阅读说明：本技术 一种工业化生产高效率电解水制氢催化电极的方法 (Method for industrially producing high-efficiency catalytic electrode for hydrogen production by water electrolysis ) 是由 陈庆 廖健淞 刘超 司文彬 于 2020-06-23 设计创作，主要内容包括：本发明涉及制氢领域,公开了一种工业化生产高效率电解水制氢催化电极的方法。包括如下生产过程：(1)将催化剂粉末和强还原性金属混合后加入球磨机,先加入分散剂干法球磨,然后加入助磨溶剂湿法球磨,制得球磨浆料；(2)向球磨浆料中加入有机硅树脂溶液,制得喷涂浆料；(3)将喷涂浆料静电喷涂于电极材料表面,惰性气氛下干燥后使用无水乙醇洗净,烘干,即得高效率催化电极。本发明制备电解水催化电极的方法与普通方法相比,通过将强还原性金属与催化剂粉末混合后进行简单地真空球磨,有效提高了催化剂的析氧活性,得到具有较高效率的电解催化剂,整个制备过程简单可控,对设备要求较低,无需高温烧结还原等工艺,可以有效节约生产成本。(The invention relates to the field of hydrogen production and discloses a method for industrially producing a high-efficiency catalytic electrode for hydrogen production by water electrolysis. Comprises the following production processes: (1) mixing catalyst powder and a strong reducing metal, adding the mixture into a ball mill, adding a dispersing agent for dry ball milling, and adding a grinding-aid solvent for wet ball milling to prepare ball milling slurry; (2) adding an organic silicon resin solution into the ball-milling slurry to prepare spraying slurry; (3) and (3) electrostatically spraying the spraying slurry on the surface of the electrode material, drying in an inert atmosphere, cleaning with absolute ethyl alcohol, and drying to obtain the high-efficiency catalytic electrode. Compared with the common method, the method for preparing the electrolytic water catalytic electrode has the advantages that the strong reducing metal and the catalyst powder are mixed and then are simply subjected to vacuum ball milling, so that the oxygen evolution activity of the catalyst is effectively improved, the electrolytic catalyst with higher efficiency is obtained, the whole preparation process is simple and controllable, the requirement on equipment is lower, high-temperature sintering reduction and other processes are not needed, and the production cost can be effectively saved.)

1. a method for industrially producing a high-efficiency water electrolysis hydrogen production catalytic electrode is characterized by comprising the following specific preparation processes:

(1) uniformly mixing catalyst powder and a strong reducing metal, then placing the mixture in a ball mill, adding a small amount of dispersant, introducing inert atmosphere for dry ball milling, and finally adding a grinding-aid solvent for continuous wet ball milling to prepare ball milling slurry; the raw materials comprise, by weight, 90-110 parts of catalyst powder, 1-30 parts of strong reducing metal, 0.5-4 parts of dispersing agent and 5-15 parts of grinding-aid solvent;

(2) adding an organic silicon resin solution into the ball-milling slurry prepared in the step (1), and uniformly mixing to prepare spraying slurry; the raw materials comprise, by weight, 50-60 parts of ball-milling slurry and 10-20 parts of organic silicon resin solution;

(3) and (3) firstly, electrostatically spraying the spraying slurry prepared in the step (2) on the surface of an electrode material, then, drying the sprayed electrode material in a drying atmosphere, then, cleaning the electrode material by using absolute ethyl alcohol, and finally, drying the electrode material to obtain the high-efficiency catalytic electrode, so that the preparation process of industrially producing the high-efficiency catalytic electrode is realized.

2. The method for industrially producing the catalytic electrode for hydrogen production by electrolyzing water according to claim 1, wherein the method comprises the following steps: the strong reducing metal in the step (1) is one of Li and Na, and the particle size D50= 100-500 nm.

3. The method for industrially producing the catalytic electrode for hydrogen production by electrolyzing water according to claim 1, wherein the method comprises the following steps: the catalyst powder is transition metal oxide spherical powder, the granularity D50= 10-100 um, and the transition metal is one of Ti, Zn, Sn and Ce.

4. The method for industrially producing the catalytic electrode for hydrogen production by electrolyzing water according to claim 1, wherein the method comprises the following steps: the dispersant in the step (1) is one of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone and N-methylpyrrolidine.

