer solution into a spinning solution, sprays the spinning solution on the surface of the fluid to obtain a catalyst layer, and then rolls to obtain the air electrode positive electrode.
  • Patent CN201711339272.4 also uses multiple sprays of catalysts, hydrophobic materials, reaction materials, etc. on the upper surface of the current collecting net to obtain metal-air electrodes.
  • this spraying method has great differences in the uniformity of catalyst distribution and the consistency of thickness and structure, resulting in unstable electrochemical performance of the catalyst.
  • the above preparation method can obtain a positive electrode catalyst with certain catalytic performance, it can generally only be prepared in a single piece, the catalyst distribution uniformity is poor, and the technical problem of poor discharge performance stability exists.
  • the present invention designs and adjusts the catalyst components according to the characteristics of the cathode catalyst of the magnesium metal-air battery, and firstly prepares the catalyst slurry to improve the uniformity, dispersibility and consistency of the catalytic active components and conductive materials in the slurry.
  • the catalyst slurry is coated on the surface of different current collector materials, and the uniformity, dispersion, composition and thickness are obtained. , Cathode catalyst for magnesium metal-air battery with highly consistent performance.
  • the present invention first provides a magnesium metal-air battery cathode catalytic slurry, the catalytic slurry is composed of 20-50% catalytic material and 50-80% solvent water composition, the raw material composition and mass percentage content of the catalytic material are: 20-70% of the conductive material, 20-75% of the active material, and 5-50% of the binder;
  • the conductive material is one or more of graphite, activated carbon, acetylene black, carbon black, carbon nanotubes and carbon fibers;
  • the active material is one or more of manganese-based oxides, silver, silver-based compounds and perovskite compounds;
  • the binder is polytetrafluoroethylene emulsion, polyvinylidene fluoride, carboxymethyl cellulose, styrene-butadiene rubber emulsion, polyacrylic acid, polyacrylonitrile, hydroxypropyl methylcellulose, polyvinyl alcohol, polyimide One or more of amines and alginates.
  • the particle size of the conductive material and the active material is 1 ⁇ m ⁇ 100 ⁇ m, and the purity is not less than 99%.
  • the viscosity of the catalytic slurry is 5000mPa ⁇ s ⁇ 20000mPa ⁇ s.
  • the present invention also provides a method for preparing a cathode catalytic slurry for a magnesium metal-air battery, which specifically includes the following steps:
  • the stirring process in the S2 is specifically as follows: the stirring speed is 200-3000 rpm, and the stirring time is 30-300 min.
  • stirring and vacuuming in described S3 are specifically:
  • the slurry is placed in a planetary mixer and stirred and vacuumed, the rotation speed is 20-80 rpm, the revolution speed is 200-1500 rpm/min, the vacuum degree is -0.08--0.1MPa, and the stirring time is 60 ⁇ 180min.
  • the present invention also provides a cathode catalyst for a magnesium metal-air battery
  • the cathode catalyst includes the above-mentioned catalytic slurry and a current collector material; the catalytic slurry is coated to the surface by a semi-continuous or continuous coating method. On the surface of the current collector material in rolls, the coating thickness is 0.1-3 mm;
  • the current collector material is any one of copper meshes with different porosity, tin-plated copper meshes, nickel-plated copper meshes, porous nickel meshes, nickel-plated punched steel strips or carbon fiber porous fabrics.
  • the thickness of the current collector material is controlled at 0.05mm ⁇ 1mm.
  • the present invention also provides a preparation method for continuous coating of a cathode catalyst of a magnesium metal-air battery, which specifically includes the following steps:
  • the catalytic slurry obtained above is applied to the surface of the current collector material in a roll by a semi-continuous or continuous coating method, and the coating thickness is 0.1-3 mm, and the catalytic slurry is treated with the current collector material. After bonding, dry at 50°C ⁇ 200°C for 10min ⁇ 300min;
  • the deformation amount of rolling in the step S3 is controlled between 10% and 50%.
  • the method of pulping ensures that the conductive material and the active material can be mixed evenly.
  • the conductive material and the catalytically active material in the slurry are matched in a certain proportion, which can effectively ensure the stability of the discharge performance of the slurry.
  • Adding a certain amount of The binder is used to adjust the viscosity of the slurry so that the slurry can adhere to the current collector material during subsequent coating.
  • the slurry can have good dispersion consistency and appropriate viscosity.
  • the catalytic activity and conductivity of the overall slurry can be effectively regulated by the addition ratio of the conductive material and the catalytically active material, and the formability, uniform dispersion and storage stability of the slurry can be ensured.
  • the continuous coating method is used to make the catalyst coating on the surface of the current collector, which not only ensures the uniformity of catalyst coverage and the consistency of thickness, but also increases the contact area between the catalyst layer and the current collector, and improves the catalyst performance.
  • Catalytic effect slowing down the occurrence of air battery polarization.
  • the continuous coating process by controlling the thickness of the coating layer, the length of the battery's subsequent discharge can be regulated. By controlling the drying temperature, thermal curing temperature and time of the slurry and other process parameters, the coating effect can be regulated and the coating efficiency can be improved.
  • the method of continuous rolling with a pair of rollers can effectively control the compactness of the catalyst, improve the adhesion tightness between it and the current collector, effectively improve the catalytic effect of the catalyst, and prolong the service life of the catalyst.
  • Fig. 1 is the structural representation of continuous coating catalyst
  • Fig. 2 is the microstructure under the electron microscope of the catalyst continuously coated on the surface of the current collector obtained in Example 1;
  • Fig. 3 is the microstructure and composition analysis under the electron microscope of the catalyst continuously coated on the surface of the current collector obtained in Example 2;
