The application claims the benefits of Taiwan Patent Application No. 110139951, filed on Oct. 27, 2021, at the Taiwan Intellectual Property Office, the disclosures of which are incorporated herein in their entirety by reference.
The present invention relates to a method for manufacturing an electrode and a catalytic layer of the electrode. In particular, the present invention relates to a method for manufacturing an oxygen generating electrode and a catalytic layer of the oxygen generating electrode.
The common oxygen generating apparatus is a continuous oxygen supply equipment. The oxygen generating apparatus uses an electric motor (or an air compressor) to input the air in the atmospheric environment through the molecular sieve to separate the oxygen and nitrogen in the air, and thus a high concentration of oxygen is obtained. Because the oxygen generating apparatus carries out the redox reaction with the electrode based on the principle of a metal-air electrochemical cell, the consumption of oxygen from the outside air on the cathode leads to a decrease in the oxygen production efficiency, so the material of the electrode and its manufacturing method are the key factors affecting the oxygen production efficiency.
In order to carry out a more efficient redox reaction, which catalyst is selected as the material of the catalytic layer of the electrode has become the research focus of a skilled person because the activity of the catalyst has a great influence on the performance of the air electrode. Generally, the air electrode is composed of a catalyst layer containing a catalyst, a conductive current collector, and a gas diffusion membrane. The inventors of the present invention focus on how to select and utilize the catalytic layer material to improve the oxygen production efficiency of the oxygen generating apparatus.
The purpose of the present invention is to provide a method for manufacturing an electrode to improve the structure of the electrode catalytic layer, increase the reaction area, and improve the oxygen production efficiency.
In accordance with one aspect of the present invention, a method for manufacturing an electrode is disclosed. The method includes steps of: mixing a first catalyst having a first average particle size, a second catalyst having a second average particle size, a first conductive agent, a first adhesive and a solvent to form a first mixture, wherein a weight ratio of the first catalyst to the second catalyst is 5:1 to 1:5; stirring the first mixture to obtain a second mixture; rolling the second mixture into a catalytic layer; and laminating the catalytic layer, a conductive current collector and a gas diffusion membrane to obtain the electrode.
In accordance with another aspect of the present invention, a method for manufacturing an electrode is disclosed. The method includes steps of: mixing a catalyst, a first conductive agent, a first adhesive and a solvent to form a first mixture, wherein the catalyst includes a relatively large particle size catalyst and a relatively small particle size catalyst; stirring the first mixture to obtain a second mixture; rolling the second mixture into a catalytic layer; and laminating the catalytic layer, a conductive current collector and a gas diffusion membrane to obtain the electrode.
In accordance with another aspect of the present invention, a catalytic layer of an electrode is disclosed. The catalytic layer includes: a relatively large particle size catalyst; a relatively small particle size catalyst; a conductive agent; and an adhesive, wherein: the relatively large particle size catalyst has a first average particle size; the relatively small particle size catalyst has a second average particle size; and the first average particle size is larger than the second average particle size.
The above objects and advantages of the present invention will become more immediately apparent to those of ordinary skill in the art upon review of the following detailed description and accompanying drawings.
The present invention will now be described more specifically with reference to the following embodiments. It is to be noted that the following descriptions of preferred embodiments of this invention are presented herein for purpose of illustration and description only; they are not intended to be exhaustive or to be limited to the precise form disclosed. In the preferred embodiments, the same reference numeral represents the same element in each embodiment.
In the catalyst layer 100 according to the embodiment of the present invention, the catalyst as the main component includes a large particle size catalyst 103 and a small particle size catalyst 104, wherein “particle size” means “average particle size”. The “average particle size” refers to the D50 value (i.e. the median value of particle size distribution) or the arithmetic mean calculated by, for example, a laser particle size analyzer known in the art. The “average particle size” can be determined by one skilled in the art according to requirements. For example, in order to keep the quality of the product stable, the catalyst particles of the appropriate particle size will be screened with a screen having a specific mesh according to the requirements. In addition, because the shape of the catalyst particles is inconsistent, the particle size is calculated based on the relatively long diameter of the particles. The selected average particle size range of the large particle size catalyst 103 of the present invention is 150-270 μm, and the selected average particle size range of the small particle size catalyst 104 is 5-50 μm. The average particle size of the large particle size catalyst 103 is 3-54 times larger than that of the small particle size catalyst 104.
In the catalyst layer 100 according to the embodiment of the present invention, either of the large particle size catalyst 103 and the small particle size catalyst 104 has a material selected from the group consisting of ruthenium dioxide, iridium dioxide, manganese dioxide, cobalt oxide, tricobalt tetraoxide, nickel hydroxide, nickel oxide, iron oxide, tungsten trioxide, vanadium pentoxide and palladium oxide.
The adhesive 102 has a material selected from a group consisting of polytetrafluoroethylene (PTFE), perfluoroethylene propylene copolymer (FEP) and polyvinylidene fluoride (PVDF). The conductive agent 101 has a material selected from a group consisting of carbon black, acetylene black and carbon nanofibers.