5. The method for industrially producing the catalytic electrode for hydrogen production by electrolyzing water according to claim 1, wherein the method comprises the following steps: the grinding-aid solvent in the step (1) is a mixed solution of kerosene and a dispersing agent; the mixed solution comprises, by weight, 60-80 parts of kerosene and 1-3 parts of a dispersing agent; the dispersing agent is polyvinylpyrrolidone.

6. The method for industrially producing the catalytic electrode for hydrogen production by electrolyzing water according to claim 1, wherein the method comprises the following steps: the grinding balls of the ball mill in the step (1) are stainless steel balls, the diameter of the grinding balls is 1-10 mm, the ball-material ratio is 2-3: 1, the ball milling rotating speed is 10-30 r/min, the dry ball milling time is 1-2 hours, and the wet ball milling rotating speed is 3-4 hours.

7. The method for industrially producing the catalytic electrode for hydrogen production by electrolyzing water according to claim 1, wherein the method comprises the following steps: the mass concentration of the organic silicon resin solution in the step (2) is 30-40%, and the organic silicon resin is polyalkyl organic silicon resin.

8. The method for industrially producing the catalytic electrode for hydrogen production by electrolyzing water according to claim 1, wherein the method comprises the following steps: the electrode material in the step (3) is a common electrode, and specifically can be one of a graphite electrode and a stainless steel electrode.

9. The method for industrially producing the catalytic electrode for hydrogen production by electrolyzing water according to claim 1, wherein the method comprises the following steps: and (3) performing electrostatic spraying by using a direct-current power supply with the voltage of 40-50kV, wherein the thickness of the sprayed film is 5-10 mu m.

10. The method for industrially producing the catalytic electrode for hydrogen production by electrolyzing water according to claim 1, wherein the method comprises the following steps: the ball milling inert atmosphere and the drying atmosphere of the electrode material are argon.

Technical Field

The invention relates to the field of hydrogen production and discloses a method for industrially producing a high-efficiency catalytic electrode for hydrogen production by water electrolysis.

Background

With the large volume production of fossil fuels in recent years, the reserves of fossil fuels on earth have been decreasing. Fossil fuel combustion generates a large amount of greenhouse gases, which causes the global warming effect to be intensified, and then causes a series of ecological and environmental problems. With the increasing situation, hydrogen energy has attracted more and more attention in the field of new energy due to its high energy conversion efficiency and cleanness without pollution. The hydrogen production by water electrolysis is an efficient and clean hydrogen production technology, the hydrogen production process is simple, the product purity is high, the purity of hydrogen and oxygen can reach 99.9 percent generally, the technology is the most potential large-scale hydrogen production technology, and the technology is widely concerned in the global scope.

The hydrogen production by water electrolysis is mainly characterized in that direct current is introduced into an electrolytic cell filled with electrolyte, and water molecules are subjected to electrochemical reaction on an electrode and are decomposed into hydrogen and oxygen. The principle is as follows: when a direct current is applied to some aqueous electrolyte solutions, the decomposed substances are completely unrelated to the original electrolyte, and water is decomposed as a solvent, and the original electrolyte remains in the water. Such as sulfuric acid, sodium hydroxide, potassium hydroxide, and the like, are among such electrolytes. In the electrolysis of water, since pure water has a low ionization degree and a low conductivity, and is typically a weak electrolyte, the electrolyte needs to be added to increase the conductivity of the solution, so that water can be smoothly electrolyzed into hydrogen and oxygen.

The hydrogen production process by water electrolysis is simple, the product purity is high, the renewable energy is adopted as an energy source, the high-efficiency, clean and large-scale hydrogen preparation can be realized, and the technology can also be used for CO₂The emission reduction and the conversion have wider development prospect. However, the existing water electrolysis process has high energy consumption, and mainly because the overpotential of the hydrogen evolution working electrode is high, the reduction of the overpotential of hydrogen evolution and the improvement of the activity of a catalyst are the main problems of water electrolysis hydrogen production at present.

The Chinese patent application No. 201811632468.7 discloses a preparation method for constructing a two-dimensional metal organic framework nano-hydrolysis electrocatalyst by taking foam copper as a substrate, firstly growing flower-shaped copper phosphate nanosheets on the surface of the foam copper in situ by a self-sacrifice template method, then growing the copper phosphate nanosheets on the surface of the foam copper in situ to be vertical to Cu on the surface of the copper phosphate nanosheets₃(PO₄)₂Copper-containing MOFs nanosheets.