  • Example 4 is the microstructure and composition analysis of the catalyst continuously coated on the surface of the current collector obtained in Example 3 under an electron microscope;
  • Example 5 is the microstructure and composition analysis of the catalyst continuously coated on the surface of the current collector obtained in Example 4 under an electron microscope;
  • Fig. 6 is the polarization curve of the electrode performance when the catalyst obtained in the embodiment of the present invention is applied to the discharge of the magnesium metal air electrode;
  • Fig. 7 is the microstructure under the electron microscope of the catalyst continuously coated on the surface of the current collector obtained in Comparative Example 1;
  • Fig. 8 is the microstructure under the electron microscope of the catalyst continuously coated on the surface of the current collector obtained in Comparative Example 2;
  • the conductive materials in the selected catalyst are: dense spherical graphite with a powder particle size of 1 ⁇ m, porous activated carbon with a particle size of 100 ⁇ m, the purity is 99%, and the active material is: powdered manganese-based oxide (MnO2), particle size 1 ⁇ m, the purity is 99%, the binder is: polytetrafluoroethylene emulsion (PTFE), and the solvent is distilled water; the conductive material powder, active material powder, and binder are weighed in proportion, and the ratio is: conductive material spherical Graphite 35%, porous activated carbon 35%, active material MnO 2 20%, binder PTFE 10%, the above materials are mixed uniformly in a three-dimensional mixer, and the mixing time is 30 minutes to obtain a mixed material.
  • Figure 1 shows a schematic diagram of the structure of the cathode catalyst for the magnesium metal-air battery obtained in this example.
  • 1 is the current collector material
  • 2 is the catalytic slurry.
  • the conductive material in the catalyst dense flake graphite with a powder particle size of 100 ⁇ m, carbon black with a particle size of 1 ⁇ m, and a purity of more than 99%
  • the active material is: powdered manganese-based oxide (MnO2) particle size of 100 ⁇ m , the purity is 99%
  • the binder is: polyvinylidene fluoride (PVDF), and the solvent is distilled water
  • the conductive material powder, active material powder, and binder are weighed in proportion, and the ratio is: conductive material flake graphite 10 %, carbon black 10%, active material (MnO 2 ) 75%, binder 5%, the above materials were mixed uniformly in a three-dimensional mixer, and the mixing time was 120min to obtain a mixed material
  • S1 Select the conductive materials in the catalyst as follows: dense spherical graphite with a powder particle size of 10 ⁇ m, acetylene black with a particle size of 10 ⁇ m, activated carbon with a particle size of 80 ⁇ m, and a purity of 99.5%.
  • the active material is: perovskite compound, 20 ⁇ m, purity At 99%, the binders are: polytetrafluoroethylene emulsion (PTFE) and carboxymethyl cellulose (CMC), and the solvent is distilled water; The ratio is: spherical graphite 10%, acetylene black 10%, activated carbon 10%; perovskite compound 20%, binder 50%, the above materials are mixed uniformly in a three-dimensional mixer, and the mixing time is 60min to obtain a mixed material
  • S4 Select the coiled current collector as a nickel-plated copper mesh with a thickness of 0.5 mm, and pass the above catalytic slurry through a semi-continuous or continuous coating machine to coat the surface of the coiled current collector.
  • the thickness of the slurry coating is determined by The coating gap was controlled at 1 mm, and after the slurry was coated on the surface of the current collector and bonded, it was dried at 100 °C for 150 min.
  • S1 Select the conductive materials in the catalyst as follows: dense spherical graphite with a powder particle size of 30 ⁇ m, carbon nanotubes with a length of 5 ⁇ m, activated carbon with a particle size of 50 ⁇ m, and a purity of 99.5%.
  • the active material is: silver-based compound AgCl with a particle size of 50 ⁇ m, The purity is 99.9%, the binders are: carboxymethyl cellulose (CMC), styrene-butadiene rubber emulsion (SBR), polyacrylic acid (PAA), and the solvent is deionized water; the conductive material powder, active material powder, adhesive 20% of spherical graphite, 10% of carbon nanotubes, 5% of activated carbon; 35% of active material AgCl, 10% of binder CMC, 10% of SBR, 10% of PAA, mix the above materials in three-dimensional mixture Mix evenly in the machine, and the mixing time is 90 min to obtain the mixed material.
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber emulsion
  • PAA polyacrylic acid
  • the dried composite material is cured by vacuum heat treatment, the heating temperature is 300 °C, and the heating time is 90 minutes, and the vacuum heat treated and cured current collector material is rolled between smooth rollers. At 30%, it is used to improve the bonding tightness between the catalyst and the current collector, and achieve the thickness required for the catalyst material. After the rolling is completed, the positive electrode catalyst of the magnesium metal-air battery is obtained.
  • the ratio of this comparative example is: the binder content is higher than 50%, when the binder is 60%, the conductive material is 20%, and the catalyst is 20%, the selection of raw materials and the preparation method are the same as in Example 4.
  • the binder content is too low, when the binder is 4%, the conductive material is 60%, and the catalyst is 36%, the average particle size of the conductive material and the catalytically active material in the raw material is 150 ⁇ m, which is larger than the selection range of the raw material.
  • Preparation method and example 4 is the same.
  • This comparative example adopts the method of spraying the slurry, using high-pressure air flow to bring the slurry into the conveying pipe, spraying the slurry directly on the surface of the collector through the nozzle, and then drying the coating process.
  • the selection of raw materials, The ratio is the same as in Example 4.
  • the performance tests of the catalyst materials obtained in Examples 1-4 and Comparative Examples specifically include the microstructure of the catalyst materials under an electron microscope, as shown in Figures 2-5 and 7-9 for details, and then the obtained catalyst materials are used for A magnesium metal air electrode was prepared, and the polarization curve of the electrode when the catalyst was discharged was measured, as shown in Fig. 6, wherein the materials obtained in Examples 1-4 correspond to curves a-d respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)

