阅读说明：本技术 一种集成催化电极的制备方法 (Preparation method of integrated catalytic electrode ) 是由 孙蓉 康佳慧 盛家利 谢金麒 符显珠 于 2018-08-27 设计创作，主要内容包括：本发明实施例提供一种集成催化电极的制备方法,涉及电极材料制备技术领域。包括：在泡沫铜上生长氢氧化铜/氧化铜纳米管活性材料,得到氢氧化铜纳米管活性材料,将氢氧化铜纳米管活性材料置于过渡金属盐溶液和尿素溶液的混合液中,并在温度为50～100℃密闭的反应釜中反应至少4h,过滤干燥,得到集成有氢氧化铜/碱式碳酸物核壳纳米管活性材料的催化电极。该方法简化了合成过程,减少了电极内阻,加速了电子传输,大大增强了电极的析氧催化剂的性能和稳定性。(The embodiment of the invention provides a preparation method of an integrated catalytic electrode, and relates to the technical field of electrode material preparation. The method comprises the following steps: growing a copper hydroxide/copper oxide nanotube active material on the copper foam to obtain a copper hydroxide nanotube active material, placing the copper hydroxide nanotube active material in a mixed solution of a transition metal salt solution and a urea solution, reacting for at least 4 hours in a closed reaction kettle at the temperature of 50-100 ℃, filtering and drying to obtain the catalytic electrode integrated with the copper hydroxide/basic carbonate core-shell nanotube active material. The method simplifies the synthesis process, reduces the internal resistance of the electrode, accelerates the electron transmission, and greatly enhances the performance and stability of the oxygen evolution catalyst of the electrode.)

1. A method of making an integrated catalytic electrode, the method comprising:

growing a copper hydroxide/copper oxide nanotube active material on the foamy copper to obtain a copper hydroxide nanotube active material;

and (2) placing the copper hydroxide nanotube active material into a mixed solution of a transition metal salt solution and a urea solution, reacting for at least 4 hours in a closed reaction kettle at the temperature of 50-100 ℃, filtering and drying to obtain the catalytic electrode integrated with the copper hydroxide/basic carbonate core-shell nanotube active material.

2. The method of claim 1, wherein growing copper hydroxide/copper oxide nanotube active material on copper foam comprises:

soaking the foamy copper in an acid solution and water for 2-15 min in sequence;

then the copper foam is put into alkaline solution and (NH)₄)₂S₂O₈Soaking the copper hydroxide/cuprous oxide nanotube active material in the mixed solution for 10-50 min, taking out and drying when the foamy copper is changed from orange to blue, and obtaining the copper hydroxide/cuprous oxide nanotube active material, wherein the concentration of the alkaline solution is 0.1-6 mol/L, (NH)₄)₂S₂O₈The concentration of the solution is 0.05-0.8 mol/L.

3. The method of claim 1, wherein the alkaline solution is NaOH solution, KOH solution, or Na₂CO₃At least one of the solutions.

4. The method of claim 2, wherein the acidic solution is dilute hydrochloric acid or dilute sulfuric acid.

5. The method according to claim 2, wherein the concentration of the alkaline solution is 1 to 4 mol/L.

6. The method of claim 2, wherein (NH)₄)₂S₂O₈The concentration of the solution is 0.1-0.6 mol/L.

7. The method of claim 2, wherein the copper foam is in an alkaline solution and (NH)₄)₂S₂O₈Soaking the mixture in the solution for 20-40 min.

8. The method according to claim 1, wherein the concentration of the transition metal salt solution is 0.1 to 2 mol/L.

9. The method of claim 1 or 8, wherein the transition metal salt solution is at least one of a ferric sulfate solution, a cobalt chloride solution, a manganese chloride solution, and a nickel sulfate solution.

10. An integrated catalytic electrode material prepared by the method of any one of claims 1 to 8.

Technical Field

The invention belongs to the technical field of battery material preparation, and particularly relates to a preparation method of an integrated catalytic electrode.

Background

At present, the environmental and energy problems are becoming more serious, and the development of renewable energy sources is imminent. The hydrogen energy is an environment-friendly energy storage material with high energy density and good stability, the obtaining way is simple and easy to obtain, and the hydrogen energy can be obtained by electric hydrolysis. Generally, under the condition that energy sources cannot be sufficiently obtained in severe environments and the like, electric energy is converted into hydrogen energy to be stored, hydrogen is obtained by converting the electric energy and decomposing water, and the method is an effective energy storage method and can simultaneously solve the problem that a photovoltaic system cannot obtain energy sources to be stored in rainy days or at night.