The Chinese patent application No. 201811096948.6 discloses a nano-porous hydrogen production catalyst and a preparation method thereof, firstly preparing an amorphous alloy strip according to the following mass ratio: 50-80% of pure Al, 5-20% of pure Cu, 10-20% of pure Ti, 10-20% of pure Pd and 100% of the total of the four components; and (3) sequentially carrying out twice dealloying on the prepared amorphous alloy strip in sodium hydroxide and sulfuric acid to obtain the nano-porous Al-Pd-Cu-Ti material.

According to the above, the overpotential of the hydrogen evolution working electrode for hydrogen production by water electrolysis in the existing scheme is high, the activity of the catalyst is poor, the hydrogen production efficiency is affected, the technical method for preparing the high-efficiency catalyst is complex in process, a large amount of acid, alkali and organic solvent are needed, and high-speed ball milling and high-temperature treatment are needed in some processes, so that the simplification and control of the production process are not facilitated. Therefore, the development of a simple synthesis process for a high-efficiency catalytic electrode has a very important practical problem. The invention provides a method for industrially producing a high-efficiency water electrolysis hydrogen production catalytic electrode, which can effectively solve the technical problems.

Disclosure of Invention

The prior technical method for producing hydrogen by electrolyzing water, which is widely applied, has the problems of high overpotential of a hydrogen evolution working electrode, low catalyst activity and unsatisfactory hydrogen production efficiency, and the prior process for preparing the high-efficiency catalytic electrode is complex, so that the application of the high-efficiency catalytic electrode is influenced.

The invention achieves the above purpose by the following technical scheme:

a method for industrially producing a high-efficiency water electrolysis hydrogen production catalytic electrode comprises the following specific preparation processes:

(1) uniformly mixing catalyst powder and a strong reducing metal, then placing the mixture in a ball mill, adding a small amount of dispersant, introducing inert atmosphere for dry ball milling, and finally adding a grinding-aid solvent for continuous wet ball milling to prepare ball milling slurry; the raw materials comprise, by weight, 90-110 parts of catalyst powder, 1-30 parts of strong reducing metal, 0.5-4 parts of dispersing agent and 5-15 parts of grinding-aid solvent;

(2) adding an organic silicon resin solution into the ball-milling slurry prepared in the step (1), and uniformly mixing to prepare spraying slurry; the raw materials comprise, by weight, 50-60 parts of ball-milling slurry and 10-20 parts of organic silicon resin solution;

(3) and (3) firstly, electrostatically spraying the spraying slurry prepared in the step (2) on the surface of an electrode material, then, drying the sprayed electrode material in a drying atmosphere, then, cleaning the electrode material by using absolute ethyl alcohol, and finally, drying the electrode material to obtain the high-efficiency catalytic electrode, so that the preparation process of industrially producing the high-efficiency catalytic electrode is realized.

The invention utilizes the strong reducing metal to react with the catalyst powder, the strong reducing metal can capture the oxygen on the surface of the catalyst powder, so that partial oxygen on the surface of the catalyst powder is lost to form a disordered structure layer rich in oxygen vacancy defects, thereby forming a certain amount of oxygen vacancy defects, and the oxygen vacancy defects can effectively improve the capture capacity of OH-in the water electrolysis process, thereby effectively improving the efficiency of hydrogen production catalyzed by electrolyzed water. Preferably, in the step (1), the strong reducing metal is one of Li and Na, and the particle size D50= 100-500 nm; the catalyst powder is transition metal oxide spherical powder, the granularity D50=10~100um, the transition metal is one of Ti, Zn, Sn, Ce.

The reaction of the strong reducing metal and the catalyst powder is carried out under a simple earth mill, and in order to improve the effect of the ball milling reaction, a solid-phase dispersant and a grinding-aid solvent are added in sequence during the ball milling. Preferably, the dispersant in the step (1) is one of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone and N-methylpyrrolidine; the grinding-aid solvent is a mixed solution of kerosene and a dispersing agent; the mixed solution comprises, by weight, 60-80 parts of kerosene and 1-3 parts of a dispersing agent; the dispersing agent in the grinding aid solvent is further preferably polyvinylpyrrolidone.