Abstract

本发明涉及新能源电池材料的开发及应用技术领域，具体涉及一种镁金属空气电池正极催化剂及其连续涂覆制备方法。正极催化剂包括催化浆料和集流体材料,所述催化浆料由质量百分含量配比为20～50％的催化材料和50～80％的溶剂水组成，所述催化材料原料组成及质量百分含量为：导电材料20～70％，活性物质20～75％，粘结剂5～50％；本发明通过搅拌制浆获得特定粘度的催化浆料，再通过连续涂覆的方法涂覆至集流体材料，经干燥、热处理固化、辊压获得的正极催化剂的催化活性和导电性明显提高，保证了浆料的成形性和均匀分散性，且该制备工艺简单，提高了生产效率，适合规模化连续生产。

Description

一种镁金属空气电池正极催化剂及其连续涂覆制备方法 技术领域
本发明涉及新能源电池材料的开发及应用技术领域，具体涉及一种镁金属空气电池正极催化剂材料及其连续涂覆制备方法。
背景技术
镁金属空气电池的正极催化剂是保证其发生电化学反应的关键材料，催化剂同时需要参与电化学反应的氧气和水共同作用，才能保证电池放电过程的持续进行，这需要催化剂材料本身在保证电化学活性的性能下，具备良好的透气性和疏水性，同时也需要催化剂在集流体材料上分布均匀性并具有适当的厚度，对催化剂的功能和结构特性要有一致性，才能具备良好的催化效果。
目前，金属空气电池正极的催化剂主要采用单片式碾压法制备，即正极的催化剂相关材料混合后，加入胶体，混捏成团，然后通过对辊机多次碾压，将催化剂和胶体一起碾成片状，一般厚度较厚，至少厚度都在1mm以上，专利CN201310745120.X将导电碳黑粉末、无水乙醇及聚四氟乙烯乳液混合加热搅拌，获得凝固的团聚物，经对辊机反复碾压成片状催化剂，再将催化剂与不锈钢网在辊压机上反复辊压获得最终的催化剂正极材料。但这种碾压成型工艺制备的催化剂往往与网状集流体接触效果不佳，造成催化剂电化学反应时电池内阻增大。专利CN201810646499.1将催化剂、导电碳材料、聚四氟乙烯粉末混合后，加入酒精，再通过振动平铺设备使其进入对辊机，碾压成片状催化剂，然后再与网状集流体复合辊压，这种方法可以提高催化剂的分布均匀性和厚度均匀性，但该方法属于单片法制备技术，无法连续化生产。专 利CN201811210775.6将催化剂与高分子溶液配成纺丝液，将该纺丝液喷涂在就流体表面得到催化剂层，然后辊压得到所述空气电极正极。专利CN201711339272.4也在集流网的上表面采用多次喷涂催化剂、疏水材料、反应材料等来获得金属空气电极。但这种喷涂的方式，在催化剂分布均匀性、厚度结构一致性上差别很大，造成催化剂电化学性能的不稳定。
上述制备方法虽然能够获得正极催化剂，具有一定的催化性能，但是一般只能单片制备，催化剂分布均匀性较差，存在放电性能稳定性差的技术问题。
发明内容
针对现有技术存在的上述问题，本发明根据镁金属空气电池正极催化剂的特性，进行催化剂成分设计和调整，先制备催化剂浆料提高浆料中催化活性成分与导电材料的均匀性、分散性和接合度，再结合与常规金属空气电池正极材料单片式制备方法不同的连续涂覆制备工艺，将催化剂浆料涂覆在不同的集流体材料表面，获得了均匀性、分散性以及成分、厚度、性能一致性高度契合的镁金属空气电池正极催化剂。
为实现上述发明目的，本发明首先提供了一种镁金属空气电池正极催化浆料，所述催化浆料由质量百分含量配比为20～50％的催化材料和50～80％的溶剂水组成，所述催化材料原料组成及质量百分含量为：导电材料20～70％，活性物质20～75％，粘结剂5～50％；
所述导电材料为石墨、活性炭、乙炔黑、炭黑、碳纳米管和碳纤维中的一种或几种；
所述活性物质为锰基氧化物、银及银基化合物和钙钛矿化合物中的一种或几种；
所述粘结剂为聚四氟乙烯乳液、聚偏氟乙烯、羧甲基纤维素、丁苯橡胶 乳液、聚丙烯酸、聚丙烯腈、羟丙基甲基纤维素、聚乙烯醇、聚酰亚胺和海藻酸盐中的一种或几种。
进一步地，所述导电材料和活性物质的粒径为1μm～100μm，纯度不低于99％。
进一步地，所述催化浆料粘度为5000mPa·s～20000mPa·s。
基于同一个发明构思，本发明还提供了一种镁金属空气电池正极催化浆料的制备方法，具体包括如下步骤：
S1:将导电材料、活性物质和粘结剂在三维混料机中混合30～120min，获得混合物料；