The amount of the conductive agent added in the above step (S1) does not exceed half of the total weight of the first mixture, preferably within the range of 20-50%, more preferably within the range of 28-46%. The conductive agent can enhance the conductivity of the electrode. If the conductive agent is added too much, the content of the catalyst will be reduced, and the reaction ability will be deteriorated. For the catalyst added in the above step (S1), the weight ratio of the large particle size catalyst to the small particle size catalyst is 10:1-1:10, preferably 5:1-1:5.
The difference between the mixing step (S1) and the stirring step (S2) is that the step (S1) is a rough mixing and does not require high uniformity, while the step (S2) is performed to achieve high uniformity of the mixture. Therefore, in the mixing step (S1), the rotating speed can be set at 50-800 rpm, preferably 100-700 rpm, more preferably 150-600 rpm. A mixer (blade shear force mixer) commonly used by those in the art can be used for manufacturing the first mixture. A planetary mixer (also known as a gravity centrifugal mixer) can be used for the stirring step (S2), and the rotation speed is set in the range of 200-2000 rpm, preferably 400-1900 rpm, more preferably 500-1400 rpm, to manufacture the second mixture. In addition, the step (S2) is not limited to using a planetary mixer, and can also be performed by a blade shearing mixer, as long as the purpose of uniform distribution of materials can be achieved.
A rolling machine commonly used by those in the art can be used for the rolling step (S3), wherein the rotation speed is set in the range of 1-30 rpm, preferably 2-28 rpm, more preferably 4-26 rpm, and the temperature of the roller is set below 15020 C., preferably 15-100° C., more preferably 20-80° C.
The function of the conductive current collector 112 is to concentrate the current, fix the catalytic layer and support the electrode structure, and the conductive current collector 112 is a metal mesh or foam having a material selected from a group consisting of stainless steel, nickel, titanium and copper. The functions of the gas diffusion membranes 111, 111a and 111b are to allow oxygen to pass therethrough and prevent the electrolyte from outflowing, and the gas diffusion membranes 111, 111a and 111b are made of the same materials as the conductive agent 101 and the adhesive 102. That is, the gas diffusion membranes 111, 111a and 111b are made of the conductive agent and the adhesive. The conductive agent is selected from one of or at least one of, for example, carbon black, acetylene black, and carbon nanofibers. The adhesive is selected from one of polytetrafluoroethylene (PTFE), perfluoroethylene propylene copolymer (FEP) and polyvinylidene fluoride (PVDF). The gas diffusion membranes 111, 111a and 111b are manufactured by mixing, stirring and rolling. The steps for manufacturing the gas diffusion membranes 111, 111a and 111b are similar to the steps S1-S3, except that no catalyst is added, and the mixing ratio can be adjusted by one skilled in the art according to needs. The ratio of the conductive agent 101 is preferably higher than that of the adhesive 102. In the gas diffusion membrane 111, the ratio of the adhesive 102 is higher than that of the catalyst layer 100.
Based on the above-mentioned manufacturing method of the catalyst layer 100 of the present invention, relevant embodiments are proposed as follows.
Regarding Embodiment 1 of the present invention, it is prepared according to the ratio of Table 1 above. Specifically, 45 g of MnO2 with an average particle size of 270 μm, 9 g of MnO2 with an average particle size of 5 μm, 103.5 g of XC72R and 67.5 g of PTFE are mixed with 112 g of 95% ethanol and 665 g of water and stirred by the DLH DC mixer (YOTEC CORPORATION, MRB-3500L) at 200 rpm for 10 minutes, and a gelatinous first mixture is produced after thorough mixing. The gelatinous first mixture is then stirred by the planetary mixer (THINKY CORPORATION) at 1900 rpm for 5 minutes to obtain an agglomerated second mixture. The agglomerated second mixture is then rolled into a catalytic layer with a thickness of 0.78 mm using the roller compactor (EKTRON TEK CO., LTD., EKT-2100SLM) at 25° C. and 50 rpm. Finally, the catalytic layer is laminated with a conductive current collector and a gas diffusion membrane (thickness of 1.2 mm) to obtain an electrode (or a cathode) with a thickness of 1.87 mm.
Regarding Embodiment 2 of the present invention, it is prepared according to the ratio of Table 2 above. Specifically, 78.75 g of MnO2 with an average particle size of 270 μm, 15.75 g of MnO2 with an average particle size of 50 μm, 56.25 g of XC72R, 6.75 g of VGCF-H and 67.5 g of PTFE are mixed with 112 g of 95% ethanol and 665 g of water and stirred by the DLH DC mixer (YOTEC CORPORATION, MRB-3500L) at 200 rpm for 10 minutes, and a gelatinous first mixture is produced after thorough mixing. The gelatinous first mixture is then stirred by the planetary mixer (THINKY CORPORATION) at 1900 rpm for 5 minutes to obtain an agglomerated second mixture. The agglomerated second mixture is then rolled into a catalytic layer with a thickness of 0.78 mm using the roller compactor (EKTRON TEK CO., LTD., EKT-2100SLM) at 25° C. and 50 rpm. Finally, the catalytic layer is laminated with a conductive current collector and a gas diffusion membrane (thickness of 1.2 mm) to obtain an electrode (or a cathode) with a thickness of 1.87 mm.