The method mainly carries out solid-phase reduction through simple physical ball milling, so that oxygen on the surface of the catalyst powder is captured by the strong reducing metal to form oxide, thereby losing part of oxygen on the surface of the catalyst powder to form a disordered structure layer rich in oxygen vacancy defects and forming a certain amount of oxygen vacancy defects, and the oxygen vacancy defects can effectively improve the capture capacity of OH < - > in the water electrolysis process, thereby effectively improving the catalytic efficiency; in the electrolytic process of the obtained product, the oxide formed by the strong reducing metal is spontaneously hydrolyzed, the ion conduction capability of the solution can be improved, and meanwhile, the surface of the electrode forms a porous structure due to the hydrolysis of the oxide, so that the catalytic reaction efficiency of the electrolyzed water is further improved, and the hydrogen production rate is accelerated. The electrolytic catalyst with higher efficiency is obtained through simple vacuum ball milling in the whole process, the preparation method is simple and controllable, the requirement on equipment is lower, processes such as high-temperature sintering reduction and the like are not needed, and the production cost can be effectively saved. Preferably, the grinding balls of the ball mill in the step (1) are stainless steel balls, the diameter of the grinding balls is 1-10 mm, the ball-material ratio is 2-3: 1, the ball milling rotating speed is 10-30 r/min, the dry ball milling time is 1-2 h, and the wet ball milling rotating speed is 3-4 h.

And mixing the obtained ball-milling slurry with an organic silicon resin solution to obtain a spraying slurry, and uniformly coating the spraying slurry on the surface of the electrode by using an electrostatic spraying process, wherein the uniform and stable catalyst coating is formed on the surface of the electrode by the slurry due to the film forming property of the organic silicon resin solution. In the present invention, the silicone resin solution in the step (2) preferably has a mass concentration of 30 to 40%, and the silicone resin is selected from polyalkyl silicone resins.

Preferably, the electrode material in step (3) is a common electrode, and specifically may be one of a graphite electrode and a stainless steel electrode.

In the present invention, the electrostatic spraying in step (3) is preferably performed by a DC power supply of 40-50kV voltage, and the thickness of the sprayed coating film is 5-10 μm.

The ball-milling slurry reaction and the spraying electrode drying are carried out in the argon atmosphere, so that the pureness of the reaction and the product is ensured. In the present invention, the ball milling inert gas atmosphere and the drying atmosphere of the electrode material are preferably argon gas.

The high-efficiency electrolytic water catalytic electrode prepared by the method has good catalytic activity, high efficiency of hydrogen production by water electrolysis, simple and controllable process and low cost. Through tests, the hydrogen production amount of the prepared electrolyzed water catalytic electrode in 10min is 626-630 mL in the electrolyzed water hydrogen production test reaction, and the hydrogen production efficiency is 70-72%.

The invention provides a method for industrially producing a high-efficiency hydrogen production catalytic electrode by electrolyzing water, which comprises the steps of uniformly mixing strong reducing metal and catalyst powder, placing the mixture into a ball mill, adding a small amount of dispersant, introducing inert atmosphere, carrying out dry ball milling, adding a grinding-aid solvent, continuing wet ball milling to obtain ball-milling slurry, and adding an organic silicon resin solution into the slurry to prepare spraying slurry; and (3) coating the prepared spraying slurry on the surface of the electrode material by adopting electrostatic spraying, drying the sprayed electrode material in a drying atmosphere, cleaning by using absolute ethyl alcohol, and drying.

The invention provides a method for industrially producing a high-efficiency water electrolysis hydrogen production catalytic electrode, which has the outstanding characteristics and excellent effects compared with the prior art:

1. provides a method for realizing the industrial production of the high-efficiency water electrolysis hydrogen production catalytic electrode by adopting a ball milling process.

2. The strong reducing metal is mixed with the catalyst powder and subjected to ball milling, and the reducing metal captures oxygen on the surface of the catalyst powder to form oxygen defects in the ball milling process, so that the oxygen evolution activity of the catalyst is effectively improved, the efficiency of hydrogen production by water electrolysis is improved, and the obtained slurry is sprayed on the surface of an electrode to obtain a high-efficiency electrolyzed water catalytic electrode.

3. The invention obtains the electrolytic catalyst with higher efficiency by simple vacuum ball milling, the preparation method is simple and controllable, the requirement on equipment is lower, processes such as high-temperature sintering reduction and the like are not needed, and the production cost can be effectively saved.

Description of the drawings:

FIG. 1 is a schematic diagram of the preparation process of the high-efficiency electrolytic water catalytic electrode of the present invention.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.