S2:向所述混合物料加入溶剂水，搅拌均匀至浆料粘度为5000mPa·s～20000mPa·s；
S3:将所述浆料进行搅拌并抽真空处理获得镁金属空气电池正极催化浆料。
进一步地，所述S2中搅拌的过程具体为：搅拌速度为200～3000转/min，搅拌时间为30～300min。
进一步地，所述S3中搅拌并抽真空处理具体为：
将所述浆料置于行星式搅拌机中搅拌并抽真空，自转速度速为20～80转/min，公转速度为200～1500转/min，抽至真空度-0.08～-0.1MPa，搅拌时间60～180min。
基于同一个发明构思，本发明还提供了一种镁金属空气电池正极催化剂，所述正极催化剂包括上述催化浆料和集流体材料；所述催化浆料通过半连续或连续涂覆方法涂覆至成卷的所述集流体材料表面，涂覆厚度为0.1～3mm；
所述集流体材料为不同孔隙率的铜网、镀锡铜网、镀镍铜网、多孔镍网、镀镍冲孔钢带或碳纤维多孔织物中的任意一种。
进一步地，所述集流体材料厚度控制在0.05mm～1mm。
基于同一个发明构思，本发明还提供了一种镁金属空气电池正极催化剂连续涂覆制备方法，具体包括如下步骤：
S1:将上述获得的所述催化浆料通过半连续或连续涂覆方法涂覆至成卷的所述集流体材料表面，涂覆厚度为0.1-3mm，待所述催化浆料与集流体材料粘结后进在50℃～200℃下干燥10min～300min；
S2:将干燥后的涂覆好催化浆料的集流体材料进行真空热处理固化，所述真空热处理固化中加热温度为120～400℃，加热固化时间为10～120min；
S3:将真空热处理固化后的集流体材料放在光滑的对辊之间连续碾压，碾压完成后获得镁金属空气电池正极催化剂。
进一步地，所述步骤S3中碾压的变形量控制在10％～50％之间。
有益效果：
(1)采用制浆的方式，保证了导电材料和活性物质能够混合均匀，浆料中导电材料与催化活性物质之间按一定比例搭配，可以有效保证浆料放电性能的稳定，添加一定量的粘结剂是为了调整浆料的粘度，以便后续涂覆时浆料可以粘附在集流体材料上。通过浆料中各组元的粒径调整和控制浆料搅拌速率等，可以使浆料具有良好的分散一致性和适当的粘度。从而可以根据实际使用效果，通过导电材料和催化活性材料加入量配比不同，有效调控整体浆料的催化活性和导电性，保证了浆料的成形性、均匀分散性和存放稳定性。
(2)由于采用连续涂覆方式在集流体表面制成催化剂涂层，既保证了催化剂覆盖的均匀性、厚度的一致性，又增大了催化层与集流体的接触面积，提高了催化剂的催化效果，减缓空气电池极化的发生。连续涂覆过程中，通过对涂覆层厚度控制，可以调控电池在后续放电的时间长短。而通过对浆料的干燥温度、热固化温度及时间的等工艺参数的控制，可以调控涂覆的效果，提高涂覆的效率。
(3)采用对辊机连续碾压方式，有效调控催化剂的密实程度，提高其与集流体的粘合紧密度，有效提高催化剂的催化效果，延长催化剂的使用寿命。
(4)连续涂覆将催化剂粘合在集流体表面，简化了金属空气电池正极的电极材料制备工艺，保证了催化剂在集流体表面性质的均匀性和一致性，并且大幅度地提高了生产效率，降低了生产成本，适合规模化连续生产。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为连续涂覆催化剂的结构示意图；
图2为实施例1获得的连续涂覆在集流体表面的催化剂的电子显微镜下的微观组织；
图3为实施例2获得的连续涂覆在集流体表面的催化剂的电子显微镜下的微观组织和成分分析；
图4为实施例3获得的连续涂覆在集流体表面的催化剂的电子显微镜下的微观组织和成分分析；
图5为实施例4获得的连续涂覆在集流体表面的催化剂的电子显微镜下的微观组织和成分分析；
图6为本发明实施例获得的催化剂应用至镁金属空气电极放电时电极性能的极化曲线；
图7为对比例1获得的连续涂覆在集流体表面的催化剂的电子显微镜下的微观组织；
图8为对比例2获得的连续涂覆在集流体表面的催化剂的电子显微镜下 的微观组织；
图9为对比例3获得的涂覆在集流体表面的催化剂的电子显微镜下的微观组织。
【附图标记说明】
1、集流体材料；2、催化浆料。
具体实施方式
为了更加清楚阐述本发明的技术内容，在此结合具体实施例予以详细说明，显然，所列举的实施例只是本技术方案的优选实施方案，本领域的技术人员可以根据所公开的技术内容显而易见地得出的其他技术方案仍属于本发明的保护范围。
实施例1
