KR-20260063484-A - Catalyst for Hydrogen Evolution Reaction and Method for Preparing the Same

Abstract

The present invention relates to a catalyst for a hydrogen generation reaction comprising cobalt and vanadium in a certain ratio. The catalyst of the present invention can exhibit catalytic activity at a level similar to that of conventional precious metals, has high hydrogen generation efficiency, and can exhibit excellent stability even under non-freshwater conditions.

Inventors

• 박성일
• 정현정
• 한세희
• 이예찬
• 정한솔
• 송지현
• 김성은
• 김민성
• 박상민
• 남재우
• 송시명
• 한정우

Assignees

• 에이치디한국조선해양 주식회사
• 에이치디현대중공업 주식회사
• 서울대학교산학협력단

Dates

Publication Date

20260507

Application Date

20241030

Claims (14)

1. It includes cobalt; and vanadium; and The molar ratio between the above cobalt and vanadium is 5:1 to 30:1. A catalyst for a hydrogen generation reaction characterized by having crystallinity.
2. In paragraph 1, A catalyst for hydrogen generation reaction having a crystal size of 5 nm or more and 15 nm or less, calculated from the (121) peak in the graph obtained from the XRD analysis result of the above catalyst.
3. In paragraph 1, A catalyst for hydrogen generation reaction having a crystal size of 7 nm or more and 17 nm or less, calculated from the (312) peak in the graph obtained from the XRD analysis result of the above catalyst.
4. In paragraph 1, The above catalyst is a catalyst for a hydrogen generation reaction having a hierarchical structure in which a plurality of nanoparticles are connected to each other.
5. In paragraph 4, A catalyst for a hydrogen generation reaction having an average particle size of 5 nm or more and 30 nm or less of the above nanoparticles.
6. In paragraph 4, The above catalyst is a catalyst for a hydrogen generation reaction in which a plurality of nanoparticles are connected to each other to form a sheet structure.
7. In paragraph 1, A catalyst for a hydrogen generation reaction in which the molar ratio between the above cobalt and vanadium is 15:1 to 25:1.
8. Step (S1) of obtaining solid particles by reacting a mixed solution containing a cobalt precursor and a vanadium precursor; Step (S2) of purifying the obtained solid particles and then freeze-drying them; and The method includes a step (S3) of heat treatment under a reducing atmosphere, A method for preparing a catalyst for a hydrogen generation reaction in which the molar ratio between the cobalt and vanadium is 5:1 to 30:1.
9. In paragraph 8, The solvent of the above mixed solution is water; and A method for preparing a catalyst for a hydrogen generation reaction comprising one or more organic solvents selected from the group consisting of ethanol, diethylene glycol, and ethylene glycol.
10. In paragraph 8, A method for preparing a catalyst for a hydrogen generation reaction, wherein the above-mentioned mixed solution further contains ammonia.
11. In paragraph 8, A method for manufacturing a catalyst for a hydrogen generation reaction, wherein the reaction of the above S1 step is carried out at 100 to 150°C.
12. In paragraph 8, A method for manufacturing a catalyst for a hydrogen generation reaction, wherein the heat treatment of the above S3 step is performed at 300 to 500℃.
13. In paragraph 8, A method for manufacturing a catalyst for a hydrogen generation reaction, wherein the above-mentioned reducing atmosphere has a hydrogen gas concentration of 5 to 15 volume%.
14. Listing; and Includes a catalyst layer formed on the above-mentioned substrate; The above catalyst layer is a cathode for electrolysis comprising the catalyst for a hydrogen generation reaction of claim 1.

Description

Catalyst for Hydrogen Evolution Reaction and Method for Preparing the Same The present invention relates to a catalyst for a hydrogen generation reaction comprising cobalt and vanadium in a predetermined molar ratio, a method for manufacturing the same, and a cathode for electrolysis comprising said catalyst. Various types of energy sources are being researched to replace fossil fuels, and a representative example is hydrogen, which has a high energy density without emitting harmful byproducts. Electrolysis is the most commonly researched and practiced method for producing hydrogen. When water is electrolyzed, oxygen is obtained from the oxidation electrode and hydrogen from the reduction electrode; as water is one of the most abundant substances on Earth, it has the advantage of being easily available as a raw material. Water electrolysis for hydrogen production can be operated under acidic or alkaline conditions. Generally, the hydrogen evolution reaction (HER) under acidic conditions is preferred for hydrogen production because it is carried out under conditions with sufficient protons compared to the HER under alkaline conditions. However, the HER under acidic conditions has the disadvantage of reduced stability due to the potential for electrode corrosion, and significantly increased electrode manufacturing costs because precious metal catalysts must be used. Therefore, there is a need to develop a catalyst that can produce hydrogen sufficiently efficiently even under alkaline conditions without the disadvantages associated with acidic conditions. As an example of such catalysts, catalysts for hydrogen evolution containing nickel oxide or hydroxide clusters have been developed; however, these have stability issues where performance degrades during long-term operation due to the oxidation of the precious metal surface, thereby limiting mass production and performance improvement. In addition, various catalysts capable of exhibiting excellent catalytic activity for hydrogen evolution without using expensive precious metals are being researched; however, there are generally problems in that their synthesis methods are very complex or the time and cost involved in synthesis are high, meaning the economic feasibility of catalyst manufacturing itself is not particularly superior to that of existing precious metal catalysts. Figure 1 shows a photograph of the catalyst manufacturing process according to Example 1 of the present invention. Figure 2 shows an XRD graph of the catalyst before and after reduction according to Example 1 of the present invention. Figure 3 shows the XRD graph before and after reduction of the catalyst according to Comparative Example 2 of the present invention. Figure 4 is an SEM image showing the shape of the catalyst before and after reduction according to Example 1 of the present invention. Figure 5 is an SEM image showing the shape of the catalyst before and after reduction according to Comparative Example 2 of the present invention. Figure 6 is a graph comparing the electrochemical activity of the catalyst according to Example 1 of the present invention and the catalyst according to Comparative Example 1. Figure 7 is a graph comparing the electrochemical activity of the catalysts according to Examples 1 and 2 and the catalysts according to Comparative Examples 3 and 4. FIG. 8 shows a graph of the voltage applied when performing electrolysis under fresh water and non-fresh water conditions using a cell (oxidation electrode: iridium oxide) configured using the catalyst according to Example 1 of the present invention and the catalyst according to Comparative Example 1. Figure 9 shows the hydrogen generation efficiency values measured when performing electrolysis under fresh water and non-fresh water conditions using a cell (oxidation electrode: iridium oxide) configured with the catalyst according to Example 1 of the present invention and the catalyst according to Comparative Example 1. Figure 10 shows a graph of the voltage applied when performing electrolysis under fresh water and non-fresh water conditions using a cell (oxidation electrode: NiFeCo LDH) configured with the catalyst according to Example 1 of the present invention and the catalyst according to Comparative Example 1. Figure 11 shows the hydrogen generation efficiency values measured when performing electrolysis under fresh water and non-fresh water conditions using a cell (oxidation electrode: NiFeCo LDH) configured with the catalyst according to Example 1 of the present invention and the catalyst according to Comparative Example 1. FIG. 12 is a graph showing the voltage change over 200 hours when electrolysis is performed under non-freshwater conditions using a cell (oxidation electrode: NiFeCo LDH) constructed using the catalyst according to Example 1 of the present invention. The present invention will be described in more detail below. Terms and words used in this specification and claims should not be interprete