Regarding Embodiment 3 of the present invention, it is prepared according to the ratio of Table 3 above. Specifically, 78.75 g of MnO2 with an average particle size of 150 μm, 15.75 g of MnO2 with an average particle size of 5 μm, 85.5 g of XC72R and 45 g of PTFE are mixed with 114 g of 95% ethanol and 662 grams of water and stirred by the DLH DC mixer (YOTEC CORPORATION, MRB-3500L) at 200 rpm for 10 minutes, and a gelatinous first mixture is produced after thorough mixing. The gelatinous first mixture is then stirred by the planetary mixer (THINKY CORPORATION) at 1900 rpm for 5 minutes to obtain an agglomerated second mixture. The agglomerated second mixture is then rolled into a catalytic layer with a thickness of 0.78 mm using the roller compactor (EKTRON TEK CO., LTD., EKT-2100SLM) at 25° C. and 50 rpm. Finally, the catalytic layer is laminated with a conductive current collector and a gas diffusion membrane (thickness of 1.2 mm) to obtain an electrode (or a cathode) with a thickness of 1.87 mm.
Regarding Embodiment 4 of the present invention, it is prepared according to the ratio of Table 4 above. Specifically, 67.5 g of MnO2 with an average particle size of 150 μm, 13.5 g of MnO2 with an average particle size of 50 μm, 99 g of XC72R and 45 g of PTFE are mixed with 114 g of 95% ethanol and 662 g of water and stirred by the DLH DC mixer (YOTEC CORPORATION, MRB-3500L) at 200 rpm for 10 minutes, and a gelatinous first mixture is produced after thorough mixing. The gelatinous first mixture is then stirred by the planetary mixer (THINKY CORPORATION) at 1900 rpm for 5 minutes to obtain an agglomerated second mixture. The agglomerated second mixture is then rolled into a catalytic layer with a thickness of 0.78 mm using the roller compactor (EKTRON TEK CO., LTD., EKT-2100SLM) at 25° C. and 50 rpm. Finally, the catalytic layer is laminated with a conductive current collector and a gas diffusion membrane (thickness of 1.2 mm) to obtain an electrode (or a cathode) with a thickness of 1.87 mm.
Regarding Embodiment 5 of the present invention, it is prepared according to the ratio of Table 5 above. Specifically, 13.5 g of MnO2 with an average particle size of 150 μm, 67.5 g of MnO2 with an average particle size of 50 μm, 69.75 g of XC72R, 6.75 g of VGCF-H and 67.5 g of PTFE are mixed with 112 g of 95% ethanol and 665 g of water and stirred by the DLH DC mixer (YOTEC CORPORATION, MRB-3500L) at 200 rpm for 10 minutes, and a gelatinous first mixture is produced after thorough mixing. The gelatinous first mixture is then stirred by the planetary mixer (THINKY CORPORATION) at 1900 rpm for 5 minutes to obtain an agglomerated second mixture. The agglomerated second mixture is then rolled into a catalytic layer with a thickness of 0.78 mm using the roller compactor (EKTRON TEK CO., LTD., EKT-2100SLM) at 25° C. and 50 rpm. Finally, the catalytic layer is laminated with a conductive current collector and a gas diffusion membrane (thickness of 1.2 mm) to obtain an electrode (or a cathode) with a thickness of 1.87 mm.
Regarding a comparative example of a single average particle size of the present invention, it is prepared according to the ratio of Table 6 above. Specifically, 45.0 g of MnO2 with a single average particle size of 150 μm (as in the above-mentioned Embodiments 1-5, the single average particle size refers to the D50 value calculated by a laser particle size analyzer known in the art), 112.5 g of XC72R, 67.5 g of PTFE, 112 g of 95% ethanol and 665 g of water are mixed by the DLH DC mixer (YOTEC CORPORATION, MRB-3500L) at 200 rpm for 10 minutes, and a gelatinous first mixture is produced after thorough mixing. The gelatinous first mixture is then stirred by the planetary mixer (THINKY CORPORATION) at 1900 rpm for 5 minutes to obtain an agglomerated second mixture. The agglomerated second mixture is then rolled into a catalytic layer with a thickness of 0.78 mm using the roller compactor (EKTRON TEK CO., LTD., EKT-2100SLM) at 25° C. and 50 rpm. Finally, the catalytic layer was laminated with a conductive current collector and a gas diffusion membrane (thickness of 1.2 mm) to obtain an electrode (or a cathode) with a thickness of 1.87 mm.
While the invention has been described in terms of what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention need not be limited to the disclosed embodiments. Therefore, it is intended to cover various modifications and similar configurations included within the spirit and scope of the appended claims, which are to be accorded with the broadest interpretation so as to encompass all such modifications and similar structures.
Number | Date | Country | Kind |
---|---|---|---|
110139951 | Oct 2021 | TW | national |