S1:选择催化剂中的导电材料为：粉末粒径为1μm的致密球状石墨、粒径为100μm的多孔型活性炭，纯度在99％，活性物质为：粉末状锰基氧化物(MnO2)，粒径1μm，纯度在99％，粘结剂为：聚四氟乙烯乳液(PTFE)，溶剂为蒸馏水；将导电材料粉末、活性物质粉末、粘结剂，按比例称量，配比为：导电材料球状石墨35％、多孔活性炭35％，活性物质MnO 220％、粘结剂PTFE10％，将上述材料在三维混料机中混合均匀，混料时间为30min获得混合物料。
S2:向所述混合物料按比例加入溶剂水，水的添加量占催化浆料的50％，添加水后，在分散搅拌器中搅拌成均匀的浆料，搅拌速度在200转/min，搅拌时间在30min，搅拌控制浆料的粘度在5000mPa·s。
S3：将上述浆料放入行星式搅拌机中搅拌并抽真空。自转速度速为20转/min，公转速度为200转/min，抽至真空度-0.08MPa，搅拌时间60min，获得催化浆料。
S4：选择成卷的集流体材料为1mm厚度多孔镍网，将上述催化浆料通过半连续或连续式涂覆机，在成卷的集流体表面进行涂覆，浆料涂层的厚度由涂覆间隙控制在0.1mm，待浆料涂覆在集流体表面粘合后，在50℃下干燥10min。
S5:将干燥处理后的复合材料进行真空热处理固化，加热温度在120℃，加热时间10min，将真空热处理固化后的集流体材料放在光滑的对辊之间进行碾压，碾压的变形量在10％，用来提高催化剂与集流体的粘合紧密度，并达到催化剂材料需要使用的厚度，碾压完成后，得到镁金属空气电池正极催化剂。
本实施例获得镁金属空气电池正极催化剂的结构示意图如图1所示。1为集流体材料，2为催化浆料。
实施例2
S1:选择催化剂中的导电材料为：粉末粒径为100μm致密片状石墨、粒径为1μm的炭黑，纯度在99％以上，活性物质为：粉末状锰基氧化物(MnO2)粒径100μm，纯度99％，粘结剂为：聚偏氟乙烯(PVDF)，溶剂为蒸馏水；将导电材料粉末、活性物质粉末、粘结剂，按比例称量，配比为：导电材料片状石墨10％、炭黑10％，活性物质(MnO 2)75％、粘结剂5％，将上述材料在三维混料机中混合均匀，混料时间为120min获得混合物料
S2:向所述混合物料中按比例加入溶剂水，水的添加量占催化浆料的80％，添加水后，在分散搅拌器中搅拌成均匀的浆料，搅拌速度在3000转/min，搅拌时间在300min，搅拌控制浆料的粘度在20000mPa·s。
S3：将上述浆料放入行星式搅拌机中搅拌并抽真空，自转速度速为80转/min，公转速度为1500转/min，抽至真空度-0.1MPa，搅拌时间180min，获得催化浆料。
S4：选择成卷的集流体为0.05mm碳纤维多孔织物，将上述催化浆料通过 半连续或连续式涂覆机，在成卷的集流体表面进行涂覆，浆料涂层的厚度由涂覆间隙控制在3mm，浆料涂覆在集流体表面粘合后，在200℃下干燥300min。
S5：将干燥后的复合材料进行真空热处理固化，加热温度在400℃，加热时间120min，将真空热处理固化后的集流体材料放在光滑的对辊之间进行碾压，碾压的变形量在50％，用来提高催化剂与集流体的粘合紧密度，并达到催化剂材料需要使用的厚度，碾压完成后，得到镁金属空气电池正极催化剂。
实施例3
S1:选择催化剂中的导电材料为：粉末粒径为10μm致密球状石墨、粒径为10μm的乙炔黑，粒径为80μm的活性炭，纯度99.5％，活性物质为：钙钛矿化合物，20μm，纯度在99％，粘结剂为：聚四氟乙烯乳液(PTFE)和羧甲基纤维素(CMC)，溶剂为蒸馏水；将导电材料粉末、活性物质粉末、粘结剂，按比例称量，配比为：球状石墨10％、乙炔黑10％、活性炭10％；钙钛矿化合物20％、粘结剂50％，将上述材料在三维混料机中混合均匀，混料时间为60min获得混合物料
S2：向所述混合物料中按比例加入溶剂水，水的添加量占催化浆料的60％，添加水后，在分散搅拌器中搅拌成均匀的浆料，搅拌速度在1000转/min，搅拌时间在200min，搅拌控制浆料的粘度在10000mPa·s。
S3：将上述浆料放入行星式搅拌机中搅拌并抽真空。自转速度速为40转/min，公转速度为1000转/min，抽至真空度-0.09MPa，搅拌时间120min，获得催化浆料。
S4：选择成卷的集流体为厚度0.5mm镀镍铜网，将上述催化浆料通过半连续或连续式涂覆机，在成卷的集流体表面进行涂覆，浆料涂层的厚度由涂覆间隙控制在1mm，浆料涂覆在集流体表面粘合后，在100℃下干燥150min。