However, in the hydrogen energy storage technology, the hydrogen evolution reaction is a two-electron reaction, and the oxygen evolution reaction is a four-proton reaction, so that the slow oxygen evolution reaction occurring at the anode brings an excessively high overpotential, thereby limiting the hydrogen evolution reaction at the cathode. It is presently best to catalyze the oxygen evolution catalyst as a noble metal catalyst, such as RuO₂And IrO₂The material is expensive, and thus cannot be applied in a large scale. To solve this problem, oxides, hydroxides, sulfides, nitrides or phosphides of transition metal elements (e.g., Co, Ni, Mn, Fe) are generally used as catalysts.

However, the conventional oxygen evolution catalyst has a small specific surface area, a high density and low electrochemical active sites, resulting in low catalytic activity and a slow rate of hydrogen generation.

Disclosure of Invention

The invention provides a preparation method of an integrated catalytic electrode, and aims to solve the problems of low catalytic activity and low hydrogen generation rate caused by small specific surface area, high density and low electrochemical active site of an oxygen evolution catalyst.

The invention provides a preparation method of an integrated catalytic electrode, which comprises the following steps:

growing a copper hydroxide/copper oxide nanotube active material on the foamy copper to obtain a copper hydroxide nanotube active material;

and (2) placing the copper hydroxide nanotube active material into a mixed solution of a transition metal salt solution and a urea solution, reacting for at least 4 hours in a closed reaction kettle at the temperature of 50-100 ℃, filtering and drying to obtain the catalytic electrode integrated with the copper hydroxide/basic carbonate core-shell nanotube active material.

The invention provides a preparation method of an integrated catalytic electrode, which obtains integrated Cu (OH)₂Oxygen evolution electrode of basic carbonate core-shell nanotube. The method simplifies the synthesis process, reduces the internal resistance of the electrode, and the spiny basic carbonate grown on the tube wall has rich active sites, accelerates the electron transmission, and greatly enhances the performance and stability of the oxygen evolution catalyst of the electrode.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention.

FIG. 1 is a Scanning Electron Microscope (SEM) test image of an integrated catalytic electrode prepared in example 1 of the present invention;

FIG. 2 is a Transmission Electron Microscope (TEM) test image of the integrated catalytic electrode prepared in example 1 of the present invention.

Detailed Description

In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a preparation method of an integrated catalytic electrode, which comprises the following steps:

growing a copper hydroxide/copper oxide nanotube active material on the foamy copper to obtain a copper hydroxide nanotube active material;

and step two, placing the copper hydroxide nanotube active material into a mixed solution of a transition metal salt solution and a urea solution, reacting for at least 4 hours in a closed reaction kettle at the temperature of 50-100 ℃, filtering and drying to obtain the catalytic electrode integrated with the copper hydroxide/basic carbonate core-shell nanotube active material.

The invention provides a preparation method of an integrated catalytic electrode, which obtains integrated Cu (OH)₂Oxygen evolution electrode of basic carbonate core-shell nanotube. The method simplifies the synthesis process, reduces the internal resistance of the electrode, and the spiny basic carbonate grown on the tube wall has rich active sites, accelerates the electron transmission, and greatly enhances the performance and stability of the oxygen evolution catalyst of the electrode.

Further, the step one of growing copper hydroxide/copper oxide nanotube active material on the copper foam comprises:

and soaking the foamy copper in the acid solution and the water for 2-15 min in sequence.

The impurities of the copper foam can be removed by soaking and cleaning the copper foam in acid and water, and the oxygen evolution stability of the oxygen evolution electrode is further improved.

Then the copper foam is put into alkaline solution and (NH)₄)₂S₂O₈Soaking the copper foam in the mixed solution of the solution for 10-50 min, taking out and drying the copper foam when the copper foam is changed from orange to blue to obtain copper hydroxide/cuprous oxideA nanotube active material.

Wherein the concentration of the alkaline solution is 0.1-6 mol/L, (NH)₄)₂S₂O₈The concentration of the solution is 0.05-0.8 mol/L.

Specifically, the alkaline solution is NaOH solution, KOH solution or Na₂CO₃At least one of solution solutions. The acid solution is dilute hydrochloric acid or dilute sulfuric acid. Preferably, the concentration of the alkaline solution is 1-4 mol/L. (NH)₄)₂S₂O₈The concentration of the solution is 0.1-0.5 mol/L. Copper foam in alkaline solution and (NH)₄)2S₂O₈Soaking the mixture in the solution for 20-40 min.

Specifically, the concentration of the transition metal salt solution is 0.1-2 mol/L. The transition metal salt solution is at least one of ferric sulfate solution, cobalt chloride solution, manganese chloride solution and nickel sulfate solution. The concentration of the urea is 0.01-1 mol/L.

Optionally, growing copper hydroxide/copper oxide nanotube active material on the copper foam further comprises:

soaking the foamy copper in sulfuric acid for 5-15 min, then soaking the foamy copper into an alkaline solution, taking out the foamy copper when the surface of the foamy copper is blue, and drying to obtain the copper hydroxide/cuprous oxide nanotube active material.