S5：将干燥后的复合材料进行真空热处理固化，加热温度在260℃，加热 时间在60min，并将真空热处理固化后的集流体材料放在光滑的对辊之间进行碾压，碾压的变形量在25％，用来提高催化剂与集流体的粘合紧密度，并达到催化剂材料需要使用的厚度，碾压完成后，得到镁金属空气电池正极催化剂。
实施例4
S1:选择催化剂中的导电材料为：粉末粒径为30μm致密球状石墨、长度5μm的碳纳米管，粒径为50μm的活性炭，纯度99.5％，活性物质为：粒径为50μm银基化合物AgCl，纯度在99.9％，粘结剂为：羧甲基纤维素(CMC)、丁苯橡胶乳液(SBR)、聚丙烯酸(PAA)，溶剂为去离子水；将导电材料粉末、活性物质粉末、粘结剂，按比例称量，配比为：球状石墨20％、碳纳米管10％，活性炭5％；活性物质AgCl35％、粘结剂CMC10％、SBR10％、PAA10％，将上述材料在三维混料机中混合均匀，混料时间为90min获得混合物料。
S2：向所述混合物料中按比例加入溶剂水，水的添加量占催化浆料的70％，添加水后，在分散搅拌器中搅拌成均匀的浆料，搅拌速度在2000转/min，搅拌时间在150min，搅拌控制浆料的粘度在15000mPa·s。
S3：将上述浆料放入行星式搅拌机中搅拌并抽真空，自转速度速为50转/min，公转速度为800转/min，抽至真空度-0.08MPa，搅拌时间90min，获得催化浆料。
S4：选择成卷的集流体为0.05mm碳纤维多孔织物，将上述活性层材料通过半连续或连续式涂覆机，在成卷的集流体材料表面进行涂覆，浆料涂层的厚度由涂覆间隙控制在2mm，浆料涂覆在集流体表面粘合后，在150℃下干燥90min。
S5：将干燥后的复合材料进行真空热处理固化，加热温度在300℃，加热时间在90min，并真空热处理固化后的集流体材料放在光滑的对辊之间进行碾压，碾压的变形量在30％，用来提高催化剂与集流体的粘合紧密度，并达 到催化剂材料需要使用的厚度，碾压完成后，得到镁金属空气电池正极催化剂。
对比例1
本对比例的配比为：粘接剂含量较高，超过50％，当粘结剂为60％，导电材料20％，催化剂20％时，原料的选择与制备方法与实施例4相同。
对比例2
粘接剂含量过低，当粘结剂为4％，导电材料60％，催化剂36％时，原料中导电材料和催化活性物质平均粒径在150μm，大于原料选择范围时，制备方法与实施例4相同。
对比例3
本对比例采用将浆料采用喷淋到方式，利用高压气流将浆料带入到输送管中，通过喷嘴将浆料直接喷射到集流体表面，然后干燥得到的涂覆工艺，原料的选择、配比与实施例4相同。
性能检测
将实施例1-4和对比例获得的催化剂材料的性能测试，具体包括采用电子显微镜下催化剂材料的微观组织结构，具体详见图2-5和7-9，再利用所得的催化剂材料用于制备获得镁金属空气电极，并测定该催化剂放电时的电极的极化曲线，详见图6，其中实施例1-4获得的材料分别对应曲线a-d。
结果分析：通过实施例1～4的显微结构分析可见，涂覆在集流体上的浆料固化后致密平整，没有裂纹、孔洞、疏松等缺陷，因此说明涂覆效果好，涂覆工艺到位，可以满足正极催化剂放电性能的稳定，同时满足涂覆的催化剂结构完整，性能均匀，且导电性能良好。而在对比例中，当催化浆料配比超出配料范围时，浆料在涂覆在集流体上的工艺参数超差时，会发生剥落、开裂、粘附性差等问题；当浆料中添加到导电材料和催化材料的粒径范围不在本发明范围内，会产生粗大的颗粒，造成涂覆层破坏，完全不能进行后续 放电；对比例中产生的典型缺陷见图7，8，9。如图7是导电材料和催化材料含量过低，粘结剂含量过高，会在涂覆的催化层表面形成胶层，阻碍导电材料和催化材料与水接触发生反应，无法导电；图8是导电材料和催化剂含量过高，粘结剂含量过低，造成涂覆层破坏；图9是未采用本发明的涂覆工艺超，造成涂覆层孔洞、疏松、开裂等缺陷，无法使用；因此本发明中催化剂的成分配比、原料的具体参数以及制备工艺参数共同影响本发明镁金属空气电池正极催化材料的性能。
以上所述实施例，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明的技术范围内，根据本发明的技术方案及其构思加以等同替换或改变，都应涵盖在本发明的保护范围内。

Claims (10)

  1. 一种镁金属空气电池正极催化浆料，其特征在于，所述催化浆料由质量百分含量配比为20～50％的催化材料和50～80％的溶剂水组成，所述催化材料原料组成及质量百分含量为：导电材料20～70％，活性物质20～75％，粘结剂5～50％；
    所述导电材料为石墨、活性炭、乙炔黑、炭黑、碳纳米管和碳纤维中的一种或几种；
    所述活性物质为锰基氧化物、银及银基化合物和钙钛矿化合物中的一种或几种；
    所述粘结剂为聚四氟乙烯乳液、聚偏氟乙烯、羧甲基纤维素、丁苯橡胶乳液、聚丙烯酸、聚丙烯腈、羟丙基甲基纤维素、聚乙烯醇、聚酰亚胺和海藻酸盐中的一种或几种。
  2. 根据权利要求1所述的镁金属空气电池正极催化浆料，其特征在于，所述导电材料和活性物质的粒径为1μm～100μm，纯度不低于99％。
  3. 根据权利要求1所述的镁金属空气电池正极催化浆料，其特征在于，所述催化浆料粘度为5000mPa·s～20000mPa·s。
  4. 一种镁金属空气电池正极催化浆料的制备方法，其特征在于，包括如下步骤：
    S1:将导电材料、活性物质和粘结剂在三维混料机中混合30～120min，获得混合物料；
    S2:向所述混合物料加入溶剂水，搅拌均匀至浆料粘度为5000mPa·s～20000mPa·s；
    S3:将所述浆料进行搅拌并抽真空处理获得镁金属空气电池正极催化浆料。
  5. 根据权利要求4所述的镁金属空气电池正极催化浆料的制备方法，其特征在于，所述S2中搅拌过程具体为：搅拌速度为200～3000转/min，搅拌 时间为30～300min。
  6. 根据权利要求4所述的镁金属空气电池正极催化浆料的制备方法，其特征在于，所述S3中搅拌并抽真空处理具体为：
    将所述浆料置于行星式搅拌机中搅拌并抽真空，自转速度速为20～80转/min，公转速度为200～1500转/min，抽至真空度-0.08～-0.1MPa，搅拌时间60～180min。
  7. 一种镁金属空气电池正极催化剂，其特征在于，所述正极催化剂包催化浆料和集流体材料；所述催化浆料为权利要求1-3任一项所述的催化浆料或权利要求4-6任一项所述制备方法制备得到的催化浆料；所述催化浆料通过半连续或连续涂覆方法涂覆至成卷的所述集流体材料表面，涂覆厚度为0.1-3mm；
    其中，所述集流体材料为不同孔隙率的铜网、镀锡铜网、镀镍铜网、多孔镍网、镀镍冲孔钢带和碳纤维多孔织物中的任意一种。
  8. 根据权利要求7所述的镁金属空气电池正极催化剂，所述集流体材料厚度控制在0.05mm～1mm之间。
  9. 一种镁金属空气电池正极催化剂连续涂覆制备方法，其特征在于，包括如下步骤：
    S1:将权利要求1-2任一项所述的催化浆料或权利要求3-5任一项所述制备方法制备得到的催化浆料通过半连续或连续涂覆方法涂覆至成卷的所述集流体材料表面，涂覆厚度为0.1～3mm，待所述催化浆料与集流体材料粘结后在50℃～200℃下干燥10min～300min；
    S2:将干燥后的涂覆好催化浆料的集流体材料进行真空热处理固化，所述真空热处理固化中加热温度为120～400℃，加热固化时间为10～120min；
    S3:将真空热处理固化后的集流体材料放在光滑的对辊之间连续碾压，碾压完成后获得镁金属空气电池正极催化剂。
  10. 根据权利要求9所述的镁金属空气电池正极催化剂连续涂覆制备方法，其特征在于，所述步骤S3中碾压的变形量控制在10％～50％。
PCT/CN2021/083990 2020-12-29 2021-03-30 一种镁金属空气电池正极催化剂及其连续涂覆制备方法 WO2022141866A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011591671.1 2020-12-29
CN202011591671.1A CN112687887A (zh) 2020-12-29 2020-12-29 一种镁金属空气电池正极催化剂及其连续涂覆制备方法

Publications (1)

Publication Number Publication Date
WO2022141866A1 true WO2022141866A1 (zh) 2022-07-07

Family

ID=75453804

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/083990 WO2022141866A1 (zh) 2020-12-29 2021-03-30 一种镁金属空气电池正极催化剂及其连续涂覆制备方法

Country Status (2)

Country Link
CN (1) CN112687887A (zh)
WO (1) WO2022141866A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115125558A (zh) * 2022-08-11 2022-09-30 氢辉能源(深圳)有限公司 一种金属基导电多孔传输层的制备方法及其在电解水电池中的应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050271932A1 (en) * 2004-06-02 2005-12-08 Nan Ya Plastics Corporation Air cathode having multiple layered sintering structure and its process for producing the same
CN103280566A (zh) * 2013-05-31 2013-09-04 广东凯德能源科技有限公司 一种锂离子电池正负极浆料的制备方法
CN108475788A (zh) * 2016-03-04 2018-08-31 昭和电工株式会社 非水系电池电极用粘合剂用共聚物、非水系电池电极用浆料、非水系电池电极及非水系电池
CN108878901A (zh) * 2018-06-21 2018-11-23 北京创能惠通新能源科技有限公司 空气电极制备方法及铝空气电池
CN109524697A (zh) * 2018-11-05 2019-03-26 东莞市中航华讯卫星技术有限公司 金属空气电池膜电极的制备方法及金属空气电池膜电极
CN111564636A (zh) * 2020-05-19 2020-08-21 苏州柔能纳米科技有限公司 一种柔性空气电池

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100373672C (zh) * 2003-11-06 2008-03-05 北京双威富能科技有限公司 用于金属空气电池的锰催化空气阴极的制作工艺
CN102074709B (zh) * 2010-12-17 2013-10-16 武汉泓元伟力新能源科技有限公司 空气电极及制造方法和具有该空气电极的金属空气电池
JP5755624B2 (ja) * 2012-10-15 2015-07-29 トヨタ自動車株式会社 空気電池用空気極及び空気電池
CN105932228A (zh) * 2014-01-28 2016-09-07 泉州劲鑫电子有限公司 一种高容量锂离子电池正极片的制备方法
CN104505520B (zh) * 2014-12-06 2017-07-04 云南冶金集团创能金属燃料电池股份有限公司 铝‑空气电池用空气电极及其制备方法
CN105810951B (zh) * 2014-12-30 2018-10-26 北京有色金属研究总院 一种锂空气电池用空气正极及其制备方法
CN105161734B (zh) * 2015-08-05 2018-01-05 中国科学院宁波材料技术与工程研究所 一种催化剂浆料及空气阴极的制备方法
CN105846015B (zh) * 2016-05-23 2018-11-13 徐嘉陵 一种金属空气电池用正极材料及其正极制备方法
CN107069046A (zh) * 2017-04-27 2017-08-18 中国科学院宁波材料技术与工程研究所 一种金属空气电池阴极及其制备方法、金属空气电池
CN108258256B (zh) * 2018-01-09 2020-08-07 广州鹏辉能源科技股份有限公司 锌空气电池正极及其正极粉干法制备工艺和锌空气电池
CN108539205B (zh) * 2018-03-15 2023-07-14 上海交通大学 铝空气电池用催化剂、空气电极及其制备方法
CN110676467B (zh) * 2018-07-03 2022-07-05 中国科学院上海高等研究院 空气电极生产设备
CN109560249A (zh) * 2018-11-30 2019-04-02 中国科学院过程工程研究所 一种双层结构正极极片、及其制备方法和用途
CN111276702A (zh) * 2019-12-23 2020-06-12 超威电源集团有限公司 金属空气电池阴极用泡沫电极的制备方法、金属空气电池阴极及金属空气电池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050271932A1 (en) * 2004-06-02 2005-12-08 Nan Ya Plastics Corporation Air cathode having multiple layered sintering structure and its process for producing the same
CN103280566A (zh) * 2013-05-31 2013-09-04 广东凯德能源科技有限公司 一种锂离子电池正负极浆料的制备方法
CN108475788A (zh) * 2016-03-04 2018-08-31 昭和电工株式会社 非水系电池电极用粘合剂用共聚物、非水系电池电极用浆料、非水系电池电极及非水系电池
CN108878901A (zh) * 2018-06-21 2018-11-23 北京创能惠通新能源科技有限公司 空气电极制备方法及铝空气电池
CN109524697A (zh) * 2018-11-05 2019-03-26 东莞市中航华讯卫星技术有限公司 金属空气电池膜电极的制备方法及金属空气电池膜电极
CN111564636A (zh) * 2020-05-19 2020-08-21 苏州柔能纳米科技有限公司 一种柔性空气电池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115125558A (zh) * 2022-08-11 2022-09-30 氢辉能源(深圳)有限公司 一种金属基导电多孔传输层的制备方法及其在电解水电池中的应用
CN115125558B (zh) * 2022-08-11 2023-11-21 氢辉能源(深圳)有限公司 一种金属基导电多孔传输层的制备方法及其在电解水电池中的应用

Also Published As

Publication number Publication date
CN112687887A (zh) 2021-04-20

Similar Documents

Publication Publication Date Title
EP2343757B1 (en) Electrode for lead storage battery and lead storage battery
CN103943378B (zh) 一种超级电容器用电极的制造方法
WO2013031060A1 (ja) 触媒インクの製造方法、および、燃料電池の製造方法、燃料電池
WO2009148114A1 (ja) 炭素触媒、炭素触媒の製造方法、膜電極接合体、及び、燃料電池
CN101355166A (zh) 质子交换膜燃料电池膜电极的制备方法
CN113871561B (zh) 干法电极极片的制备方法及电极极片和电芯
CN113422006B (zh) 正极极片及其制备方法、锂离子电池
CN107403933A (zh) 一种锂离子电池电极极片及其制作方法和应用
KR20060039428A (ko) 가스 확산 전극의 생산 방법
WO2022141866A1 (zh) 一种镁金属空气电池正极催化剂及其连续涂覆制备方法
JPH08236123A (ja) 燃料電池用電極及びその製造方法
CN116387509A (zh) 一种锂金属电池用复合正极及其制备方法
CN101794671B (zh) 一种超级电容器及其制造方法
CN117747778A (zh) 一种正极活性材料及其制备方法和应用
CN112687888A (zh) 一种镁金属空气电池正极材料及其连续涂覆制备方法
JP2019121423A (ja) 燃料電池用ガス拡散層及びその製造方法
JPS5944749B2 (ja) ガス拡散電極
JPH09180727A (ja) 燃料電池用電極、その製造方法及び装置
JP2009193777A (ja) 燃料電池及び燃料電池製造方法
CN112687889A (zh) 一种镁金属空气电池防水透气膜及其连续涂覆制备方法
JP4352187B2 (ja) 空気電池用正極の製造方法
JPH10189002A (ja) 燃料電池用電極及びその製造方法
CN111268673A (zh) 一种以泡沫镍为模板的超级电容器电极材料的制备方法
CN116581308B (zh) 一种膜燃料电池的干法膜电极制备方法
JP5880562B2 (ja) 触媒インクの製造方法、および、燃料電池の製造方法、燃料電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21912636

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21912636

Country of ref document: EP

Kind code of ref document: A1